JP2014500309A - Composition of metal-plant hair dye containing cysteine and hair dyeing method using the same - Google Patents

Abstract

Provided is a hair dye composition comprising a dye extracted or derived from a plant and cysteine or its hydrochloride.
Compared with the fact that the dyeing treatment in the composition of the natural hair dye of the vegetable dye containing the conventional metal salt requires a long time of 40 minutes or more, the dye containing cysteine or its hydrochloride of the present invention is used. According to the composition of the hair agent, the dyeing time can be shortened to 10 to 20 minutes.
[Selection] Figure 1

Description

  The present invention relates to a metal-plant mixed hair dye composition containing cysteine and a hair dyeing method using the same.

Hair dyes are generally divided into three types. Temporary dyeing, semi-permanent dyeing, and permanent dyeing. This classification is based on the degree to which the dye is first fastened to the hair.
The permanent hair dye according to the present invention is classified into a vegetable permanent hair dye, an oxidized permanent hair dye, a metal-plant mixed permanent hair dye, and the like according to the dye used and the color reaction principle.
The plant permanent hair dye is a dyeing method that has been used for a long time, and is dyed using logwood, indigo, chamomile, henna, and the like. However, vegetable permanent hair dyes do not have a hypersensitive reaction to the skin, but have very poor coloring ability and long-lasting ability. Therefore, in recent years, vegetable dyes are rarely used alone, and are used as auxiliary components such as oxidized permanent hair dyes and metallic permanent hair dyes.

  Currently, oxidized permanent hair dyes are most often used as hair dyes. In the oxidized permanent hair dye, the oxidized dye penetrates the cuticle layer and precipitates pigment molecules in the furtex. These oxidation stains function as decolorizers and colorants due to penetration and the additional action of oxidants. Oxidation tints are synthetic organic dyes derived from aniline, and are most excellent in hair dyeing power and color retention in hair dyeing methods. At present, it has been developed to generate about 60,000 or more colors as oxidizing dyes. In general, an oxidized permanent hair dye is composed of a first agent of a hair dye and a second agent of an oxidant. The first agent contains an oxidation type dye and an alkaline agent that is ammonia (Ammonia) and monoethanolamine (Monoethanolamine). The alkaline agent swells the hair shaft and helps the intermediate of the oxidized dye to settle in the fur through the hair epidermis of the hair shaft portion. The second agent, which is also called an oxidant, contains hydrogen peroxide. When the first and second agents of the oxidized permanent hair dye are mixed, the dye and oxygen molecules produced by hydrogen peroxide start to react. This oxidation type dye colors hair by inducing an oxidation reaction with each other. In addition, the dye molecular polymers having a relatively large molecular weight due to a binding reaction with each other change to an insoluble solid with the passage of time, and thus cannot pass between narrow hair epidermis. As a result, the oxidative dye remains in the interior of the fur and as a result, the oxidative permanent hair dye has the advantage that it has a very good color retention. However, such an oxidized permanent hair dye has a problem in that hair proteins are damaged by the use of an alkaline agent and hydrogen peroxide, and a hypersensitive reaction is caused on the skin by an oxidation reaction of the dye. This hypersensitivity reaction, often said to be lacquered, is due to the normal immune function of the human body. Oxidized permanent hair dye induces, for example, pruritus, erythema, or inflammation in the scalp, and in severe cases it may induce blisters and pruritus throughout the body as well as the scalp. Oxidized permanent hair dye is a very convenient hair dye because of its excellent color retention and relatively short treatment time. Once such a hypersensitivity reaction occurs, skin sensitization will occur every time it is dyed. Becomes more and more intense. As a result, those who have a hypersensitive reaction to the oxidized permanent hair dye will never use the oxidized permanent hair dye again.

  The metal-plant mixed hair dye according to the present invention is also called a plant natural dye hair dye containing a metal salt, and does not induce a skin hypersensitivity reaction such as a scalp when dyeing hair. It is a hair dye useful for those who cannot use an oxidized permanent hair dye due to a hypersensitive reaction of a dye (aniline dye intermediate).

A vegetable natural dye hair dye containing a metal salt is a mordant hair dye composed of a first agent containing a vegetable natural dye and a second agent containing a mordant containing a metal salt. It is.
The mordanting means smoothly mediating the dyeing when the dye cannot be dyed on an object to be dyed, that is, hair or fibers. One of the mordants binds to the dye to produce a colored insoluble compound, and the other adheres to the object to be dyed and improves the fixing of the dye.

  Plant-based natural dye hair dyes containing such metal salts do not use synthetic oxidized dyes such as oxidized permanent hair dyes, and therefore do not cause skin hypersensitivity reactions and are less harmful to the human body. There is. However, since the oxidation-type permanent hair dye uses a highly reactive oxidation-type dye, the dyeing time is relatively short, about 10 to 30 minutes, but the vegetable natural dye hair dye containing a metal salt is This is inconvenient because it requires a minimum of 40 minutes to a maximum of 2 hours or more. In addition, due to the dyeing principle in which vegetable dyes form metal salts and complex salts used as mordants near the hair surface, discoloration and discoloration may occur due to external conditions such as sunlight, hair washing, friction, and sweat. There is also a problem that it cannot last for a long time. In general, an oxidation-type permanent hair dye has a dyeing retention period of about 4 weeks, but a conventional plant natural dye hair dye containing a metal salt is very short in about 7 to 12 days. When using and dyeing hair mixed with gray hair, there was an annoyance that had to be dyed about 3 times a month.

  The present invention provides a plant natural dye hair dye that has a shorter dyeing time than conventional plant natural dye hair dyes and has a fastness to dyeing that is superior to conventional plant natural dye hair dyes. For the purpose.

The present invention provides a mixed metal-plant hair dye composition comprising a dye extracted or derived from a plant and cysteine or its hydrochloride.
Since the composition of the hair dye of the present invention contains cysteine or its hydrochloride, the dyeing treatment in the natural hair dye composition of a vegetable dye containing a conventional metal salt takes a long time of 40 minutes or more. Compared with this, the staining time can be shortened to 10 to 20 minutes.
In addition, the present invention uses a dyeing principle in which a vegetable dye forms a metal salt and complex salt of a mordant near the hair surface, and even if dyed, discoloration or discoloration may occur due to external conditions such as sunlight, hair washing, friction, and sweat. The present invention solves the problem that it occurs and cannot be maintained for a long time, and provides a hair dye composition having the functional advantages of a plant natural dye hair dye containing a metal salt without a skin hypersensitivity reaction.

The composition of the natural hair dye without skin hypersensitivity reaction according to the present invention contains cysteine or its hydrochloride, so that the cystine of the hair chain bond and the metal ion of the mordant form a strong bond. As a result, the staining time can be shortened from about 40 minutes or more to about 10 to 20 minutes.
In addition, the effect that the dyeing fastness is maintained for 30 days or more by the above components can be further expected, whereby the fastness of the conventional natural hair dyeing agent is shortened in about 7 to 12 days, and it is 1 The problem that had to be dyed about three times a month or more can be solved.

It is the photograph which compared the hair dyeing power of Experimental example 1. FIG. It is the photograph which compared the hair dyeing power of Experimental example 2. FIG. It is the photograph which compared the hair dyeing power of Experimental example 3. FIG. It is the photograph which compared the dye fastness of Experimental example 4. FIG.

Hereinafter, the present invention will be described in more detail.
The present invention relates to a metal-plant mixed hair dye composition comprising a natural dye extracted or derived from a plant and cysteine or its hydrochloride.
Of the 20 basic amino acids, cysteine is the only neutral amino acid containing a thiol group, ie sulfur (S). The thiol group of cysteine is oxidized to form cystine and is reduced again to form a cysteine. This is shown in Chemical Formula 1 below.

  Cysteine is an element that plays an important role in the structure of many proteins, particularly keratin, which is a major component of nails and hair. The keratin structure of hair is known as a disulfide bond in which a helical peptide bond (Peptide bond) which is a main chain bond in the longitudinal direction with respect to the longitudinal direction of the hair is a horizontal chain measurement bond. It is stabilized by cross-linking of cystine bonds. These side chains frequently appear in the hair fiber, and one cystine bond is formed for every 4 helical rotating portions (helical turn).

  In addition, since the thiol group of cysteine has a strong affinity for heavy metals, cysteine strongly forms chelate bonds with metal ions such as iron, nickel, lead, and silver. This chelate binding affinity is very strong and has a strength about 100 times that of a general chemical bond. Therefore, cysteine or its hydrochloride is used to reduce and cleave the cystine disulfide bond (SS) to form a sulfhydryl group (-SH), and then bind a metal compound used as a mordant to form a powerful compound. Form a chelate conjugate. The formation of this strong chelate-bonded product can shorten the dyeing time of hair and can maintain the long-lasting color strength.

Dyes extracted or derived from plants of the present application include dyes extracted or derived from logwood, yellowfin, yellow ream, purple grass, cochineal, safflower, turmeric, indigo, oak, chestnut tree, oak, or gardenia Can be used. More specifically, a dye extracted or derived from the plant containing pyrogallol, gallic acid, hematoxylin, hematein, tannic acid, or esters thereof can be used. The plant-derived natural dye has a structure containing a large number of hydroxyl groups (—OH), and this hydroxyl group forms a coordinate bond with the metallic component of the mordant to form a metal complex. The produced metal complex adheres to the hair and dyes it. Among these plant-derived natural dyes, pyrogallol (C ₆ H ₆ O ₃ , MW; 126.11, Pyrogallol), gallic acid (C ₇ H ₆ O ₅ , MW; 170.12, Gallic Acid), And hematein (C ₁₆ H ₁₂ O ₆ , MW; 300.26, Hematein) are represented by the following chemical formulas 2 to 4.

  The amount of cysteine or its hydrochloride used is preferably 0.02 to 20% by weight based on the total weight of the hair dye composition. If the amount of cysteine or its hydrochloride used exceeds 20% by weight, the disulfide bond or cystine bond, which is a chain measuring bond of hair, may be cleaved excessively, resulting in hair damage and deformation. Therefore, it is preferable that the amount of cysteine or its hydrochloride used does not deviate from the above range.

The dye extracted or originated from the plant is preferably 0.01 to 10% by weight based on the total weight of the hair dye composition.
In addition to the plant natural dye and cysteine or its hydrochloride, the conventional hair dye used for the hair dye of the present application is an ingredient excluding the oxidized dye and hydrogen peroxide solution. The form of the hair dye composition may be liquid or cream and is not particularly limited.

  Specifically, in addition to the dye extracted from or derived from the plant and cysteine or its hydrochloride, the hair dye composition of the present application comprises an antioxidant, a fatty acid or a fatty alcohol, a swelling agent, a buffer, a surfactant. , PH adjusting agent, and water. Specific content of each component is 0.01 to 10% by weight of vegetable natural dye, 0.02 to 20% by weight of cysteine or its hydrochloride, based on the total amount of the hair dye composition, antioxidant 0.1 to 5% by weight, fatty acid or fatty alcohol 1 to 10% by weight, swelling agent 1 to 10% by weight, buffering agent 0.1 to 15% by weight, surfactant 1 to 20% by weight, pH adjusting agent 0. 1-6% by weight and 25-95% by weight of water can be used.

As an antioxidant suitable for the hair dye composition of the present application, sodium sulfite (Sodium Sulfite), sodium ascorbate (Sodium Ascorbate), ascorbic acid (Ascorbic Acid) or the like can be used.
As a fatty acid suitable for the hair dye composition of the present application, a saturated or unsaturated fatty acid having 16 to 22 carbon atoms can be used, and in particular, oleic acid (Oleic Acid) is preferably used. As the fatty alcohol suitable for the hair dye composition of the present application, it is possible to use a fatty alcohol having 16 to 22 carbon atoms such as cetyl alcohol (Cetyl Alcohol), stearyl alcohol (Stealyl Alcohol), and behenyl alcohol (Behenyl Alcohol). it can.

  As a swelling agent suitable for the hair dye composition of the present application, urea having an amino group that has a low molecular weight and can easily penetrate into the hair and can break a hydrogen bond, which is one of the chain-measurement bonds of hair (Urea) ), Thiourea, urea peroxide, polyoxymethylene urea, hydroxyethyl urea, ammonia, and salts thereof can be used.

  As a buffer (Buffer) suitable for the hair dye composition of the present application, salicylic acid (Salicylic Acid), sodium salicylate (Sodium Salicylate), lactic acid (Lactic Acid) and sodium lactate (Sodium Lactate) may be used. it can.

  As the surfactant suitable for the hair dye composition of the present application, those used in conventional hair dyes as cation, anion, and nonionic surfactants can be used. Alkyltrimethylammonium (Alkyl Trimethylethyl), Polyoxyethylene cetyl ether, Polyoxyethylene cetyl ether, Polyoxyethylene cetyl ether, Polyoxyethylene cetyl ether Oleyl ether (Polyoxyethylene Oley ether) and the like can be used.

  In addition, as the pH adjusting agent suitable for the hair dye composition of the present application, ammonia (Ammonia), ammonium hydrogen carbonate (Ammonium Bicarbonate), monoethanolamine (Monoethanolamine), triethanolamine (Triethanolamine) and the like are used. be able to.

The present invention also relates to a hair dye comprising the aforementioned metal-plant mixed hair dye composition and a mordant composition containing a metal salt.
The dosage form of the hair dye may be liquid or cream and is not particularly limited.
The mordant composition may include a metal salt, a fatty acid or fatty alcohol, a surfactant, a pH adjuster, and water. More specifically, 0.1 to 20.0% by weight of a metal salt, 1.0 to 20.0% by weight of a fatty acid or fatty alcohol, 1.0 to 20.0% by weight of a surfactant, 1 to 10.0% by weight and water 25.0 to 97.8% by weight.

  What is used as a metal salt suitable for the dyeing agent of the present application is a divalent or trivalent water-soluble metal salt. Many metal ions have a plurality of hands that can bind to other compositions. This bond is called the coordination number, and the number ranges from 2 to 8. What is used as a mordant is a tetracoordinate or hexacoordinate metal ion. Examples of metal ions having tetracoordination include nickel ions (Ni + 2) and zinc ions (Zn + 2). Examples of metal ions having 6 coordination are ferrous ions (Fe + 2), ferric ions (Fe + 3), aluminum ions (Al + 3), chromium ions (Cr + 3), copper ions (Cu + 2), cobalt ions (Co + 2) , Stannous ion (tin (II) ion) (Sn + 2), second tin ion (tin (IV) ion) (Sn + 4), magnesium ion (Mg + 2), and the like. All of these six-coordinate metal ions have their hands spread in the octahedral direction centering on the metal ions. Therefore, in the mordanting process, metal ions combine with dye molecules and fibers diffused in various directions to form a very complicated form. When a dye molecule binds to another molecule using such a metal ion as a medium, electrons move and the color tone moves deeply and the color stability increases. In addition, a resonance phenomenon occurs due to the movement of electrons, and a slightly different color tone overlaps depending on the number and intensity of resonances. Therefore, the color tone after mordanting becomes dark and dull. In particular, mordanting with iron ions has many overlapping colors, so the iron ion concentration increases and appears black.

  Suitable metal salts for the staining agent of the present application include copper (Cu), cadmium (Cd), arsenic (As), mercury (Ag), lead (Pb), chromium (Cr), iron (Fe), tin ( Although salts of metals such as Sn) can be used, copper, cadmium, arsenic, mercury, lead, and hexavalent chromium are heavy metal contaminants that adversely affect the human body, and preferably form a six-coordination complex. Ferrous sulfate, ferric sulfate, ferrous hydrochloride, ferric hydrochloride, ferric hydrochloride, and hydrates thereof containing iron ions having high coordination binding ability are preferable.

  The coordinate bond mechanism between the disulfide bond of cystine cleaved by cysteine or its hydrochloride and the iron ion (Fe + 3) is represented by the following chemical formula 5. As seen in Formula 5, the (a), (b), (c), (d), and (e) moieties bind to other ligands, ie, hair fibers, dyes, or water molecules. In the case where a plurality of disulfide bonds are formed in this part, the hair dyeing power is increased, and a hair dye composition having excellent color retention can be obtained.

  There are three types of mordanting methods: a pre-mordanting method in which hair is dyed with a dye after mordanting treatment, a post-mordanting method in which hair is first dyed and then mordanted, and a simultaneous mordant method in which a mordant is mixed with a dye to dye hair. However, since the speed at which the mordant is bound to the dye is higher than the speed at which the mordant is bound to the mordant, that is, the hair, the fastness to dyeing is lowered when the mordant or simultaneous mordanting is performed.

Accordingly, in the present invention, after mordanting method is used, cysteine or its hydrochloride is used to cleave more cystine disulfide bonds, which are the main chain-bonding bonds of hair, and then binds more strongly to iron ions here. Form things. As a result, the hair dyeing time can be shortened, the hair dyeing power can be increased, and the color retention of hair dyeing can be maintained.
Specifically, in the hair dyeing method of the present invention, the hair dye composition is applied to the hair and left for 3 to 20 minutes, and then the mordant composition containing a metal salt is applied and left for 3 to 20 minutes. To do. More preferably, in the hair dyeing method of the present invention, the hair dye composition is applied to the hair and allowed to stand for 5 to 10 minutes, and then the mordant composition containing a metal salt is applied and left for 5 to 10 minutes. . When using the hair dye composition of the present invention, the hair dye composition is 10 minutes or less and the mordant composition is 10 minutes or less. can get.

The mordant composition comprising the metal salt of the present invention may comprise a metal salt, a fatty acid or fatty alcohol, a surfactant, a pH adjuster, and water. Specifically, metal salt 0.1-20.0% by weight, fatty acid or fatty alcohol 1.0-20.0% by weight, surfactant 1.0-20.0% by weight, pH adjuster 0.1 -10.0 wt% and water 25.0-97.8 wt%.
Hereinafter, the present invention will be described in detail by way of specific examples, but the scope of rights of the present invention is not limited by these examples.

<Example 1>
As a hair dye composition, pyrogallol (trade name: RODOL PG, manufacturer: Jos. H. Lowenstein Sons, Inc.) as a dye extracted or derived from plants. .)) 2% by weight, 4% by weight of cysteine, 0.5% by weight of sodium ascorbate as an antioxidant, 5% by weight of urea as a swelling agent, 1% by weight of salicylic acid and 2.0% by weight of sodium salicylate as a buffering agent The mixture was mixed with 59.5% by weight of water and dissolved by heating to 75 to 85 ° C. Further, 8% by weight of cetyl alcohol as a fatty alcohol and 15% by weight of polyoxyethylene cetostearyl ether as a surfactant were mixed and dissolved by heating to 75 to 85 ° C. The dissolved mixture is stirred and mixed, then cooled to 50 to 55 ° C., 3% by weight of ammonium hydrogen carbonate as a pH adjuster is added and stirred, and a creamy metal-plant mixed hair dye composition is prepared. The thing was manufactured.

<Example 2>
As a hair dye composition, pyrogallol (trade name: RODOL PG, manufacturer: Jos. H. Lowenstein Sons, Inc.) as a dye extracted or derived from plants. .)) 2% by weight, 2% by weight of cysteine, 0.5% by weight of sodium ascorbate as an antioxidant, 5% by weight of urea as a swelling agent, 1% by weight of salicylic acid and 2% by weight of sodium salicylate as buffering agents It was mixed with 5% by weight and dissolved by heating to 75 to 85 ° C. Further, 8% by weight of cetyl alcohol as a fatty alcohol and 15% by weight of polyoxyethylene cetostearyl ether as a surfactant were mixed and dissolved by heating to 75 to 85 ° C. The dissolved mixture is stirred and mixed, then cooled to 50 to 55 ° C., 3% by weight of ammonium hydrogen carbonate as a pH adjuster is added and stirred, and a creamy metal-plant mixed hair dye composition is prepared. The thing was manufactured.

<Comparative example>
A metal-plant mixed hair dye composition was produced in the same manner as in Example 1 except that 63.5 wt% of purified water was used without using cysteine.

  The contents of the metal-plant mixed hair dye compositions of Examples 1 and 2 and Comparative Example are summarized in Table 1 below.

<Production Example: Production of mordant composition>
As a mordant composition, 3% by weight of ferrous sulfate as a metal salt and 1% by weight of ascorbic acid as a pH adjuster were mixed in 90% by weight of purified water, and heated to 75 to 85 ° C. to dissolve. Further, 5% by weight of stearyl alcohol as a fatty alcohol and 2% by weight of polyoxyethylene cetostearyl ether as a surfactant were mixed and dissolved by heating to 75 to 85 ° C. The dissolved mixture was stirred and mixed to prepare a creamy mordant composition.

<Experimental example 1>
In order to test the hair coloring power dyed on the hair, three standard white hairs having a weight of 1.0 g and a length of 8.0 cm were prepared, and the hair dyes produced in Examples 1 and 2 and the comparative example. The composition of No. 1 was applied and allowed to stand for 20 minutes, and then the mordant composition produced in the above production example was further applied and left for 20 minutes, then washed with running water for 2 minutes using a shampoo solution, and dried. The hair dyeing power was observed. The result is shown in FIG. The test evaluation of the hair dyeing power uses a color difference meter (model name: Spectrophotometer CM-508C, manufacturing company: Minolta Co., Ltd. (MINOLTA CO. LTD., JAPAN)), and the brightness value of each sample using standard white hair as a reference value. (L ^* ) was measured. The L ^* value is a numerical value of brightness, and the larger the L ^* value, the brighter the color. The results of the test evaluation of the hair dyeing power are shown in Table 3 below. As shown in FIG. 1 and Table 3, it was confirmed that the hair sample dyed with the hair dye composition of Examples 1 and 2 was dyed darker than the hair sample dyed in the comparative example.

<Experimental example 2>
The experiment was conducted in the same manner as in Experimental Example 1 except that the hair dye composition and the mordant composition were applied and then allowed to stand for 10 minutes. The result is shown in FIG. 2 by taking a photograph, and the hair coloring power is tested and evaluated in the same manner as in Experimental Example 1 and shown in Table 3 below. As shown in FIG. 2 and Table 3, it was confirmed that the hair samples dyed with the hair dye compositions of Examples 1 and 2 were dyed darker than the hair samples dyed in the comparative example.

<Experimental example 3>
The experiment was conducted in the same manner as in Experimental Example 1 except that the hair dye composition and the mordant composition were applied and left for 5 minutes. The results are shown in FIG. 3 by taking a photograph, and the hair dyeing power is tested and evaluated in the same manner as in Experimental Example 1, and is shown in Table 3 below. As shown in FIG. 3 and Table 3, it was confirmed that the hair samples dyed with the hair dye compositions of Examples 1 and 2 were dyed darker than the hair samples dyed in the comparative example.

<Experimental example 4: Experiment of dyeing fastness>
Standard gray hairs of 1.0 g in weight and 8.0 cm in length were prepared. The hair dye compositions prepared in Examples 1 and 2 and Comparative Example were applied and left for 10 minutes. The mordant composition produced in the above production example was further applied and allowed to stand for 10 minutes, then washed with running water for 2 minutes using a shampoo solution and dried.

  In order to confirm the effect of cysteine or its hydrochloride according to the present invention on dyeing fastness, the dyed hair sample was exposed to sunlight for 7 days from 10 am to 4 pm and the results were observed. The results are shown in FIG. 4 and the brightness values measured in the same manner as in Experimental Example 1 are shown in Table 4 below.

  As shown in FIG. 4 and Table 4, the hair samples dyed with the hair dye compositions of Examples 1 and 2 did not change much before and after washing, but the hair dye composition of the comparative example. It was confirmed that the dyeing fastness of the hair dye composition of the present invention was excellent because the difference was large not only in Examples 1 and 2 but also in Comparative Example 2 before washing. it can.

Claims (19)

Pyrogallol, gallic acid, hematoxylin, hematein, tannic acid, or esters derived from or derived from logwood, yellowfin, yellow reed, purple grass, cochineal, safflower, turmeric, indigo, oak tree, chestnut tree, oak, or gardenia A dye containing,
Cysteine or its hydrochloride,
The 1st agent composition of the metal-plant mixed hair dye containing this.   2. The first composition of a mixed metal-plant hair dye according to claim 1, comprising 0.02 to 20.0 wt% of the cysteine or a hydrochloride thereof.   Pyrogallol, gallic acid, hematoxylin, hematein, tannic acid, or esters derived from or derived from logwood, yellowfin, yellow reed, purple grass, cochineal, safflower, turmeric, indigo, oak tree, chestnut tree, oak, or gardenia The 1st agent composition of the metal-plant mixed hair dye of Claim 1 characterized by including 0.01-10.0 weight% of said dyes containing.   The first agent of the mixed metal-plant hair dye according to claim 1, further comprising an antioxidant, a fatty acid or fatty alcohol, a swelling agent, a buffering agent, a surfactant, a pH adjusting agent, or water. Composition.   0.1 to 5% by weight of the antioxidant, 1 to 10% by weight of the fatty acid or fatty alcohol, and 1 to 10% of the swelling agent based on the total weight of the first agent composition of the metal-plant mixed hair dye. And further comprising 0.1 to 15% by weight of the buffer, 1 to 20% by weight of the surfactant, 0.1 to 6% by weight of the pH adjuster, or 25 to 95% by weight of the water. The 1st agent composition of the metal-plant mixed hair dye of Claim 4.   The said antioxidant is sodium sulfite, sodium ascorbate, or ascorbic acid, The 1st agent composition of the metal-plant mixed hair dye of Claim 4 characterized by the above-mentioned.   The said fatty acid or fatty alcohol is oleic acid, cetyl alcohol, stearyl alcohol, or behenyl alcohol, The 1st agent composition of the metal-plant mixed hair dye of Claim 4 characterized by the above-mentioned.   The metal-plant mixed hair dye according to claim 4, wherein the swelling agent is urea, thiourea, urea peroxide, polyoxymethylene urea, hydroxyethyl urea, ammonia, or a salt thereof. First agent composition.   The said buffering agent is salicylic acid, sodium salicylate, lactic acid, or sodium lactate, The 1st agent composition of the metal-plant mixed hair dye of Claim 4 characterized by the above-mentioned.   5. The surfactant is alkyltrimethylammonium chloride, sojam polyoxyethylene lauryl ether sulfate, polyoxyethylene cetyl ether, polyoxyethylene cetostearyl ether, or polyoxyethylene oleyl ether. 1st agent composition of the metal-plant mixed hair dye described in 1.   The said pH adjuster is ammonia, ammonium hydrogencarbonate, monoethanolamine, or triethanolamine, The 1st agent composition of the metal-plant mixed hair dye of Claim 4 characterized by the above-mentioned. The 1st agent composition of the metal-plant mixed hair dye of any one of Claims 1 thru | or 11,
A second agent composition of a metal-plant mixed mordant containing a metal salt;
Hair dye containing.   The hair dyeing agent according to claim 12, wherein the second agent composition of the metal-plant mixed mordant contains a metal salt, a fatty acid or a fatty alcohol, a surfactant, a pH adjusting agent, and water.   The second agent composition of the metal-plant mixed mordant comprises 0.1 to 20.0% by weight of the metal salt, 1.0 to 20.0% by weight of the fatty acid or fatty alcohol, and 1.0 to 2% of the surfactant. The hair dye according to claim 13, comprising 20.0% by weight, 0.1 to 10.0% by weight of the pH adjuster, and 25.0 to 97.8% by weight of the water.   The metal salt is at least one selected from ferrous sulfate, ferric sulfate, ferrous hydrochloride, ferric hydrochloride, and hydrates thereof. Hair dye.   The metal-plant mixed hair dye first agent composition according to any one of claims 1 to 11 is applied to hair and left for 3 to 20 minutes, and then the metal-plant mixed mordant containing a metal salt is used. A hair dyeing method, wherein the second agent composition is applied and left for 3 to 20 minutes.   The first composition of the metal-plant mixed hair dye is applied to the hair and allowed to stand for 5 to 10 minutes, and then the second composition of the metal-plant mixed mordant is applied and left for 5 to 10 minutes. The hair dyeing method according to claim 16.   The hair dyeing method according to claim 16, wherein the second agent composition of the metal-plant mixed mordant contains a metal salt, a fatty acid or a fatty alcohol, a surfactant, a pH adjuster, and water. The second agent composition of the metal-plant mixed mordant comprises 0.1 to 20.0% by weight of the metal salt, 1.0 to 20.0% by weight of the fatty acid or fatty alcohol, and 1.0 to 2% of the surfactant. The hair dyeing method according to claim 16, comprising 20.0% by weight, 0.1 to 10.0% by weight of the pH adjusting agent, and 25.0 to 97.8% by weight of the water.