JP2006298863A - Hair treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair treating agent suppressing the deterioration of dyeability of a hair dye in a hair dyeing treatment after dye removal with ascorbic acids as a reducing agent. <P>SOLUTION: The hair treating agent is applied to hair dyed by color developing of a polynuclear compound produced according to oxidative polymerization of an oxidation dye after application of a dye-removing agent for removing the dye by reducing actions of the ascorbic acids. The hair treating agent comprises an ascorbate oxidase. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hair treatment agent, and more particularly, to a hair treatment agent capable of suppressing a decrease in dyeability in hair treatment after decoloring with a reducing agent.

Generally, a hair dye composition composed of a dye carrier material containing an oxidative dye, ammonia or the like and an oxidant such as hydrogen peroxide is known as a hair dye composition. Conventionally, reduction of ascorbic acids as reducing agents for hair dyed by coloring of polynuclear compounds produced by oxidative polymerization of oxidative dyes contained in hair dye compositions as described in Patent Document 1 Destaining agents that are decolorized (colorless) by action are known.
Special Table 2000-504348

  However, after the hair is destained after applying the destaining agent, the dyeing property is lowered as compared with the first hair dyeing treatment when the hair dyed again with the oxidative dye. There was a problem.

  The present invention has been made by finding that ascorbic acid as a reducing agent blended in a decoloring agent is a decrease in dyeability as a result of intensive studies by the present inventors. The object is to provide a hair treatment agent that can suppress a decrease in the dyeability of the hair dye in the hair dyeing treatment after decoloring with ascorbic acids as a reducing agent.

  In order to achieve the above object, the invention according to claim 1 is directed to decolorization for decoloring hair dyed by color development of a polynuclear compound produced by oxidative polymerization of an oxidative dye by the reducing action of ascorbic acids. The gist of the present invention is that the hair treatment agent to be applied after the dye is applied contains ascorbate oxidase.

  The invention according to claim 2 is applied after a decoloring agent is applied to hair dyed by color development of a polynuclear compound produced by oxidative polymerization of an oxidative dye, by decolorization by the reducing action of ascorbic acids. The hair treatment agent comprises at least one extract selected from carrot, cucumber, cauliflower, spring chrysanthemum, pumpkin, cabbage, banana, apple, zucchini, lettuce, spinach, potato and bitter gourd.

The gist of the invention described in claim 3 is that, in the invention described in claim 1 or 2, it is used as a pretreatment agent for a hair dye containing an oxidation dye.
The gist of the invention described in claim 4 is that, in the invention described in claim 1 or claim 2, an oxidation dye is further blended and used as a hair dyeing agent.

  ADVANTAGE OF THE INVENTION According to this invention, the fall of the dyeability of a hair dye can be suppressed in the hair dyeing process after the decoloring by ascorbic acids as a reducing agent.

(First embodiment)
Hereinafter, a first embodiment in which the present invention is embodied as a hair treatment agent will be described in detail.
The hair treatment agent of the first embodiment contains ascorbate oxidase. Ascorbate oxidase in the present invention is also called ascorbinase, and is a copper protein having a copper atom in the enzyme. Ascorbate oxidase is an enzyme that catalyzes a reaction of oxidizing L-ascorbic acid to dehydroascorbic acid with molecular oxygen. Ascorbate oxidase catalyzes the following reaction, for example.

L-ascorbic acid + 1 / 2O ₂ → dehydroascorbic acid + H ₂ O
Ascorbate oxidase is classified as EC 1.10.3.3 in the International Biochemical Union (I.U.B) classification. Ascorbate oxidase is present in plant bodies such as carrots such as ginseng, cucumber, cauliflower, spring chrysanthemum, pumpkin, cabbage, banana, apple, zucchini, lettuce, spinach, potato and bitter gourd. In addition, ascorbate oxidase includes the genus Myrothecium, the genus Aerobacter, the genus Aspergillus, the genus Penicillium, the genus Acremonium, the genus Volutella, the Trichoderma ) It is known to exist in the living body of microorganisms of the genus.

  Ascorbate oxidase may be blended into the hair treatment agent as purified from the living body, or an extract extracted with water or an organic solvent such as 1,3-butylene glycol (BG) and glycerin. You may mix | blend. Moreover, it is good also considering the extract from an organism as an ascorbate oxidase containing extract. Moreover, you may use what was biosynthesized in colon_bacillus | E._coli etc. using the genetic engineering technique using the gene which codes ascorbate oxidase protein. You may mix | blend independently from these, and may mix | blend 2 or more types in combination. Among these ascorbate oxidases, those derived from plants are preferably used from the viewpoint of safety. Moreover, a carrot extract and / or a cucumber extract are particularly preferable from the viewpoints of safety and availability.

  Ascorbate oxidase is widely known to have substrate specificity with respect to ascorbate analogs other than ascorbate, and ascorbate oxidase includes not only ascorbate but also ascorbate and derivatives thereof. Specific examples of ascorbate include sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate and the like. Specific examples of ascorbic acid derivatives include erythorbic acid, sodium erythorbate, disodium ascorbate sulfate, magnesium ascorbate phosphate, ascorbyl palmitate, ascorbyl stearate, ascorbyl dipalmitate, ascorbyl tetra-2-hexyldecanoate, Ascorbyl myristate, ascorbyl laurate, ascorbyl acetate, ascorbyl propionate, ascorbyl tartrate, ascorbyl citrate, ascorbyl succinate, ascorbyl benzoate, (ascorbyl / tocopheryl) potassium phosphate, ascorbyl ethyl, ascorbyl allantoin, chitosan ascorbate, Methylsilanol ascorbate, tetradecylhexyl ascorbyl, aminopropyl asco Building phosphate, ascorbic acid poly peptides, ascorbyl glucoside, and the like ascorbyl methylsilanol pectinate, and the like.

  The amount of ascorbate oxidase used in the present invention to the hair treatment agent depends on the type of reducing agent (reaction substrate) incorporated in the decoloring agent, the treatment time, and the enzyme titer. Although not specified, it is blended in an amount of 0.00005 to 50% by weight, preferably 0.0005 to 20% by weight, based on the hair treatment agent when applied to hair. If the amount is less than 0.00005% by weight, it is not possible to sufficiently suppress the decrease in the dyeability of the hair dye, and even if the amount exceeds 50% by weight, an increase in effect commensurate with the increase in the added amount is not observed. .

In the hair treatment agent, an oily component, a hydrocarbon, a surfactant, a pH adjuster, and the like can be blended as other components.
The oil component is preferably blended from the viewpoint of imparting moisture to the hair. Examples of the oil component include polyhydric alcohols, fats and oils, waxes, higher alcohols, higher fatty acids, alkyl glyceryl ethers, esters, silicones, and the like.

  Examples of the polyhydric alcohol include glycols and glycerins. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, and 1,3-butylene glycol. Examples of glycerins include glycerin, diglycerin, and polyglycerin.

  Oils include olive oil, rosehip oil, camellia oil, shea fat, macadamia nut oil, almond oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef fat, cocoa butter, corn oil , Peanut oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, avocado oil, carrot oil, macadamia nut oil, castor oil, linseed oil, palm oil, mink oil, egg yolk oil, etc. Is mentioned. Examples of waxes include beeswax, candelilla wax, carnauba wax, jojoba oil, and lanolin.

  Higher alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, aralkyl alcohol, behenyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol, oleyl Alcohol, linoleyl alcohol, linolenyl alcohol, lanolin alcohol, etc. are mentioned. Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolin fatty acid. It is done.

  Examples of the alkyl glyceryl ether include batyl alcohol (monostearyl glyceryl ether), chimyl alcohol (monocetyl glyceryl ether), selachyl alcohol (monooleyl glyceryl ether), and isostearyl glyceryl ether.

  Esters include diisopropyl adipate, diisobutyl adipate, dioctyl adipate, 2-hexyldecyl adipate, diisostearyl adipate, isopropyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, isodecyl isononanoate , Isotridecyl isononanoate, diisopropyl sebacate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, stearyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, triisodecyl myristate, myristic acid Isostearyl, 2-ethylhexyl palmitate, octyldodecyl ricinoleate, fatty acid (C10-30) (choleste Lanylyl), lauryl lactate, cetyl lactate, myristyl lactate, octyldodecyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid Examples thereof include esters, N-alkyl glycol monoisostearate, cetyl caprate, glyceryl tricaprylate, neopentyl glycol dicaprate, diisostearyl malate, and lanolin derivatives. These oil components may be blended alone or in combination of two or more.

  Examples of silicones include dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, fatty acid-modified polysiloxane, alcohol-modified silicone, aliphatic alcohol-modified polysiloxane, polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, Examples include alkyl-modified silicone.

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

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.
Specific examples of the nonionic surfactant include polyoxyethylene (hereinafter referred to as POE) alkyl ethers, POE alkylphenyl ethers, POE / polyoxypropylene alkyl ethers, POE sorbitan fatty acid esters, POE propylene glycol fatty acid. Examples thereof include esters and aliphatic alkanolamides.

  Cationic surfactants include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, stearyl trimethyl ammonium saccharin. And cetyltrimethylammonium saccharin.

  Examples of anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, POE alkyl sulfates such as POE lauryl ether sodium sulfate, alkyl sulfate esters such as lauryl sulfate triethanolamine, stearoylmethyl taurine sodium, dodecylbenzenesulfonic acid Examples include triethanolamine, sodium tetradecenesulfonate, POE lauryl ether phosphate and salts thereof, N-lauroyl glutamates, and N-lauroylmethyl-β-alanine salts.

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

  Examples of the pH adjuster include citric acid, lactic acid, 2-amino-2-methyl-1-propanol and the like. In addition, the hair treatment agent is mixed with water as a solvent or dispersion medium for each component described above, and the concentration of each component is adjusted. The pH of the hair treatment agent is preferably adjusted to the optimum pH for the enzyme activity of ascorbate oxidase. Although the optimum pH of ascorbate oxidase varies depending on the origin, it is preferably 3-9. In addition, when using a hair treatment agent as a hair dyeing pretreatment agent, since an alkali treatment is accompanied in a hair dyeing process, it is more preferable to raise pH.

  Further, other components include anionic polymers such as carboxyvinyl polymer, cationized cellulose derivatives, cationized guar gum, cationized polymers such as diallyl quaternary ammonium salt / acrylamide copolymer, diallyl quaternary ammonium salt / acrylic acid co Water-soluble polymers such as amphoteric polymers such as polymers, preservatives such as methylparaben and phenoxyethanol, ceramides, vitamins, PPTs, chelating agents, fragrances and the like can be blended.

  The hair treatment agent can be in the form of a liquid, mist, gel, foam, cream or the like. This hair treatment agent may be applied to hair care agents such as shampoos, rinses, treatments, hair styling agents and the like. This hair treatment agent may be used after being applied to the hair and washed away with water or warm water, or the same composition adhering to the hair may be used without being washed away with water or warm water.

  The hair treatment agent of the present invention is applied to a hair dyed by color development of a polynuclear compound generated by oxidative polymerization of an oxidative dye after a decoloring agent for decoloring by applying a reducing action of ascorbic acids is applied.

  Next, the destaining agent will be described. The destaining agent in the present embodiment is composed of a destaining agent first agent (hereinafter referred to as a destaining first agent) and a destaining agent second agent (hereinafter referred to as a destaining second agent). The destaining first agent contains water and the like. The first destaining agent is a liquid, gel or cream composition. On the other hand, the second dyeing agent contains ascorbic acids as a reducing agent. This destaining second agent is a solid composition. A destaining mixture in which ascorbic acids contained in the destaining second agent are dissolved in the destaining first agent is obtained by mixing and preparing the destaining first agent and the destaining second agent. it can.

<Destaining first agent>
In addition to water, other components described in the first dyeing agent such as a water-soluble polymer compound, a surfactant, and an oil component can be appropriately blended with the first dyeing agent.

  Water is blended as a solubilizing agent for ascorbic acids contained in the second hair coloring agent. The water-soluble polymer compound is blended as a thickener that gives an appropriate viscosity to the decoloring agent. The oil component is blended in order to form a stable emulsified state. Surfactant is mix | blended in order to improve stability of the decoloring 1st agent.

<Destaining second agent>
In addition to ascorbic acid as a reducing agent, fumaric acid, a dispersing agent, and the like can be blended with the second dyeing agent.

  Ascorbic acids are blended to reduce polynuclear compounds produced by oxidative polymerization of oxidative dyes that dye hair. Ascorbic acids can depolymerize or deresonate a polynuclear compound having a low polymerization rate by its reducing action, and can easily depolymerize or deresonate the multinuclear compound. Ascorbic acids include the compounds listed as substrates that are oxidized by the ascorbate oxidase. These ascorbic acids may be blended singly or in combination of two or more. Among these ascorbic acids, ascorbic acid or a salt thereof, which is excellent in the action of depolymerizing or non-resonating a polynuclear compound having a low polymerization rate, is preferable as an ascorbate oxidase substrate. Moreover, when ascorbic acid is mix | blended as a reducing agent, while being able to reduce the odor in a destaining 2nd agent and a destaining mixture, the hair damage degree in the hair after a destaining process can also be reduced.

Fumaric acid is blended in order to suppress reoxidation of components produced by depolymerization or non-resonance of a polynuclear compound having a low polymerization rate, and to suppress recoloration of hair.
The dispersing agent suppresses ascorbic acid and the like from agglomerating to form a lump state, and the destaining second agent in the destaining first agent during mixing preparation of the destaining first agent and the destaining second agent. Is added to improve the dispersibility. Specific examples of the dispersant include stearic acid metal salts such as calcium stearate and magnesium stearate, talc, crystalline cellulose, low-substituted hydroxypropylcellulose, dextrin and the like.

<Destaining mixture>
When using a destaining agent, a destaining mixture in which ascorbic acids are dissolved in water can be obtained by mixing and preparing a destaining first agent and a destaining second agent at a predetermined ratio.

Next, the effect | action of the hair processing agent comprised as mentioned above is demonstrated.
First, the above-mentioned destaining mixture is applied to hair dyed by color development of a polynuclear compound produced by oxidative polymerization of an oxidative dye using an applicator such as a brush or a comb. Here, the polynuclear compound dyeing hair is depolymerized (decomposed) or non-resonated by the reducing action of ascorbic acids. The hair dye containing the oxidation dye should contain a polymerization inhibitor so that when the oxidation dye is oxidatively polymerized by the oxidant, a polynuclear compound having a low polymerization rate that is easily decolored by the decoloring agent is produced. Is preferred. The hair treatment agent of the present invention is applied to hair that has been applied with a decoloring agent for decoloring by the reducing action of ascorbic acids on hair dyed by color development of polynuclear compounds produced by oxidative polymerization of oxidative dyes. Is done. The hair treatment agent of the present invention is applied to the hair with an applicator such as a brush or a comb. Here, the ascorbic acid derived from the decoloring agent remaining in the hair is oxidized to dehydroascorbic acid having no reducing power by the ascorbate oxidase blended in the hair treatment agent.

The effects exhibited by the first embodiment will be described below.
(1) In the first embodiment, after the dyeing mixture for applying the dyeing by the reducing action of ascorbic acids is applied to the hair dyed by the color development of the polynuclear compound generated by the oxidative polymerization of the oxidation dye. Ascorbate oxidase was blended in the hair treatment agent applied to the hair. Ascorbic acid oxidase oxidizes the ascorbic acid derived from the destaining agent into dehydroascorbic acid having no reducing power. Thereby, in the hair dyeing process using the oxidation dye performed after that, there is no possibility that the ascorbic acids remaining on the hair may inhibit the oxidation polymerization reaction of the oxidation dye, and the decrease in dyeability can be suppressed.

(2) In the first embodiment, the ascorbate oxidase is preferably derived from a plant. By using plant-derived ascorbate oxidase, the safety of the hair treatment agent can be increased.
(Second Embodiment)
Hereinafter, a second embodiment in which the hair treatment agent of the present invention is embodied as a hair dye treatment agent will be described.

  The hair dye treatment agent in the second embodiment is composed of a hair dye first agent (hereinafter referred to as hair dye first agent) and a hair dye second agent (hereinafter referred to as hair dye second agent). The hair dye first agent contains an oxidation dye, an alkali agent and the like. The second dyeing agent contains an oxidizing agent and the like. Ascorbate oxidase may be added to either the first dyeing agent or the second dyeing agent. Moreover, you may comprise so that ascorbic acid oxidase may be mix | blended with the liquid mixture with which the hair dye 1st agent and the hair dye 2nd agent were mixed. The content of ascorbate oxidase is 0.00005 to 50% by weight, preferably 0.0005 to 20% by weight, in the mixed solution when applied to hair.

<Hair dyeing first agent>
The oxidative dye indicates a compound capable of developing color by oxidative polymerization with an oxidant mixed in the second dyeing agent, and is specifically classified into a main intermediate and a coupler. Here, a compound produced by oxidative polymerization of an oxidative dye is referred to as a polynuclear compound, and specific examples of the polynuclear compound include a homopolymer of a single kind of oxidative dye and a copolymer of a plurality of kinds of oxidative dyes. Hair is dyed with these polynuclear compounds.

  Specific examples of the main intermediate include phenylenediamines (excluding m-phenylenediamine), aminophenols (excluding m-aminophenol and 2,4-diaminophenol), and toluylenediamines. , Diphenylamines, diaminophenylamines, N-phenylphenylenediamines, diaminopyridines, salts thereof and the like. Examples of the salt include hydrochloride, sulfate, acetate and the like. Among the main intermediates, p-phenylenediamine, p-toluylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, 2-chloro-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, p-aminophenol, o-aminophenol, 2,6-dichloroparaphenylenediamine, p-amino At least one selected from phenylsulfamic acid and salts thereof is preferable. These main intermediates may be blended singly or in combination of two or more.

  As couplers, resorcin, pyrogallol, catechol, m-aminophenol, m-phenylenediamine, o-aminophenol, 2,4-diaminophenol, 1,2,4-benzenetriol, toluene-3,4-diamine, toluene -2,4-diamine, hydroquinone, α-naphthol, 2,6-diaminopyridine, 1,5-dihydroxynaphthalene, 5-amino-o-cresol, diphenylamine, p-methylaminophenol, phloroglucin, 2,4-diamino Phenoxyethanol, gallic acid, tannic acid, ethyl gallate, methyl gallate, propyl gallate, pentaploid, 1-methoxy-2-amino-4- (2-hydroxyethyl) aminobenzene, 5- (2-hydroxyethylamino) -2-methylphenol, These salts, and the like. These couplers may be blended singly or in combination of two or more.

  Since this oxidation dye can be changed to various color tones, it is preferably composed of at least one selected from main intermediates and at least one selected from couplers.

  The content of the oxidation dye in the hair dye mixture is preferably 0.02 to 25% by weight, more preferably 0.2 to 15% by weight. If the content is less than 0.02% by weight, sufficient dyeability may not be obtained. On the other hand, adding more than 25% by weight does not improve dyeability and is not economical.

  The content of the main intermediate in the hair dye mixture is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight. If the content is less than 0.01% by weight, sufficient dyeability may not be obtained. On the other hand, even if it exceeds 15% by weight, the dyeability is not improved and it is not economical.

  The content of the coupler in the hair dye mixture is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. If the content is less than 0.01% by weight, sufficient dyeability may not be obtained. On the other hand, if it exceeds 10% by weight, the dyeability is not improved and it is not economical.

In addition, direct dyes and the like can be appropriately blended as oxidation dyes and dyes other than oxidation dyes listed in the “Quasi-drug raw material standards” (issued in June 1991, Yakuji Nippo).
The alkaline agent is blended to promote the action of the oxidizing agent blended in the hair dyeing second agent and to improve the dye penetration into the hair by swelling the hair and to improve the dyeability. Specific examples of the alkali agent include ammonia, alkanolamine, ammonium salt, organic amines (2-amino-2-methyl-1,3-propanediol, guanidine, etc.), inorganic alkali (sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, etc.), basic amino acids (arginine, lysine, etc.) and their salts.

  These alkaline agents may be blended singly or in combination of two or more. The blending amount of the alkaline agent is preferably set to an amount that makes the pH of the hair dye first agent in the range of 8-9. If the pH of the first dyeing agent is less than 8, the action of hydrogen peroxide may not be sufficiently promoted when the first dyeing agent is mixed with the second dyeing agent. On the other hand, when pH exceeds 9, there exists a possibility of inhibiting the activity of ascorbate oxidase.

Water, a surfactant, an oily component, and the like are blended with the first component of hair dye as other components.
Water is blended in an appropriate amount as a solvent or dispersion medium for each component.
The surfactant is blended in order to maintain the stability of the first dyeing agent as an emulsifier or solubilizer. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

  Furthermore, as other components, fatty acids such as lauric acid, myristic acid and linolenic acid, sugars such as sorbitol and maltose, alkyl glyceryl ethers such as polyhydric alcohol, batyl alcohol and chimyl alcohol, gum arabic, caraya gum, gum tragacanth and sodium alginate , Xanthan gum, cellulose derivatives, crosslinked polyacrylic acid, water-soluble polymer compounds such as polydimethylmethylenepiperidinium chloride, preservatives such as parabens, chelating agents such as EDTA-2Na, phenacetin, 8-hydroxyquinoline, acetanilide, pyrophosphoric acid Stabilizers such as sodium, barbituric acid, uric acid, tannic acid, pH adjusters such as phosphoric acid, citric acid, sulfuric acid, acetic acid, lactic acid, tartaric acid, plant extracts, herbal extracts, vitamins, fragrances, UV absorbers Etc.Moreover, you may mix | blend at least 1 type chosen from what is listed in "quasi-drug material standard" (June 1991 issue, Yakuji Nippo).

The dosage form of the first hair dyeing agent is not particularly limited, such as a liquid such as an aqueous solution, a dispersion or an emulsion, a gel, a foam or a cream.
<Hair dyeing second agent>
This hair dye second agent contains an oxidizing agent. Moreover, this hair dye 2nd agent contains the component normally used for the hair dye 2nd agent of an oxidation hair dye as another component.

  The oxidizing agent is blended to decolorize melanin contained in the hair and to oxidize and color the oxidizing dye blended in the first hair dyeing agent. Examples of the oxidizing agent include potassium bromate, sodium bromate, sodium perborate and hydrogen peroxide. The blending amount is preferably 0.1 to 15.0% by weight based on 100% by weight of the total amount of the second dyeing agent.

  Other components described in the first hair dyeing agent can be appropriately mixed with the second hair dyeing agent. Further, when hydrogen peroxide is blended as an oxidizing agent, it is preferable to blend a stabilizer in order to suppress decomposition of hydrogen peroxide. Specific examples of the stabilizer include urea, phenacetin, sodium stannate, ethylene glycol phenyl ether, 8-oxyquinoline, phosphoric acid and the like.

The dosage form of the second hair dyeing agent is not particularly limited, such as a liquid such as an aqueous solution, a dispersion, or an emulsion, a gel, a foam, and a cream.
<Hair dye mixture>
When using an oxidative hair dye, a hair dye mixture can be obtained by mixing and preparing the first hair dye agent and the second hair dye agent at a predetermined ratio. The dosage form of this hair dye mixture is not particularly limited, such as liquid, cream, gel, and foam.

Next, the effect | action of the hair dyeing agent comprised as mentioned above is demonstrated.
First, the above-described destaining mixture is applied to hair dyed by color development of a polynuclear compound generated by oxidative polymerization of an oxidative dye using an applicator such as a brush or a comb. Here, the polynuclear compound dyeing hair is depolymerized (decomposed) or non-resonated by the reducing action of ascorbic acids.

  The hair dye treatment agent of the present invention is applied to the hair after the dyeing agent for decoloring by the reducing action of ascorbic acids is applied to the hair dyed by the coloration of the polynuclear compound produced by the oxidative polymerization of the oxidative dye. Applied. The hair dye mixture of the present invention is applied to the hair with an applicator such as a brush or a comb. Here, the ascorbic acid derived from the decoloring agent remaining on the hair is oxidized to dehydroascorbic acid having no reducing power by the ascorbate oxidase in the hair dye mixture. At the same time, the hair is dyed by oxidative polymerization of the oxidative dye by the action of the alkaline agent and the oxidant.

The effect exhibited by the above second embodiment will be described below.
(1) In the second embodiment, ascorbate oxidase was blended in the hair dye treatment agent. Accordingly, ascorbic acid oxidase oxidizes ascorbic acid derived from the destaining agent into dehydroascorbic acid having no reducing power. Thereby, there is no possibility that ascorbic acid remaining in the hair inhibits the oxidative polymerization reaction of the oxidative dye in the hair dyeing treatment, and it is possible to suppress a decrease in dyeability.

  (2) In the second embodiment, ascorbate oxidase is blended with a hair dye treatment agent containing an oxidation dye. Therefore, the hair dyeing treatment and the oxidation treatment reaction of residual ascorbic acids can be performed simultaneously.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1 to 8 and Comparative Examples 1 and 2, hair treatment agent)
First destaining agent and ascorbine containing 1.5% by weight of Karaya gum, 1.5% by weight of carboxymethylcellulose, 1.0% by weight of propylene glycol, 1.0% by weight of polyoxyethylene nonylphenyl ether and the remaining amount of purified water A desiccant second agent containing 90.0% by weight of acid, 5.0% by weight of fumaric acid and 5.0% by weight of magnesium stearate was mixed and prepared at a weight ratio of 1: 1 to obtain a desiccant mixture. It was. The obtained depigmenting agent mixture was applied to each hair bundle of white hair and light brown hair using a brush and allowed to stand at room temperature for 30 minutes. Then, after the hair dye mixture adhering to each hair bundle was washed away with water, shampoo was applied twice, rinse was performed once, and it dried with warm air.

  Next, each component shown in Table 1 was mixed to obtain hair treatment agents of Examples and Comparative Examples. As plant extracts containing ascorbate oxidase, Homo Fruit Cucumber Deo (manufactured by Koei Kogyo Co., Ltd.), Cucumber Extract BG (Maruzen Pharmaceutical Co., Ltd.), Homo Fruit Carrot N (manufactured by Koei Kogyo Co., Ltd.), carrot extract Liquid BG (made by Koei Kogyo Co., Ltd.) was used. The peach fruit cucumber Deo is obtained by diluting the extract of the peach fruit cucumber with a solvent to obtain an extract containing ascorbate oxidase. Cucumber extract BG uses 1,3-butylene glycol as a solvent, and a soluble component is an extract containing ascorbate oxidase. The peach fruit carrot N is obtained by diluting the peach fruit carrot extract with a solvent to obtain an ascorbate oxidase-containing extract. The carrot extract BG is obtained by using 1,3-butylene glycol as a solvent and using a soluble component as an ascorbate oxidase-containing extract. The obtained hair treatment agent was applied to human hair bundles of white hair and light brown hair after treatment with a destaining agent using a brush, and left at room temperature for 30 minutes. Next, the hair dye mixture adhering to each hair bundle was washed away with water and then dried with warm air.

  Next, the hair dye 1st agent and the hair dye 2nd agent which mixed each component shown below are mixed by the weight ratio of 1: 1, The white hair and light brown hair after the process by a hair treatment agent are mixed. After being applied to the human hair bundle, it was left for 40 minutes. Then, after the hair dye mixture adhering to each hair bundle was washed away with water, shampoo was applied twice, rinse was performed once, and it dried with warm air.

<Oxidative hair dye>
(First agent) Weight%
Cetostearyl alcohol ・ ・ ・ 15.0
Polyoxyethylene oleyl ether ... 10.0
Cyclomethicone 0.5
Dimethicone ... 0.5
Glycerin ... 10.0
Polyquaternium-51 ... 1.0
Lanolin ... 2.0
Strong ammonia water (28%) …… 8.0
Methylparaben ... 0.2
Lauryl sulfate ... 2.0
Thioglycolic acid ... 0.5
EDTA ... 1.0
Orthoaminophenol ... 0.1
Metaaminophenol ... 0.05
Paraaminophenol ... 0.3
5-Aminoorthocresol ... 0.6
Paraphenylenediamine ... 0.1
Purified water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount (second agent)
Hydrogen peroxide (35%) ... 17.0
Purified water ......... Remaining amount Human hair of gray and light brown hair that has been subjected to these decolorization treatments, treatments with hair treatment agents, and dyeing treatments The bundle was evaluated for dyeability. In addition, the unit of the numerical value which shows the mixing | blending of each component in Table 1 is weight%.

<Dyeability>
About the hair | bristle bundle of each Example and a comparative example, the value in a L * a * b * colorimetric system (CIE1976) was measured using the spectrocolorimeter (the Minolta Co., Ltd. make, model number: CM-508d). The color difference (ΔE) is a numerical value representing the degree of dyeing based on the hair bundle before the dyeing process calculated from the following formula. The larger the numerical value, the higher the hair dyeing power. The evaluation results are shown in Table 1. Table 1 also shows conversion values when the value of ΔE in the case where no ascorbate oxidase-containing extract is added (Comparative Examples 1 and 2) is set to 100 for each of human hair bundles of white hair and light brown hair. .

ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2

表１の結果から、染色前にアスコルビン酸オキシダーゼを含有する毛髪処理剤で処理した実施例１〜８においては、アスコルビン酸オキシダーゼを含有しない毛髪処理剤で処理した比較例１，２より染色性が優れていることが確認された。

From the results of Table 1, in Examples 1 to 8 treated with a hair treatment agent containing ascorbate oxidase before dyeing, the dyeability was higher than those of Comparative Examples 1 and 2 treated with a hair treatment agent not containing ascorbate oxidase. It was confirmed to be excellent.

(Examples 9 to 16 and Comparative Examples 3 and 4, hair dye treatment agent)
The decoloring agent mixture used in Example 1 was applied to a human hair bundle of white hair and light brown hair using a brush and allowed to stand at room temperature for 30 minutes. Then, after the hair dye mixture adhering to each hair bundle was washed away with water, shampoo was applied twice, rinse was performed once, and it dried with warm air.

  Next, each component shown in Table 2 was mixed, and the hair dyeing treatment agent which consists of the hair dye 1st agent and the hair dye 2nd agent of each Example and a comparative example was obtained. As plant extracts containing ascorbate oxidase, Homo Fruit Cucumber Deo (manufactured by Koei Kogyo Co., Ltd.), Cucumber Extract BG (Maruzen Pharmaceutical Co., Ltd.), Homo Fruit Carrot N (manufactured by Koei Kogyo Co., Ltd.), carrot extract Liquid BG (made by Koei Kogyo Co., Ltd.) was used.

  The first hair dyeing agent and the second hair dyeing agent were mixed at a weight ratio of 1: 1, and the mixture was applied to human hair bundles of white hair and light brown hair after destaining, and then allowed to stand for 40 minutes. Then, after the hair dye mixture adhering to each hair bundle was washed away with water, shampoo was applied twice, rinse was performed once, and it dried with warm air. The dyeability was evaluated for the human hair bundles of gray hair and light brown hair that had been subjected to these decoloring treatment, treatment with a hair treatment agent, and dyeing treatment. The evaluation results are shown in Table 2. Table 2 also shows the converted values when the value of ΔE in the case where the ascorbate oxidase-containing extract is not added (Comparative Examples 3 and 4) is set to 100 for each of human hair bundles of white hair and light brown hair. . In addition, the unit of the numerical value which shows the mixing | blending of each component in Table 2 is weight%.

表２の結果から、アスコルビン酸オキシダーゼを含有する染毛処理剤で処理した実施例９〜１６においては、アスコルビン酸オキシダーゼを含有しない染毛処理剤で処理した比較例３，４より染色性が優れていることが確認された。
（実施例１７〜２０、比較例５，６、濃度依存性試験）
表３に示される各成分を混合した毛髪処理剤を使用した以外は、実施例１と同様の方法により白髪毛及びライトブラウン毛の人毛毛束を処理した。アスコルビン酸オキシダーゼ（ナガセ生化学工業株式会社製）の配合量を増やした場合における染色性を評価した。それらの評価結果を表３に示す。また、白髪毛及びライトブラウン毛の人毛毛束のそれぞれについて、アスコルビン酸オキシダーゼを添加しない場合（比較例５，６）のΔＥの値を１００とした場合の換算値も表３に示す。なお、表３における各成分の配合を示す数値の単位は重量％である。

From the results of Table 2, in Examples 9 to 16 treated with the hair dye treatment agent containing ascorbate oxidase, the dyeability is superior to Comparative Examples 3 and 4 treated with the hair dye treatment agent not containing ascorbate oxidase. It was confirmed that
(Examples 17 to 20, Comparative Examples 5 and 6, concentration dependency test)
Human hair bundles of white hair and light brown hair were treated in the same manner as in Example 1 except that the hair treatment agent in which the respective components shown in Table 3 were mixed was used. The dyeability when the amount of ascorbate oxidase (Nagase Seikagaku Corporation) was increased was evaluated. The evaluation results are shown in Table 3. Table 3 also shows the converted values when the value of ΔE in the case where no ascorbate oxidase is added (Comparative Examples 5 and 6) is set to 100 for each of the human hair bundles of white hair and light brown hair. In addition, the unit of the numerical value which shows the mixing | blending of each component in Table 3 is weight%.

表３の結果から、アスコルビン酸オキシダーゼを配合する量を上昇させる染色性も同時に上昇することが示される。
（比較例７〜１２）
表４に示される各成分を混合した毛髪処理剤を使用した以外は、実施例１と同様の方法により白髪毛及びライトブラウン毛の人毛毛束を処理した。アスコルビン酸オキシダーゼを含有しない植物抽出液としてゴボウ抽出液（ファルコレックス株式会社製）及び大豆抽出液（香栄興業株式会社製）を使用した。これらの脱染処理、毛髪処理剤による処理及び染色処理が施された白髪毛及びライトブラウン毛の人毛毛束のそれぞれについて、染色性を評価した。それらの評価結果を表４に示す。また、白髪毛及びライトブラウン毛の人毛毛束のそれぞれについて、植物抽出液を添加しない場合（比較例７，１０）のΔＥの値を１００とした場合の換算値も表４に示す。なお、表４における各成分の配合を示す数値の単位は重量％である。

From the results of Table 3, it is shown that the dyeability that increases the amount of ascorbate oxidase is also increased.
(Comparative Examples 7-12)
Human hair bundles of gray hair and light brown hair were treated in the same manner as in Example 1 except that the hair treatment agent in which the respective components shown in Table 4 were mixed was used. As plant extracts not containing ascorbate oxidase, burdock extract (Falco Rex Co., Ltd.) and soybean extract (Koei Kogyo Co., Ltd.) were used. The dyeability was evaluated for each of the white hair and light brown hair bundles that had been subjected to the destaining treatment, the treatment with the hair treatment agent, and the dyeing treatment. The evaluation results are shown in Table 4. Table 4 also shows the converted values when the value of ΔE in the case where the plant extract is not added (Comparative Examples 7 and 10) is set to 100 for each of human hair bundles of white hair and light brown hair. In addition, the unit of the numerical value which shows the mixing | blending of each component in Table 4 is weight%.

表４の結果から、アスコルビン酸オキシダーゼを含有しない植物抽出液を使用した場合には、染色性は何ら上昇しないことが示される。

From the results of Table 4, it is shown that when a plant extract not containing ascorbate oxidase is used, the dyeability does not increase at all.

In addition, you may change the said embodiment as follows.
In the above embodiment, the destaining agent is configured as a destaining first agent and a destaining second agent and mixed immediately before use. In addition, it is good also as a 1 agent type decoloring agent comprised from the solution which mix | blended all the components which comprise decoloring agents, such as ascorbic acids and water. Alternatively, solid ascorbic acids such as powders may be used as a decoloring agent, and the decoloring agent may be dissolved in water and applied to the hair by the user. Moreover, you may divide | segment arbitrarily the component which comprises the destaining 1st agent and the destaining 2nd agent, and you may comprise in 3 or more types.

  -In the said embodiment, the extraction method from the biological body of ascorbate oxidase is not specifically limited. For example, an ascorbate oxidase-containing extract may be obtained by adding a living organism in water or an organic solvent such as 1,3-butylene glycol and glycerin, and then pulverizing and then extracting only a soluble component using filter paper or the like. .

  In the first embodiment, the hair treatment agent may be applied as a pretreatment agent for a hair dye containing an oxidation dye. In such a case, the hair treatment agent may be applied only when performing the hair dyeing treatment.

  -In 2nd Embodiment, it was set as the structure which comprised the hair dye treatment agent as the hair dye 1st agent and the hair dye 2nd agent, and mixed just before use. However, each component constituting the first hair dyeing agent and the second hair dyeing agent may be separated into three or more agents. For example, the hair dyeing agent which consists of the hair dye 1 agent which mix | blends oxidation dye and ascorbate oxidase, the hair dye 2 agent which mix | blends an alkaline agent, and the hair dye 3 agent which mix | blends an oxidizing agent is mentioned. In such a configuration, the storage stability of the oxidation dye and ascorbate oxidase can be enhanced by configuring the oxidation dye and ascorbate oxidase separately from the second dyeing agent in which the alkaline agent is blended. Moreover, you may comprise as 1 agent type which mixes and prepares each component which comprises a hair dyeing treatment agent immediately before use.

Next, technical ideas that can be grasped from the above-described embodiment and other examples will be described below together with their effects.
(A) The ascorbic acid compounded in the decoloring agent is ascorbic acid. The hair treatment agent according to any one of claims 1 to 4. Therefore, according to the invention described in (a), ascorbic acid is excellent in the action of depolymerizing or deresonating a polynuclear compound having a low polymerization rate, and is an optimum substrate for ascorbate oxidase to be blended in the hair treatment agent. Therefore, the remaining ascorbic acid is efficiently oxidized.

Claims (4)

In the hair treatment agent applied after the decoloring agent for decoloring by the reducing action of ascorbic acid is applied to the hair dyed by the color development of the polynuclear compound generated by the oxidative polymerization of the oxidative dye,
A hair treatment agent containing ascorbate oxidase. In the hair treatment agent applied after the decoloring agent for decoloring by the reducing action of ascorbic acid is applied to the hair dyed by the color development of the polynuclear compound generated by the oxidative polymerization of the oxidative dye,
A hair treatment agent comprising at least one extract selected from carrot, cucumber, cauliflower, spring chrysanthemum, pumpkin, cabbage, banana, apple, zucchini, lettuce, spinach, potato and bitter gourd.   The hair treatment agent according to claim 1 or 2, which is used as a pretreatment agent for a hair dye containing an oxidation dye.   The hair treatment agent according to claim 1 or 2, further comprising an oxidation dye and used as a hair dyeing treatment agent.