JP4804573B2 - Photosensitive hair dye - Google Patents

Description

  The present invention relates to a hair dye, and more particularly to a photosensitive hair dye containing a silver salt, which develops color when irradiated with light.

  At present, the hair color market is mainly oxidative hair dyes using oxidative dyes and hydrogen peroxide, so-called hair dyes, because they are easy to operate, have abundant color tone, and have excellent hair dyeing effects. However, since oxidative hair dyes have problems such as hair damage, skin irritation or allergy, hair dyes that anyone can use with confidence are desired. Hair dyes using acidic dyes and hair dyes using plants or plant-derived dyes and metals have been put on the market in order to eliminate the drawbacks of such oxidative hair dyes. Disadvantages such as not falling off and difficult to operate, while the latter has disadvantages such as insufficient hair dyeing effect and does not satisfy consumers.

  As hair dyes, those using silver salts in addition to oxidative hair dyes have been known for a long time. As a hair dye using a silver salt, for example, silver sulfide is attached to keratin on the hair surface by reacting two agents, a sulfide aqueous solution and a silver nitrate aqueous solution, on the hair surface. However, this hair dye has a problem that the smell of hydrogen sulfide adheres to the hair.

  In addition, there are many reports on hair dyes using silver salts (for example, Patent Documents 1 to 8). Patent Document 1 describes a one-component hair dye in which silver sulfate and citric acid are mixed with a substrate material having moisture, and is reduced by irradiation with ultraviolet rays or visible light to deposit metallic silver. Has been. In Patent Document 2, hair dyeing power is improved by adding an amino acid to a silver salt in a hair dye cream base, and the color tone and hue range to some extent by combining the type of amino acid and the blending ratio. A one-component hair dye using light energy that has become possible to have a hair is described. Patent Document 3 discloses a silver colloid-L-amino acid complex solution produced by mixing an L-amino acid such as L-histidine with a silver colloid solution produced by mixing finely divided silver below a set particle size in a liquid. The hair dye characterized by using is described. Patent Document 4 describes a hair dye that uses a silver salt and a hydrazine compound, has high hair dyeability and high hair color reproducibility, develops a natural color, has little damage to the hair, and does not easily lose color. ing. Patent Document 5 contains an acid dye and a silver salt as essential components, an acid as a pH adjuster, an aromatic alcohol as a penetrating agent, a lower alcohol as a solvent, a polymer compound as a thickener, and sulfur. A photosensitive acidic hair dye composition is described. Patent Document 6 includes a silver carboxylate salt and / or a sulfonate silver salt and reductones simultaneously or separately, and is excellent in hair dyeability and hair color reproducibility. For shampoo, rinse, light, etc. In addition, a hair dye that has high fastness in a hair dyeing state and little damage to hair is described. Patent Document 7 contains silver salt, organic acid salt, and dyeable plant powder and / or an extract thereof. A hair-dyeing cosmetic is described that allows hair to naturally conform to the surrounding hair. Patent Document 8 describes a hair dye composition containing a silver compound, sulfur, and a water-soluble polymer substance.

Japanese Patent No. 3881688 Japanese Patent No. 4184385 JP 2008-280321 A JP 2008-247842 A JP 2008-0669131 A JP 2008-050340 A JP 2006-176486 A JP-A-2005-060354

  Silver nitrate having high solubility in water has been mainly used as a silver salt in hair dyes that use silver salt to develop color by irradiation with light such as sunlight. However, in recent years, since silver nitrate is a raw material for pharmaceuticals, its incorporation into cosmetics and quasi drugs has been prohibited.

  Therefore, hair dyes using silver sulfate, silver lactate, silver citrate, etc. have been put on the market as alternatives to silver nitrate. However, since all silver compounds are less soluble in water and other solvents than silver nitrate, Under the present circumstances, a sufficient hair dyeing effect cannot be obtained even if long intense light is irradiated.

  Then, this invention aims at providing the photosensitive hair dye which was excellent in the hair dyeing effect using the silver salt with low solubility to a solvent.

  As a result of intensive investigations in view of the above situation, the present inventors have combined a silver salt having low solubility in a solvent and a chelating agent, so that even when the silver salt is used at a low concentration, it is sufficient. The present invention has been completed by finding that a hair dyeing effect can be obtained and further studying this.

That is, the present invention provides the following photosensitive hair dye.
1. (A) One or more silver salts selected from the group consisting of silver sulfate, silver lactate, and silver citrate, and (b) a chelating agent, the content of (a) being in the total amount of the hair dye A photosensitive hair dye characterized by having 0.01 to 2% by mass and a pH of 1 to 5.
2. The chelating agent is diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid, edetic acid, (2S, 2 ′S) -2,2 ′-(ethylenebisimino) bissuccinic acid, 1,3-diamino-2-propanol-N , N, N ′, N′-tetraacetic acid, N, N-di (2-hydroxyethyl) glycine, and nitrilotris (methylenephosphonic acid), the content of which is one or more. The photosensitive hair dye according to Item 1, which is 0.01 to 5% by mass in the total amount of the hair dye.
3. Furthermore, the photosensitive hair dye of said claim | item 1 or 2 which contains 0.1-20 mass% of bamboo vinegar liquid and / or wood vinegar liquid as a component in the hair dye whole quantity.

  The photosensitive hair dye of the present invention comprises one or more silver salts selected from the group consisting of silver sulfate, silver lactate and silver citrate as component (a), and a chelating agent as component (b). By including it as an essential component, a sufficient hair dyeing effect can be exhibited even with a light source with weak light energy such as a fluorescent lamp used in daily life without irradiating strong light such as sunlight. . Furthermore, the more superior hair dyeing effect can be exhibited by including the bamboo vinegar and / or wood vinegar of the component (c).

  Therefore, by using the photosensitive hair dye of the present invention, hair can be easily dyed without damaging the hair.

  The silver salt of component (a) used in the present invention is one or more selected from silver sulfate, silver lactate and silver citrate. Silver nitrate, which has been used in the past, is prohibited from blending into cosmetics and quasi-drugs because it is a raw material for pharmaceuticals and is difficult to use as a general hair dye. , Silver sulfate, silver lactate, or silver citrate is used. Among these, silver sulfate is preferable from the viewpoint of excellent hair dyeing effect. Any of those used as industrial raw materials or those sold as reagents can be used.

  These silver salts are blended at a ratio of 0.01 to 2% by mass, preferably 0.1 to 1.0% by mass in the total amount of the hair dye. When the blending ratio of the silver salt is less than 0.01% by mass, a sufficient hair dyeing effect cannot be obtained, and when it exceeds 2% by mass, the silver salt may precipitate in the preparation, which is not preferable.

  Examples of the chelating agent for component (b) used in the present invention include diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid, edetic acid, (2S, 2 ′S) -2,2 ′-(ethylenebisimino) bissuccinic acid, 1 , 3-Diamino-2-propanol-N, N, N ′, N′-tetraacetic acid, N, N-di (2-hydroxyethyl) glycine, nitrilotris (methylenephosphonic acid), hydroxyethylethylenediaminetriacetic acid, phytin Examples include acids, polyaspartic acid, polyglutamic acid, aspartic acid diacetic acid, glutamic acid diacetic acid, sodium polyphosphate, sodium metaphosphate, phosphoric acid, dihydroxyethylglycine, gluconic acid, succinic acid, and tartaric acid. Among them, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid, edetic acid, (2S, 2 ′S) -2,2 ′-(ethylenebisimino) bissuccinic acid, 1,3-diamino-2-propanol-N, One or more selected from N, N ′, N′-tetraacetic acid, N, N-di (2-hydroxyethyl) glycine, and nitrilotris (methylenephosphonic acid) are used for formulation stability and hair damage. It is preferable from the viewpoint of difficulty in raising and the hair dyeing effect. However, these chelating agents do not include a salt form because the dyeing effect tends to be remarkably lowered when they become salts.

  As a compounding quantity of a chelating agent, 0.01-5 mass% is preferable in the hair dye whole quantity, and 0.1-1 mass% is further more preferable. When the chelating agent is contained in the hair dye in the range of 0.01 to 5% by mass, a sufficient hair dyeing effect can be exhibited.

  The pH of the photosensitive hair dye of the present invention is 1 to 5, and preferably 2 to 3.5. If the pH is less than 1, sufficient hair dyeing effect cannot be obtained, and if it exceeds pH 5, the hair dyeing effect is lowered, which is not preferable.

  Bamboo vinegar and / or wood vinegar can be further added to the photosensitive hair dye of the present invention as component (c). Bamboo vinegar and wood vinegar keep the silver salt in the preparation stable and have the effect of penetrating the silver salt or silver ions into the hair. By adding bamboo vinegar and / or wood vinegar to the hair dye, Thus, a photosensitive hair dye having excellent formulation stability and excellent hair dyeing effect can be obtained.

  As the bamboo vinegar, a dry distillation liquid usually obtained as a by-product at the time of bamboo charcoal production from true bamboo, subfamily bamboo, black bamboo, etc. can be used, but impurities were removed by further distillation of the dry distillation liquid, etc. It is preferable to use one.

  As a compounding quantity of a bamboo vinegar liquid, 0.1-20 mass% is preferable in the hair dye whole quantity, and 1-10 mass% is further more preferable. When the blending amount is less than 0.1% by mass, a sufficient hair dyeing effect cannot be obtained, and when the blending amount exceeds 20% by mass, the odor and the stability of the preparation are deteriorated.

  As the wood vinegar liquid, a dry distillation liquid usually obtained as a by-product during the production of charcoal from oak, kunugi, oak, etc. can be used, but it is preferable to use a liquid obtained by removing impurities by distillation or the like.

  The blending amount of the wood vinegar is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass in the total amount of the hair dye. When the blending amount is less than 0.1% by mass, a sufficient hair dyeing effect cannot be obtained, and when the blending amount exceeds 20% by mass, the odor and the stability of the preparation are deteriorated.

  In addition, what is necessary is just to adjust a mixing | blending ratio suitably, when using both bamboo vinegar liquid and wood vinegar liquid for hair dye, so that the total amount may be 0.1-20 mass%.

  The light source for coloring the photosensitive hair dye of the present invention is not particularly limited to sunlight, fluorescent lamps, solar fluorescent lamps (fluorescent lamps having spectral components close to sunlight), black light, etc. Solar fluorescent lamps and black lights are preferred, and fluorescent lamps are particularly preferred. When sunlight is used, color development tends to be fast but uneven.

  In addition to the above components, the photosensitive hair dye of the present invention is generally used as a blending component in cosmetics and quasi-drugs as other components, surfactants, fats and oils, pH adjusters, humectants, Solvents, preservatives, plant extracts, anti-inflammatory agents, pigments, fragrances and the like can be appropriately blended.

  Surfactants include polyoxyethylene (hereinafter abbreviated as “POE-”) octyldodecyl alcohol, POE-2-decyltetradecyl alcohol, and other POE branched alkyl ethers; POE-oleyl alcohol ether, POE-cetyl alcohol ether POE-alkyl ethers such as sorbitan monooleate, sorbitan monoisostearate, sorbitan esters such as sorbitan monolaurate; POE-sorbitan monooleate, POE-sorbitan monoisostearate, POE-sorbitan monolaurate POE-sorbitan esters such as glyceryl monooleate, glyceryl monostearate, glyceryl fatty acid esters such as glyceryl monomyristate; POE-glyceryl monooleate, POE- POE-glycerin fatty acid esters such as lysyl monostearate and POE-glyceryl monomyristate; POE-cured castor oil fatty acid esters such as POE-dihydrocholesterol ester, POE-cured castor oil, POE-cured castor oil isostearate POE-alkyl aryl ethers such as POE-octylphenol ether; glycerol ethers such as glycerol monoisostearate and glycerol monomyristate; POE-glycerol ethers such as POE-glycerol monoisostearate and POE-glycerol monomyristate Polyglycerin fats such as diglyceryl monostearate, decaglyceryl decastearate, decaglyceryl decaisostearate, diglyceryl diisostearate Acid esters; nonionic surfactants such as sucrose fatty acid esters such as sucrose palmitate, sucrose myristic acid, and sucrose stearate, or myristic acid, stearic acid, palmitic acid, behenic acid, isostearic acid, oleic acid, etc. Higher fatty acid salts of potassium, sodium, diethanolamine, triethanolamine, amino acids, etc .; anionic surfactants such as the above alkali salts, N-acylamino acid salts, N-acyl sarcon salts, higher alkyl sulfonates of ether carboxylic acids, etc. Can be illustrated.

  As fats and oils, castor oil, olive oil, cacao oil, coconut oil, palm oil, tree wax, jojoba oil, grape seed oil, avocado oil, etc .; vegetable oils such as mink oil, egg yolk oil; beeswax, whale Waxes such as wax, lanolin, carnauba wax, 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, octyldodecanol, lauryl alcohol; isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, olei Octyldodecyl, and esters such as cholesterol oleate can be exemplified.

  Examples of the pH adjuster include citric acid, DL-malic acid, gluconic acid, lactic acid, fumaric acid, acetic acid, potassium hydroxide, sodium hydroxide, and triethanolamine.

  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, sorbitol, xylitol, erythrulose, mannitol Sugar alcohols such as maltitol, glucose, fructose, galactose, mannose, threose, xylose, arabinose, fucose, ribose, deoxyribo Sugars such as sugar, maltose, trehalose, lactose, raffinose, glycol alkyl ethers such as diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, (eicosane diacid / tetradecane Diacid) water-soluble esters such as polyglyceryl-10 ester, 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, 2-pyrrolidone-5-carboxylic acid and its sodium, betaine (trimethylglycine), 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, soybean Acylated peptides such as proteolytic peptides, wheat proteolytic peptides, hydrolyzed wheat protein, casein degrading peptides, palmitoyl oligopeptides, silyl Peptides, lactic acid bacteria culture, yeast extract, eggshell membrane protein, bovine submandibular mucin, hypotaurine, sesameignan glycoside, albumin, whey, choline chloride, phosphorylcholine, placental extract, elastin, collagen, natural ceramide ( Examples include ceramides such as type 1, 2, 3, 4, 5, 6), hydroxyceramide, pseudoceramide, glycosphingolipid, ceramide, and sugar-ceramide-containing extract.

  Examples of the solvent include ethanol, isopropanol, n-butanol, dipropylene glycol, benzyl alcohol, N-methyl-2-pyrrolidone and the like.

  Preservatives include benzoic acid, benzoic acid pantothenyl ethyl ether, benzoate, isopropylmethylphenol, undecylenic acid, undecylenic acid MEA, alkylcyaminoethylglycine hydrochloride, chlorhexidine hydrochloride, cetylpyridinium chloride, benzalkonium chloride, chloride Benzethonium salt, 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, Trichlorocarbanide, Hinokitiol , Paraoxybenzoic acid ester, parachlorophenol, paraphenolsulfonic acid Na (dihydrate), pyrithione zinc, phenoxyethanol, phenol, hexanediol, 1,2-pentanediol, methylchloroisothiazolinone / methylisothiazolinone solution L. Examples thereof include dl-menthol and paradimethylaminostyrylpeptylmethylthiazolinium iodide.

  Plant 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 , Fennel extract, turmeric extract, oolong tea extract, walrus extract, ages extract, echinacea leaf extract, enmeo extract, peony extract, duckweed extract, auren extract, barley extract, ginseng extract, hypericum extract, adrianthus extract, onionis extract, Dutch mustard extract , Orange extract, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, cuckoo extract, duck La extract, oil-soluble chamomile extract, carrot extract, oak wormwood extract, oat extract, calcade extract, licorice extract, oil-soluble licorice extract, kiwi extract, kiou extract, jellyfish extract, quina extract, cucumber extract, giraffe leaf extract, guanosine, guava extract, kudin 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, gentian extract, gentian pepper extract, tea extract, kokuboku extract, coffee Extract, Burdock extract, Rice extract, Rice fermented extract, Rice bran fermented extract, Rice germ oil, Comfrey extract, Cowberry extract, Saisin extract, Psychoe , Saitai extract, Saffron extract, Salvia extract, Sabon extract, Sasa extract, Hawthorn extract, Sansha extract, Salamander extract, Shiitake extract, Giant extract, Shikon extract, Perilla extract, Linden extract, Shimotake extract, Jatoba extract, Peonies extract, Pepper extract Extract, ginger root extract, birch extract, white jellyfish extract, horsetail extract, stevia extract, stevia fermented product, Nishikawa willow extract, horseshoe extract, hawthorn extract, elderberry extract, yarrow extract, mint extract, sage extract, mallow Extract, Senkyu Extract, Assembly Extract, Sakuhakuhi Extract, Daio Extract, Soybean Extract, Taisou Extract, Thyme Extract, Dandelion , Lichen extract, tea extract, clove extract, chigaya extract, chimpi extract, tea tree oil, strawberry tea extract, red pepper extract, touki extract, tofu extract, tonin extract, spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic Extract, Novara extract, Hibiscus extract, Bakumondo extract, Lotus extract, Parsley extract, Birch extract, Hamamelis extract, Parietalia extract, Toad extract, Bisabolol, Hinoki extract, Bifidobacterium extract, Biwa extract, Fukitampo pop extract, Fukinoto extract, Bucurio extract, Butcher Bloom Extract, Grape Extract, Grape Seed Extract, Propolis, Loofah Extract, Safflower Extract, Peppermint Extract, Bodaige Extract, Bota Extract, hop extract, squid extract, pine extract, maroonnier extract, mizubasho extract, mugwort extract, melissa extract, mozuku extract, peach extract, cornflower extract, eucalyptus extract, yukinoshita extract, yuzu extract, lily extract, juniper extract, mugwort extract, lavender extract, Examples include green tea extract, apple extract, rooibos tea extract, litchi extract, lettuce extract, lemon extract, forsythia extract, forsythia extract, rose extract, rosemary extract, roman chamomile extract, royal jelly extract, and bitumen extract.

  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, etc. It can be illustrated.

  As the form of the photosensitive hair dye of the present invention, it can be formulated in a liquid form, gel form, cream form, stick form, aerosol form, etc., but in consideration of the usage, the gel form or cream form may be used. It is preferable because the effects of the invention are easily exhibited.

  Examples The present invention will be described in detail below by showing examples of the present invention, but the present invention is not limited to these examples.

  Tables 1 to 5 show cream hair dyes of Examples 1 to 13 and Comparative Examples 1 to 7 which are products of the present invention. As a manufacturing method of the creamy hair dye of this invention, first, 1-4 oil phase components are mixed, and it heat-dissolves at 80-85 degreeC. Separately, 5 or less aqueous phase components are sequentially weighed and similarly heated and dissolved at 80 to 85 ° C. After premixing by gradually adding 5 or less aqueous phase components to the above oil phase components 1 to 4, the mixture is emulsified with a high-speed homomixer and mixed and homogenized. Then, it cools to room temperature vicinity and takes out. In addition, the number in a table | surface has shown the mass%.

About the cream-like hair dye of manufactured Examples 1-13 and Comparative Examples 1-7, the following dyeability tests were done. The results are shown in Tables 1-5.
[Dyeability test]
Apply 0.5 g of sample to human hair gray hair (commercial product) 10 cm long and 0.3 g, leave it for 4 hours in 1 m directly under 30 W fluorescent lamp, wash with sodium lauryl sulfate (2%), air dry, Again, after leaving still for 4 hours in 1 m directly under a 30 W fluorescent lamp, the dyeability was visually evaluated.
(Evaluation criteria)
A: Very good dyeability (dye dark brown to black)
○: Excellent dyeability (stained in dark brown)
Δ: Dyeing property is not very good (stained in light reddish brown)
X: Dyeability is poor (almost not dyed)

  As shown in Tables 1 to 5, it was found that the photosensitive hair dyes of Examples 1 to 13 were excellent hair dyes that exhibited a sufficient hair dyeing effect even under a weak light source such as a fluorescent lamp. On the other hand, it was confirmed that the photosensitive hair dyes of Comparative Examples 1 to 7 were clearly inferior in dyeability. Furthermore, about the photosensitive hair dye of Examples 1-13, when the hair after dyeing | staining test was observed, changes, such as damage of hair, were not seen.

Claims (1)

(A) One or more silver salts selected from the group consisting of silver sulfate, silver lactate, and silver citrate are blended in an amount of 0.01 to 2 % by mass in the total amount of the hair dye,
(B) Diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid, edetic acid, (2S, 2 ′S) -2,2 ′-(ethylenebisimino) bissuccinic acid, 1,3-diamino-2-propanol-N, N , N ′, N′-tetraacetic acid, N, N-di (2-hydroxyethyl) glycine, and nitrilotris (methylenephosphonic acid) are added in one or more chelating agents in a total amount of 0. In a blending amount of 01-5% by weight, and
(C) Bamboo vinegar and / or wood vinegar with a blending amount of 0.1 to 20% by mass in the total amount of hair dye
A free, light-sensitive hair dye, wherein the p H is 1-5.