JP4891449B1 - Hair dye composition for hair dyeing - Google Patents

Abstract

The present invention relates to a hair dye composition that uses a direct dye, is excellent in safety, is not easily dyed on the skin, is excellent in dyeability, is not easily dyed unevenly, has little deterioration in dyeability over time, and is less likely to lose color. To provide.
A hair dye composition comprising a direct dye, glycine and a pH adjuster, wherein the direct dye is at least 2,2 ′-[[4- [2-hydroxyethyl] amino] -3-nitro Phenyl] bisethanol and / or 4-hydroxypropylamino-3-nitrophenol, and a hair dye composition having a pH of 6.0 to 9.0.
[Selection figure] None

Description

The present invention relates to a hair dye composition for dyeing gray hair , which is excellent in dyeability, excellent in safety and stability over time.

Hair dyeing has been practiced and established in a wide range of age, from gray hair dyeing to fashionable dyeing. The hair dye used mainly is a so-called hair dye that uses a combination of an oxidative dye and an oxidant.
Hair dyes are rich in color and have the advantages of being dyed well, brightly dyed, good color, easy to treat, etc., but also have drawbacks such as damaging hair and skin irritation such as allergies. .

So-called hair manicure using acid dyes and hair dyes using direct dyes (HC dyes, basic dyes, disperse dyes, etc.) do not damage hair for the purpose of eliminating the drawbacks of hair dyes as described above. It has been put on the market with a complaint of high safety.
However, the former is easy to dye on the skin and difficult to remove once it is dyed, so it is well established for professional use in hair salons and the like, but is not very popular for general use.
On the other hand, the latter has advantages such as low skin dyeability and high safety, but weak dyeability, deterioration of dyeability over time, uneven dyeing, easy discoloration during hair washing, etc. It has not been able to satisfy consumers.

With respect to hair dyes using direct dyes, various ideas have been studied to improve the above-described drawbacks.
As a method for enhancing dyeability and a method for eliminating uneven dyeing, a method using benzyloxyethanol (Patent Document 1), a method using organic carboxylic acid, benzyloxyethanol and a cationic surfactant (Patent Document 2), tannic acid (Patent Document 3), a method using a cationic plant protein hydrolyzate (Patent Document 4), a method using an optical brightener (Patent Document 5), a method using cystine bisPG-propylsilanetriol (Patent Document 6) and the like are disclosed.
As a method for preventing discoloration and fading over time, a method using a cationic surfactant, a phosphate, an alkanolamine or the like (Patent Document 7) is disclosed.

However, the disadvantages of hair dyes using direct dyes, such as poor dyeability, deterioration of dyeability over time, uneven dyeing, and fading easily when washing hair, are particularly dark brown to black. This is prominent in hair dyeing, and in this respect the hair dyes of the above documents are not satisfactory.
Hair dyes using direct dyes, especially when made into water-based creams and gels, have the disadvantage that the dyeability deteriorates over time and discolors. In this respect as well, the hair dyes described in the above documents are not satisfactory. Absent.

Japanese Patent No. 4490701 Japanese Patent No. 4509462 Japanese Patent No. 4133785 JP-A-11-92348 JP 2001-294519 A JP 2004-75630 A Japanese Laid-Open Patent Publication No. 9-100284

The present invention has been made to solve the above-mentioned problems, using a direct dye, excellent in safety, difficult to dye on the skin, excellent in dyeability, difficult to uneven dye, The present invention provides a hair dye composition for white hair dyeing , which is less likely to cause color fading and has little deterioration in dyeability.

The invention according to claim 1 is a hair dye composition for gray hair containing a direct dye, glycine and a pH adjuster, wherein the direct dye is at least 2,2 ′-[[4- [2-hydroxyethyl ] amino] -3-nitrophenyl] bis ethanol及beauty 4 - a first essential dye that Do hydroxy propylamino-3-nitrophenol, HC yellow 2, basic blue 99, basic brown 16, purple No. 401, It consists of a combination with one or more second essential pigments selected from the group consisting of basic red 76 and basic yellow 57. The glycine is contained as a stabilizer in an amount of 0.1 to 10% by weight, and has a pH of It is related with the hair dye composition for hair dyeing characterized by being 6.0-9.0.

In the invention according to claim 2, the second essential pigment comprises HC yellow 2 and basic blue 99, or basic blue 99, basic brown 16, purple 401, basic red 76, and basic yellow 57. The present invention relates to a hair dye composition for gray hair dyeing according to claim 1.

The invention according to claim 3 is characterized in that the pH adjuster is sodium lactate, sodium hydroxide, potassium hydroxide, triethanolamine (TEA), monoethanolamine (MEA), aminomethylpropanol (AMP), aminomethylpropanediol. 1 selected from the group consisting of (AMPD), arginine, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium bicarbonate, ammonium carbonate, a mixture of ammonium bicarbonate and ammonium carbamate, and ammonium bicarbonate. It is the above, It is related with the hair dye composition for hair dyeing of Claim 1 or 2 .

According to inventions according to claims 1 and 2 , it is a hair dye composition for hair dyeing containing a direct dye, glycine and a pH adjuster, wherein the direct dye is at least 2,2 ′-[[4- [ 2-hydroxyethyl] amino] -3-nitrophenyl] bis ethanol及beauty 4 - a first essential dye that Do hydroxy propylamino-3-nitrophenol, second essential comprising a combination according to claim 1 or 2 A hair dye composition for hair dyeing comprising a combination with a pigment , wherein the glycine is contained in an amount of 0.1 to 10% by weight as a stabilizer, and the pH is 6.0 to 9.0. Provides a hair dye composition for hair dyeing that is superior in safety, has less dyeability on the skin, has excellent dyeability, is less susceptible to uneven dyeing, has little deterioration over time, and is less likely to lose color. can do.
In addition, by containing 0.1 to 10% by weight of the glycine as a stabilizer, it is possible to maintain the stability of the direct dye, and a hair dye for white hair dyeing that has more excellent dyeability and color fading prevention effect. A composition can be provided.

According to the invention of claim 3 , the pH adjuster is sodium lactate, sodium hydroxide, potassium hydroxide, triethanolamine (TEA), monoethanolamine (MEA), aminomethylpropanol (AMP), aminomethyl. Selected from the group consisting of propanediol (AMPD), arginine, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium bicarbonate, ammonium carbonate, a mixture of ammonium bicarbonate and ammonium carbamate, and ammonium bicarbonate The pH of the hair dye composition can be adjusted to 6.0 to 9.0 by being a cream-like or gel-like hair dye composition that is 1 or more. Can maintain stability, excellent dyeability and colorfastness prevention It is possible to provide a hair dye for hair dye composition having an effect.

Hereinafter, the hair dye composition for hair dyeing according to the present invention will be described.

The hair dye composition for gray hair dyeing according to the present invention contains a direct dye, glycine and a pH adjuster.
In the present invention, the dye directly, at least, 2,2 '- first consisting of hydroxy propyl-amino-3-nitrophenol - [[4- [2-hydroxyethyl] amino] -3-nitrophenyl] bis ethanol及beauty 4 Contains 1 essential dye .

  2,2 '-[[4- [2-Hydroxyethyl] amino] -3-nitrophenyl] bisethanol is a blue direct dye that is widely used as an essential dye for dark brown to black hair coloring. Specifically, it is called HC Blue 2 and has the structure shown in the following formula (Formula 1).

  4-Hydroxypropylamino-3-nitrophenol is a red direct dye widely used for dyeing brown to black hair, and has a structure represented by the following formula (Chemical Formula 2).

  The direct dye may include direct dyes other than the above direct dyes, yellow dyes such as HC yellow 2 and HC yellow 4, blue dyes such as basic blue 99, red dyes such as basic red 76, In addition to dispersed black, HC purple 1, etc., acidic dyes such as acidic orange 3, purple 401, black 401 may be included.

The hair dye composition for dyeing gray hair according to the present invention contains glycine. Stability of direct dyes 2,2 '-[[4- [2-hydroxyethyl] amino] -3-nitrophenyl] bisethanol and 4-hydroxypropylamino-3-nitrophenol by containing glycine Can be improved. The blending amount is 0.1 to 10% by weight. If the blending amount is less than 0.1% by weight, sufficient stability of the direct dye cannot be obtained, and if the blending amount exceeds 10% by weight, skin irritation occurs, which is not preferable.

The hair dye composition for white hair dyeing according to the present invention contains a pH adjuster, and is adjusted to pH 6.0 to 9.0 by this pH adjuster. If the pH is less than 6.0, a sufficient hair dyeing effect cannot be obtained. If the pH exceeds 9.0, it causes skin irritation, which is not preferable.
Examples of pH adjusters include sodium lactate, sodium hydroxide, potassium hydroxide, triethanolamine (TEA), monoethanolamine (MEA), aminomethylpropanol (AMP), aminomethylpropanediol (AMPD), arginine, ammonia, Sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, ammonium carbonate, a mixture of ammonium hydrogen carbonate and ammonium carbamate, and ammonium hydrogen carbonate are preferably used.

In general, 2,2 '-[[4- [2-hydroxyethyl] amino] -3-nitrophenyl] bisethanol is dyeable in the pH range of 3.0 to 10 in the form of an aqueous solution, cream or gel. Degradation with time, 4-hydroxypropylamino-3-nitrophenol deteriorates with time in the pH range of 6.0 to 9.0.
However, the hair dye composition for dyeing gray hair of the present invention contains glycine in an amount of 0 . By containing 1-10% by weight and keeping the pH 6.0-9.0 with a pH adjuster, 2,2 ′-[[4- [2-hydroxyethyl] amino] -3-nitrophenyl] bisethanol and It is possible to prevent deterioration of the dyeability of 4-hydroxypropylamino-3-nitrophenol over time.

In the hair dye composition for gray hair dyeing according to the present invention, in addition to the above components, surfactants, fats and oils, moisturizers, thickeners, chelating agents, preservatives, anti-inflammatory agents generally used as cosmetic ingredients Agents, extracts, antioxidants, solvents, ultraviolet absorbers, pigments, fragrances and the like can be appropriately blended.
Specific examples of these blending components are shown below.

  Examples of surfactants include cationic surfactants, amidoamine type surfactants, and nonionic surfactants, which may be commercially available, but are cationic surfactants and amidoamine type surfactants that are sold as cosmetics or pharmaceutical grades. It is preferable to blend one or more selected from an agent and a nonionic surfactant.

  Fats and oils include castor oil, olive oil, cacao oil, coconut oil, palm oil, tree wax, jojoba oil, grape seed oil, avocado oil and other animal fats such as mink oil and egg yolk oil, beeswax, whale Waxes such as wax, lanolin, carnauba wax and candelilla wax, hydrocarbons such as liquid paraffin, squalene, microcrystalline wax, ceresin wax, paraffin wax, petrolatum, lauric acid, myristic acid, stearic acid, oleic acid, isostearic acid Natural and synthetic fatty acids such as behenic acid, natural and higher alcohols such as cetanol, stearyl alcohol, hexyl decanol, octyl decanol, lauryl alcohol, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, olein Octyldodecyl ester such as cholesterol oleate can be exemplified.

  As the humectant, glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, trimethylolpropane, Polyols such as pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer, and polymers thereof, diethylene glycol monoethyl ether (ethoxydiglycol) ), Glycol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, Water-soluble esters such as cosandioic acid / tetradecandioic acid polyglyceryl-10 ester, sugar alcohols such as sorbitol, xylitol, erythritol, mannitol, maltitol, glucose, fructose, galactose, mannose, threose, xylose, arabinose, fucose , Ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid, glucuronic acid, β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabinogalactan, dextrin, dextran, glycogen, ethyl glucoside, glucosyl methacrylate Ethyl polymer or copolymer, hyaluronic acid, sodium hyaluronate, sodium chondroitin sulfate, caroline sulfate, keratosulfuric acid, Dermatan sulfate, white jellyfish extract, fucoidan, tuberose polysaccharide, urea, hydroxyurea, 2-pyrrolidone-5-carboxylic acid and its sodium, betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, alanine, phenylalanine , Tyrosine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, valine, tryptophan, histidine, taurine, collagen, fish collagen, atelocollagen, gelatin, elastin, collagen degradation Peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin degrading peptide, keratin degrading peptide Hydrolyzed keratin, conchiolin degrading peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl hydrolyzed silk sodium, soy proteolytic peptide, wheat proteolytic peptide, hydrolyzed wheat protein, casein degrading peptide, palmitoyl oligo Acylated peptides such as peptides, silylated peptides, lactic acid bacteria culture solution, yeast extract, eggshell membrane protein, bovine submandibular gland mucin, hypotaurine, sesameignan glycoside, albumin, whey, choline chloride, phosphorylcholine, placenta extract Examples include ceramides such as liquid, elastin, collagen, natural ceramide (types 1, 2, 3, 4, 5, 6), hydroxyceramide, pseudoceramide, glycosphingolipid, ceramide, and sugar-ceramide-containing extract.

  Thickeners include natural polymer materials such as sodium alginate, xanthan gum, aluminum silicate, quince seed extract, tragacanth gum, starch, and semi-synthetic polymer materials such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, soluble starch, and cationized cellulose. , Carboxyvinyl polymer, polyvinyl alcohol and the like.

  Examples of chelating agents include edetate (ethylenediaminetetraacetate; EDTA, EDTA2Na, EDTA3Na, EDTA4Na, etc.), hydroxyethylethylenediamine triacetate (HEDTA3Na, etc.), pentetate (diethylenetriaminepentaacetate), phytic acid, etidronate Etc. (hydroxyethanediphosphonic acid and its salt), sodium oxalate, polyamino acids (polyaspartic acid, polyglutamic acid, etc.), aspartic acid diacetic acid and its salt, glutamic acid diacetic acid and its salt, sodium polyphosphate, metaphosphoric acid Examples include sodium, phosphoric acid, citric acid, alanine, dihydroxyethyl glycine, gluconic acid, succinic acid, tartaric acid and the like. Among these, hydroxyethanediphosphonic acid and its salt, aspartic acid diacetic acid and its salt, glutamic acid diacetic acid and its salt are preferably used.

  Preservatives include zinc / ammonia / silver composite substituted zeolite, benzoic acid, benzoic acid pantothenyl ethyl ether, benzoate, isopropylmethylphenol, undecylenic acid, undecylenic acid MEA, alkylcyaminoethylglycine hydrochloride, chlorhexidine hydrochloride, chloride Cetylpyridinium, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, delicanium chloride, chlorhexidine hydrochloride, octanediol, octoxyglycerin, photosensitizer 101.201.301.401, d-camphor, dl-camphor, chlorhexidine glucuronate, chlorcresol, Chlorobutanol, Chloroxylenol, Chlorhexidine, Cresol, Shikonin, Scordinin, Thianthol, Thioxolone, Thymol, Triclosan, Trichlorocar Nido, hinokitiol, paraoxybenzoate, parachlorophenol, sodium paraphenol sulfonate (dihydrate), pyrithione zinc, phenoxyethanol, phenol, hexanediol, 1,2-pentanediol, methylchloroisothiazolinone / methylisothi Examples include an azolinone solution, l.dl-menthol, iodoparadimethylaminostyrylpeptylmethylthiazolinium, octoxyglycerin and the like.

  Examples of anti-inflammatory agents include glycyrrhizic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, guaiazulene, allantoin, indomethacin, zinc oxide, hydrocortisone acetate, acidic xylooligosaccharides, prednisone, diphedramine hydrochloride, chlorpheniramine maleate .

  Extracts include: Iris extract, Ashitaba extract, Asunaro extract, Asparagus extract, Avocado extract, Achacha extract, Almond extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot extract, Ginkgo biloba extract, Inchikou extract, Fennel Extract, Turmeric Extract, Oolong Tea Extract, Walnut Extract, Ages Extract, Echinacea Leaf Extract, Enmeiso Extract, Ogon Extract, Oat Extract, Auren Extract, Barley Extract, Panax Ginseng Extract, Hypericum Extract, Odrianthus Extract, Onionis Extract, Dutch Mustard Extract, Orange extract, dried seawater, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, cuckoo , Chamomile extract, oil-soluble chamomile extract, carrot extract, oak wormwood extract, oat extract, calkade extract, licorice extract, oil-soluble licorice extract, kiwi extract, kiou extract, jellyfish extract, quina extract, cucumber extract, giraffe leaf extract, guanosine, guava Extract, Kujin Extract, Gardenia Extract, Kumazasa Extract, Clara Extract, Walnut Extract, Chestnut Extract, Grapefruit Extract, Clematis Extract, Black Rice Extract, Brown Sugar Extract, Black Vinegar, Chlorella Extract, Mulberry Extract, Gentianana Extract, Gennoshoco Extract, Black Tea Extract, Yeast Extract, kokuboku extract, coffee extract, burdock extract, rice extract, fermented rice extract, fermented rice bran extract, rice germ oil, comfrey extract, collagen, bryo Extracts , Peonies extract, Pepper extract, Pepper root extract, White birch extract, White jellyfish extract, Horsetail extract, Stevia extract, Stevia fermented product, Nishikawa willow extract, Horseshoe extract, Hawthorn extract, Horseshoe extract, Achillea millefolium extract Extract, sage extract, mallow extract, senkyu extract, assembly extract, Sakuhakuhi extract, Diou extract, soybean extract, tisoiso Extract, thyme extract, dandelion extract, lichen extract, tea extract, clove extract, chigaya extract, chimpi extract, tea tree oil, bonito tea extract, red pepper extract, touki extract, tokisenka extract, tonin extract, spruce extract, dokudami extract, tomato extract, natto Extract, carrot extract, garlic extract, wild rose extract, hibiscus extract, bacmond extract, lotus extract, parsley extract, birch extract, honey, hamamelis extract, parietalia extract, cassava extract, bisabolol, hinoki extract, bifidobacteria extract, biwa extract, fukitan popo Extract, Fukinoto extract, Bukuryu extract, butcher bloom extract, grape extract, grape seed extract, propolis, loofah extract, safflower extract, pe -Mint extract, Bodaiju extract, Button extract, Hops extract, Maikai extract, Pine extract, Maronier extract, Citrus extract, Mukuroji extract, Melissa extract, Mozuku extract, Peach extract, Cornflower extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yuri extract, Yokuinin extract, Artemisia extract, Lavender extract, Green tea extract, Egg shell membrane extract, Apple extract, Rooibos tea extract, Ganoderma extract, Lettuce extract, Lemon extract, Forsythia extract, Forsythia extract, Rose extract, Rosemary extract, Roman chamomile extract, Royal jelly extract, Waremokou Examples are extracts.

  Antioxidants include BHT, BHA, ascorbic acid and its salts, ascorbic acid derivatives, sodium sulfite, sodium hydrogen sulfite, gallic acid esters, tocopherols, cysteines, thioglycolates, nordihydroguaiaretic acid, erythorbine Examples thereof include acids and salts thereof, dilauryl thiodipropionate, tolyl biguanide, ortho tribiguanide, tea extract, and apple extract.

  Solvents include ethanol, n-propanol, isopropanol, n-butanol, isoamyl alcohol, benzyl alcohol, benzyloxyethanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, N-methylpyrrolidone, N-ethylpyrrolidone N-octylpyrrolidone, N-butylpyrrolidone, POE-2 benzyl ether, propylene carbonate, ethylene carbonate and the like.

  UV absorbers include paraaminobenzoic acid, paramethoxycinnamate-2-ethoxyethyl, isopropyl paramethoxycinnamate, butylmethoxybenzoylmethane, glyceryl-mono-2-ethylhexanoyl-di-paramethoxybenzophenone, diga Royltrioleate, 2-2′-dihydroxy-4-methoxybenzophenone, ethyl-4-bishydroxypropylaminobezoate, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethylhexyl paramethoxycinnamate 2-ethylhexyl salicylate, glyceryl paraaminobenzoate, homomethyl salicylate, methyl orthoaminobenzoate, 2-hydroxy-4-methoxybenzophenone, amyl-para-dimethylamibenzoate, 2-phenyl Benzimidazole-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid can be exemplified.

There is no limitation on the dosage form of the hair dye composition for gray hair dyeing according to the present invention, and for example, it can be in a form known in the art such as liquid, emulsion, cream, gel or foam.

Although it demonstrates still in detail based on the following examples, the hair dye composition for hair dyeing concerning the present invention is not limited to these.

Preparation of hair dye composition sample 1
PH adjustment to direct dye COLOREX HCB2 (manufactured by Chemical Compound, display name: HC Blue 2, chemical name: 2,2 '-[[4- [2-hydroxyethyl] amino] -3-nitrophenyl] bisethanol) Citric acid, sodium citrate and purified water were added as agents to adjust the pH to 3.2 to 10.2, and creamy hair dye composition samples ( Reference Examples 1 to 8) were prepared. The pH of the sample stock solution was measured using a pH meter F-22 type (manufactured by Horiba, Ltd.). In the following Reference Examples, Examples and Comparative Examples, pH was measured by the same method.

Preparation of hair dye composition sample 2
Direct dye TM Red No. 2 (manufactured by Kasei Chemical Co., Ltd., display name: 4-hydroxypropylamino-3-nitrophenol, chemical name: 4-hydroxypropylamino-3-nitrophenol), citric acid and sodium citrate as a pH adjuster, and purification Water was added to adjust the pH to 6.1 to 10.1 to prepare cream samples ( Reference Examples 9 to 13).

Test example 1
Next, 2.0 g of the creamy hair dye composition sample of Reference Examples 1 to 13 prepared above was applied to an attached white cloth (nominal number 1, 5 cm × 5 cm) for dyeing fastness test according to JISL0803, After standing at 20 ° C. for 10 minutes, it was washed with water and air-dried.
The Lab of the dyed portion of the white cloth was measured using a color reader CR-13 (manufactured by Konica Minol) immediately after air drying and after being left at 50 ° C. for 1 month. The color characteristic evaluation was evaluated by the color difference ΔE.
A: ΔE 0.0 or more and less than 5.0 (no discoloration / discoloration to slightly discoloration / discoloration)
○: ΔE5.0 or more and less than 8.0 (slightly discolored / fading)
Δ: ΔE8.0 to less than 10.0 (very discoloration / fading)
×: ΔE10.0 or more (discoloration / fading is remarkable)
It was evaluated with. The results are shown in Tables 1 and 2. Hereinafter, the composition is shown in wt% in the table.

It can be seen that the hair dye compositions of Reference Examples 1 to 13 have large discoloration / fading.

Preparation of hair dye composition sample 3
A cream-like hair dye composition sample ( Reference Examples 14 to 22 ) having the composition shown in Table 4 below, and a cream-like hair dye composition sample ( Reference Examples 23 to 30 ) having the composition shown in Table 5 below. Was prepared.
The direct dyes used in the following Reference Examples, Examples and Comparative Examples are shown in Table 3.

Test example 2
In the same manner as in Test Example 1, the discoloration / fading degree of the hair dye composition samples of Reference Examples 14 to 30 was evaluated.

Compared with the hair dye composition samples of Reference Examples 20 , 29 and Reference Examples 21, 22, and 30 which are outside the range of pH 6.0 to 9.0 without glycine, Reference Examples 14 to 19, 23 to 28 In the hair dye composition sample, no deterioration in dyeability was observed in a severe test at a high temperature (50 ° C.).

Preparation of hair dye composition sample for hair dyeing 4
Cream-type hair dye composition sample (Examples 1 to 9 ) of brown gray hair dyed in the composition shown in Table 6 below, and a cream-like hair dye composition of brown gray hair dyed in the composition shown in Table 7 Samples ( Comparative Examples 1 to 5 ) were prepared.

Test example 3
In the same manner as in Test Example 1, the discoloration / fading degree of the cream-like hair dye composition samples of Examples 1 to 9 and Comparative Examples 1 to 5 were dyed. The results are shown in Tables 6 and 7.

Test example 4
Human hair white hair BM-WA (Burex Co., Ltd.) 8 cm (0.4 g), cream-like hair dye composition samples of Examples 1 to 9 and Comparative Examples 1 to 5 prepared above. Each 0 g was applied, left at 20 ° C. for 10 minutes, washed with water and air-dried.
The Lab of the white hair dyed portion was evaluated visually by the following four steps immediately after air drying and after standing at 50 ° C. for 1 month.
1 No discoloration / fading 2 Slight discoloration / fading 3 Discoloration / fading 4 Results of remarkable discoloration / fading are shown in Tables 8 and 9.

Compared with the hair dye composition sample of Comparative Example 3 and Comparative Example 4 and 5 which are outside the range of pH 6.0 to 9.0, which does not contain glycine, the brownish white hair dyed cream of Examples 1 to 9 In the hair dye composition sample, no deterioration in dyeability was observed in a severe test at a high temperature (50 ° C.). Compared with Examples 1-9, the hair dye composition samples of Comparative Examples 1 and 2 were less deteriorated in dyeability in severe tests at high temperatures (50 ° C.) compared with Comparative Examples 3-5. The deterioration of the dyeability was great .

Preparation of hair dye composition sample for hair dye 5
Cream-type hair dye composition sample (Examples 10 to 17 ) for black gray hair dyed in the composition shown in Table 10 below, and a cream-like hair dye composition for black white hair dyed in the composition shown in Table 11 Samples ( Comparative Examples 6 to 10 ) were prepared.

Test Example 5
In the same manner as in Test Example 1, the discoloration and fading degree of the black hair dyed creamy hair dye composition samples of Examples 10 to 17 and Comparative Examples 6 to 10 were evaluated. The results are shown in Tables 10 and 11.

Test Example 6
In the same manner as in Test Example 4, the discoloration / fading degree of the black hair dyed creamy hair dye composition samples of Examples 10 to 17 and Comparative Examples 6 to 10 was evaluated. The results are shown in Tables 12 and 13.

Compared with the hair dye composition samples of Comparative Example 8 and Comparative Examples 9 and 10 which are outside the range of pH 6.0 to 9.0, which does not contain glycine, the cream color of the black gray hair dye of Examples 10 to 17 In the hair dye composition sample, no deterioration in dyeability was observed in a severe test at a high temperature (50 ° C.). The hair dye composition samples of Comparative Examples 6 and 7 also had less dyeing deterioration in severe tests at high temperatures (50 ° C.) compared to Comparative Examples 8 to 10, but compared with Examples 10 to 17. The deterioration of the dyeability was great . Moreover, although the sample of the comparative example 9 with a low pH value is light black immediately after dyeing | staining, it turns out that the color of a sample of an Example is black immediately after dyeing | staining and the dyeing | staining property immediately after is also favorable.

Test Example 7 Wash Resistance Test A wash resistance test was performed under the following conditions using the dyed cloths of the hair dye composition samples of Example 12 and Comparative Examples 8 and 9 .
(Test conditions)
Cleaning solution: 3% POE (2) Aqueous sodium lauryl ether sulfate Temperature: 40 ° C
Cleaning conditions: Each dyed cloth was immersed in 30 mL cleaning solution for 10 minutes, then washed with water and air-dried.
The color difference ΔE when the above operation was repeated 3 times and 5 times was evaluated in the same manner as in Test Example 1.
The results are shown in Table 14.

It can be seen that the dyed fabric of Example 12 hardly discolors and fades even when the washing operation is repeated 5 times, and has excellent washing resistance.

Test Example 8 Safety Evaluation Test 20 to 50s Applying an appropriate amount of brown cream (Examples 1-9 , Comparative Examples 1-5 ) to the inner arms of 20 men and women, leaving it open for 24 hours, and then using purified water Wipe off with wet cotton wool. The state at the time of leaving and 48 hours after being left was evaluated by the subject's report and visual inspection. Evaluation was performed in the following five stages.
0: Uncomfortable, not irritating 1: Slightly uncomfortable, irritating 2: Itching 3: Pain 4: Severe pain, itching The results are shown in Tables 15 and 16.

  In the examples, subjects who feel a little uncomfortable are recognized, but it can be said that the hair dye is excellent in safety without any irritation such as pain.

From the above results, it can be seen that the hair dye composition for gray hair dyeing of the present invention is excellent in safety, excellent in dyeability, little deterioration in dyeability over time, and difficult to lose color.

  The present invention is preferably used as a hair dye for dyeing gray hair.

Claims (3)

A hair dye composition for gray hair containing a direct dye, glycine and a pH adjuster,
The direct dye is at least
2,2 '- a first essential dye that Do hydroxy propylamino-3-nitrophenol, - [[4- [2-hydroxyethyl] amino] -3-nitrophenyl] bis ethanol及beauty 4
HC yellow 2, basic blue 99, basic brown 16, purple 401, basic red 76, and a combination with a second essential pigment consisting of one or more selected from the group consisting of basic yellow 57 ,
A hair dye composition for white hair dyeing, wherein the glycine is contained as a stabilizer in an amount of 0.1 to 10% by weight and has a pH of 6.0 to 9.0. The second essential dye is
HC yellow 2 and basic blue 99, or
The hair dye composition for white hair dyeing according to claim 1, comprising basic blue 99, basic brown 16, purple 401, basic red 76 and basic yellow 57. The pH adjuster is sodium lactate, sodium hydroxide, potassium hydroxide, triethanolamine (TEA), monoethanolamine (MEA), aminomethylpropanol (AMP), aminomethylpropanediol (AMPD), arginine, ammonia, It is one or more selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium bicarbonate, ammonium carbonate, a mixture of ammonium bicarbonate and ammonium carbamate, and ammonium bicarbonate The hair dye composition for hair dyeing according to claim 1 or 2 .