JP4083702B2 - Oxidative hair dye composition - Google Patents

Description

  The present invention relates to an oxidative hair dye composition that is mixed with an oxidant composition, applied to hair, and used for dyeing hair.

Conventionally, as this type of oxidative hair dye composition, a first agent containing an oxidative dye, ascorbic acid and carbonate, which is used by being mixed with a second agent containing an oxidant or the like has been known. (For example, refer to Patent Document 1). Moreover, the 1st agent containing an oxidation dye, ascorbic acid, an alkaline agent, etc. is known (for example, refer patent document 2). These 1st agent and 2nd agent are mixed and prepared at the time of use, and the hair dyeing process is given to hair by applying the mixture of 1st agent and 2nd agent to hair. In this hair dye, the oxidizing agent such as hydrogen peroxide in the second agent has a function of coloring the oxidation dye. These oxidative hair dye compositions can prevent background stains without reducing hair dyeing power by adding ascorbic acids, carbonates, alkaline agents, and the like to the oxidative dye.
JP 2003-40747 A (pages 2 to 4) JP 2002-29946 A (page 2, page 9 and page 10)

  The oxidative hair dye composition described in Patent Document 1 prevents background stains due to hair dyeing of hair dyes based on the reducing action of ascorbic acids, and carbonate promotes the effect. However, among the carbonates, ammonium carbonate has a problem in that it decomposes while the oxidative hair dye composition is stored in the container, generates carbon dioxide gas, and expands the container.

  On the other hand, in the oxidative hair dye composition described in Patent Document 2, p-phenylenediamine 4.0% by mass (0.37 mol), ascorbic acid 1.0% by mass (0.057 mol) and alkali are used as the oxidative dye. As an agent, 5.5% (0.91 mol) of 28% ammonia water is blended (Example 6 of Patent Document 2).

  However, although this oxidative hair dye composition is effective from the viewpoint of preventing background stains, since the balance of these three components is poor, the hair dyeing power of p-phenylenediamine has been sufficiently drawn out. Absent. Furthermore, since the bleaching power (bleaching power) is too strong, there is a problem that the melanin pigment of the hair is decomposed more than necessary, resulting in an unnatural hair coloring state over time. Moreover, when the oxidant composition is mixed with the oxidative hair dye composition, the hair tends to be easily damaged (damaged) by the oxidant. Therefore, if the blending amount of the oxidizing agent is reduced, damage to the hair can be suppressed, but there is a problem that the required hair dyeing power cannot be obtained.

  The present invention has been made paying attention to the problems existing in the prior art as described above. The purpose of the dyeing is that it is excellent in hair coloring power without generating gas during storage in a container, can obtain a natural hair dyeing state, and can prevent damage to hair. The object is to provide a hair composition.

In order to achieve the above object, the oxidative hair dye composition of the invention described in claim 1 is an oxidative hair dye composition containing an oxidative dye and used by being mixed with the oxidant composition. As a component for accelerating the oxidative polymerization action of the oxidative dye by the oxidant composition , 1.0 to 8.0% by mass of component (A) ascorbic acid and component (B) ammonium salt of inorganic acid or organic acid It contains 0.3 to 8.0% by mass of components (excluding monoammonium phosphate and diammonium phosphate) other than the carbonates that generate water.

Oxidation hair dye composition of the invention according to claim 2 is the invention according to claim 1, the ammonium salt of component (B) inorganic or organic acids, ammonium sulfate, ammonium chloride, ammonium acetate,-phosphate Triammonium, diammonium citrate, triammonium citrate, ammonium oxalate, ammonium lactate, ammonium tartrate or ammonium nitrate.

  The oxidative hair dye composition according to claim 3 is the invention according to claim 1 or claim 2, wherein the ammonium salt of component (B) inorganic acid or organic acid has a solubility in 100 g of water. 20 g or more at 25 ° C.

According to the present invention, the following effects can be exhibited.
According to the oxidative hair dye composition of the invention described in claim 1, the oxidative polymerization promoting action and pH control action of the oxidative dye by the oxidant can be exhibited based on the component (A) ascorbic acid, and the component. (B) The oxidative polymerization promoting action of the oxidative dye by the oxidizing agent can be exhibited by the inorganic acid or organic acid ammonium salt. Therefore, it is excellent in hair dyeing power, a natural hair dyeing state can be obtained, and damage to the hair can be suppressed. In addition, since no carbonate is contained as the ammonium salt of component (B) inorganic acid or organic acid, there is no risk of decomposition and generation of gas during storage of the oxidative hair dye composition in the container. As a result, it is possible to avoid a situation where the container expands during storage of the oxidative hair dye composition.

According to the oxidation hair dye composition of the invention described in claim 2, in addition to the effect of the invention described in claim 1, the hair dyeing power can be improved based on the specific component (B).
According to the oxidative hair dye composition of the invention described in claim 3, the solubility of the ammonium salt of component (B) inorganic acid or organic acid in the oxidative hair dye composition is good. The effect of the invention described in 2 can be improved.

Hereinafter, an embodiment in which the present invention is applied to a first agent of a two-component hair dye composed of a first agent and a second agent will be described in detail.
The first agent of the hair dye contains an oxidative dye, ascorbic acid, an ammonium salt of an inorganic acid or an organic acid, an alkali agent, and the like, and the second agent contains an oxidant and the like. These first agent and second agent are mixed, and the mixture is applied to the hair, whereby the hair can be dyed in a desired color.
[First agent]
In addition to the oxidation dye, the first agent contains ascorbic acids as component (A) and ammonium salt of inorganic acid or organic acid as component (B).

  The oxidative dye is a compound capable of color development by oxidative polymerization with an oxidant in the second agent. Specifically, it is classified into main intermediates and couplers. Examples of main intermediates include phenylenediamines and salts thereof, aminophenols and salts thereof, diaminopyridines and salts thereof, and the like. Examples of the salt include hydrochloride, sulfate, acetate and the like. These main intermediates may be blended singly or in combination of two or more. Among these, since it has excellent hair dyeing power, it is preferably p-phenylenediamine, toluene-2,5-diamine, 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, 2,6-dichloro-p-phenylenediamine, p-amino It is at least one selected from phenylsulfamic acid and salts thereof. These components can be used alone or in combination.

  On the other hand, 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 -Diaminophenoxyethanol, gallic acid, tannic acid, ethyl gallate, methyl gallate, propyl gallate, pentaploid, 1-methoxy-2-amino-4- (2-hydroxyethyl) aminobenzene, 5- (2-hydroxyethyl) Amino) -2-methylpheno Le, like their salts. These couplers may be used alone or in combination of two or more.

  The content of the oxidation dye is preferably 0.005 to 7.5% by weight. When the content is less than 0.005% by weight, it is difficult to obtain sufficient hair coloring power. On the other hand, even if it exceeds 7.5% by weight, it is difficult to further improve the hair dyeing power.

  Next, the ascorbic acid component (A) is a compound having an enediol structure represented by the following chemical formula (1). These ascorbic acids exhibit the function of controlling the pH of the mixture while promoting the oxidative polymerization reaction of the oxidative dye by the second oxidizing agent.

（式中のＲ¹及びＲ²は、水素原子、炭素数１〜３０の脂肪族基、５〜１０員の複素環基又はＣ６〜Ｃ１０員の芳香族基を表し、前記脂肪族基はその一部がカルボニル基、ヒドロキシル基、ハロゲン元素、スルホ基、カルボキシル基、ニトロ基又はフェニル基により置換可能であるものを示し、前記複素環基はその一部が炭素数１〜３０のアルキル基、ハロゲン元素、フェニル基又はヒドロキシル基により置換可能であるものを示し、前記芳香族基はその一部が炭素数１〜４のアルキル基、ハロゲン元素、スルホ基、カルボキシル基、ニトロ基、ヒドロキシル基又はニトロソ基により置換可能であるものを示す。なお、Ｒ¹及びＲ²は同一でも異なってもよく、Ｒ¹及びＲ²は部分的に結合されていてもよい。また、水酸基の水素は金属元素に置換されているものを含む。ただし、Ｒ¹とＲ²を部分的に結合する場合、Ｒ¹が結合するカルボニル炭素とＲ²とが直接結合されたものを含む。）
アスコルビン酸類の具体例としては、アスコルビン酸、エリソルビン酸、それらの塩及び誘導体、３，４−ジヒドロキシ−３−シクロブテン−１，２−ジオン、２，３−ジヒドロキシ−２−シクロペンテン−１−オン等が挙げられる。

(In the formula, R ¹ and R ² represent a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, a 5- to 10-membered heterocyclic group, or a C6-C10 member aromatic group, A part of which represents a group that can be substituted by a carbonyl group, a hydroxyl group, a halogen element, a sulfo group, a carboxyl group, a nitro group, or a phenyl group, and the heterocyclic group is a part of the alkyl group having 1 to 30 carbon atoms, A group that can be substituted by a halogen element, a phenyl group, or a hydroxyl group, wherein the aromatic group is partly an alkyl group having 1 to 4 carbon atoms, a halogen element, a sulfo group, a carboxyl group, a nitro group, a hydroxyl group, or R ¹ and R ² may be the same or different, R ¹ and R ² may be partially bonded, and the hydrogen atom of the hydroxyl group is a metal element Placed in Including those. However, to partially bind the R ¹ and R ^2, including those with carbonyl carbon and R ² wherein R ¹ is attached is bound directly.)
Specific examples of ascorbic acids include ascorbic acid, erythorbic acid, salts and derivatives thereof, 3,4-dihydroxy-3-cyclobutene-1,2-dione, 2,3-dihydroxy-2-cyclopenten-1-one, etc. Is mentioned.

  Examples of the salt of ascorbic acid include sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, and diethanolamine ascorbate. Examples of the salt of erythorbic acid include sodium erythorbate.

  Furthermore, ascorbic acid derivatives include ascorbic acid sulfate disodium, ascorbic acid magnesium phosphate, ascorbic acid sodium phosphate, ascorbic acid isopalmitate, ascorbic acid palmitate, ascorbyl palmitate, ascorbyl stearate , Ascorbyl dipalmitate, ascorbyl tetrahexyldecanoate, ascorbyl myristate, ascorbyl laurate, ascorbyl acetate, ascorbyl propionate, ascorbyl tartrate, ascorbyl citrate, ascorbyl succinate, ascorbyl benzoate, (ascorbyl / tocopheryl) phosphate Potassium, ascorbyl ethyl, ascorbic acid allantoin, ascorbic acid chitosan, ascorbic acid Chill silanol, tetradecyl hexyl ascorbyl, aminopropyl ascorbyl phosphate, ascorbic acid poly peptides, ascorbyl glucoside, and the like ascorbyl methylsilanol pectinate, and the like.

  These components (A) may be blended singly or in combination of two or more. Among these components (A), at least one selected from ascorbic acid and salts thereof is preferable because the oxidizing action of the oxidizing agent can be further promoted.

  The compounding quantity of (A) ascorbic acid in an oxidative hair dye composition is 1.0-8.0 mass%, Preferably it is 2.0-6.0 mass%. When the blending amount is less than 1.0% by mass, sufficient hair dyeing power and hair damage preventing effect cannot be obtained. When the blending amount exceeds 8.0% by mass, the oxidative polymerization of the oxidative dye is inhibited, and the hair is dyed. Power is reduced.

  Next, the ammonium salt of component (B) inorganic acid or organic acid is blended to exert an oxidative polymerization reaction accelerating action of the oxidative dye by the oxidant contained in the second agent, and has lightness on the hair. Give. The alkaline agent described later exhibits the same action, but the alkaline agent is damaging to the hair, whereas the component (B) can avoid such damage. As this component (B), ammonium sulfate, ammonium chloride, ammonium acetate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, diammonium citrate, triammonium citrate, ammonium oxalate, ammonium lactate, ammonium tartrate Or it is preferable that it is ammonium nitrate. These ammonium salts can be used individually by 1 type or in combination of 2 or more types.

  However, carbonates are inappropriate as the ammonium salt of component (B) inorganic acid or organic acid. This is because the carbonate decomposes during storage and generates carbon dioxide gas, which may cause the container containing the oxidative hair dye composition to expand.

  Furthermore, as the component (B), an ammonium salt of an inorganic acid or an organic acid, those having a solubility in 100 g of water of 20 g or more at 25 ° C. are preferable. Among the ammonium salts listed above, by satisfying this solubility condition, the mixed ammonium salt can be sufficiently dissolved in the base component [component other than component (B)], and oxidation of the oxidation dye The polymerization reaction can be promoted to improve the hair dyeing power. Moreover, precipitation of the ammonium salt can be prevented during storage of the oxidative hair dye composition. Ingredients with poor solubility are restricted in the amount of the base component, so that improvement in hair dyeing power is limited. In particular, the above-mentioned component (B), which has good solubility and is easy to be blended, increases the hair dyeing power when actually formulating a hair dye (hair color) in which the first agent and the second agent are mixed. Can be achieved in reality.

  Examples of ammonium salts having such solubility include ammonium sulfate (solubility 76.4 g / 100 g water), ammonium chloride (solubility 39.7 g / 100 g water), ammonium acetate (solubility 148.0 g or more / 100 g water), phosphoric acid. Monoammonium (solubility 42.9 g / 100 g water), diammonium phosphate (solubility 72.3 g / 100 g water), triammonium phosphate (solubility 26.8 g / 100 g water), diammonium citrate (solubility 30.0 g or more) / 100 g water), ammonium lactate (solubility 30.0 g or more / 100 g water), ammonium tartrate (solubility 50.0 g or more / 100 g water) and ammonium nitrate (solubility 231.6 g / 100 g water). Although the upper limit of the solubility of this ammonium salt is desirable, from the viewpoint of easy availability, the upper limit is about 250 g / 100 g water.

  The compounding quantity of the component (B) inorganic acid or organic acid ammonium salt in an oxidative hair dye composition is 0.3-8.0 mass%, Preferably it is 1.0-6.0 mass%. If the blending amount is less than 0.3% by mass, sufficient hair dyeing power cannot be obtained. If the blending amount exceeds 8.0% by mass, the base component is separated, and white hair is further dyed. I can't. The mass ratio of the component (A) and the component (B) is preferably 1: 0.1 to 5.0, and more preferably 1: 0.2 to 2.5.

  An alkaline agent is mix | blended in order to provide the lightness to hair by promoting the effect | action of the oxidizing agent contained in a 2nd agent. Specific examples of the alkali agent include ammonia, alkanolamine, 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. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, isopropanolamine and the like. These alkaline agents may be blended singly or in combination of two or more. Among the alkaline agents, alkanolamines are preferable because they can suppress irritating odors. In addition, monoethanolamine is more preferable because the effect of imparting lightness to hair is high.

  The content of the alkaline agent in the mixture of the first agent and the second agent is preferably 0.008 to 0.90 mol, more preferably 0.016 to 0.75 mol in 1 kg of the mixture. When this content is less than 0.008 mol, sufficient brightness may not be obtained. On the other hand, when it exceeds 0.90 mol, there is a possibility that a good touch cannot be obtained on the finished hair.

  Next, the pH of the first agent is preferably 8 to 12, more preferably 9 to 11. If the pH of the first agent is less than 8, the action of the oxidizing agent may not be sufficiently promoted. On the other hand, when the pH exceeds 12, when hair is dyed, there is a risk that problems such as damage occur in the hair.

  The first agent may contain water, a pH adjuster, a surfactant, an oily component, etc. as other components. Water is blended in an appropriate amount to make the first agent as a solution, dispersion or emulsion as a solvent or dispersion medium for each component. The water content in the mixture is preferably 50 to 95% by mass, more preferably 70 to 90% by mass. If the content is less than 50% by mass, it may be difficult to stably form an aqueous solution, dispersion or emulsion. On the other hand, when it exceeds 95 mass%, it becomes difficult to ensure the uniformity and stability of the mixture.

  In order to set the pH of the first agent within the above range, the first agent preferably contains a pH adjuster. Specific examples of the pH adjuster include phosphoric acid, citric acid, sulfuric acid, acetic acid, lactic acid, tartaric acid and the like. It is preferable that the blending amount of the pH adjusting agent in the first agent is an amount such that the pH of the first agent is in the above range.

  The surfactant is blended to maintain the stability of the first agent. Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

  Specific examples of nonionic surfactants include polyoxyethylene (hereinafter referred to as POE) alkyl ethers, POE alkylphenyl ethers, POE / polyoxypropylene (hereinafter referred to as POP) alkyl ethers, and POE sorbitan fatty acid esters. And POE propylene glycol fatty acid ester. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, and POE behenyl ether.

  Specific examples of the cationic surfactant include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, ethyl lanolin sulfate fatty acid aminopropyl Examples thereof include ethyldimethylammonium, stearyltrimethylammonium saccharin, cetyltrimethylammonium saccharin and the like.

  Specific examples of the anionic surfactant include alkyl sulfates such as sodium lauryl sulfate, POE alkyl sulfates such as POE sodium lauryl ether sulfate, alkyl sulfate esters such as lauryl sulfate triethanolamine, stearoylmethyl taurine sodium, dodecyl Examples include benzene sulfonic acid triethanolamine, sodium tetradecene sulfonate, POE lauryl ether phosphoric acid and salts thereof.

  Specific examples of the amphoteric surfactant include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, cocoamidopropyl betaine, lauryldimethylaminoacetic acid betaine and the like.

  Examples of the oil component include higher alcohols, fats and oils, waxes, hydrocarbons, esters, and silicones. Specific examples of the higher alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, and behenyl alcohol.

  Specific examples of fats and oils include jojoba oil and glyceride of olive oil. Specific examples of waxes include beeswax and lanolin. Specific examples of hydrocarbons include liquid paraffin, solid paraffin, isoparaffin, and squalane. It is done. Specific examples of esters include isopropyl myristate and octyldodecyl myristate. Specific examples of silicones include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, highly polymerized silicone, and amino-modified silicone. It is done.

  In addition, as other components, fatty acids such as lauric acid, myristic acid, 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 and tannic acid, plant extracts, herbal extracts, vitamins, fragrances, ultraviolet absorbers and the like can be mentioned. Moreover, you may mix | blend at least 1 type chosen from what is listed in "quasi-drug material standard" (June 1991 issue, Yakuji Nippo).

Examples of the dosage form of the first agent include aqueous solutions, dispersions, emulsions, gels, foams, and creams.
[Second agent]
The second agent contains an oxidizing agent and the like. This oxidizing agent is blended to oxidize and polymerize the component (a) oxidation dye to develop a color and decolorize melanin contained in the hair. Specific examples of the oxidizing agent include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, sodium peroxide, potassium peroxide, peroxide. Examples thereof include magnesium oxide, barium peroxide, calcium peroxide, strontium peroxide, a hydrogen peroxide adduct of sulfate, a hydrogen peroxide adduct of phosphate, and a hydrogen peroxide adduct of pyrophosphate. These oxidizing agents may be blended singly or in combination of two or more. Among these oxidizing agents, hydrogen peroxide is preferred because of its excellent melanin decolorizing power.

  The content of the oxidizing agent in the mixture is preferably 0.1 to 4.5% by mass, more preferably 0.3 to 4.0% by mass. When the content is less than 0.1% by mass, the oxidation dye cannot be sufficiently oxidized and polymerized. On the other hand, if it exceeds 4.5 mass%, hair damage cannot be reduced.

  The second agent contains water, oily components, surfactants and the like described in the first agent as other components. Moreover, when hydrogen peroxide is contained as an oxidizing agent, it is preferable to contain a stabilizer in order to improve the storage stability of hydrogen peroxide. Examples of hydrogen peroxide stabilizers include urea, phenacetin, sodium stannate, ethylene glycol phenyl ether, 8-oxyquinoline, phosphoric acid, 1-hydroxyethane-1,1-diphosphonic acid and its salts, dibutylhydroxytoluene, etc. Is mentioned. Moreover, you may mix | blend at least 1 type chosen from what is listed in "quasi-drug material standard" (June 1991 issue, Yakuji Nippo).

Examples of the dosage form of the second agent include aqueous solutions, dispersions, emulsions, gels, foams, and creams.
〔blend〕
The mixture is obtained by mixing and preparing the first agent and the second agent at a predetermined ratio. The mixing ratio of the first agent and the second agent is preferably the first agent: second agent = 1: 0.5 to 1: 5 in mass ratio. When the amount of the first agent increases or the amount of the second agent increases from this mixing ratio, the content of each component in the first agent and the second agent is determined in terms of hair dyeing power and suppression of damage to the hair. It becomes difficult to set.

  The pH of the mixture at the time of mixing preparation is preferably 8 to 12, more preferably 9 to 11. If this pH is less than 8, the action of the oxidizing agent may not be sufficiently promoted. On the other hand, when the pH exceeds 12, there is a risk that defects such as damage occur in the hair. Examples of the dosage form of this mixture include aqueous solutions, dispersions, emulsions, gels, foams, and creams.

  The mixture is applied to the hair, and the hair to which the mixture is applied is gradually dyed by being left for a certain period of time. Here, since the ascorbic acids are contained in the mixture, the pH of the mixture applied to the hair is gradually lowered with the standing time. The pH of the mixture after completion of the hair dyeing time is shifted to the neutral or acidic side because the alkaline agent can be reduced from remaining as alkali in the hair and the hair feel can be improved. More preferably, it is weakly acidic.

  The difference between the pH of the mixture at the time of mixing preparation and the pH of the mixture after 30 minutes from the time of mixing preparation (pH lowering value) is preferably 1 to 10, more preferably 2 to 9, and further preferably 3 to 8. is there. If this pH drop value is less than 1, there is a risk that defects such as damage to the hair may occur due to residual alkali. On the other hand, a drop in pH exceeding 10 may cause hair to converge excessively and cause problems such as damage to the hair.

  The pH of the mixture after 30 minutes from the time of mixing preparation is preferably 2 to 8, more preferably 3 to 7, and further preferably 4 to 6. If this pH is less than 2, the hair will be excessively constrained, and there is a risk that problems such as damage will occur in the hair. On the other hand, when the pH exceeds 8, there is a risk that the hair may be damaged due to the influence of residual alkali.

  Now, in order to prepare the 1st agent and 2nd agent as an oxidative hair dye composition, each component is mix | blended in consideration of the mixing ratio of a 1st agent and a 2nd agent, and it stirs and mixes. Next, in order to use the first agent and the second agent, a mixture is prepared by mixing the first agent and the second agent, for example, in a mixing ratio of 1: 1 by mass ratio, and the required amount of the mixture is combed. (Comb) or brush and apply to hair. Then, the hair to which the mixture is applied is left in this state for a certain time (for example, 10 to 40 minutes). At this time, the oxidation dye is oxidized and polymerized by the oxidizing agent in the mixture, so that the oxidation dye is colored.

  Furthermore, 1.0 to 8.0 mass% of ascorbic acid of component (A) is blended in the mixture in addition to the oxidation dye. Since the ascorbic acids sufficiently draw out the oxidizing power of the oxidizing agent, the oxidation polymerization reaction of the oxidation dye by the oxidizing agent is accelerated. Therefore, even with a small amount of oxidant, the oxidative dye can be colored efficiently. Therefore, the content of the oxidizing agent that causes hair damage can be reduced.

  Moreover, the compounding quantity of the inorganic acid of the component (B) or the ammonium salt of organic acid is contained in the mixture by 0.3-8.0 mass%. For this reason, the oxidative polymerization reaction of the oxidative dye based on the oxidant is promoted by the component (B). In addition, the component (B) or the alkaline agent is gradually neutralized by the pH control action of ascorbic acids, and the pH of the chemical solution can be controlled near the isoelectric point of the hair at the end of the hair dyeing. Therefore, with the passage of the standing time, the pH of the mixture is gradually lowered from the pH at the time of mixing preparation. Here, the pH control action refers to an action in which hydrogen ions generated by the reaction process of the component (A) neutralize the component (B) or the alkaline agent in the presence of an oxidizing agent. As a result, the cuticle (scale-like epidermis) opened by the component (B) is closed, a smooth feel can be obtained, and hair damage due to residual alkali can be prevented.

  The hair that has been left for a certain period of time is subjected to plain rinse (rinsing of the hair with water, warm water, etc.) to finish the hair dyeing process. At this time, since the pH of the mixture is lowered by the pH control action of ascorbic acids, residual alkali in the finished hair can be reduced.

The effects exhibited by the above embodiment will be described below.
In the oxidative hair dye composition of the embodiment, the component (A) ascorbic acid is 1.0 to 8.0% by mass and the component (B) is a carbonate that generates gas with an ammonium salt of an inorganic acid or an organic acid. Is contained in an amount of 0.3 to 8.0% by mass. Therefore, the oxidative polymerization promoting action and pH control action of the component (A) ascorbic acids can be exhibited, and the oxidative polymerization promoting action can be exerted by the component (B) ammonium salt of an inorganic acid or an organic acid. Therefore, it is excellent in hair dyeing power, a natural hair dyeing state can be obtained, and damage to the hair can be suppressed. Moreover, since the ammonium salt of the inorganic acid or organic acid does not contain carbonate, there is no risk of decomposition and generation of gas during storage of the oxidative hair dye composition in the container.

  -As the inorganic acid or organic acid ammonium salt of component (B), ammonium sulfate, ammonium chloride, ammonium acetate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, diammonium citrate, triammonium citrate, Ammonium oxalate, ammonium lactate, ammonium tartrate or ammonium nitrate are preferred. These components (B) can improve the hair dyeing power.

  -Furthermore, the ammonium salt of component (B) inorganic acid or organic acid preferably has a solubility in 100 g of water of 20 g or more at 25 ° C. In this case, the solubility of the component (B) ammonium salt of the inorganic acid or organic acid in the oxidative hair dye composition is good, and the effect based on the component (B) can be further improved. Furthermore, there is no fear that the component (B) is precipitated during the storage of the oxidative hair dye composition, and it can be stored in a stable state.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1 to 10 and Comparative Examples 1 to 4, two-component hair dye)
The 1st agent was prepared by mixing each ingredient shown in Table 1, Table 2, and Table 3. On the other hand, 35% by mass of hydrogen peroxide 12% by mass, sodium stannate 0.1% by mass, stearyl alcohol 5.0% by mass, polyoxyethylene (POE) cetyl alcohol 3.0% by mass, stearyltrimethylammonium chloride. A second agent was prepared by mixing 0 mass%, disodium monohydrogen phosphate 0.1 mass%, methylparaben 0.1 mass%, and water (purified water). And the 1st agent and the 2nd agent were mixed in the ratio of 1: 1 by mass ratio, and the mixture was prepared. This mixture was applied to the hair bundle. After the hair bundle to which the mixture was applied was allowed to stand for 30 minutes, plain hair rinsing was performed to complete the hair dyeing treatment of the hair bundle. About the hair | bristle bundle which the hair dyeing process was performed, the test of the hair dyeing power shown below and hair surface observation were performed. These evaluation results are shown in Table 1, Table 2 and Table 3.

The abbreviations in the following Table 1, Table 2, and Table 3 represent the following meanings.
POE stearyl ether: polyoxyethylene stearyl ether PEG400: polyethylene glycol with a molecular weight of 400 (Test of hair dyeing power)
The white hair bundles dyed in Examples and Comparative Examples were measured for values in the L * a * b * color system (CIE 1976) using a spectrocolorimeter CM-50d (standard light source D65) manufactured by Minolta. did.

The color difference (ΔE) is a numerical value representing the degree of dyeing based on the white hair bundle, calculated from the following equation. The larger the numerical value, the higher the hair dyeing power.
ΔE = [(ΔL) ² + (Δa) ² + (Δb) ² ] ^1/2
The value of ΔE was evaluated in the following five stages.

A: ΔE is 55 or more, O: ΔE is less than 54.5 to 55, Δ: ΔE is less than 54 to 54.5, X: ΔE is less than 53.5 to 54, XX: ΔE is Less than 53.5 The L value is a number representing the color tone, and the lower the value, the darker the color.

This L value was evaluated in the following five stages.
A: L value is less than 20, O: L value is less than 20 to 20.2, Δ: L value is less than 20.2 to 20.4, X: L value is less than 20.4 to 20.6, XX : L value is 20.6 or more (observation of hair surface)
The white hair bundles dyed in Examples and Comparative Examples were observed using an electron microscope (350 times). The hair damage level was divided into the following 5 levels, and the closest one was selected.

Level 1: No damage is seen.
Level 2: Slight uplift of hairy skin is observed.
Level 3: Moderate hairy skin lift and partial peeling.

Level 4: There is considerable uplifting and peeling of hair cuticles.
Level 5: A rather large hair skin is lifted and peeled.
The level 1 was evaluated as ◎, level 2 as ◯, level 3 as Δ, level 4 as ×, and level 5 as XX.

表１及び表２に示したように、実施例１〜１０では色差(ΔE)が５４．５以上で染毛力が高く、Ｌ値が２０．２未満で毛髪が濃く染まっており、かつ毛髪の表面には殆ど損傷が見られないという良好な結果を得た。また、実施例１〜５に示すように、アスコルビン酸の含有量を一定にし、リン酸三アンモニウムの含有量を増加させた場合、その含有量が６．０質量％までは染毛力が上昇傾向を示すが、含有量が８．０質量％では染毛力が若干低下する傾向を示した。従って、リン酸三アンモニウムの含有量の好ましい範囲は、１．０〜６．０質量％であることがわかった。更に、実施例６〜１０に示すように、リン酸三アンモニウムの含有量を一定にし、アスコルビン酸の含有量を増加させた場合、アスコルビン酸の含有量が１．０質量％では色差(ΔE)が若干低く、８．０質量％ではＬ値が若干高くなるため、アスコルビン酸の含有量の好ましい範囲は、２．０〜６．０質量％であることがわかった。

As shown in Table 1 and Table 2, in Examples 1 to 10, the color difference (ΔE) is 54.5 or more and the hair dyeing power is high, the L value is less than 20.2, and the hair is dyed darkly, and the hair A good result was obtained that almost no damage was observed on the surface of the film. In addition, as shown in Examples 1 to 5, when the content of ascorbic acid is made constant and the content of triammonium phosphate is increased, the hair dyeing power is increased up to 6.0% by mass. Although a tendency was shown, the hair dyeing power tended to slightly decrease at a content of 8.0% by mass. Therefore, it was found that the preferable range of the content of triammonium phosphate is 1.0 to 6.0% by mass. Further, as shown in Examples 6 to 10, when the content of triammonium phosphate is made constant and the content of ascorbic acid is increased, the color difference (ΔE) is obtained when the content of ascorbic acid is 1.0% by mass. Since the L value is slightly higher at 8.0% by mass, the preferred range for the ascorbic acid content is 2.0 to 6.0% by mass.

In contrast, as shown in Table 3, when triammonium phosphate was not included (Comparative Example 1), the hair dyeing power indicated by the color difference (ΔE) and L value was low. Even when the content of triammonium phosphate was excessive (Comparative Example 2), the hair dyeing power was very low. When the ascorbic acid content was too low (Comparative Example 3), the hair dyeing power was insufficient, and the hair surface was lifted and partially peeled. When the content of ascorbic acid was excessive (Comparative Example 4), no damage was observed on the hair surface, but the hair dyeing power was very low.
(Example 11 and Comparative Examples 5-9)
In order to show the effect of the ammonium salt of an inorganic acid, the 1st agent as an oxidative hair dye composition was prepared with the composition shown in Table 4. In Example 11, ammonium chloride was blended as an inorganic acid ammonium salt, and in Comparative Examples 5 to 9, no ammonium chloride was blended. Further, the dye concentrations of Comparative Examples 5 to 9 were changed with respect to the dye concentration of Example 11. These first agents were mixed with the same second agent as in Example 1 to prepare a mixture, and this mixture was applied to the hair bundle. Then, it processed similarly to Example 1, the hair dyeing power (L value) was measured, and the result was shown in Table 4.

表４に示したように、実施例１１のＬ値（２６．４）は、比較例７（染料濃度１１７％、Ｌ値２７．３）と比較例８（染料濃度１２５％、Ｌ値２６．０）との間にあることがわかる。すなわち、塩化アンモニウムを配合しない場合（比較例５〜９）、塩化アンモニウムを配合した実施例１１と同等の染毛力を得るためには染料濃度を２０％以上多く配合する必要があることがわかる。言い換えれば、本発明では少ない染料で、高い染毛力を得ることができる。

As shown in Table 4, the L value (26.4) of Example 11 is that of Comparative Example 7 (dye concentration 117%, L value 27.3) and Comparative Example 8 (dye concentration 125%, L value 26. 0). That is, when ammonium chloride is not blended (Comparative Examples 5 to 9), it is found that the dye concentration needs to be blended by 20% or more in order to obtain the same hair dyeing power as Example 11 blended with ammonium chloride. . In other words, high hair dyeing power can be obtained with a small amount of dye in the present invention.

In addition, this embodiment can also be changed and embodied as follows.
The component (A) ascorbic acid in the first agent may be a third agent that is separate from the first agent. Alternatively, a part of ascorbic acid may be contained in the first agent, and the remaining may be the third agent. In this case, alteration of ascorbic acids can be suppressed.

-The compounding quantity of an oxidation dye, a component (A), and a component (B) can also be determined on the basis of the quantity of the oxidizing agent in a 2nd agent.
-It is possible to omit the alkaline agent in the first agent.

-It is also possible to use the oxidative hair dye composition of embodiment for hair treatment agents, such as a permanent wave treatment agent.
-As an oxidative hair dye composition, it is also possible to implement with the composition shown below other than the said Example. However,% represents mass%.

  1) Ascorbic acid 3.0%, ammonium chloride 3.0%, toluene-2,5-diamine 1.5%, p-aminophenol 1.0%, m-aminophenol 0.3%, resorcin 0.4 %, P-amino-o-cresol 0.2%, o-aminophenol 0.3%, oleyl alcohol 2.0%, propylene glycol 4.0%, benzyl alcohol 8.0%, polyoxyethylene (repeat number) 25) Behenyl ether 12.0%, polyoxyethylene (repetition number 10) oleyl ether 8.0%, stearyltrimethylammonium chloride 1.0%, amodimethicone 0.3%, 28% ammonia water 4.0%, sulfurous acid Sodium 0.1%, ethylenediaminetetraacetic acid (EDTA) disodium 0.1%, remaining amount of purified water.

  2) Sodium ascorbate 4.0%, ammonium acetate 5.0%, paraphenylenediamine 1.5%, resorcin 0.5%, p-methylaminophenol 0.1%, m-aminophenol 0.1%, 5- (2-hydroxyethylamino) -2-methylphenol 0.1%, o-aminophenol 0.1%, stearyl alcohol 2.0%, cetyl alcohol 5.0%, polyoxyethylene (repetition number 2) Cetyl ether 2.0%, polyoxyethylene (repetition number 40) cetyl ether 3.0%, stearyltrimethylammonium chloride 1.0%, liquid paraffin 0.7%, propylene glycol 5.0%, dimethylpolysiloxane 5%, 28% ammonia water 2.0%, monoethanolamine 2.0%, sodium sulfite 0.1% Ethylenediaminetetraacetic acid (EDTA) disodium 0.1%, Purified water Balance.

  3) Ascorbic acid 3.0%, ammonium nitrate 6.0%, N, N-bis (β-hydroxyethyl) -paraphenylenediamine sulfate 2.5%, m-aminophenol 0.6%, resorcin 0.2% 2,4-diaminophenoxyethanol hydrochloride 0.1%, o-aminophenol 0.3%, 2,6-diaminopyridine 0.3%, cetyl alcohol 5.0%, stearyl alcohol 5.0%, oleyl alcohol 2 0.0%, oleic acid 2.0%, polyoxyethylene (repetition number 30) oleyl ether 4.0%, o- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose 1.0%, 28% ammonia water 4.0%, sodium sulfite 0.1%, ethylenediaminetetraacetic acid (EDTA) disodium 0.1%, Water balance.

  4) Ascorbic acid 3.0%, diammonium citrate 4.0%, toluene-2,5-diamine 0.8%, paraphenylenediamine 0.3%, p-aminophenol 0.6%, resorcinol. 4%, m-aminophenol 0.3%, p-amino-o-cresol 0.1%, o-aminophenol 0.1%, cetyl alcohol 3.5%, stearyl alcohol 3.5%, lanolin alcohol 0 0.2%, sodium lauryl sulfate 0.5%, sodium polyoxyethylene lauryl ether sulfate 0.5%, liquid paraffin 0.1%, cetyl palmitate 0.2%, stearyl stearate 0.2%, glycerin 1. 0%, polydimethylmethylenepiperidinium chloride 0.5%, 28% ammonia water 3.0%, monoethanolamine 1.0%, sodium sulfite Potassium 0.1%, ethylenediaminetetraacetic acid (EDTA) disodium 0.1%, Purified water Balance.

5) (Reference Example) sodium ascorbate 3.0%, diammonium phosphate 8.0%, paraphenylenediamine 0.3%, toluene-2,5-diamine 0.2%, sulfuric acid N, N-bis ( β-hydroxyethyl) -paraphenylenediamine 2.0%, p-aminophenol 0.8%, resorcin 0.1%, p-amino-o-cresol 0.2%, m-aminophenol 0.2%, p-methylaminophenol 0.5%, o-aminophenol 0.2%, 5- (2-hydroxyethylamino) -2-methylphenol 0.3%, cetyl alcohol 8.0%, stearyl alcohol 8.0 %, Oleyl alcohol 2.0%, oleic acid 2.0%, polyoxyethylene (repetition number 10) cetyl ether 5.0%, polyoxyethylene (repetition number 30) Oleyl ether 3.0%, propylene glycol 8.0%, dimethyldiallylammonium chloride / acrylic acid copolymer 0.5%, monoethanolamine 4.0%, sodium sulfite 0.1%, ethylenediaminetetraacetic acid (EDTA) Disodium 0.1%, remaining amount of purified water.

Further, the technical idea that can be grasped from the embodiment will be described below.
The oxidative hair dye composition according to claim 1 or 2, wherein a blending amount of the oxidant composition is 0.5 to 5.0 by mass ratio with respect to the oxidative hair dye composition. According to this configuration, the hair dyeing power and the suppression of damage to the hair can be exhibited in a well-balanced manner.

  A hair dye comprising the oxidizing hair dye composition according to any one of claims 1 to 3 and an oxidizing agent composition containing an oxidizing agent. According to this hair dye, the effect of the invention according to any one of claims 1 to 3 can be exhibited.

Claims (3)

An oxidative hair dye composition containing an oxidative dye and used by mixing with an oxidant composition, the component (A) ascorbic acid as a component for promoting the oxidative polymerization action of the oxidative dye by the oxidant composition 1.0 to 8.0% by mass of component (B) and components other than carbonates that generate gas with ammonium salts of inorganic or organic acids (excluding monoammonium phosphate and diammonium phosphate) -Oxidative hair dye composition characterized by containing -8.0 mass%. Component (B) ammonium salts of inorganic acids or organic acids, ammonium sulfate, ammonium chloride, ammonium acetate, Li down tribasic ammonium citrate diammonium, ammonium citrate tribasic, ammonium oxalate, ammonium lactate, tartaric acid ammonium or ammonium nitrate The oxidative hair dye composition according to claim 1. The oxidative hair dye composition according to claim 1 or 2, wherein the ammonium salt of component (B) inorganic acid or organic acid has a solubility in 100 g of water of 20 g or more at 25 ° C.