KR101312171B1 - Dyeing method, Preparation method for blue pigments and Kit for the same - Google Patents

Abstract

The present invention relates to a method for dyeing an amine, amino acid or peptide-containing dye, which comprises contacting amine, amino acid or peptide-containing content in the presence of a reducing agent with alkali in alkaline conditions, in an amine, amino acid or peptide in the presence of a reducing agent in alkaline conditions. A method for dyeing an amine, amino acid or peptide-free, comprising, in contacting at least one selected with a geniepin with or at the same time of contact with the amine, amino acid or peptide-free, in alkaline conditions, in the presence of a reducing agent, an amine, an amino acid Or a blue pigment manufacturing method comprising the step of contacting at least one selected from peptides with genipine; a first agent comprising genipine as a dye; And a dyeing kit comprising a second agent in an alkaline condition including a reducing agent, and a third agent including at least one selected from an amine, an amino acid, or a peptide. By the dyeing method and kit of the present invention it is possible to dye blue quickly. In addition, it is possible to produce blue pigments in a short time by the production method and kit of the present invention.

Description

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

The present invention relates to a dyeing method, a method for producing blue pigment, and a kit therefor, and more particularly, to a hair, fiber, leather, food or paper dyeing method, a method for producing blue pigment, and a kit for the same.

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 dyeing and blue pigment production which developed in blue were not easy. In particular, blue dyeing and blue pigment production using a natural material 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, and thus are not easily applied 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, Geni pin is known as a dye derived from natural products, and dyeing methods using Geni pin are known in Japan and overseas patent literature (Japanese Patent Laid-Open No. 11-12955, Japanese Patent Laid-Open No. 8-67828, Japanese Patent Laid-Open No. 7-111896, Japan). Japanese Patent Application Laid-Open No. 1-79690, Japanese Laid-Open 56-92792, Japanese Laid-Open 63-125573, European Patent Publication EP 0251063, Korean Patent Publication 10-2010-0039991 and the like.

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.

Japanese Patent Laid-Open No. 11-12955, published on January 19, 1999. Japanese Patent Laid-Open No. 8-67828, publication date: March 12, 1996. Japanese Patent Laid-Open No. 7-111896, published date: May 2, 1995. Japanese Laid Open Patent Application Japan 56-92792, published date: July 27, 1981 Japanese small 63-125573, published date: May 28, 1988 European Patent EP 0251063, published date: 1988.01.07 Republic of Korea Patent Publication 10-2010-0039991, Publication date: April 19, 2010

It is an object of the present invention to provide a dyeing method using genepin.

Another object of the present invention is to provide a method for producing blue pigment using geni pin.

Still another object of the present invention is to provide a dyeing kit containing genipine.

Still another object of the present invention is to provide a blue pigment preparation kit including genipine.

The present invention provides a method for dyeing an amine, amino acid or peptide content, comprising contacting genine with an amine, amino acid or peptide content in alkaline conditions, in the presence of a reducing agent.

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 to this, but is not limited to cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, thioglycolic acid derivative, sodium sulfide, sulfide Alkali salt, sodium hydrogen sulfite (Sodium Hydrogen Sulfite), sulfite (Sulfite) alkali salt and / or alkaline electrolytic water.

The concentration of the reducing agent is not limited in principle, but when the concentration of the reducing agent is thick at a predetermined temperature (-10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, and even more preferably 20 to 40 degrees Celsius), the reaction is performed. Since it tends to take a long time, it is preferable to use at 5 wt% / vol% or less of each reducing agent, and the reaction time may be within about 1 hour, and more preferably at 2 wt% / vol% or less. It may be desirable to proceed quickly within 30 minutes.

The concentration of the reducing agent may be 0.1 weight / vol% or more, preferably 0.1 to 5.0 weight / vol%, and more preferably 0.1 to 2.0 weight / vol%.

The alkaline electrolytic water used as the reducing agent has a redox potential of -50 to -1000 mV, preferably -100 to -500 mV, and more preferably -150 to -500 mV.

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.

The food is not limited thereto as long as it includes amines, amino acids or peptides, and may be animal foods or foods based on soybeans, and specifically include animal meat or animal eggs, vegetable proteins and processed products thereof. Include.

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 genipin may be present in the worms (Eucommia ulmoides Oliv.), Gardenia (Gardenia jasminoides Ellis.), Etc., the glycosides of the genifin geniposide (Geniposide), genipin-1-O-genthio Hydrolysis of bioseed (Genipin-1-O-gentiobioside) and 6 "-p-coumaroyl-genifine-genthiobioside (6" -p-Coumaroyl-genipin-gentiobioside) by hydrolysis with enzymes or acids It can manufacture. The glycosides are not limited thereto as long as they contain genipine as an aglycone, but may be included in gardenia, worms, and the like. The genipine may be commercially available or prepared by a known method.

Under the alkaline conditions, the contact of the step of contacting the amine, amino acid or peptide-containing content with the geniepin in the presence of a reducing agent is at least -10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius More preferably, it may be left to stand for 1 minute or more, preferably 5 to 30 minutes at 20-40 degrees Celsius.

Under the alkaline conditions, at least one selected from the sources of hematoxylin, hematein, Lawson, Gardeniax or other pigments is added to the genipine in the step of contacting the amine, amino acid or peptide-containing substance with genipin in the presence of a reducing agent. It can develop color in colors other than blue by making it contact.

The hematoxylin, hematein, Lawson and Gardeniax may be colored in red, brown, orange and yellow, respectively.

The pigment is not limited to include only natural-derived pigments such as hematoxylin, hematein, Lawson, Gardenia x, and the like, and synthetic derivatives may also be included.

Various colors can be developed by adjusting the type and the mixing ratio of the raw material of the pigment mixed with the geni pin.

For example, in the above alkaline conditions, by contacting the amine, amino acid or peptide-containing content with the genipin in the presence of a reducing agent, hematoxylin may be added to the genipin to make it purple.

For example, in the above alkaline conditions, by contacting amine, amino acid or peptide-containing content with genipin in the presence of a reducing agent, hematein may be added to contact with genipin to develop a dark brown color.

For example, in the above alkaline conditions, by contacting the amine, amino acid or peptide-containing content with genipin in the presence of a reducing agent, by adding Lawson to the genipin, it can be colored green.

For example, under the alkaline conditions, the green color can be developed by adding Gardenia X to the genipine by contacting the amine, amino acid or peptide-containing compound with the genipine in the presence of a reducing agent.

For example, in the above alkaline conditions, in the step of contacting amine, amino acid or peptide-containing content with genipin in the presence of a reducing agent, hematein and Lawson can be added to genipin to make the color black.

For example, in the above alkaline conditions, in the step of contacting amine, amino acid, or peptide-containing substance with genipin in the presence of a reducing agent, hematein and Gardenia x may be added to the genipin to make it black.

For example, in the above alkaline conditions, in the step of contacting amine, amino acid or peptide-containing substance with genipine in the presence of a reducing agent, hematoxylin and Lawson can be added to the genipine to be colored in black.

For example, in the above alkaline conditions, in the step of contacting amine, amino acid or peptide-containing content with genipin in the presence of a reducing agent, hematoxylin and Gardeniax may be added to the genipin to make it black.

The present invention also provides for contacting an amine, amino acid or peptide-free product with alkaline amines, in contact with at least one selected from amines, amino acids or peptides in the presence of a reducing agent, or simultaneously with the contact with amines, amino acids or peptides. Or a peptide-free staining method.

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 is not limited to cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfite, sulfite alkali salts and / Or alkaline electrolytic water.

The concentration of the reducing agent is not limited in principle, but when the concentration of the reducing agent is thick at a predetermined temperature (-10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, and even more preferably 20 to 40 degrees Celsius), the reaction is performed. Since it tends to take a long time, it is preferable to use at 5 wt% / vol% or less of each reducing agent, and the reaction time may be within about 1 hour, and more preferably at 2 wt% / vol% or less. It may be desirable to proceed quickly within 30 minutes.

The concentration of the reducing agent may be 0.1 weight / vol% or more, preferably 0.1 to 5.0 weight / vol%, and more preferably 0.1 to 2.0 weight / vol%.

The alkaline electrolytic water used as the reducing agent has a redox potential of -50 to -1000 mV, preferably -100 to -500 mV, and more preferably -150 to -500 mV.

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, gardenia, etc., the glycosides of the genifin, geniposide, genifin-1-O-genthiobioside, 6 "-p-coumaroyl-genipine-genthiobio The seed 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, tofu and the like. It may be commercially available or manufactured by a known method.

Under the alkaline conditions, contacting at least one selected from amines, amino acids, or peptides with geniepin in the presence of a reducing agent, or simultaneously with the amines, amino acids, or peptides containing The contact 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 5 to 30 degrees Celsius. It may be a minute contact.

Under the alkaline conditions, hematoxylin, hemate to genipine in contact with at least one selected from amines, amino acids or peptides in the presence of a reducing agent or with amines, amino acids or peptides-free at the same time as contacting By adding and contacting at least one selected from the group consisting of phosphorus, Lawson, gardenia extract or other pigments, it can be colored in a color other than blue.

The present invention also provides a method for producing blue pigment, which comprises contacting at least one selected from amines, amino acids or peptides with genipin in alkaline conditions in the presence of a reducing agent.

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 is not limited to cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfite, sulfite alkali salts and / Or alkaline electrolytic water.

The concentration of the reducing agent is not limited in principle, but when the concentration of the reducing agent is thick at a predetermined temperature (-10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, and even more preferably 20 to 40 degrees Celsius), the reaction is performed. Since it tends to take a long time, it is preferable to use at 5 wt% / vol% or less of each reducing agent, and the reaction time may be within about 1 hour, and more preferably at 2 wt% / vol% or less. It may be desirable to proceed quickly within 30 minutes.

The concentration of the reducing agent may be 0.1 weight / vol% or more, preferably 0.1 to 5.0 weight / vol%, and more preferably 0.1 to 2.0 weight / vol%.

The alkaline electrolytic water used as the reducing agent has a redox potential of -50 to -1000 mV, preferably -100 to -500 mV, and more preferably -150 to -500 mV.

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, gardenia, etc., the glycosides of the genifin, geniposide, genifin-1-O-genthiobioside, 6 "-p-coumaroyl-genipine-genthiobio The seed 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, tofu and the like. It may be commercially available or manufactured by a known method.

Under the alkaline conditions, the contact of the step of contacting the genipine with at least one selected from amines, amino acids or peptides in the presence of a reducing agent is at least 10 degrees Celsius, preferably -10 to 100 degrees Celsius, more preferably 10 to Celsius At 60 degrees, even more preferably 20 to 40 degrees Celsius, the contact may be at least 1 minute, preferably 5 to 30 minutes.

In addition, the present invention comprises a first agent comprising genipine as a dye; And it provides a dyeing kit comprising a second agent of alkaline conditions containing a reducing agent.

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 genipine may be present in the worms, gardenia, etc., the glycosides of the genifin, geniposide, genifin-1-O-genthiobioside, 6 "-p-coumaroyl-genipine-genthiobio The seed 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, tofu and the like. It may be commercially available or manufactured by a known method.

The reducing agent is not limited thereto, but is not limited to cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfite, sulfite alkali salts and / Or alkaline electrolytic water.

The concentration of the reducing agent is not limited in principle, but when the concentration of the reducing agent is thick at a predetermined temperature (-10 to 100 degrees Celsius, more preferably 10 to 60 degrees Celsius, and even more preferably 20 to 40 degrees Celsius), the reaction is performed. Since it tends to take a long time, it is preferable to use at 5 wt% / vol% or less of each reducing agent, and the reaction time may be within about 1 hour, and more preferably at 2 wt% / vol% or less. It may be desirable to proceed quickly within 30 minutes.

The concentration of the reducing agent may be 0.1 weight / vol% or more, preferably 0.1 to 5.0 weight / vol%, and more preferably 0.1 to 2.0 weight / vol%.

The alkaline electrolytic water used as the reducing agent has a redox potential of -50 to -1000 mV, preferably -100 to -500 mV, and more preferably -150 to -500 mV.

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.

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 in alkaline conditions including a reducing agent; And a third agent comprising at least one selected from amines, amino acids, or peptides.

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 second agent and the third agent may be mixed.

The first agent, second agent and / or third agent included in the kit of the present invention may further include a viscosity enhancer, 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.

By the dyeing method and kit of the present invention it is possible to dye blue quickly. 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 picture showing a blue hair dye process according to an embodiment 15 of the present invention.
Figure 2 is a photograph showing the blue dyeing process of the silk fiber according to Example 16 of the present invention.
Figure 3 is a photograph showing the blue dyeing process of the cotton fiber according to an embodiment 17 of the present invention.
Figure 4 is a photograph showing the blue dyeing process of boiled eggs according to an embodiment 18 of the present invention.
5 is a photograph showing a manufacturing process of blue pigment according to an embodiment 19 of the present invention.
Figure 6 is a picture showing a black hair dye process according to an embodiment 20 of the present invention.
7 is a photograph showing a blue dyeing process according to Comparative Example 3.
Figure 8 is a photograph showing the blue dyeing process of the silk fiber according to Comparative Example 4.
9 is a photograph showing a blue dyeing process of the cotton fiber according to Comparative Example 5.
10 is a photograph showing a manufacturing process of blue pigment according to Comparative Example 6.
11 is a photograph showing a black dyeing process according to Comparative Example 7.
Figure 12 is a photograph showing the result of the measurement of hair dye persistence by the shampoo of the blue hair dye hair samples by Experimental Example 2-1 of the present invention.
Figure 13 is a photograph showing the result of measuring the measurement of hair dye persistence by detergent of the blue-dyed silk fiber sample according to Experimental Example 2-2 of the present invention.

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 Preparation of Dyeing Kit (Blue Hair dye)

1-1. Dye Preparation

5 g of Genipin (Wako Chemical Co, 078-03021, Japan) was prepared.

1-2. Preparation of reducing agent for dyeing

1 g of Seastein (Samchun Chemical Co. Ltd., 041006, Korea) as a dyeing reducing agent and 10 g of stearic acid (stearic acid, Wako Pure Chemical Industries Ltd., 194-14085, Osaka, Japan) as a viscosity enhancer Then, pH was adjusted with 28 weight / vol% NH ₄ OH (Junsei Chemical Co., Ltd., 13370-0380, Japan) to prepare 100 ml of cysteine cream solution having a cysteine concentration of 1.0 weight / vol% and pH 9.6. It was.

1-3. Packing

Each staining agent (5 g) and reducing agent (100 mL) prepared in 1-1 to 1-2 were packaged in glass bottles, and then packaged in one box to prepare a kit.

Example 2 Preparation of Dyeing Kit (Blue Hair dye)

Kits were prepared in substantially the same manner as in Example 1, except that ethanolamine thioglycolate was prepared as a reducing agent for dyeing. The reducing agent is 1g of ethanolamine thioglycolate (Tokyo Chemical Industry Co., Ltd., MFCD00050789, Japan), which is a kind of thioglycolate, and stearic acid (Stearic acid, Wako Pure Chemical Industries Ltd., 194) as a viscosity increasing agent. Ethanolamine thioglycolate concentration by dissolving 10 g in purified water and adjusting the pH with 28 wt / vol% NH ₄ OH (Junsei Chemical Co., Ltd., 13370-0380, Japan). 100 ml of an ethanolamine thioglycolate cream solution having a weight of 1.0 weight / vol% and a pH of 9.6 was prepared.

Example 3 Preparation of Textile, Leather, Food or Paper Dyeing Kits

A kit was prepared in substantially the same manner as in Example 1, except that alkaline electrolytic water was prepared as a reducing agent. The reducing agent was prepared with alkaline electrolytic water (Alkaline ionic water; Korea Electrolytic Water System Co., Ltd.) having a pH of 9.0 and a redox potential of -500 mV, and then stearic acid (Stearic acid, Wako Pure Chemical Industries Ltd., 194-14085). , Osaka, Japan) 10g was dissolved in the alkaline electrolytic water, and 100ml of alkaline electrolytic water cream having a stearic acid concentration of 10% by weight / vol% and pH 9.0 was prepared.

Example 4 Preparation of Textile, Leather, Food or Paper Dyeing Kits

Kits were prepared in substantially the same manner as in Example 3, except that no viscosity enhancer was added.

Example 5 Preparation of Fiber, Leather, Food or Paper Dyeing Kit (Amino Acid Salt Containing Kit)

Kits were prepared in substantially the same manner as in Example 3, except that arginine hydrochloride, an amino acid salt, was further prepared as a dye. 0.5 g of arginine hydrochloride (Arginine hydrochloride, Junsei Chemical Co., Ltd., 13020-0410, Japan) was prepared. The dyes genipine and arginine hydrochloride were each packed in separate glass bottles.

Example 6 Textile, Leather, Food or Paper Dyeing Kits (Amino Acid Salt Preparation

Kits were prepared in substantially the same manner as in Example 5, except that no viscosity enhancer was added.

Example 7 Preparation of Blue Pigment Production Kit

Kits were prepared in substantially the same manner as in Example 4, except that 0.5 g of Egg White powder (Wako Chemical Co, 596-31245, Japan) was further prepared as a dye. The dyes, genipine and egg white powder, were packed in separate glass bottles, respectively.

Example 8 Preparation of a Dyeing Kit (Natural Pigment Containing Kit Other than Blue Pigment)

2 g of hematoxylin (hematoxylin, Acros Organics, 411180250, New Jersey, USA), 2 g of Lawson (2-hydroxy-1,4-naphthoquinone, sigma-aldrich) , 34196BJ, St Louis, USA) Kits were prepared in substantially the same manner as in Example 2, except that 0.5 g was added thereto. Hair dyes genipine, hematoxylin and Lawson were packaged in the same glass bottle.

Example 9 Preparation of a Dyeing Kit (Natural Pigment Containing Kit Other than Blue Pigment)

A kit was prepared in substantially 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 (Wako Chemical Co, 078-03021, Japan) 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 the genipine. . Hair dyes genipine, hematein and Lawson were packaged in the same glass bottle.

Example 10 Preparation of a Dyeing Kit (Natural Pigment Containing Kit Other than Blue Pigment)

Add 2g of hematein (hematein, Acros Organics, 370840050, New Jersey, USA) and 1.0g of Gardenia Ex (Gardenia Ex, Korea New Drug, Korea) to 2g of Genipine (Wako Chemical Co, 078-03021, Japan) A kit was prepared in substantially the same manner as in Example 2, except that the kit was prepared by the method. Hair dyes, genipine and gardeniax were packed in the same glass bottle.

Example 11 Preparation of Fiber, Leather, Food, or Paper Dyeing Kit (Natural Pigment Kit Other than Blue Pigment)

2 g of hematoxylin (hematoxylin, Acros Organics, 411180250, New Jersey, USA), 2 g of Lawen (2-hydroxy-1,4-naphthoquinone, sigma-aldrich) , 34196BJ, St Louis, USA) Kit was prepared in substantially the same manner as in Example 3, except that 0.5 g was added thereto. Hair dyes genipine, hematoxylin and Lawson were packaged in the same glass bottle.

Example 12 Preparation of Fiber, Leather, Food, or Paper Dyeing Kit (Natural Pigment Kit Other than Blue Pigment)

The kit was prepared in substantially the same manner as in Example 11 except that no viscosity enhancer was added.

Example 13 Preparation of Fiber, Leather, Food, or Paper Dyeing Kit (Natural Pigment and Amino Acid-Containing Kit)

2 g of hematoxylin (hematoxylin, Acros Organics, 411180250, New Jersey, USA), 2 g of Lawen (2-hydroxy-1,4-naphthoquinone, sigma-aldrich) , 34196BJ, St Louis, USA) Kits were prepared in substantially the same manner as in Example 5, except that 0.5 g was added thereto. Hair dyes genipine, hematoxylin and Lawson were packaged in the same glass bottle.

Example 14 Preparation of Fiber, Leather, Food, or Paper Dyeing Kit (Natural Pigment and Amino Acid-Containing Kit)

The kit was prepared in substantially the same manner as in Example 13 except that no viscosity enhancer was added.

Example 15 Blue Hair Color

Using the kit of <Example 1>, hair dye was performed in the following manner. First, add 0.25 g of geinipine, a dyeing agent, to 5 ml of reducing agent Csteine cream solution containing stearic acid as a viscosity enhancer, mix well, and apply to commercially available depigmented human hair (crown wig, 208-17-97354), and then to room temperature (Celsius). 20 minutes), and then shampooed. The hair dyeing process is shown in FIG.

Referring to FIG. 1, when the cysteine cream solution and the geni pin were added and mixed well (see photo 1), the yellowish color appeared as soon as the photo 2. Put the cysteine cream solution and the genie pin and apply the well mixed cream to the human hair as shown in picture 3, comb the hair dye as shown in picture 4, mix it with the hair, and leave it for 10 minutes at room temperature as shown in picture 5 After 20 minutes, the color became orange as shown in Photo 6, and after 30 minutes, it turned blue as shown in Photo 7. Photo 8 is a picture showing that after drying the blue hair dye, after shampooing, the blue hair dye is completed without fear of hair damage.

Therefore, it was confirmed that the blue hair dye can be easily performed by the kit and the method according to the present invention without fear of hair damage.

Example 16 Blue Silk Fiber Dyeing

Using the kit of <Example 3>, silk fibers were dyed blue in the following manner. First, add 0.25 g of genifin to 5 ml of dye electrolytic water cream mixed with stearic acid as a viscosity enhancer, mix well, apply to white silk fiber, leave at room temperature (20 degrees Celsius) for 30 minutes, and then wash. And silk fibers were dried. The blue staining process is shown in FIG. 2. In Figure 2, Photo 1 is a silk fiber swatch photograph, Photo 2 is a silk fiber swatch, alkaline electrolytic water cream solution and the gunnipin photo, Photo 3 is a photograph of a mixture of silk fiber cloth and alkaline electrolytic water cream solution and genipin.

Referring to FIG. 2, the alkaline electrolytic water cream solution and the geni pin were mixed well, and when applied to the silk fiber cloth sufficiently and left at room temperature, the yellowish color initially appeared as shown in the photograph 4. After about 10 minutes, orange gradually began to develop as shown in Photo 5, and after 20 minutes, the orange became darker as in Photo 6, and gradually turned blue as in Photo 7, and after 30 minutes, it turned completely blue as in Photo 8. Photo 9 shows that the blue-dyed silk fiber cloth was washed with detergent and dried, and it was confirmed that it could be dyed blue without fear of damaging the silk fiber.

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 17 Blue Cotton Fiber Dyeing

Using the kit of <Example 5>, cotton fibers were dyed blue in the following manner. First, mix 5 g of alkaline electrolytic water cream for dyeing with stearic acid, a viscosity-increasing agent, and add 0.25 g of genipine and arginine hydrochloride (Arginine hydrochloride, Junsei Chemical Co., Ltd., 13020-0410, Japan 0.025 g). After applying to the white cotton fiber, it was left for 30 minutes at room temperature (20 degrees Celsius), washed, and then dried the cotton fiber blue dyeing process is shown in Figure 3. Figure 1 in Figure 1 is a cotton fiber fabric Photo 2 is a photo of cotton fiber cloth, alkaline electrolytic water cream solution, genipine and arginine hydrochloride, Photo 3 is a photo of a mixture of cotton fiber cloth and alkaline electrolytic water cream solution, genipine and arginine hydrochloride.

Referring to FIG. 3, the alkaline electrolytic water cream solution, genipine, and arginine hydrochloride were mixed well, and when applied to a cotton fiber cloth, it was pale yellow as shown in FIG. 4. After about 10 minutes, orange gradually began to develop as shown in Photo 5, and the orange gradually became darker as in Photo 6, and after 20 minutes, it turned into scarlet as in Photo 7, and after 30 minutes, it turned completely blue as in Photo 8. Photo 9 shows that the blue dyeing was completed without fear of damage to the cotton fibers, as seen after washing the dyed cotton fabric with detergent.

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 18 Dyeing Blue Food (Boiled Egg)

Using the kit of <Example 4>, boiled eggs were dyed blue in the following manner. First, 0.25 g of genifin was added to 5 ml of alkaline electrolyzed water for dyeing, mixed well, and then applied to boiled eggs and left at room temperature (20 degrees Celsius) for 30 minutes. The blue staining process is shown in FIG. 2. In Fig. 4, photographs 1 and 2 are photographs of boiled eggs, photograph 3 is photographs of boiled eggs, alkaline electrolytic water solution and genipine, photograph 4 is photograph of mixtures of alkaline electrolytic water solution and genipine, and photograph 5 is photographed on boiled eggs. It is a photograph immediately after brushing the mixture of photo 4.

Referring to FIG. 4, the alkaline electrolytic water cream and the geni pin were mixed well, and applied to the boiled egg sufficiently and left at room temperature, and initially yellowish as shown in the photo 7. After 10 minutes, the orange color gradually begins to develop as shown in Photo 8, and after 20 minutes, the orange color becomes darker as shown in Photo 9, gradually turns to blue as shown in Photo 10 and 11, and after 30 minutes, it becomes completely blue as shown in Photo 12. Confirmed that it can.

Therefore, it was confirmed that foods such as boiled eggs can be dyed blue by the kit and the method according to the present invention.

Example 19 Preparation of Blue Pigment

Using the kit of Example 7, first, 0.5 g of genipine and 50 mg of egg white powder (Wako Chemical Co, 596-31245, Japan) were added to 10 ml of alkaline electrolytic water for dyeing, and then mixed well. It was left to stand at room temperature (20 degrees Celsius) for 30 minutes and then dried. The blue pigment manufacturing process is shown in FIG. 5.

Referring to FIG. 5, alkaline electrolytic water, genipine and egg white powder are mixed as shown in picture 1, and when left at room temperature, they are initially yellowish as shown in picture 2, and gradually change to orange as shown in picture 3 after 10 minutes and gradually after 20 minutes. The orange color became darker as shown in picture 4, and after 30 minutes, it turned to a blue solution completely as shown in picture 5. When the blue solution is naturally dried, it becomes a blue powder as shown in picture 6, and when the powder is collected, blue pigment is produced as shown in picture 7.

Therefore, it was confirmed that the blue pigment can be prepared by the kit and the method according to the present invention.

Example 20 Dyeing (Black Dye) Method

Using the kit of <Example 8>, black dyeing was performed in the following manner. First, 0.1 g of genipine (Wako Chemical Co, 078-03021, Japan) and 5% hematoxylin (hematoxylin, Acros Organics, 411180250, New Jersey, USA) 0.1 g, Lawson (2-hydroxy-1,4-naphthoquinone, sigma-aldrich, 34196BJ, St Louis, USA) add 0.025 g and mix well, then commercially available depigmented hair (crown wig, 208-17-97354) ), And allowed to stand at room temperature (20 degrees Celsius) for 30 minutes, followed by shampooing. The hair dyeing process is shown in FIG. 6.

Referring to FIG. 6, Genipine, Hematoxylin and Lawson are added to the ethanolamine thioglycolate cream solution as shown in Photo 1, mixed well, and spread well on the bleached hair as shown in Photo 2, as shown in Photo 3 at room temperature. After 30 minutes of incubation, the color gradually turns black as shown in picture 4, and when shampooed, you can see that the black hair is finished without worrying about hair damage as shown in picture 7. Therefore, it was confirmed that the black hairs can be dyed without fear of hair damage by the kit and the method according to the present invention.

<Comparative Example 1> Preparation of blue pigment (see the method disclosed in Japanese Patent Laid-Open No. 8-67828)

Add 1 g of Genipine (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and pepton S 150 mg (Acumedia Manufacturers Inc., 7180, Lansing, USA), dissolve in 10 ml of purified water, pH 7 and mix well Thereafter, the reaction solution vessel was blocked well and left to stir at 40 ° C. for 5 days (120 hours), and blue pigment was formed after 5 days.

The above method for producing blue pigment refers to the method disclosed in Japanese Patent Application Laid-Open No. 8-67828, but instead of Gardenia hydrolyzate, Geniepin was used, and the company disclosed in Japanese Patent Application Laid-open No. Hei 8-67828. Reagents were used instead of similar reagents and the dosage of each reagent was also changed slightly to the extent that it did not affect the reaction results.

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

0.2 g of Genipine (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) and 0.1 g of Taurine (Taurine, DAEJUNG Chemical & Metals Co .. Ltd., 8505-4400, Shiheung, Korea) (0.2M Na ₂ HPO ₄ : 0.1M citric acid: H ₂ O = 12.6: 7.4: 80.0) Dissolve in 40 ml and mix well, and leave it for 4 hours in air at 80 degrees Celsius. Blue pigment was produced.

The above method for preparing blue pigment was referred to the method disclosed in European Patent Publication (EP 0 251 063 A2), but instead of Gardenia hydrolyzate, Geniepin was used and the company disclosed in European Patent Publication (EP 0 251 063 A2). Reagents were used instead of similar reagents and the dosage of each reagent was also changed slightly to the extent that it did not affect the reaction results.

Comparative Example 3 Blue Hair Color

10 g of reducing agent ethanolamine thioglycolate (Tokyo Chemical Industry Co., Ltd., MFCD00050789, Japan) and stearic acid as a viscosity enhancer (stearic acid, Wako Pure Chemical Industries Ltd., 194-14085, Osaka, Japan) 10.0 wt / vol% ethanolamine thioglycolate, a reducing agent dissolved in purified water and adjusted to pH 9.6 with 28 wt / vol% NH ₄ OH (Junsei Chemical Co., Ltd., 13370-0380, Japan) To 100 ml of the cream solution, add 5 g of Genifin (Wako Pure Chemical Industries Ltd., 078-03021, Osaka, Japan) as a dye, mix well, apply to the scab, and leave for 20 minutes at room temperature (20 degrees Celsius). After applying 3% / vol% hydrogen peroxide solution (Wako Chemical Co., 081-04215, Japan), pH 4, 100ml with an oxidizing agent, the solution was left for 10 minutes and shampooed. Could be dyed. The blue hair dye process is shown in FIG. 7. 7 shows the state before, during and after the implementation, and as shown in FIG. 7, it can be seen that the blue hair dye is completed.

Comparative Example 4 Dyeing Blue Silk Fibers

0.5 g of dye, Wako Chemical Co, 078-03021, Japan, in 10 ml of alkaline ionic water with a redox potential of -500 mV at pH 9.0 and stearic acid as a viscosity enhancer (stearic acid, Wako Pure Chemical Industries Ltd., 194-14085, Osaka, Japan) add 1 g, mix well, apply to white silk fibers, leave for 10 minutes at room temperature (20 degrees Celsius), After applying weight / volume of hydrogen peroxide solution (Wako Chemical Co, 081-04215, Japan), pH 4, 10 ml, leave it for 10 minutes and wash it. After drying, the silk fiber can be dyed blue without fear of fiber damage. Could. The blue hair dye process is shown in FIG. 8. 8 shows the state before and after the execution from left to right according to the elapsed time, and as shown in FIG. 8, the dyeing of blue is completed.

Comparative Example 5 Dyeing Blue Cotton Fiber

0.5 g of dye (Wako Chemical Co, 078-03021, Japan) and arginine hydrochloride (Arginine) in 10 ml of alkaline ionic water having a pH of 9.0 and a redox potential of -500 mV. hydrochloride, Junsei Chemical Co., Ltd., 13020-0410, Japan) 50 mg and 1 g of stearic acid (stearic acid, Wako Pure Chemical Industries Ltd., 194-14085, Osaka, Japan) as a viscosity enhancer After applying to white cotton fiber, it was left for 10 minutes at room temperature (20 degrees Celsius), and then applied with an oxidizing agent at a concentration of 3% by weight / volume of hydrogen peroxide solution (Wako Chemical Co, 081-04215, Japan), pH 4, 10ml After 10 minutes of washing and washing, the cotton fibers were dried. The blue hair dye process is shown in FIG. 9. Figure 9 shows the state before and after the implementation from left to right according to the elapsed time, as shown in Figure 9 it was confirmed that can be dyed blue without fear of fiber damage.

Comparative Example 6 Blue Pigment Preparation

First, egg white powder separated from 0.5 g of Genipin (Wako Chemical Co, 078-03021, Japan) and egg in 10 ml of alkaline ionic water (Korea Electrolytic Water System) with pH 9.0 and redox potential of -500 mV. (Egg White powder) (Wako Chemical Co, 596-31245, Japan) Add 50 mg, mix well, and leave at room temperature (20 degrees Celsius) for 10 minutes, and then 5 ml of ferric chloride solution of 5% by weight (FeCl) ₃ · 6H ₂ O, Kanto Chemical Co., Inc., 16018-01, Tokyo, Japan) was added dropwise, and left for 10 minutes and dried to produce blue pigment. The blue pigment manufacturing process is shown in FIG. 10. FIG. 10 shows the state before, during, and after implementation from left to right according to the elapsed time, and as shown in FIG. 10, the blue pigment is generated.

Comparative Example 7 Dyeing (Black Dyeing) Method

First, 100 g of a reducing agent ethanol amine thioglycolate (Ethanolamine Thioglycolate; Tokyo Chemical Industry Co., Ltd., MFCD00050789, Japan, concentration 10.0 wt. 2 g of hematoxylin, 0.5 g of Lawson, and 10 g of stearic acid (Stearic acid, Wako Pure Chemical Industries Ltd., 194-14085, Osaka, Japan) as a viscosity-increasing agent, mix well, apply to the swordfish, and then room temperature (Celsius) 20 minutes), and then applied with hydrogen peroxide solution (Wako Chemical Co, 081-04215, Japan), pH 4, 100 ml of concentration 3% / vol% as an oxidizing agent, and then left for 10 minutes and shampooed. It was possible to get black hair without worrying about hair damage. The black hair dye process is shown in FIG. 11. FIG. 11 shows the state after the application of the mixture of the reducing agent, the dyeing agent and the viscosity increasing agent to the first agent, the application of the oxidizing agent to the second agent, and after the shampoo cleaning. You can see that it is complete.

Experimental Example 1 Measurement of Blue Pigment Production Over Time

In Comparative Examples 1 to 7 and Examples 15 to 20, the time for generating blue pigments was measured on the neck side. The measurements were taken at 10, 30, 4 and 120 hours, respectively. The time was based on the time for confirming the state in which blue pigments and black pigments were produced in Comparative Examples and Examples, respectively. The results are shown in the following table.

[Table 1]

By the method of Example 16, it was confirmed that these fibers can be dyed blue in a short time of about 30 minutes at room temperature by utilizing the amine group of the silk or hair fibers.

The method of Example 17 is a blue dyeing method of the cotton fiber, it can be dyed blue at room temperature for about 30 minutes by simultaneously providing a compound having an amine group, such as arginine, without the amine group in the cotton fiber.

By the method of Example 18 it was confirmed that these foods can be dyed blue in a short time of about 30 minutes at room temperature by utilizing the amine group possessed by the food.

The method of Example 19 is a method for producing blue pigment, and can produce blue pigment at 20 ° C. under relatively mild conditions with a time of about 30 minutes which is much shorter than several hours of Comparative Examples 1 to 3.

The method of Examples 16 to 19 is a method using alkaline electrolytic water having a reducing, the method of Examples 16 to 19 is easy to remove the remaining alkaline electrolyte water is easily volatilized after the reaction, the remaining reagents can be easily removed The point is advantageous. That is, the excess alkali electrolyzed water that does not participate in the reaction is easily changed to water at room temperature over time, in particular, Examples 18 and 19 do not contain a viscosity enhancer, such as stearic acid, the excess reagent (alkaline electrolytic water, Additional processes (such as washing, purifying, etc.) may be unnecessary to remove viscosity enhancers.

In the method of Example 20 it was confirmed that it is possible to dye in a variety of colors by mixing with a dyeing agent of the geni pin and other colors, by applying this black dyeing.

As compared with Comparative Examples 1 and 2, it was confirmed that Examples 15 to 20 can shorten the color development time of blue pigments to enable blue coloration within minutes to 1 hour even at room temperature.

In addition, when compared with Comparative Examples 3 to 7, Examples 15 to 20 is reduced in the process step for the color development of blue pigment from 2 steps to 1 step to simplify the process, generally low concentration for the reducing agent used in step 1 It is also possible to reduce the cost because the color is also possible. And, in Examples 15 to 20, since there is almost no excess reducing agent used and remaining in the reaction solution after the reaction, it is less necessary to remove the excess reducing agent.

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

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

A blue hair dye hair sample (Example 15) was prepared to have a length of 15 cm and a weight of 5 g, soaked in distilled water, 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. The test results are shown in FIG. The upper three photographs of FIG. 12 are photographs related to the cleaning of the blue hair dye samples, wherein the photograph 1 is a photograph of the blue dye hair samples before the shampoo cleaning and the photograph 2 is the shampoo to the blue dye hair samples. After washing, the picture is taken during the cleaning process. Picture 3 shows the picture after the shampoo is washed and dried with the blue hair dye. Referring to FIG. 12, when the color changes before and after washing of the blue haired hair sample were visually compared, it was confirmed that the blue haired hair sample was not discolored by washing.

In addition, a black hair dye sample (Example 20) was prepared to be 15 cm long and 5 g in weight, soaked in distilled water, 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. The test results are shown in FIG. 12 is a photograph related to the cleaning of the black hair hair samples, respectively, wherein the photograph 1 is a photograph of the black hair dye sample before the shampoo cleaning and the photograph 2 is a shampoo to the black dye hair sample. After rinsing, the photograph is taken during the washing process, and Photo 3 shows the photograph after shampoo washing and drying of the black hair dye. Referring to FIG. 12, when the color change before and after washing of the black hair dye was visually compared, it was confirmed that the black hair dye was not discolored by washing.

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

A blue-dyed silk fiber sample (Example 16) was prepared to have an area of 6 cm 2, a thickness of 1 mm, and a weight of 5 g, soaked in distilled water, and then rubbed 1 ml of neutral detergent (Joy, Procter & Gamble), rubbed 20 times with a brush, and washed for 5 minutes. It was. 5 times in the same manner and dried naturally. The test results are shown in FIG. 13. 13 is a photograph related to the cleaning of the blue haired silk fiber samples, wherein picture 1 is a picture of the blue haired silk fiber sample before the neutral detergent cleaning and picture 2 is a neutral detergent to the blue haired silk fiber sample. After being buried, it is a photograph during a washing operation, and Photo 3 shows a photograph of a blue hair dyeing silk fiber sample washed with a neutral detergent and dried. Referring to FIG. 13, when the color change before and after the washing of the blue haired silk fiber sample was visually observed, it was confirmed that the blue haired silk fiber sample was not discolored by washing.

A blue-dyed cotton fiber sample (Example 17) was prepared to have an area of 4 cm 2, a thickness of 1 mm, and a weight of 5 g, soaked in distilled water, rubbed with 1 ml of neutral detergent (Joy, Procter & Gamble), rubbed 20 times with a brush, and washed for 5 minutes. 5 times in the same manner and dried naturally. The test results are shown in FIG. 13. FIG. 13 is a photograph related to the cleaning of the blue hair dye cotton fiber sample, and FIG. 1 is a photograph of the blue hair dye cotton fiber sample before the neutral detergent cleaning, and FIG. 2 is a neutral detergent applied to the blue hair dye cotton fiber sample. After being buried, it is a photograph during the washing operation, and Photo 3 shows a photograph after the blue hair dyeing cotton fiber sample is washed with a neutral detergent and dried. Referring to FIG. 13, when the color changes before and after the washing of the blue dyeing cotton fiber sample were visually compared, it was confirmed that the blue dyeing cotton fiber sample was not discolored by washing.

From the above results, the dyeing method of the present invention, hair dyed by the dyeing kit, fibers can be confirmed that the dyeing effect continuously without causing problems such as discoloration even by detergent.

Claims (37)

Under alkaline conditions, cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogengen sulfite or sulfite (Sulfite) contacting the amine, amino acid or peptide content with genipin in the presence of at least one reducing agent selected from alkaline salts, wherein the concentration of the reducing agent is from 0.1 to 5% w / v amine, amino acid or peptide. Inclusion dyeing method. The method of claim 1, wherein the alkaline conditions are pH 7.1-14. delete delete A method for staining amines, amino acids or peptides containing alkaline contacting amines, amino acids or peptides with genipin in the presence of a reducing agent which is alkaline electrolytic water. The method according to claim 5, wherein the redox potential of the alkaline electrolyzed water is -50 to -1000 mV. The method of claim 1, wherein the amine, amino acid or peptide content is one or more selected from hair, fibers, leather, protein containing food or paper. 8. The method of claim 7, wherein the fiber is at least one selected from silk or wool. 8. The method of claim 7, wherein the paper is at least one animal paper selected from parchment paper, veal, goat skin or silk wallpaper. 8. The method according to claim 7, wherein the food is an animal food or a food based on soybeans. The method of claim 1, wherein in the alkaline conditions, cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite ( In the presence of at least one reducing agent selected from sodium hydrogen sulfate or sulfite alkaline salts, amine, amino acid, or peptide-containing compounds are contacted with genipine by hematoxylin, hematein, Lawson, or Gardenia x. Method of contacting by adding one or more selected from. Under alkaline conditions, cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogengen sulfite or sulfite (Sulfite) After contacting or simultaneously with one or two or more selected from the group consisting of amines, amino acids, peptides and salts thereof in the presence of at least one reducing agent selected from alkaline salts, with or without amines, amino acids or peptides. A method of dyeing an amine, amino acid or peptide-free containing a step of contacting and the concentration of the reducing agent is 0.1 to 5% by weight. delete delete Under alkaline conditions, contacting or simultaneously with or contacting an amine, amino acid, peptide or one or more selected from the group consisting of amines, amino acids, peptides and salts thereof in the presence of a reducing agent which is alkaline electrolyzed water Amine, amino acid or peptide-free staining method comprising the step. The method according to claim 15, wherein the redox potential of said alkaline electrolyzed water is -50 to -1000mV. The method of claim 12, wherein the alkaline conditions are pH 7.1-14. The method of claim 12, 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. 13. The method of claim 12, wherein the amine, amino acid or peptide free is at least one selected from synthetic amine hair, fiber, synthetic leather, protein free food or paper without amine, amino acid or peptide. The method of claim 19, wherein the fiber is at least one selected from amines, amino acids, or peptide-free synthetic fibers or vegetable fibers. The method of claim 19, wherein the paper is a vegetable species free of amines, amino acids, or peptides. The method according to claim 12, wherein in alkaline conditions, cysteine, cysteine derivative, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivative, sodium sulfide, sulfide alkali salt, sodium hydrogen sulfite ( Contacting at least one selected from amines, amino acids, or peptides with or after the simultaneous contact of genipine with or without amines, amino acids, or peptides in the presence of a reducing agent that is at least one selected from sodium hydrogengen sulfate or sulfite alkaline salts. Contacting by adding at least one selected from hematoxylin, hematein, Lawson, or Gardenia x to the genipine in step. Under alkaline conditions, cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogengen sulfite or sulfite (Sulfite) Blue pigment manufacturing method comprising the step of contacting at least one selected from amines, amino acids or peptides with genipin in the presence of at least one reducing agent selected from alkali salts and the concentration of the reducing agent is 0.1 to 5% by weight. The method of claim 23, wherein the alkaline conditions are pH 7.1-14. delete delete In alkaline conditions, a blue pigment manufacturing method comprising the step of contacting at least one selected from amines, amino acids, or peptides with genipin in the presence of a reducing agent which is alkaline electrolytic water. 28. The method of claim 27, wherein the redox potential of said alkaline electrolyzed water is -50 to -1000 mV. The method of claim 23, 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 decomposition products Way. A first agent comprising genipine as a dye; And
Cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfide, sulfite alkali A dyeing kit comprising a second agent in an alkaline condition including a reducing agent which is at least one selected from salt or alkaline electrolyzed water. 31. The kit of claim 30, further comprising at least one selected from hematoxylin, hematein, Lawson, or Gardenia x as the dye. delete 33. The kit of claim 30 for dyeing amine, amino acid or peptide containing hair, fibers, leather, protein containing food or paper. 31. The kit of claim 30, further comprising one or more selected from amines, amino acids or peptides. 35. The kit of claim 34, for staining amine, amino acid or peptide free. A first agent comprising genipine as a dye;
Cysteine, cysteine derivatives, ethanolamine thioglycolate, thioglycolic acid, thioglycolic acid derivatives, sodium sulfide, sulfide alkali salts, sodium hydrogen sulfide, sulfite alkali A second agent under alkaline conditions including a reducing agent which is at least one selected from a salt or alkaline electrolyzed water; And
Blue pigment production kit comprising a third agent comprising at least one selected from amines, amino acids or peptides. The kit of claim 36, wherein the second agent and the third agent are mixed.

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