KR20120046984A - Dyeing method, preparation method for blue pigments and kit for the same - Google Patents

Abstract

PURPOSE: A method for dyeing an amine, amino acid, or peptide-containing material and a method for preparing blue pigment are provided to enable dyeing and permanent. CONSTITUTION: A method for dyeing an amine, amino acid, or peptide-containing material comprises: a step of contacting reducing genipin with amine, amino acid, or peptide-containing material under an alkali condition; and a step of adding oxidizer. The alkali condition is pH 7.1-14. The amine, amino acid, or peptide-containing material is hair, fiber, leather, or paper. The oxidizer is used for permanent and hair dyeing.

Description

Dyeing method, Preparation method for blue pigments and Kit for the same}

The present invention relates to a dyeing method, a blue pigment manufacturing method and a kit therefor, and more particularly, to a hair, fiber, leather or paper dyeing method, a blue pigment manufacturing method and a kit therefor.

Dyeing is mainly applied to hair, fibers, leather or paper and the like, and pigments are mainly used for food and the like. Among them, blue color development, in particular blue dyeing using natural materials and manufacturing blue pigments was not easy.

In order to dye white hair blue, there is an oxidation dyeing method in which paratoluenediamine and metaphenylenediamine, which are commonly used in dyes, are mixed.However, allergic to skin is sensitive to health. There is a problem that causes.

Indigo-based blue pigments contained in plants such as spines are often used for blue dyeing fibers, but are not easily fixed to hair, so they are not easy to apply to dyeing white hair.

The brilliant blue FCF, which is a synthetic blue pigment, and Ultramarine Blue, which is an inorganic mixture, are also difficult to penetrate the hair and have poor hair dye.

On the other hand, Geniepin is known as a dye derived from natural products, and dyeing methods using Geniepin are disclosed in domestic and international patent literature (Japanese Patent Laid-Open No. 11-12955, Japanese Patent Laid-Open No. 8-67828, Japanese Patent Laid-Open No. 7-111896, Japanese Patent Laid-Open No. 1). 179690, SO 56-92792, SO 63-125573, EP 0 251 063 A2, Korean Laid-Open Patent Publication 10-2010-0039991, etc.). However, this method was inconvenient to react for several hours in the state of applying heat and the like.

Therefore, there is a need to develop a technique for safely and efficiently dyeing blue pigment using gelatin.

One problem to be solved by the present invention is to provide a dyeing method using geni pin.

Another problem to be solved by the present invention is to provide a method for producing blue pigment using geni pin.

Another problem to be solved by the present invention is to provide a blue pigment prepared using the geni pin.

Another problem to be solved by the present invention is to provide a dyeing kit containing the geni pin.

Another problem to be solved by the present invention is to provide a blue pigment manufacturing kit comprising a geni pin.

The present invention comprises the steps of (A) contacting the amine, amino acid or peptide-containing and genipine in alkaline conditions, in the presence of a reducing agent; And (B) adding an oxidant to the contact of step (A).

The alkali conditions may be pH 7.1 or more, preferably pH 7.1-14, more preferably pH 8-12, even more preferably pH 8-10. The contact is The contact may be in solution, preferably in aqueous solution.

The reducing agent is not limited thereto, but cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite Sulfite), sulfite alkaline salts and / or alkaline electrolyzed water.

The amines may be, but are not limited to, primary, secondary, tertiary amines and / or derivatives thereof, preferably primary amines.

The amino acids are all amino acids including amino groups and carboxy groups, including but not limited to arginine, glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diyod Tyrosine, lysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline, and / or oxyproline and the like.

The peptide may be an oligopeptide or a polypeptide, and the polypeptide is meant to include a protein. The peptides may be natural peptides and / or artificial peptides, and eggs of animals such as birds and reptiles, milk of animals such as mammals, meat of animals, skin of animals, feathers of birds, silk feathers, silkworm cocoons and silk. Or it may be included in one or more selected from their decomposition products. The egg of the animal may preferably be egg white.

The amine, amino acid or peptide content may be hair, fibers, leather and / or paper, and the like, as long as it contains amines, amino acids or peptides and is the material to be dyed.

The hair is not limited thereto as long as it includes amines, amino acids or peptides, and includes hairs of animals such as mammals including humans or feathers of birds.

The fiber is not limited thereto as long as it includes amines, amino acids or peptides, but may be one or more selected from silk or wool.

The leather includes, but is not limited to, amines, amino acids or peptides, including animal skins, furs, animal meats, or animal cells.

As long as the paper includes an amine, an amino acid or a peptide, there is no limitation, but may be an animal paper, and the animal paper contains an animal vellum or an amine, amino acid or peptide such as parchment, calf or goat sebum. One kind of special building equipment may be silk wallpaper, which is a special synthetic paper.

The genipine may be present in the worms (Eucommia ulmoides Oliv.), Gardenia (Gardenia jasminoides Ellis.) And the like, Geniposide, Genipin-1-O-gentiobioside, 6 "-p-Coumaroyl-genipin- gentiobioside may be prepared by hydrolysis with an enzyme, an acid, etc. The glycoside is not limited thereto, as long as it contains genipine as a non-saccharide, but may be included in gardenia, worms, and the like. It may be commercially available or manufactured by a known method.

The contact of step (A) is at least 10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, even more preferably at 20 to 40 degrees Celsius, at least 1 minute, Preferably it may be left to stand for 5 to 30 minutes.

In the step (A) by adding at least one selected from the raw materials of hematoxylin, hematein, Lawson, Gardenia X or other pigments in the genie pin, color can be developed in a color other than blue.

The oxidant may be at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride or inorganic oxidant derivatives.

The amine, amino acid or peptide content may be hair, the reducing agent may be a reducing agent for permanents, the oxidant may be an oxidizing agent for permanents, and the method may be for perming and hair dyeing. The hair may be a hair on a curling aid (for example, a lot), and the hair is fixed on the curling aid after applying permanent reducing agent and genipin to the curling aid, and dyeing is possible at the same time as perming. Preferably, the reducing agent for permanents is at least one selected from cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, or thioglycolic acid derivatives, and the oxidizing agent for permanents is hydrogen peroxide, sodium bromide, or It may be at least one selected from its derivatives.

After the addition of the oxidizing agent in step (B) -10 degrees Celsius or more, preferably -10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, even more preferably at 20 to 40 degrees Celsius, at least 1 minute Preferably, it can be left to stand for 5 to 30 minutes.

In addition, the present invention provides a method for preparing a pharmaceutical composition comprising (a) contacting at least one selected from an amine, an amino acid, or a peptide with an amine, an amino acid, or a peptide-free material in contact with an amine, amino acid, or peptide in the presence of a reducing agent; And (b) provides a method for staining amine, amino acid or peptide-free containing a step of adding an oxidizing agent to the contact of step (a).

The alkali conditions may be pH 7.1 or more, preferably pH 7.1-14, more preferably pH 8-12, even more preferably pH 8-10. The contact may be contact in solution, preferably in aqueous solution.

The reducing agent is not limited thereto, but cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite Sulfite), sulfite alkaline salts and / or alkaline electrolyzed water.

The amines may be, but are not limited to, primary, secondary, tertiary amines and / or derivatives thereof, preferably primary amines.

The amino acids are all amino acids including amino groups and carboxy groups, including but not limited to arginine, glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diyod Tyrosine, lysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline, and / or oxyproline and the like.

The peptide may be an oligopeptide or a polypeptide, and the polypeptide is meant to include a protein. The peptides may be natural peptides and / or artificial peptides, and eggs of animals such as birds and reptiles, milk of animals such as mammals, meat of animals, skin of animals, feathers of birds, silk feathers, silkworm cocoons and silk. Or it may be included in one or more selected from their decomposition products. The egg of the animal may preferably be egg white.

The amines, amino acids or peptide-free materials do not contain amines, amino acids or peptides, and are not limited thereto, but may be hair, fibers, leather and / or paper, etc., without amines, amino acids or peptides. have.

The hair is not limited thereto unless it includes amines, amino acids or peptides, and may be synthetic hair without amines, amino acids or peptides.

The fibers may be, but are not limited to, amines, amino acids or peptides, but may be synthetic fibers and / or vegetable fibers free of amines, amino acids or peptides. The synthetic fibers may be rayon or the like, and the vegetable fibers May be natural plant material fibers such as hemp or ramie.

The leather may be, but is not limited to, an amine, amino acid or peptide-free synthetic leather, unless it includes amines, amino acids or peptides. The synthetic leather may be urethane leather, PVC leather or other synthetic resin leather.

The paper may be a vegetable paper as long as it does not include amines, amino acids or peptides, but may be a vegetable paper, and the vegetable paper may be a paper, a bank paper, a banana paper, a bond paper, a book paper. (Book paper), Coated paper: glossy and matte surface, Construction paper / sugar paper, Cotton paper, Electronic paper, Fish paper {Fish paper ( vulcanized fibers for electrical insulation}, inkjet paper, kraft paper, laid paper, mother paper, sandpaper, tyvek paper, wallpaper ), Washi paper, waterproof paper, wax paper, woven paper, and / or Xuan paper.

The genipine may be present in the worms (Eucommia ulmoides Oliv.), Gardenia (Gardenia jasminoides Ellis.) And the like, Geniposide, Genipin-1-O-gentiobioside, 6 "-p-Coumaroyl-genipin- gentiobioside may be prepared by hydrolysis with an enzyme, an acid, etc. The glycoside is not limited thereto, as long as it contains genipine as a non-saccharide, but may be included in gardenia, worms, and the like. It may be commercially available or manufactured by a known method.

Contact with the amine, amino acid or peptide-free of step (a) is at least 10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, even more preferably 20 degrees Celsius At -40 degrees, one minute or more, preferably 5 to 30 minutes may be in contact.

In the step (a) by adding at least one selected from the raw materials of hematoxylin, hematein, Lawson, gardenia or other pigments in the genie pin, color can be developed in a color other than blue.

The oxidant may be at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride or inorganic oxidant derivatives.

The amine, amino acid or peptide-free may be hair, the reducing agent may be a reducing agent for permanents, the oxidant may be an oxidizing agent for permanents, the method may be for perming and hair dyeing. The hair may be a hair on a curl molding aid (for example, a lot), and the hair is coated with one or more selected from amines, amino acids, or peptides, a reducing agent for perming and genipine, and then fixed on a curl molding aid, followed by oxidizing agent. It can be dyed and permeated by treatment. Preferably, the reducing agent for permanents is at least one selected from cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, or thioglycolic acid derivatives, and the oxidizing agent for permanents is hydrogen peroxide, sodium bromide, or It may be at least one selected from its derivatives.

After the addition of the oxidant in step (b) at least 10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, even more preferably at 20 to 40 degrees Celsius, at least 1 minute Preferably, it can be left to stand for 5 to 30 minutes.

In addition, the present invention provides a method for preparing an amine, comprising: (I) contacting at least one selected from amines, amino acids, or peptides with genipin in alkaline conditions; And (II) adding an oxidizing agent to the contact of step (I).

The alkali conditions may be pH 7.1 or more, preferably pH 7.1-14, more preferably pH 8-12, even more preferably pH 8-10. The contact may be contact in solution, preferably in aqueous solution.

The reducing agent is not limited thereto, but cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite Sulfite), sulfite alkaline salts and / or alkaline electrolyzed water.

The amines may be, but are not limited to, primary, secondary, tertiary amines and / or derivatives thereof, preferably primary amines.

The amino acids are all amino acids including amino groups and carboxy groups, including but not limited to arginine, glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diyod Tyrosine, lysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, proline, and / or oxyproline and the like.

The peptide may be an oligopeptide or a polypeptide, and the polypeptide is meant to include a protein. The peptides may be natural peptides and / or artificial peptides, and eggs of animals such as birds and reptiles, milk of animals such as mammals, meat of animals, skin of animals, feathers of birds, silk feathers, silkworm cocoons and silk. Or it may be included in one or more selected from their decomposition products. The egg of the animal may preferably be egg white.

The genipine may be present in the worms (Eucommia ulmoides Oliv.), Gardenia (Gardenia jasminoides Ellis.) And the like, Geniposide, Genipin-1-O-gentiobioside, 6 "-p-Coumaroyl-genipin- gentiobioside may be prepared by hydrolysis with an enzyme, an acid, etc. The glycoside is not limited thereto, as long as it contains genipine as a non-saccharide, but may be included in gardenia, worms, and the like. It may be commercially available or manufactured by a known method.

The contact of step (I) is at least 10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably at 10 to 60 degrees Celsius, even more preferably at 20 to 40 degrees Celsius, at least 1 minute, Preferably, the contact may be for 5 to 30 minutes.

The oxidant may be at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride or inorganic oxidant derivatives.

After the addition of the oxidizing agent in step (II), at least 10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, even more preferably at 20 to 40 degrees Celsius, at least 1 minute. Preferably, it can contact for 5 to 30 minutes.

Moreover, this invention provides the blue pigment manufactured by the blue pigment manufacturing method of this invention.

In addition, the present invention comprises a first agent comprising genipine as a dye; A dyeing kit comprising a second agent comprising a reducing agent and a third agent comprising an oxidant is provided.

The genipine may be present in the worms (Eucommia ulmoides Oliv.), Gardenia (Gardenia jasminoides Ellis.) And the like, Geniposide, Genipin-1-O-gentiobioside, 6 "-p-Coumaroyl-genipin- gentiobioside may be prepared by hydrolysis with an enzyme, an acid, etc. The glycoside is not limited thereto, as long as it contains genipine as a non-saccharide, but may be included in gardenia, worms, and the like. It may be commercially available or manufactured by a known method.

The reducing agent is not limited thereto, but cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite Sulfite), sulfite alkaline salts and / or alkaline electrolyzed water.

The oxidant may be at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride or inorganic oxidant derivatives.

The kit may further include one or more selected from the sources of hematoxylin, hematein, lawson, gardenia or other pigments as the dye, and the hematoxylin, hematein, lawson, gardenia or other At least one selected from the raw materials of the dye may be mixed with the genipin or may be separately packaged and separated.

The kit may be for dyeing hair, fibers, leather or paper containing amines, amino acids or peptides.

The reducing agent is a reducing agent for permanent, the oxidizing agent is an oxidizing agent for permanent, and the kit may be for perm and hair dyeing.

Kits of the present invention may further comprise one or more selected from amines, amino acids or peptides, said kits being free of amines, amino acids or peptides, preferably amines, amino acids or peptides-free hair, fibers, leather or It may be for paper dyeing.

Kits of the invention may further comprise instructions.

In addition, the present invention comprises a first agent comprising genipine as a dye; A second agent comprising a reducing agent; A third agent comprising an oxidizing agent; And a fourth agent comprising at least one selected from amines, amino acids, or peptides.

The first agent and the fourth agent may be mixed.

The first agent, second agent, third agent and / or fourth agent included in the kit of the present invention may further include a viscosity increasing agent, a surfactant, a preservative and / or a fragrance.

The contents mentioned in the dyeing method, preparation method, blue pigment and kit of the present invention are equally applicable unless they contradict each other.

The dyeing method and kit of the present invention can be quickly dyed blue, and can be permeated with dyeing. In addition, it is possible to produce blue pigments in a short time by the production method and kit of the present invention.

1 is a photograph of the decolorized human hair state before and after dyeing according to the sixteenth embodiment.
2 is a photograph of a change in hair state during dyeing according to Example 17. FIG.
Figure 3 is a photograph of the fiber state changes during the silk fiber dyeing process according to Example 18.
Figure 4 is a photograph of the fiber state change during the cotton fiber dyeing process according to an embodiment 19.
5 is a photograph of a change in state of the blue pigment manufacturing process according to an embodiment 20.
FIG. 6 is a photograph of a change in state of the blue pigment manufacturing process according to Example 21. FIG.
7 is a photograph of the blue pigment produced in Example 22. FIG.
8 is a photograph of the blue pigment prepared in Example 23;
9 is a photograph of a change in hair state of perm and hair dye according to an embodiment 24.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. Since these Examples and Experimental Examples are only for illustrating the present invention, the scope of the present invention is not to be construed as being limited by these Examples and Experimental Examples.

<Example 1> Pharma and dyeing kit (for blue dyeing)

1-1. Dye Preparation

genipin (Wako Chemical Co, 078-03021, Japan) was prepared.

1-2. Preparation of reducing agent for permanent

Cysteine (Samchun Chemical Co. Ltd., 041006, Korea) was purchased as a reducing agent for the permanent, and was prepared by adjusting the concentration to 15 w / v% and pH 9.6 with purified water and 0.1N NaOH.

1-3. Oxidant preparation

Purchasing 30% hydrogen peroxide (Wako Chemical Co, 081-04215, Japan), purified water, 0.2M Na ₂ HPO ₄ , 0.1M citric acid concentration 3vol%, pH 4 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ 0 = 7.7: 12.3: 80.0) was prepared.

1-4. Packing

Each of the dyeing agents, reducing agents, and oxidizing agents prepared in 1-1 to 1-3 were packed in glass bottles, and then packaged in one box to prepare a kit.

<Example 2> perm and dyeing (blue hair dye) kit production

A kit was prepared in the same manner as in Example 1, except that ethanolamine thioglycolate was prepared as a reducing agent for the permanent. The reducing agent was purchased as ethanolamine thioglycolate (Tokyo Chemical Industry Co., Ltd., MFCD00050789, Japan), which is a kind of thioglycolate, and adjusted to 2.7% by volume of purified water and 0.1N NaOH and pH 9.6. It was prepared by.

<Example 3> Pharma cum dyeing (blue hair dye) kit production

A kit was prepared in the same manner as in Example 1, except that sodium bromate solution was prepared as the oxidant for the permanent instead of the oxidizing agent of 1-3. The oxidant was purchased with sodium bromide solution (Sigma-Aldrich Inc., 224871, USA), purified water, 0.2M Na ₂ HPO ₄ , 0.1M citric acid concentration 6% by volume, pH 7 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ 0 = 16.5: 3.5: 80.0) was prepared by adjusting.

Example 4 Pharma and Dyeing (Blue Dyeing) Kit Preparation

A kit was prepared in the same manner as in Example 2, except that the oxidant for permanent was prepared in the same manner as in Example 3.

Example 5 Preparation of Dyeing (Blue Dye) Kits

A kit was prepared in the same manner as in Example 2, except that ethanolamine thioglycolate (0.9% by volume) was prepared instead of ethanolamine thioglycolate (2.7% by volume) as a reducing agent.

Example 6 Preparation of Textile, Leather or Paper Dyeing Kits

A kit was prepared in the same manner as in Example 5, except that alkaline electrolytic water was prepared as a reducing agent. The reducing agent prepared alkaline electrolytic water (Alkaline ionic water; Korea Electrolytic Water System Co., Ltd.) of pH 13.0, and diluted with purified water to adjust to pH 9.0.

Example 7 Preparation of Fiber, Leather or Paper Dyeing Kit (Amino Acid Containing Kit)

A kit was prepared in the same manner as in Example 6, except that arginine, an amino acid, was further prepared as a staining agent. Arginine (Arginine hydrochloride, Junsei Chemical Co., Ltd., 13020-0410, Japan) was prepared.

Example 8 Preparation of Blue Pigment Production Kit

A kit was prepared in the same manner as in Example 7, except that egg white was further prepared instead of arginine as a dye. The egg white prepared whites separated from the egg.

Example 9 Preparation of Blue Pigment Production Kit

A kit was prepared in the same manner as in Example 8, except that ferric chloride was prepared as the oxidizing agent. The oxidant was prepared by dissolving 5 g of ferric chloride (FeCl ₃ .6H ₂ O, Kanto Chemical Co., Inc., 16018-01, Tokyo, Japan) in 100 mL of distilled water, and then adding 1 g of gelatin to increase.

<Example 10> Pharma and dyeing kit (natural pigments other than blue pigment)

To hair dye, add 2 g of genipine to 2 g of hematoxylin (Acros Organics, 411180250, New Jersey, USA) and 0.5 g of Lawson (2-hydroxy-1.4-naphthoquinone, sigma-aldrich, 34196BJ, St Louis, USA) Except that prepared, the kit was prepared in the same manner as in Example 2.

<Example 11> Pharma and dyeing kit (kit including natural dyes other than blue pigment)

A kit was prepared in the same manner as in Example 2, except that 2 g of hematein and 0.5 g of Lawson were added to 2 g of genipine as a hair dye. Hematein (hematein, Acros Organics, 370840050, New Jersey, USA) and Lawson (2-hydroxy-1.4-naphthoquinone, sigma-aldrich, 34196BJ, St Louis, USA) were prepared as natural pigments other than genipine.

<Example 12> Pharma and dyeing kit (natural pigment other than blue pigment)

Same as Example 2, except that 2g of henpine was prepared by adding 2g of hematein (hematein, Acros Organics, 370840050, New Jersey, USA) and 1.0g of Gardenia X (Gardenia Ex, Korea New Drug, Korea) as a hair dye. Kits were prepared by the method.

Example 13 Preparation of a Dyeing Kit (Natural Pigment Containing Kit Other than Blue Pigment)

2 g of hemitoxine (hematoxylin, Acros Organics, 411180250, New Jersey, USA), 2 g of hematein (hematein, Acros Organics, 370840050, New Jersey, USA), Lawson (2-hydroxy-1.4-) Naphthoquinone, sigma-aldrich, 34196BJ, St Louis, USA) kit was prepared in the same manner as in Example 5, except that 0.5g was added.

Example 14 Preparation of Fiber, Leather or Paper Dyeing Kits (Natural Pigments Other Than Blue Pigments)

To hair dye, add 2 g of genipine to 2 g of hematoxylin (Acros Organics, 411180250, New Jersey, USA) and 0.5 g of Lawson (2-hydroxy-1.4-naphthoquinone, sigma-aldrich, 34196BJ, St Louis, USA) Except that prepared, the kit was prepared in the same manner as in Example 6.

Example 15 Preparation of Fiber, Leather or Paper Dyeing Kits (Natural Pigments and Amino Acid Kits Other Than Blue Pigments)

To hair dye, add 2 g of genipine to 2 g of hematoxylin (Acros Organics, 411180250, New Jersey, USA) and 0.5 g of Lawson (2-hydroxy-1.4-naphthoquinone, sigma-aldrich, 34196BJ, St Louis, USA) Except that prepared, the kit was prepared in the same manner as in Example 7.

<Example 16> Blue perm and hair dye

Using the kit of <Example 1>, perm and hair dye were performed by the following method. First, add 0.5 g of a dye, genipin, to 10 mL of reducing agent for permant, mix well, apply it to a commercially available depigmented human hair (crown wig, 208-17-97354), and make curls using a curl molding aid, and then room temperature (20 degrees Celsius). After standing for 20 minutes in Fig.), The hydrogen peroxide solution was applied with an oxidizing agent, and then left for 10 minutes. The curl molding machine was removed and then shampooed. The perm and hair dye process is shown in FIG. 1. Figure 1 shows the state before and after the perm and hair dye method from left to right, as shown in Figure 1 can be seen that the blue hair dye and perm is completed at the same time. Therefore, it was confirmed that the kit and the method according to the present invention can simultaneously perform blue hair dye and perm without fear of hair damage.

Example 17 Blue Hair Color

Using the kit of <Example 5>, blue dyeing was performed in the following manner. First, 5g of genipin, a dye, is mixed well with 100mL of the reducing agent for dyeing, and then applied to the scorpion head, and then allowed to stand at room temperature (20 degrees Celsius) for 20 minutes, followed by applying hydrogen peroxide solution with an oxidizing agent, and then left for 10 minutes and shampooed. It was. The blue hair dye process is shown in FIG. 2.

Figure 2 shows the state before, during and after the implementation, as shown in Figure 2 it can be seen that the blue hair dye is completed.

Therefore, the kit and the method according to the present invention was confirmed that blue hair dye without fear of hair damage.

Example 18 Blue Silk Fiber Dyeing

Using the kit of <Example 6>, silk fibers were dyed blue in the following manner. First, add 0.5 g of a dye, genipin, to 10 mL of alkaline electrolytic water for dyeing, mix well, apply to white silk fiber, leave for 10 minutes at room temperature (20 degrees Celsius), apply hydrogen peroxide solution with oxidizing agent, and then leave for 10 minutes. After washing, the silk fibers were dried. The blue hair dye process is shown in FIG. 3. Figure 3 shows the state before and after the implementation from the left to the right according to the elapsed time, it can be seen that the dyeing of blue is completed as shown in FIG. Therefore, it was confirmed that the kit and the method according to the present invention can be dyed blue without fear of fiber damage.

Example 19 Blue Cotton Fiber Dyeing

Using the kit of <Example 7>, cotton fibers were dyed blue in the following manner. First, add 0.5 g of dye, genipin, and 10 mg of arginine hydrochloride to 10 mL of alkaline electrolytic water for dyeing, mix well, apply to white cotton fiber, leave at room temperature (20 degrees Celsius) for 10 minutes, and then apply hydrogen peroxide solution with oxidizing agent. After standing for 10 minutes and washing, the cotton fibers were dried. The blue hair dye process is shown in FIG. 4. Figure 4 shows the state before and after the implementation from the left to the right according to the elapsed time, it can be seen that the dyeing of blue is completed as shown in FIG. Therefore, it was confirmed that the kit and the method according to the present invention can be dyed blue without fear of fiber damage.

Example 20 Preparation of Blue Pigment

Using the kit of <Example 1> and egg white separated from the egg was prepared blue pigment in the following manner. First, 100 mg of genipin and 1 g of egg white were mixed in 10 mL of a Cysteine (Samchun Chemical Co. Ltd., 041006, Korea) reducing agent prepared by adjusting the concentration to 15w / v% and pH 9.6, and mixing well, and then mixed at room temperature (20 degrees Celsius) for 20 minutes. After leaving, 10 ml of hydrogen peroxide solution was added with an oxidizing agent, and then left for 10 minutes and dried. The blue pigment manufacturing process is shown in FIG. 5. Figure 5 shows the state before, during and after the implementation from left to right, it can be seen that the blue pigment is generated as shown in FIG. Therefore, it was confirmed that the blue pigment can be prepared by the kit and the method according to the present invention.

Example 21 Blue Pigment Preparation

Using the kit of <Example 5> and egg white separated from the egg was prepared blue pigment in the following manner. First, add 100 mg of dye, genipin, and 1 g of egg white to 10 mL of a reducing agent prepared with a concentration of 0.9% ethanolamine thioglycolate, mix well, and leave it for 20 minutes at room temperature (20 degrees Celsius). After the addition, it was left to stand for 10 minutes and dried. The blue pigment manufacturing process is shown in FIG. 6. Figure 6 shows the state before and after the implementation from the left to the right according to the elapsed time, it can be seen that the blue pigment is generated as shown in FIG. Therefore, it was confirmed that the blue pigment can be prepared by the kit and the method according to the present invention.

Example 22 Preparation of Blue Pigment

Using the kit of <Example 8> to prepare a blue pigment in the following manner.

First, add 10 mg of dye staining genipin and 1 g of egg white to 10 mL of alkaline electrolytic water for dyeing, mix well, and let stand for 10 minutes at room temperature (20 degrees Celsius), add 10 ml of hydrogen peroxide solution slowly with an oxidizing agent, and leave for 10 minutes. And dried. The prepared blue pigment is shown in FIG. 7. As shown in FIG. 7, it can be seen that blue pigment is generated. Therefore, it was confirmed that the blue pigment can be prepared by the kit and the method according to the present invention.

Example 23 Preparation of Blue Pigment

Using the kit of Example 9, blue pigments were prepared in the following manner.

First, 100 mg of genipin and 1 g of egg white were added to 10 mL of alkaline electrolyzed water, and the mixture was mixed well. After leaving for 10 minutes at room temperature (20 degrees Celsius), 10 ml of ferric chloride solution was slowly added dropwise, and then left for 10 minutes and dried. The prepared blue pigment is shown in FIG. 8. As shown in FIG. 8, it can be seen that blue pigment is generated. Therefore, it was confirmed that the blue pigment can be prepared by the kit and the method according to the present invention.

Example 24 Perm and Dyeing (Black Dye) Method

Perm and hair dye was performed using the kit of Example 10 in the following manner.

First, add 2 g of genipine, 2 g of hematoxylin, and 0.5 g of Lawson to 100 mL of the reducing agent for dyeing, mix well, apply to the scab, make curls using a curling aid, and then room temperature (20 degrees Celsius). After standing for 20 minutes at, the hydrogen peroxide solution was applied with an oxidizing agent and left for 10 minutes. The curl molding machine was removed and then shampooed. The perm and hair dye process is shown in FIG. 9. 9 shows the state of curling after applying the dye, and after applying the dye, the state of applying the oxidant, and the state after the implementation, as shown in FIG. 9, black hair and perm are simultaneously completed. Therefore, it was confirmed that the black hair and hair dye can be performed by the kit and the method according to the present invention without fear of hair damage.

<Comparative Example 1> Preparation of blue pigment by the method disclosed in Japanese Patent Application Laid-Open No. Hei 8-67828

Genipin 1 g (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and soybean hydrolyzate 150 mg (pepton S, Acumedia Manufacturers, Inc, 7180, Lansing,) under the same conditions as the method disclosed in Japanese Patent Application Laid-Open No. 8-67828 USA) was added, dissolved in 10 mL of purified water, mixed well, and then the reaction liquid container was well blocked and left to stir at 40 ° C. for 5 days. As a result, blue pigment was formed after 5 days.

<Comparative Example 2> Preparation of blue pigment by the method disclosed in European Patent Publication (EP 0 251 063 A2)

0.2 g of genipin (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and 0.1 g of taurine (Taurine, DAEJUNG Chemical & Metals Co .. Ltd., 8505) under the same conditions as described in EP 0 251 063 A2 -4400, Shiheung, Korea) dissolved in 40 ml of an aqueous solution of pH 6 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 12.6: 7.4: 80.0), mixed well, and left for 4 hours at 80 degrees Celsius. As a result, blue pigment was produced after 4 hours.

<Comparative Example 3> Preparation of blue pigment by the method disclosed in Japanese Patent Laid-Open No. 63-125573

0.1 g of genipin (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and 0.1 g of glycine (Wako Pure Chemical Industries Ltd., 2709, Osaka, Japan), which were subjected to the same conditions as those described in sub-63-125573, Dissolve in 10 ml of an aqueous solution of pH 7 (0.2 M Na ₂ HPO ₄ : 0.1 M citric acid: H ₂ O = 16.5: 3.5: 80.0), mix well, and leave for 4 hours at 80 degrees Celsius. Was created.

<Comparative Example 4> Preparation of blue pigment by the method disclosed in Korean Unexamined Patent Publication (10-2010-0039991)

Genipin 1g (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and 0.5 g of glycine (Wako Pure Chemical Industries Ltd., 2709) under the same conditions as the method disclosed in Korean Laid-Open Patent Publication (10-2010-0039991) , Osaka, Japan) dissolved in 100 ml of an aqueous solution of pH 7 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 16.5: 3.5: 80.0), mixed well, and left for 5 hours at 70 degrees Celsius. After 5 hours, blue pigment was formed.

<Comparative Example 5> Preparation of blue pigment by the method disclosed in Japanese Patent Laid-Open No. 56-92792

Blue pigments were prepared under conditions similar to those disclosed in SO 56-92792.

(5-1) pH of 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan) and 0.15 g of acylase (Acylase, Wako Pure Chemical Industries Ltd., 327-58431, Osaka, Japan) Dissolved in 60 ml of aqueous solution of 6 (0.2 M Na ₂ HPO ₄ : 0.1 M citric acid: H ₂ O = 12.6: 7.4: 80.0) and 0.4 g of gelatin (Wako Pure Chemical Industries Ltd., 077-03155, Osaka, Japan) After mixing, the mixture was left at 50 ° C. for 48 hours, and then stirred well for 20 hours. As a result, blue pigment was generated 68 hours after geniposide.

(5-2) 0.1 g Geniposide (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan) and 0.1 g Acylase (Acylase, Wako Pure Chemical Industries Ltd., 327-58431, Osaka, Japan), Gelatin 0.4 g (Wako Pure Chemical Industries Ltd., 077-03155, Osaka, Japan) is dissolved in 60 ml of an aqueous solution of pH 5 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 10.3: 9.7: 80.0) After mixing, the mixture was left at 50 ° C. for 15 hours, and then stirred well for 40 hours. As a result, blue pigment was produced after 55 hours from geniposide.

(5-3) Geniposide 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan), 0.12 g acylase (Acylase, Wako Pure Chemical Industries Ltd., 327-58431, Osaka, Japan), gelatin 0.4 g (Wako Pure Chemical Industries Ltd., 077-03155, Osaka, Japan) is dissolved in 30 ml of an aqueous solution of pH 5 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 10.3: 9.7: 80.0) After mixing, the mixture was slightly stirred at 50 degrees Celsius for 15 hours, and then stirred for 10 hours with strong air injection for 20 hours. As a result, blue pigment was generated 35 hours after geniposide.

(5-4) Geniposide 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan), Gelatin 0.4 g (Wako Pure Chemical Industries Ltd., 077-03155, Osaka, Japan), Lipase 0.12 g ( Wako Pure Chemical Industries Ltd., 100817, Osaka, Japan) was dissolved in 100 ml of an aqueous solution of pH 5.5 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 11.4: 8.6: 80.0), mixed well, and then After standing for 20 hours at 40 ° C, the mixture was stirred well for 20 hours, and blue pigment was formed after 40 hours from geniposide.

(5-5) Geniposide 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan), Gelatin 0.4 g (Wako Pure Chemical Industries Ltd., 077-03155, Osaka, Japan), Pepton 1 g (pepton S, Acumedia Manufacturers, Inc, 7180, Lansing, USA), 0.3 g of pepsin (Wako Pure Chemical Industries Ltd., 102598, Osaka, Japan) was added to an aqueous solution of pH 7 (0.2 M Na ₂ HPO ₄ : 0.1 M citric acid: H ₂ O = 16.5: 3.5: 80.0) After dissolving in 100 ml and mixing well, the mixture was left at 40 degrees Celsius for 20 hours, and stirred well while injecting air for 20 hours. As a result, blue pigment was produced after 40 hours from geniposide.

(5-6) Geniposide 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan), Gelatin 0.4 g (Wako Pure Chemical Industries Ltd., 077-03155, Osaka, Japan), Lipase 0.12 g ( Wako Pure Chemical Industries Ltd., 100817, Osaka, Japan) was dissolved in 60 ml of an aqueous solution of pH 5.5 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 11.4: 8.6: 80.0), mixed well, and then After 40 hours of stirring well at 40 degrees, blue pigment was produced 40 hours after geniposide.

<Comparative Example 6> Preparation of blue pigment by the method disclosed in Japanese Patent Application Laid-Open No. Hei 11-12955 and dyeing fibers using the same

Geniposide 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan), 0.2 g of cellulase (Wako Pure Chemical Industries Ltd., 152337, Osaka, Japan), arginine 0.2g (Arginine, Wako Pure Chemical Industries Ltd., ASB-00001980-005, Osaka, Japan) was added to an aqueous solution of pH 5 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 10.3: 9.7: 80.0) dissolved in 10 ml, mixed well, and stirred in air at 50 degrees Celsius for 42 hours. After 42 hours, blue pigment was formed, which was used as a dye, and was previously 0.2% tannic acid (Wako Pure Chemical Industries Ltd., 201). -06332, Osaka, Japan) was immersed in a cotton cloth soaked for 10 minutes at 70 degrees Celsius for 10 minutes, soaked in a dye at 50 degrees Celsius for 1 hour and dyed blue.

<Comparative Example 7> Production of blue pigment by the method disclosed in Japanese Patent Application Laid-Open No. Hei 7-111896

Genipin 1g (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and taurine 0.5g (Taurine, DAEJUNG Chemical & Metals Co. -4400, Shiheung, Korea), 0.5 g of soybean hydrolyzate (pepton S, Acumedia Manufacturers, Inc, 7180, Lansing, USA) was dissolved in 10 ml of water and mixed well, followed by pH 8 (0.2 M Na ₂ HPO ₄ : 0.1M citric acid: H2O = 19.5: 0.5: 80.0), the cover was closed at 50 ° C for 1 hour, and left for 20 hours in air to produce blue pigment after 21 hours.

<Comparative Example 8> Production of blue pigment by the method disclosed in Japanese Patent Laid-Open No. 1-179690

Geniposide 0.1 g (Wako Pure Chemical Industries Ltd., 071-05071, Osaka, Japan) and arginine 0.1 g (Arginine, Wako Pure Chemical Industries Ltd., ASB-00001980) -005, Osaka, Japan) is dissolved in 10 ml of an aqueous solution of pH6.8 (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H 2 O = 15.4: 4.6: 80.0) and mixed well, then beta-glucosidase (Beta- 30 mg of Glucosidase (G035-5Ku / 058K4066, Sigma-Aldrich Inc.) was added every 6 hours and left at room temperature (20 degrees Celsius) for 48 hours with stirring. This can be seen that it takes at least one day for the genipine to form blue pigment, considering the maximum time for the decomposition of the geniposide to genipin is about 1 day.

Experimental Example 1 Measurement of Blue Pigment Production Over Time

In Comparative Examples 1-8 and Examples 16-24, the time which produces blue pigment for every time was measured on the neck side. 10, 20, 30 minutes and 4 hours, 5 hours, 20 hours, 24 hours, 42 hours, 48 hours, 72 hours, 96 hours and 120 hours, respectively, described in the prior literature. The time was based on the time at which the blue pigment was produced in the comparative examples and the examples, respectively. The results are shown in the following table.

[Table 1]

From the above results, it can be seen that when using the conventional geniepin, the blue pigment, which is heated at high temperature or took more than one day, can be shortened to a very short time, which is a very short time, even at room temperature by 1 hour. Specifically, the advantages of the method of the present invention will be described by way of example.

The method of Example 16 has the advantage that it is possible to apply a conventional perm method using a reducing agent and an oxidant sequentially by mixing the geni pins with the Pharma 1 agent and at the same time blue dyeing.

By the method of Example 18, there is an advantage that can be dyed blue in a short time of about 20 minutes at room temperature by utilizing the amine group of the silk or hair fibers.

The method of Example 19 is a blue dyeing method of the cotton fibers, there is no amine group, etc. in the cotton fibers, but by providing amines and the like, it can be dyed blue in about 20 minutes at room temperature much shorter than Comparative Example 6.

Examples 20, 21 and the like can produce blue pigment in about 30 minutes at room temperature much shorter than the several hours of Comparative Examples 1-8.

Examples 22, 23, and the like are methods using alkaline electrolytic water having reducibility. Example 22 has advantages in that there are no remaining reagents, especially since the remaining alkaline electrolytic water and hydrogen peroxide water are easily volatilized and removed after the reaction. That is, excess alkaline electrolyzed water that does not participate in the reaction is easily changed to water at room temperature over time, and hydrogen peroxide water is also changed to water, so that additional processes (eg, alkaline electrolyzed water, hydrogen peroxide water, etc.) are removed. , Purification and the like) are unnecessary.

The method of Example 24 can be dyed in a variety of colors by mixing with a colorant of a different color, by applying it can be perm with a black hair dye.

Experimental Example 2 Shampoo Fastness or Coloring Stability, Washing Durability Test

(2-1) Determination of washing hair persistence by shampoo

Ten samples of the dyed hair samples (Examples 16, 17, 24) were taken as samples, soaked in distilled water, and 1 mL of shampoo (Head & Shoulders, Procter & Gamble) was dropped, rubbed 20 times with a brush, and washed for 5 minutes. 5 times in the same manner and dried naturally. Visual comparison of the color change before and after the test resulted in no discoloration.

(2-2) Determination of washing dyeing persistence with detergent

After dyeing the fibrous samples (Examples 18 and 19) in distilled water, respectively, 1 mL of a neutral detergent (Joy, Procter & Gamble) was dropped and rubbed 20 times with a brush and washed for 5 minutes. 5 times in the same manner and dried naturally. Visual comparison of the color change before and after the test resulted in no discoloration.

It can be seen from the above results that the dyeing method of the present invention, the hair dyed by the dyeing kit, and the fiber have a continuous dyeing effect without causing a problem such as decolorization even by a detergent or the like.

Claims (47)

(A) contacting genipin with an amine, amino acid or peptide content in the presence of a reducing agent in alkaline conditions; And
(B) A method for dyeing an amine, amino acid or peptide containing a step of adding an oxidizing agent to the contact in step (A). The method of claim 1, wherein the alkaline conditions are pH 7.1-14. The method of claim 1, wherein the reducing agent is cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfite Sulfite), sulfite alkali salt or alkaline electrolytic water. The method of claim 1, wherein the amine is at least one selected from primary amines, secondary amines, tertiary amines or derivatives thereof. The method according to claim 1, wherein the amino acid is arginine, glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diyotyrosine, lysine, arginine, histidine, phenylalanine, At least one selected from tyrosine, tryptophan, proline, or oxyproline. The method of claim 1, wherein the amine, amino acid or peptide content is one or more selected from hair, fibers, leather or paper. The method of claim 6, wherein the fiber is at least one selected from silk or wool. The method of claim 6, wherein the paper is an animal paper. The method of claim 8, wherein the animal paper is at least one selected from parchment paper, veal, goat skin or silk wallpaper. The method of claim 1, wherein in the step (A), genipine is contacted by adding one or more selected from hematoxylin, hematein, Lawson, or Gardenia x. The method of claim 1, wherein the oxidant is at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride, or inorganic oxidant derivatives. The dyeing method according to claim 1, wherein the amine, amino acid or peptide-containing substance is hair, the reducing agent is a reducing agent for perming, the oxidizing agent is an oxidizing agent for perming, and the method is for perming and hair dyeing. The method of claim 12, wherein the hair is hair on a curling aid. The method of claim 12, wherein the reducing agent for permanents is at least one selected from cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, or thioglycolic acid derivatives, and the oxidizing agent for permanents is hydrogen peroxide, sodium bromide. Or at least one selected from derivatives thereof. (a) in alkaline conditions, contacting at least one selected from amines, amino acids, or peptides with genipin in the presence of a reducing agent, or simultaneously with the amines, amino acids, or peptides-free; And
(b) adding an oxidizing agent to the contact of step (a). The method of claim 15, wherein the alkaline conditions are pH 7.1-14. The method of claim 15, wherein the reducing agent is cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfite Sulfite), sulfite alkali salt or alkaline electrolytic water. The method of claim 15, wherein the amine is at least one selected from primary amines, secondary amines, tertiary amines or derivatives thereof. The method of claim 15, wherein the amino acids are arginine, glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diyotyrosine, lysine, arginine, histidine, phenylalanine, At least one selected from tyrosine, tryptophan, proline, or oxyproline. The method of claim 15, wherein the amine, amino acid or peptide free is at least one selected from amine, amino acid or peptide free hair, fibers, leather or paper. The method of claim 20, wherein the hair is synthetic artificial hair free of amines, amino acids, or peptides. 21. The method of claim 20, wherein the fiber is at least one selected from synthetic fibers or vegetable fibers without amines, amino acids or peptides. The method of claim 20, wherein the leather is a synthetic leather free of amines, amino acids or peptides. The method of claim 20, wherein the paper is a vegetable species free of amines, amino acids or peptides. 16. The method of claim 15, wherein in the step (a), genipine is contacted by adding one or more selected from hematoxylin, hematein, Lawson, or Gardenia x. The method of claim 15, wherein the oxidant is at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride, or inorganic oxidant derivatives. The method of claim 15, wherein the amine, amino acid or peptide-free hair is amine, amino acid or peptide-free hair, the reducing agent is a reducing agent for permanents, the oxidant is an oxidizing agent for permanents, the method is for perming and hair dyeing Dyeing method. The method of claim 27, wherein the hair is hair on a curling aid. 28. The method of claim 27, wherein the reducing agent for permanents is at least one selected from cysteine, cysteine derivatives, ethanolamine thioglycolate, or thioglycolic acid derivatives, and the oxidizing agent for permanents is hydrogen peroxide, sodium bromide, or derivatives thereof. One or more selected. (I) contacting genipine with at least one selected from amines, amino acids or peptides in the presence of a reducing agent in alkaline conditions; And
(II) Blue pigment manufacturing method comprising the step of adding an oxidizing agent to the contact of step (I). The method of claim 30, wherein the alkaline conditions are pH 7.1-14. The method of claim 30, wherein the reducing agent is cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfite Sulfite), sulfite alkali salt or alkaline electrolytic water. 31. The method of claim 30, wherein the amine is at least one selected from primary amines, secondary amines, tertiary amines or derivatives thereof. The method of claim 30, wherein the amino acids are arginine, glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diyotyrosine, lysine, arginine, histidine, phenylalanine, At least one selected from tyrosine, tryptophan, proline, or oxyproline. 31. The method of claim 30, wherein the peptide is contained in one or more selected from animal eggs, animal milk, animal meat, animal skin, bird feathers, animal hair, cocoon, silk or their degraded products Way. 31. The method of claim 30, wherein the oxidant is at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride, or inorganic oxidant derivatives. Blue pigment manufactured by the manufacturing method of any one of Claims 30-36. A first agent comprising genipine as a dye;
A second agent comprising a reducing agent; And
A dyeing kit comprising a third agent comprising an oxidant. The kit of claim 38, further comprising at least one selected from hematoxylin, hematein, Lawson, or Gardenia x as said dye. The method of claim 38, wherein the reducing agent is cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite Sulfite), a kit of at least one selected from sulfite alkaline salts or alkaline electrolyzed water. The kit of claim 38 wherein the oxidant is at least one selected from hydrogen peroxide, sodium bromide, sodium bromide derivatives, ferric chloride, or inorganic oxidant derivatives. 39. The kit of claim 38 for dyeing hair, fibers, leather or paper containing amines, amino acids or peptides. The kit according to claim 38, wherein the reducing agent is a reducing agent for permanents, and the oxidizing agent is an oxidizing agent for permanents, and is used for perm and hair dyeing. The kit of claim 38, comprising one or more selected from amines, amino acids or peptides. 45. The kit of claim 44, for staining amine, amino acid or peptide free. A first agent comprising genipine as a dye;
A second agent comprising a reducing agent;
A third agent comprising an oxidizing agent; And
Blue pigment manufacturing kit comprising a fourth agent comprising at least one selected from amines, amino acids or peptides. 47. The kit of claim 46, wherein the first agent and the fourth agent are mixed.

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