WO2023053980A1 - Water-insoluble colorant composition - Google Patents

Abstract

The purpose of the present invention is to provide: a flavonoid colorant composition having been made insoluble in water; and a food, a cosmetic, a coating material for medicines or agrochemicals, a printing marker, stationery, a writing utensil, a printing ink, an ink-jet ink, a metallic ink, a paint, a colorant for plastics, a color toner, a florescent labeling agent, a fluorescent probe, or a chemical sensor, each containing the colorant composition. The present invention has been achieved based on the findings that a water-insoluble colorant composition comprising a flavonoid colorant coated with, infiltrated into, combined with, or adsorbed onto a metal or metal compound is insoluble in water and that the water-insoluble colorant composition is usable as a colorant in various applications.

Description

Water-insoluble dye composition

The present invention relates to a water-insoluble dye composition.

　There is a demand for environmentally friendly coloring materials, and under these circumstances, the use of flavonoid pigments is being considered. However, many of the flavonoid pigments are water-soluble, and it has been clarified that when they are used in cosmetics or food pigments, problems such as elution into water and accompanying color fading tend to occur. Therefore, it is currently used only in very limited applications.　

For example, as a method of extracting natural pigments and their uses, they are being studied as orally administered cosmetics, dairy products, dyeing methods for pet foods and fibers, and conditioners (see Patent Documents 1, 2, and 3).

Therefore, as a study on the insolubilization of flavonoid pigments, water-insolubilization by encapsulating a water-soluble dye with a matrix of a silicon compound is being studied (see Patent Document 4).

However, studies on insolubilization are still inadequate, and an approach to further insolubilization is essential and desired as a further development of applications as a coloring agent for flavonoid pigments.

Special Table No. 2009-508508 Japanese Patent Application Publication No. 2017-145257 JP-A-7-304639 Special Table No. 2012-528913

The present invention provides a water-insolubilized flavonoid dye composition, and food, cosmetics, pharmaceuticals or agricultural chemicals containing the dye composition, coating materials or printed markers, stationery, writing instruments, printing inks, inkjet inks, metallic inks, and paints. , plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.

As a result of extensive research to solve the above problems, the present inventors have found that a water-insoluble dye composition in which a metal or metal compound is coated, impregnated, complexed, or adsorbed with a flavonoid dye is soluble in water. The present inventors have found that the water-insoluble dye composition is insoluble and that the water-insoluble dye composition can be used as a coloring agent in a variety of applications, thereby completing the present invention.

That is, the present invention includes the following aspects.
[1]
A water-insoluble dye composition in which a flavonoid dye is coated, impregnated, complexed or adsorbed onto a metal or metal compound.
[2]
2. The water-insoluble dye composition according to 1, wherein the mass ratio of the flavonoid dye to the metal or metal compound is flavonoid dye:metal or metal compound=0.1:99.9 to 90:10.
[3]
3. The water-insoluble pigment composition according to 1 or 2, wherein the flavonoid pigment is anthocyanin, safromin, or cartamine.
[4]
4. The water-insoluble dye composition according to any one of 1 to 3, wherein the metal compound is a metal hydroxide or metal oxide.
[5]
5. The water-insoluble dye composition according to any one of 1 to 4, wherein the metal element of the metal or metal compound is aluminum.
[6]
Coating materials for foods, cosmetics, pharmaceuticals or agricultural chemicals, printed markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, characterized by containing the water-insoluble dye composition according to any one of 1 to 5. , paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.

According to the present invention, it is possible to provide a water-insoluble pigment composition.

Hereinafter, the water-insoluble dye composition of the present invention will be described in detail, but the description of the constituent elements described below is an example as one embodiment of the present invention, and is not limited to these contents. .

(Flavonoid pigment)
The flavonoid dye used in the present invention is a general term for plant dyes, and has a heterocyclic structure in which two benzene rings are linked by three carbon atoms and the central C3 contains oxygen. Classified into chalcones, anthocyanidins, 3-deoxyanthocyanins, flavones, isoflavonoids, flavonols, flavanones, anthocyans, catechins (flavanols), flavonoid polymers, etc., depending on the redox state of the heterocycle. be done. It is contained in various parts of plants such as leaves and flowers, and is widely distributed in higher plants. Typical examples are the yellow chalcone pigment safromin, and the anthocyanin pigment that expresses the red, purple, and blue colors of flowers. The former is chemically stable and is used as a dye. The latter is an unstable substance that is easily discolored by light and differences in hydrogen ion concentration index (pH), and its use as a dye is limited. Flavonoids are produced in plants from cinnamic acids derived from malonyl CoA and phenylalanine, which are composed of three acetic acid units. Since flavonoids absorb ultraviolet rays well, it is said that higher plants contain these pigments in their epidermis to prevent damage caused by ultraviolet rays.

(red cabbage pigment)
Since red cabbage contains a large amount of flavonoid pigments, red cabbage pigment, which is an extract thereof, is used as a coloring agent. The red cabbage pigment is a red to purple-red pigment obtained by extracting the red leaves of red cabbage or purple cabbage with a weakly acidic aqueous solution. Since the main component is anthocyanin, the color tone varies greatly depending on the pH, exhibiting reddish purple in the acidic range, violet to bluish purple in the neutral range, and bluish green in the alkaline range. In addition, it is unstable in a high pH range. The main component of red cabbage pigment is anthocyanin, and it is said that there are about 11 types. Five of them have a basic structure of rubrobradine in which sugars, sophorose and glucose are bound to cyanidin. Two acylated anthocyanins, cyanidin-3-paracoumaroylsophoroside-5-glucoside with p-coumaric acid or cyanidin-3-sinapoylsophoroside-5-glucoside with sinapinic acid, are present in the total account for about half. Others contain diacylated anthocyanins bound with sinapinic acid, ferulic acid and p-coumaric acid. Since acylated anthocyanins and diacylated anthocyanins account for most of them, they are considered to be highly stable among anthocyanin dyes. Red cabbage pigment is readily soluble in water, soluble in alcohol, and insoluble in fats and oils. In a buffer solution of pH 3, it exhibits a reddish purple color with relatively little purplish tint, and the maximum absorption wavelength in the visible region at that time is 530 nm. Since it has a peculiar smell of cruciferous plants, red cabbage pigment preparations have been developed in which the smell is suppressed by adding a deodorizing process. Red cabbage pigment has relatively excellent heat resistance and light resistance, and is considered to be the most used pigment among anthocyanin pigments. It is often used for coloring daikon radish pickled in cherry blossoms, as well as pickles such as plum pickles, shibazuke, sweet vinegar ginger, and red pickled ginger, as well as beverages, frozen desserts, sweets, and jellies.

(safflower yellow pigment)
Since safflower contains safromine and carthamine, which are flavonoid pigments, safflower yellow pigment, which is an extract thereof, is used as a coloring agent. Both safromin and cartamine have a chalcone skeleton and are therefore classified as flavonoid pigments. Both safromine and carthamine are readily extracted with water. The safflower yellow pigment exhibits a slightly bluish bright yellow color compared to the gardenia yellow pigment, hardly changes in color tone due to pH, is easily soluble in water, and is soluble in alcohol. It has excellent light resistance, but it is weak against heat and tends to lose its brightness when heated. It is known that addition of ascorbic acid improves heat resistance and light resistance. It is difficult to use in food applications because it does not easily adhere to proteins and has a slightly unique aroma. It is widely used in beverages due to its good lightfastness and its lemon-like color tone. In addition, it is also used for frozen desserts, sweets, and Chinese noodles. It is also used as a green pigment in combination with blue pigments such as gardenia blue pigments.

As the flavonoid pigment according to the present invention, general flavonoid pigments can be used, but anthocyanin pigments, safromine pigments, or carthamine pigments are preferable in terms of color development and insolubility.

(metals, metal compounds)
Any metal or metal compound can be used as long as it has a supporting action for insolubilizing the flavonoid dye. Metal simple substances, metal oxides, metal hydroxides, etc., and particularly aluminum and aluminum hydroxide can be preferably used. The metal elements in the metals or metal compounds used in the present invention include those belonging to Groups 1 to 15 of the periodic table, excluding those belonging to the first period and the second period. Among them, metal elements such as iron, cobalt, nickel, zinc, aluminum, and titanium can be used, and one or more metal elements selected from them can be used. Metals or metal compounds that have no effect on the human body are particularly preferred for use in foods and cosmetics, and aluminum, titanium, and zinc are particularly preferred in the embodiment of the present invention. In the embodiment of the present invention, metal hydroxides and oxides are preferably used as metals or metal compounds in order to make the physical adsorption of flavonoid dyes and metals or metal compounds stronger, particularly aluminum hydroxide. , titanium oxide and zinc oxide are preferably used. Add alkali to chlorides such as aluminum chloride, titanium tetrachloride, and zinc chloride, and use a slurry of aluminum hydroxide, titanium oxide, zinc hydroxide, etc. for better physical adsorption with flavonoid dyes. Be strong and be favorable. Furthermore, in order to strengthen the physical adsorption, it is more preferable that the surface of the metal or metal compound is coated with a flavonoid dye. As a definition of coating, it indicates a state in which a flavonoid pigment partially or uniformly exists on a metal surface and covers it. The suitable particle size of the metal or metal compound particles varies depending on the application, and the hue of the metal or metal compound particles varies depending on the particle size. For example, it is preferably 100 nm to 20 μm for food and cosmetic applications, and 50 to 500 nm for other applications.

(Water-insoluble dye composition)
Conventional flavonoid dyes are water-soluble because they are in the form of dyes. In the present invention, it has been found that by forming a water-insoluble dye composition in which a flavonoid dye is firmly coated, impregnated, complexed, or adsorbed onto a metal or metal compound, it becomes insoluble in water. . An example of the insolubilization mechanism is shown below, but it is not limited to this.
Flavonoid dyes have many oxygen functional groups such as hydroxy, carboxy, formyl, carbonyl and alkoxy groups. Therefore, when the pH of the aqueous solution is changed, the molecular charge of the flavonoid-based pigment changes greatly. Similarly, metal compounds also exhibit large changes in particle charge with pH changes in aqueous solutions. Therefore, by adjusting the pH of the aqueous dispersion of these two substances, the metal compound and the flavonoid pigment are physically adsorbed by electrical interaction, precipitated as a complex, and are insoluble in water.

Due to the insolubilization obtained by the present invention, flavonoid pigments, which have been limited to food and cosmetic applications, can be used as coloring materials equivalent to ordinary pigments for food, cosmetics, pharmaceuticals, or agricultural chemicals. , printing inks, inkjet inks, metal inks, paints, plastic coloring agents, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors. Moreover, along with the insolubilization, an improvement in properties such as heat resistance and light resistance can be expected. The uses of the water-insoluble dye composition of the present invention are not limited to the uses described above.

As the water-insoluble dye composition of the present invention, the mass ratio of the composition of the flavonoid dye and the metal or metal compound can be arbitrarily designed, and the flavonoid dye: metal or metal compound = 0.1: 99.9. It can be used by setting at a ratio of ~99.9:0.1. Preferably, the ratio of flavonoid dye:metal or metal compound=0.1:99.9 to 90:10.

(Method for producing water-insoluble dye composition)
As a method for producing the water-insoluble dye composition of the present invention, a method of mixing a flavonoid dye and a metal or a metal compound in a solvent is preferable because the most uniform water-insoluble dye composition can be produced.

As a method for producing a water-insoluble dye composition by mixing each substance in a solvent, 1) first, a metal or metal compound is dissolved in a dilute aqueous acid or base solution to prepare a solution. 2) On the other hand, a flavonoid pigment or a preparation containing a flavonoid pigment is dissolved in water to prepare an aqueous solution. 3) Next, the above two liquids are mixed to prepare a mixed liquid. 4) Further, a pH adjuster is added to the mixed solution to adjust the pH to prepare a mixed solution containing the water-insoluble dye composition. 5) A method of filtering and drying the resulting mixture containing the water-insoluble dye composition can be mentioned.　

As a method for mixing the metal or metal compound solution and the flavonoid dye-containing aqueous solution, the metal or metal compound solution may be mixed with the flavonoid dye-containing aqueous solution, or conversely, the metal or metal compound may be mixed with the flavonoid dye-containing aqueous solution. The solutions may be mixed, or these two liquids may be mixed little by little. In addition, the metal or metal compound solution may be a state in which the metal or metal compound is completely dissolved in the liquid, or the metal or metal compound is partially dissolved in the liquid and partially dispersed in the liquid. It's okay. Alternatively, a flavonoid dye or metal or metal compound powder may be added to a liquid of a metal, metal compound, or flavonoid dye, or a metal, metal compound, or flavonoid dye powder may be mixed and water added. Also good. The temperature for mixing may be room temperature or may be heated. Considering the decomposition temperature of the flavonoid dye alone, the mixing temperature is preferably 10 to 60°C, more preferably 20 to 50°C. The pH range for mixing the metal or metal compound solution and the flavonoid dye-containing aqueous solution is preferably 2.0 to 6.0, more preferably 3.0 to 5.0.

Examples of pH adjusters for adjusting pH include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate. The pH range of the mixed solution when the pH adjuster is added is preferably 6.0 to 8.5 from the viewpoint of efficiently adsorbing and insolubilizing the metal or metal compound and the flavonoid pigment in the mixed solution. It is more preferable to adjust to 0.5 to 8.0.

The resulting mixture containing the water-insoluble dye composition can be filtered and dried to obtain the water-insoluble dye composition. When the mixed solution is filtered through a filter such as Nutsche, the filtrate is not colored, so it can be confirmed that the flavonoid pigment and the metal or metal compound are adsorbed. The water-containing wet cake of the obtained water-insoluble dye composition can be dried at room temperature, by heating, in vacuum, under reduced pressure, or the like, to obtain a dry water-insoluble dye composition. The drying method and the dryer are not limited as long as they are ordinary methods and devices.　　

The water-insoluble dye composition of the present invention can be used properly depending on the application whether it is a wet cake containing water or a dry dry water-insoluble dye composition. When used in water-based dispersions and inks, the wet cake can be used as it is, and when used in solvent-based dispersions, it can be used after replacing the water-based with solvent-based. The dry water-insoluble dye composition can be used as it is, or it can be used after being redispersed in water, an organic solvent, a resin solution, or the like.

(stabilizer, additive)
Of course, it is also possible to mix other organic pigments, inorganic pigments, dyes, and pigments in arbitrary proportions with the water-insoluble dye composition of the present invention, and the desired and required hue can be satisfied.
Stabilizers and additives can also be added to the water-insoluble dye composition of the present invention in order to further impart light resistance and heat resistance.

The stabilizers and additives can be added to each or both of the aqueous solution of the metal or metal compound, the aqueous solution containing the flavonoid pigment, or the prepared water-insoluble pigment composition.

The water-insoluble dye composition of the present invention can be mixed with other resins, rubbers, additives, pigments, dyes, etc., if necessary, to form the final coating material for food, cosmetics, pharmaceuticals or agricultural chemicals, printing markers, stationery. , writing instruments, printing inks, inkjet inks, metal inks, paints, plastic coloring agents, color toners, fluorescent labeling agents, fluorescent probes, chemical sensors, etc. An example of the above application is shown below.

(Cosmetics use)
The water-insoluble dye composition of the present invention can be used as cosmetics. The cosmetics used are not particularly limited, and the water-insoluble dye composition of the present invention can be used in various types of cosmetics.

The cosmetics may be of any type as long as they can effectively exhibit their functions. The cosmetics may be lotions, cream gels, sprays and the like. Examples of the cosmetics include skin care cosmetics such as face wash, makeup remover, lotion, serum, face pack, protective milky lotion, protective cream, whitening cosmetics, and UV protection cosmetics, foundation, white powder, makeup base, lipstick, eye makeup, Make-up cosmetics such as cheek rouge and nail enamel, hair care cosmetics such as shampoo, hair rinse, hair treatment, hair styling agents, permanent waving agents, hair dyes, and hair growth agents, body care cosmetics such as body wash cosmetics, deodorant cosmetics, and bath agents Cosmetics etc. can be mentioned.      

The amount of the water-insoluble dye composition of the present invention used in the cosmetics can be appropriately set according to the type of cosmetics. The content in the cosmetics is usually in the range of 0.1 to 99% by mass, and generally preferably in the range of 0.1 to 10% by mass. On the other hand, in makeup cosmetics intended for coloring, the amount is preferably in the range of 5 to 80% by mass, more preferably in the range of 10 to 70% by mass, and most preferably in the range of 20 to 60% by mass. is preferred. When the amount of the water-insoluble dye composition of the present invention contained in the cosmetic product is within the above range, it is possible to effectively exhibit functions such as coloring properties, and to maintain the functions required of the cosmetic product. .   

Depending on the type of cosmetic, the cosmetic may contain, in addition to the water-insoluble dye composition of the present invention, a carrier, pigment, oil, sterol, amino acid, moisturizer, powder, colorant, pH Regulators, fragrances, essential oils, cosmetic active ingredients, vitamins, essential fatty acids, sphingolipids, self-tanning agents, excipients, fillers, emulsifiers, antioxidants, surfactants, chelating agents, gelling agents, thickeners, Emollients, humectants, moisturizers, minerals, viscosity modifiers, rheology modifiers, keratolytics, retinoids, hormonal compounds, alpha hydroxy acids, alpha keto acids, antimycobacterials, antifungals, antibacterials, antivirals pain relievers, anti-allergic agents, antihistamines, anti-inflammatory agents, anti-irritants, antineoplastic agents, immune system boosters, immune system suppressants, anti-acne agents, anesthetics, disinfectants, insect repellents, skin cooling compounds, skin protectants, skin penetration enhancers, exfoliants, lubricants, fragrances, dyes, bleaching agents, hypopigmenting agents, preservatives, stabilizers, pharmaceuticals, light stabilizers, and Spherical powders and the like can be included.   

The cosmetics can be prepared by mixing the water-insoluble pigment composition of the present invention and other cosmetic ingredients.
Cosmetics containing the water-insoluble dye composition of the present invention can be used in the same manner as ordinary cosmetics, depending on the type of the cosmetic.

(For ink and paint applications)
The water-insoluble dye composition of the present invention can be used as inks and paints. However, the uses and compositions of inks and paints are described, but are not limited to these.
The water-insoluble dye composition of the present invention may be dispersed only in a thermoplastic resin, but it can also be dispersed in a printing ink vehicle or paint vehicle containing a thermoplastic resin as an essential component.

As thermoplastic resins, resins such as polyester resins, polyamide resins, styrene resins, acrylic resins, polyolefins, polyalkylene terephthalates, and polyvinyl chloride resins can be used as dispersing resins.   

For example, the vehicle of the lithographic printing ink contains 20 to 50 (mass)% of resin such as rosin-modified phenolic resin, petroleum resin and alkyd resin, and 0 to 30 (mass)% of animal and vegetable oil such as linseed oil, tung oil and soybean oil. , n-paraffin, isoparaffin, naphthene, α-olefin, aromatic solvents, etc. 10 to 60 (mass)%, and other additives such as solubilizers and gelling agents at several (mass)% raw materials. be.   

In the case of vehicles for gravure printing inks and flexographic printing inks, for example, rosins, maleic acid resins, polyamide resins, vinyl resins, cyclized rubbers, chlorinated rubbers, ethylene-vinyl acetate copolymer resins, urethane resins, polyester resins, 10 to 50 (mass)% of one or more resin selected from alkyd resin, nitrocellulose, cellulose acetate, etc., 30 to 80 (mass) of solvent such as alcohol, toluene, n-hexane, ethyl acetate, cellosolve, butyl cellosolve, etc. % raw materials.   

Vehicles for paints include, for example, alkyd resins, epoxy resins, acrylic resins, polyurethane resins, polyester resins, melamine resins, urea resins, water-soluble resins, etc. 20 to 80 (mass)% of resins, hydrocarbons, alcohols, ketones It is manufactured from raw materials containing 10 to 60 (mass)% of solvent such as water.   

(for plastics)
The water-insoluble dye composition of the present invention can also be used for plastic coloring applications. In the case of obtaining colored plastic molded articles, thermoplastic resins (plastics) for thermoforming such as injection molding and press molding, such as polyolefins such as polyethylene and polypropylene, and polyvinyl chloride resins, are used. The water-insoluble dye composition can be kneaded into these resins by a conventionally known method.

(for toner)
The water-insoluble dye composition of the present invention can also be used for toner coloring applications.
In the case of obtaining a toner for electrostatic charge image development, thermoplastic resins such as polyester resins, polyamide resins, styrene resins and acrylic resins, which are solid at room temperature and have film-forming properties, are used as dispersing resins.

The toner for electrostatic image development produced using the water-insoluble dye composition of the present invention as a constituent component includes a one-component color magnetic toner (color toner for magnetic one-component development) containing a magnetic substance in the toner, and a magnetic toner containing a magnetic substance. It can be used as a non-magnetic one-component color toner (color toner for non-magnetic one-component development) that does not contain a carrier, or a color toner for a two-component color developer mixed with a carrier (color toner for two-component development).   

The one-component color magnetic toner can be composed of, for example, colorants, binder resins, magnetic powders, charge control agents (CCA), and other additives such as release agents, in the same manner as those commonly used.

The amount of the water-insoluble dye composition used in the toner for electrostatic charge image development is not particularly limited, but it is preferably used in a proportion of 0.5 to 25 parts by mass with respect to 100 parts by mass of the binder resin. It is more preferable that the amount is 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin in order to make the charging performance of the binder more remarkable.

As the binder resin used in the toner for electrostatic charge image development, any of the known and commonly used thermoplastic resins exemplified above can be used. Any of natural rubber, synthetic rubber, synthetic wax, etc. can be used. 

(for fluorescent labeling agents and fluorescent probes)
Flavonoid dyes are known to have fluorescence. In the flavonoid dye composition of the present invention, since the structure of the flavonoid dye is maintained, it can be used for applications utilizing fluorescence, such as fluorescent labeling agents and fluorescent probes.

For example, the metal or metal compound in the flavonoid dye composition of the present invention can be used as a fluorescent labeling agent by binding or adsorbing a substance that recognizes a desired target biomolecule to its surface. Specifically, target biomolecules (including physiologically active substances) in specimens (eg, any cell extract, lysate, medium/culture solution, solution, buffer) can be fluorescently labeled. Substances that molecularly recognize the target biomolecules include antibodies, antigens, peptides, DNA, RNA, sugar chains, ligands, receptors, chemical substances, and the like. When the molecular recognition with the target biomolecule is an antigen-antibody reaction, it can be used as an immunostaining reagent.

(for chemical sensors)
The hue of flavonoid pigments changes with pH changes. Therefore, by utilizing this color change, it can also be used as a chemical sensor for detecting pH.

For example, ions contained in environmental river water, groundwater, and industrial wastewater can be easily detected. In daily environmental monitoring, factory wastewater management, etc., there are many problems in terms of time, cost, and labor to use instrumental analysis using a large-sized measuring instrument as a means, but the flavonoid dye of the present invention By using the composition, the pH change can be easily observed at the site of measurement, and since it is water-insoluble, it can be recovered by filtration or the like, so process control can be performed without causing the dye to flow out into the aqueous medium. It is also possible to use

Although the present invention will be described in more detail with examples below, the scope of the present invention is not limited to these examples.

(Example 1)
46.4 g of aluminum (III) chloride hexahydrate (manufactured by Kanto Kagaku Co., Ltd.) was dissolved in 1000 mL of deionized water in a 2 L beaker. Subsequently, a 4.8% sodium hydroxide aqueous solution diluted from a 48% sodium hydroxide aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) was added to adjust the pH to 4.0 to prepare an aluminum hydroxide slurry. To this solution, 5.29 g of safflower yellow pigment powder (safflower Y1500, safflower pigment 85%, dextrin 15%, manufactured by Daiwa Kasei Co., Ltd.) was added, and after 1 hour at room temperature, a 4.8% aqueous sodium hydroxide solution was added. , pH was adjusted to 7.0, and stirred for 30 minutes. The filtered solid was dried in a vacuum dryer (740 mmHg) at 30° C. for 14 hours to obtain 19.5 g of powder (1). The composition ratio of aluminum hydroxide: safflower yellow pigment in powder (1), which is obtained by subtracting the charged safflower yellow pigment from the yield of powder (1), is the mass ratio, aluminum hydroxide: safflower yellow. Dye = 77:23. The obtained powder (1) exhibited a yellow color similar to that of safflower yellow pigment. After adding 10 mg of powder (1) and 1.0 g of water to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (1). When one drop of Dispersion (1) was dropped onto the filter paper, it was observed that the dropped portion turned yellow in a circular shape, and then the colorless and transparent liquid spread concentrically. The portion that first turned yellow in a circular shape was the powder (1) that was insoluble in water, and then the portion where the transparent liquid spread concentrically was water, and the powder (1) was insoluble in water. I found out.

(Example 2)
46.4 g of aluminum (III) chloride hexahydrate (manufactured by Kanto Kagaku Co., Ltd.) was dissolved in 1000 mL of deionized water in a 2 L beaker. Subsequently, a 4.8% sodium hydroxide aqueous solution diluted from a 48% sodium hydroxide aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) was added to adjust the pH to 4.0 to prepare an aluminum hydroxide slurry. To this solution, 4.50 g of red cabbage pigment powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and after 1 hour at room temperature, a 4.8% aqueous sodium hydroxide solution was added to adjust the pH to 7.0, and the mixture was allowed to stand for 30 minutes. Stirred. The filtered solid was dried in a vacuum dryer (740 mmHg) at 30° C. for 14 hours to obtain 18.0 g of powder (2). The composition ratio of aluminum hydroxide:red cabbage pigment in powder (2), which is obtained by subtracting the charged red cabbage pigment from the yield of powder (2), is a mass ratio of aluminum hydroxide: red cabbage. Dye = 75:25. The obtained powder (2) exhibited a bluish purple color derived from red cabbage pigment. After adding 10 mg of powder (2) and 1.0 g of water to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (2). When one drop of Dispersion (2) was dropped onto the filter paper, the dropped portion was circularly colored in bluish violet, and then it was observed that the colorless and transparent liquid spread concentrically. The first circle-shaped bluish-purple colored portion was the water-insoluble powder (2), and the portion where the transparent liquid spread concentrically after that was water, and the powder (2) was insoluble in water. I found out.

<Comparative Example 1>
After adding 10 mg of safflower yellow pigment powder (safflower Y1500, safflower pigment 85%, dextrin 15%, manufactured by Daiwa Kasei Co., Ltd.) and 1.0 g of water to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion (3). When one drop of Dispersion (3) was dropped onto the filter paper, it was observed that the yellow liquid spread uniformly concentrically around the dropped portion. This indicates that the safflower yellow pigment is dissolved in water in dispersion (3).

<Comparative Example 2>
2.7 mg of safflower yellow pigment powder (safflower Y1500, safflower pigment 85%, dextrin 15%, manufactured by Daiwa Kasei Co., Ltd.) in a 10 mL vial, and aluminum hydroxide prepared in the same manner as in Example 1 without adding pigment After adding 7.7 mg and 1.0 g of water, the mixture was stirred for 5 minutes to prepare dispersion liquid (4). When one drop of Dispersion (4) was dropped onto the filter paper, it was observed that the yellow liquid spread uniformly concentrically around the dropped portion. This indicates that the safflower yellow pigment is dissolved in water in the dispersion (4).

<Comparative Example 3>
After adding 10 mg of red cabbage pigment powder (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 1.0 g of water to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (5). When one drop of the dispersion liquid (5) was dropped onto the filter paper, it was observed that the yellow liquid spread uniformly concentrically around the dropped portion. This indicates that the red cabbage pigment is dissolved in water in dispersion (5).

<Comparative Example 4>
After adding 2.5 mg of red cabbage pigment powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 7.5 mg of aluminum hydroxide prepared without adding pigment in the same manner as in Example 1, and 1.0 g of water in a 10 mL vial , and stirred for 5 minutes to prepare a dispersion (6). When one drop of the dispersion liquid (6) was dropped onto the filter paper, it was observed that the reddish-purple liquid spread uniformly concentrically around the dropped portion. This indicates that the red cabbage pigment is dissolved in water in dispersion (6).

Claims (6)

A water-insoluble dye composition in which a flavonoid dye is coated, impregnated, complexed or adsorbed onto a metal or metal compound. 2. The water-insoluble dye composition according to claim 1, wherein the weight ratio of said flavonoid dye to said metal or metal compound is flavonoid dye:metal or metal compound=0.1:99.9 to 90:10. 3. The water-insoluble pigment composition according to claim 1, wherein the flavonoid pigment is anthocyanin, safromin, or carthamine. 3. The water-insoluble dye composition according to claim 1, wherein said metal compound is a metal hydroxide or metal oxide. 3. The water-insoluble dye composition according to claim 1, wherein the metal element of said metal or metal compound is aluminum. 3. Coating materials for foods, cosmetics, pharmaceuticals or agricultural chemicals, printed markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, and paints, which contain the water-insoluble dye composition according to claim 1 or 2. , plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.