WO2023053981A1 - Water-insoluble, oil-insoluble pigment composition - Google Patents
Water-insoluble, oil-insoluble pigment composition Download PDFInfo
- Publication number
- WO2023053981A1 WO2023053981A1 PCT/JP2022/034504 JP2022034504W WO2023053981A1 WO 2023053981 A1 WO2023053981 A1 WO 2023053981A1 JP 2022034504 W JP2022034504 W JP 2022034504W WO 2023053981 A1 WO2023053981 A1 WO 2023053981A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- insoluble
- water
- metal
- oil
- chlorophyll
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B63/00—Lakes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
Definitions
- the present invention relates to water-insoluble and oil-insoluble dye compositions.
- chlorophyll-based pigments are oil-soluble or water-soluble, and when used in cosmetics or food coloring, it has been clarified that problems such as elution into water or solvents and accompanying color fading tend to occur. Therefore, it is currently used only in very limited applications.
- the present invention provides a chlorophyll-based dye composition that has excellent stability and dispersibility when used as a coloring agent, and coating materials or printed markers, stationery, and writing instruments for foods, cosmetics, pharmaceuticals, or agricultural chemicals containing the dye composition. , printing inks, inkjet inks, metal inks, paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.
- a dye composition in which a metal or metal compound is coated, impregnated, complexed, or adsorbed with a chlorophyll dye is water-insoluble and non-water-insoluble.
- the present inventors have found that the dye composition is oil-soluble and that the dye composition can be used as a coloring agent in a variety of applications, thereby completing the present invention.
- a water-insoluble and oil-insoluble dye composition in which a chlorophyll-based dye is coated, impregnated, complexed, or adsorbed onto a metal or metal compound.
- [2] 2. The water-insoluble and oil-insoluble dye composition according to 1, wherein the mass ratio of the chlorophyll-based dye to the metal or metal compound is chlorophyll-based dye:metal or metal compound 0.1:99.9 to 90:10. thing.
- [3] 3.
- the water-insoluble and oil-insoluble pigment composition according to 1 or 2 wherein the chlorophyll pigment is copper chlorophyll or copper chlorophyllin sodium.
- chlorophyll pigment used in the present invention is also called chlorophyll. It has a basic structure in which a long-chain alcohol called phytol is ester-bonded to tetrapyrrole, which is a structure in which four pyrroles are wound around a ring. Naturally occurring compounds generally have a structure in which magnesium is coordinated to the tetrapyrrole ring center. Besides magnesium, examples of zinc coordination have been reported in red photosynthetic bacteria. The substance with the metal removed and replaced with two hydrogens is called pheophytin.
- Chlorophyll is a green pigment that is insoluble in water, soluble in alcohol, and readily soluble in fats and oils, and is the only natural pigment recognized as a coloring agent that exhibits a green color by itself.
- the magnesium in the tetrapyrrole ring is easily detached by acid or light and destabilized.
- the central element can be artificially substituted by chemical reaction.
- those with copper coordination are more stable to light and acid than those with magnesium, and are used as additives for cosmetics and foods.
- Copper chlorophyll pigment Copper chlorophyll and copper chlorophyllin sodium are classified as designated additives under the Food Sanitation Act and used as coloring agents. Natural chlorophyll is unstable against light and oxygen in the air, and copper chlorophyll is made by reacting with copper (Cu) to improve this.
- Copper copper chlorophyllin is a sodium salt obtained by hydrolyzing a terminal ester of copper chlorophyll, which is water-soluble, stable, and bright green.
- chlorophyll pigment As the chlorophyll pigment according to the present invention, general chlorophyll pigments can be used, but copper chlorophyll or copper chlorophyllin sodium is 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 chlorophyll 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.
- metal hydroxides and oxides are preferably used as metals or metal compounds in order to strengthen the physical adsorption of chlorophyll-based dyes and metals or metal compounds, particularly aluminum hydroxide.
- titanium oxide and zinc oxide are preferably used.
- Add alkali to chlorides such as aluminum chloride, titanium tetrachloride, zinc chloride, etc., and use aluminum hydroxide, titanium oxide, zinc hydroxide, etc. as a slurry for better physical adsorption with chlorophyll dyes. Be strong and be favorable.
- the surface of the metal or metal compound is coated with a chlorophyll-based dye.
- coating indicates a state in which a chlorophyll-based dye 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 ⁇ m for food and cosmetic applications, and 50 to 500 nm for other applications.
- the chlorophyll-based pigment undergoes a large change in molecular charge when the pH of the aqueous solution is changed.
- 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 chlorophyll pigment physically adsorbed through electrical interaction, precipitated as a complex, and became insoluble in water and solvents. ing.
- chlorophyll-based 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 and oil-insoluble dye composition of the present invention are not limited to the above uses.
- the chlorophyll-based pigment:metal or metal compound 0.1:99.9 to 90:10.
- Method for producing water-insoluble and oil-insoluble dye composition As a method for producing the water-insoluble color and oil-insoluble pigment composition of the present invention, a method of mixing a chlorophyll-based pigment and a metal or a metal compound in a solvent is the most uniform water-insoluble and oil-insoluble pigment composition. It is preferable because it can manufacture things.
- a method for producing a water-insoluble and oil-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 chlorophyll-based dye or a preparation containing a chlorophyll-based dye is dissolved or dispersed in water to prepare an aqueous solution or aqueous dispersion. 3) Next, the above two liquids are mixed to prepare a mixed liquid. 4) Further, a pH adjuster is added to the mixture to adjust the pH, thereby preparing a mixture containing the water-insoluble and oil-insoluble dye composition. 5) A method of filtering and drying the resulting mixture containing the water-insoluble and oil-insoluble dye composition.
- the metal or metal compound solution may be mixed with the chlorophyll dye-containing aqueous solution or aqueous dispersion, or the chlorophyll dye may be mixed.
- the powder may be added and mixed as it is, or conversely, the metal or metal compound solution may be mixed with the chlorophyll pigment-containing aqueous solution or aqueous dispersion, or these two liquids may be mixed little by little. I don't mind.
- 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.
- the temperature for mixing may be room temperature or may be heated. Considering the decomposition temperature of the chlorophyll pigment, the mixing temperature is preferably 10 to 60°C, more preferably 20 to 50°C.
- the pH range when mixing the metal or metal compound solution and the chlorophyll dye-containing aqueous solution or aqueous dispersion is preferably 2.0 to 6.0, and more preferably adjusted to 3.0 to 5.0. preferable.
- Aqueous solutions such as sodium hydroxide and potassium hydroxide can be used as pH adjusters when adjusting the pH.
- 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 chlorophyll-based dye in the mixed solution. It is more preferable to adjust to 0.5 to 8.0.
- the resulting mixture containing the water-insoluble and oil-insoluble dye composition is filtered and dried to obtain the water-insoluble and oil-insoluble dye composition.
- the mixed liquid was filtered with a filter such as Nutsche, the filtrate was not colored, so it was confirmed that the chlorophyll-based pigment and the metal or metal compound were adsorbed.
- the water-containing wet cake of the obtained water-insoluble and oil-insoluble dye composition is dried at room temperature, by heating, in vacuum, by drying under reduced pressure, etc., to obtain a dry water-insoluble and oil-insoluble dye composition. can be done.
- the drying method and the dryer are not limited as long as they are ordinary methods and devices.
- the water-insoluble and oil-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 and oil-insoluble dye composition. It is possible. When used in water-based dispersions and inks, the wet cake can be used as it is, and when used in solvent-dispersed systems, it can be used after replacing the water-based with solvent-based.
- the dry water-insoluble and oil-insoluble dye composition can be used as it is, or can of course be used after being redispersed in water, an organic solvent, a resin solution, or the like.
- stabilizer additive
- Stabilizers and additives can also be added to the water-insoluble and oil-insoluble dye composition of the present invention in order to further impart light resistance and heat resistance.
- Stabilizers and additives can be added to each or both of the aqueous solution of the metal hydroxide and the aqueous solution containing the chlorophyll dye, or added to the prepared water-insoluble and oil-insoluble dye composition. can be
- the water-insoluble and oil-insoluble dye composition of the present invention is optionally mixed with other resins, rubbers, additives, pigments, dyes, etc., and is used as the final coating material for food, cosmetics, pharmaceuticals, or agricultural chemicals. It can be adjusted and used for printing markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, paints, plastic coloring agents, color toners, fluorescent labeling agents, fluorescent probes, chemical sensors, and the like. An example of the above application is shown below.
- the water-insoluble and oil-insoluble dye composition of the present invention can be used as cosmetics.
- the cosmetics used are not particularly limited, and the water-insoluble and oil-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 and oil-insoluble dye composition of the present invention used in the cosmetics can be appropriately set according to the type of the 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.
- 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.
- the amount of the water-insoluble and oil-insoluble dye composition of the present invention contained in the cosmetic product is within the above range, it is possible to effectively express functions such as coloring properties, and to retain the functions required for the cosmetic product. can do.
- the cosmetic may include the water-insoluble and oil-insoluble dye composition of the present invention, as well as carriers, pigments, oils, sterols, amino acids, moisturizers, powders, and other ingredients acceptable as cosmetic ingredients.
- the cosmetics can be produced by mixing the water-insoluble and oil-insoluble pigment composition of the present invention and other cosmetic ingredients.
- Cosmetics containing the water-insoluble and oil-insoluble dye composition of the present invention can be used in the same manner as ordinary cosmetics, depending on the type of the cosmetic.
- the water-insoluble and oil-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 and oil-insoluble dye composition of the present invention may be dispersed only in a thermoplastic resin, but may be dispersed in a vehicle for printing ink, a vehicle for paint, etc. containing a thermoplastic resin as an essential component. can also
- 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.
- 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, ⁇ -olefin, aromatic solvents at 10-60% (mass), and other additives such as solubilizers and gelling agents at several (mass)%. be done.
- resin such as rosin-modified phenolic resin, petroleum resin and alkyd resin
- animal and vegetable oil such as linseed oil, tung oil and soybean oil.
- other additives such as solubilizers and gelling agents at several (mass)%.
- 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.
- 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.
- the water-insoluble and oil-insoluble dye composition of the present invention can also be used for plastic coloring applications.
- 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 and oil-insoluble dye composition can be used by kneading into these resins by a conventionally known method.
- 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 electrostatic charge image developing toner produced using the water-insoluble and oil-insoluble dye composition of the present invention as a constituent component is a one-component color magnetic toner (color toner for magnetic one-component development) containing a magnetic substance in the toner. 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 magnetic substance, or a color toner for a two-component color developer mixed with a carrier (color toner for two-component development). can.
- 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.
- CCA charge control agents
- release agents in the same manner as those commonly used.
- the amount of the water-insoluble and oil-insoluble dye composition used in the toner for electrostatic charge image development is not particularly limited, but it can be used at a rate of 0.5 to 25 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, the amount is from 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 colorant itself more remarkable.
- thermoplastic resins 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.
- Chlorophyll pigments are known to have red fluorescence.
- the chlorophyll-based dye composition of the present invention since the chlorophyll-based dye composition maintains its structure, it can be used for applications utilizing fluorescence, such as fluorescent labeling agents and fluorescent probes.
- the metal or metal compound in the chlorophyll-based 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.
- target biomolecules including physiologically active substances
- specimens eg, any cell extract, lysate, medium/culture solution, solution, buffer
- substances that molecularly recognize the target biomolecules include antibodies, antigens, peptides, DNA, RNA, sugar chains, ligands, receptors, chemical substances, and the like.
- the molecular recognition with the target biomolecule is an antigen-antibody reaction, it can be used as an immunostaining reagent.
- ions contained in environmental river water, groundwater, and industrial wastewater can be easily detected.
- daily environmental monitoring, factory wastewater management, etc. there are many problems in terms of time, cost, and labor to use instrumental analysis using large-sized measuring instruments as a means, but the chlorophyll-based dye of the present invention
- 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
- 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.
- aluminum (III) chloride hexahydrate manufactured by Kanto Kagaku Co., Ltd.
- dispersion liquid (1) 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 green in a circular shape, and then the colorless and transparent liquid spread concentrically. The green circular portion at first was the water-insoluble powder (1), and the portion where the transparent liquid spread concentrically was water, and the powder (1) was insoluble in water. I found out. Next, after adding 10 mg of powder (1) and 1.0 g of ethanol to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (2).
- the dropped portion When one drop of Dispersion (2) was dropped onto the filter paper, the dropped portion turned green in a circular shape, and then it was observed that the colorless and transparent liquid spread concentrically.
- the green circular portion at first was the powder (2) insoluble in ethanol, and the portion where the transparent liquid spread concentrically was ethanol, and the powder (2) was insoluble in ethanol. I found out.
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- Chemical & Material Sciences (AREA)
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The purpose of the present invention is to provide: a water-insoluble, oil-insoluble chlorophyll pigment composition; and a food, cosmetic, pharmaceutical, or agrochemical coating material, or a print marker, stationery, writing implement, printing ink, inkjet ink, metal ink, paint, plastic coloring agent, color toner, fluorescent labeling agent, fluorescent probe, or chemical sensor, that contains said pigment composition. A pigment composition in which a metal or a metal compound is coated, impregnated, or complexed with a chlorophyll pigment, or in which the chlorophyll pigment is adsorbed to the metal or the metal compound, was discovered to be water-insoluble and oil-insoluble, and it was furthermore discovered that the water-insoluble, oil-insoluble pigment composition can be deployed as a coloring agent for a variety of purposes, whereupon the present invention was perfected.
Description
本発明は、非水溶性、非油溶性色素組成物に関する。
The present invention relates to water-insoluble and oil-insoluble dye compositions.
環境に優しい色材が求められおり、このような状況下で、クロロフィル色素の活用が検討されている。しかしながらクロロフィル系色素は、油溶性または水溶性であり、化粧品や食用色素に用いた場合水や溶剤への溶出やそれに伴う色落ちの問題も起こりやすいことが明らかになっている。そのため現状ではごく限られた用途でしか使用されていない。
There is a demand for environmentally friendly coloring materials, and under these circumstances, the use of chlorophyll pigments is being considered. However, chlorophyll-based pigments are oil-soluble or water-soluble, and when used in cosmetics or food coloring, it has been clarified that problems such as elution into water or solvents and accompanying color fading tend to occur. Therefore, it is currently used only in very limited applications.
例えば、アルカリ加水分解によるクロロフィルの製造方法や、抽出方法が検討されており、用途として、食品、化粧品、紙、樹脂等の利用が検討されている（特許文献１、２、３参照）。
For example, a method for producing chlorophyll by alkaline hydrolysis and an extraction method are being studied, and uses such as food, cosmetics, paper, and resin are being studied (see Patent Documents 1, 2, and 3).
しかし、不溶化の検討がまだまだ不十分であり、クロロフィル系色素のさらな着色剤として用途展開として、さらなる不溶化へのアプローチは必須であり、希求されている課題である。
However, the study of insolubilization is still inadequate, and in order to expand its use as a coloring agent for chlorophyll-based pigments, it is essential to approach further insolubilization, and this is a much-needed issue.
本発明は、着色剤として使用した場合、安定性、分散性に優れたクロロフィル系色素組成物、および該色素組成物を含有した食品、化粧品、医薬品または農薬のコーティング材または印字マーカー、文房具、筆記具、印刷インキ、インクジェットインキ、金属インキ、塗料、プラスチック着色剤、カラートナー、蛍光標識剤、蛍光プローブ、または化学センサーを提供することを目的とする。
The present invention provides a chlorophyll-based dye composition that has excellent stability and dispersibility when used as a coloring agent, and coating materials or printed markers, stationery, and writing instruments for foods, cosmetics, pharmaceuticals, or agricultural chemicals containing the dye composition. , printing inks, inkjet inks, metal inks, paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、金属または金属化合物に、クロロフィル系色素が被覆、含浸、複合化、あるいは吸着した色素組成物が、非水溶性且つ、非油溶性であることを見出し、さらに該色素組成物が着色剤として多種の用途として展開が可能であることを見出し、本発明を完成するに至った。
As a result of extensive research to solve the above problems, the present inventors have found that a dye composition in which a metal or metal compound is coated, impregnated, complexed, or adsorbed with a chlorophyll dye is water-insoluble and non-water-insoluble. The present inventors have found that the dye composition is oil-soluble and that the dye composition can be used as a coloring agent in a variety of applications, thereby completing the present invention.
すなわち、本発明は、以下の態様を包含するものである。
［１］
金属または金属化合物に、クロロフィル系色素が被覆、含浸、複合化、あるいは吸着された非水溶性且つ、非油溶性色素組成物。
［２］
前記クロロフィル系色素と、金属または金属化合物が質量比で、クロロフィル系色素：金属または金属化合物＝０．１：９９．９～９０：１０である１記載の非水溶性且つ、非油溶性色素組成物。
［３］
前記クロロフィル系色素が銅クロロフィル、または銅クロロフィリンナトリウムである１または２に記載の非水溶性且つ、非油溶性色素組成物。
［４］
前記金属化合物が金属水酸化物または金属酸化物である１～３いずれか１つに記載の非水溶性且つ、非油溶性色素組成物。
［５］
前記金属または金属化合物の金属元素がアルミニウムである１～４いずれか１つに記載の非水溶性且つ、非油溶性色素組成物。
［６］
１～５いずれか１つに記載の非水溶性且つ、非油溶性色素組成物を含有することを特徴とする食品、化粧品、医薬品または農薬のコーティング材または印字マーカー、文房具、筆記具、印刷インキ、インクジェットインキ、金属インキ、塗料、プラスチック着色剤、カラートナー、蛍光標識剤、蛍光プローブ、または化学センサー。 That is, the present invention includes the following aspects.
[1]
A water-insoluble and oil-insoluble dye composition in which a chlorophyll-based dye is coated, impregnated, complexed, or adsorbed onto a metal or metal compound.
[2]
2. The water-insoluble and oil-insoluble dye composition according to 1, wherein the mass ratio of the chlorophyll-based dye to the metal or metal compound is chlorophyll-based dye:metal or metal compound=0.1:99.9 to 90:10. thing.
[3]
3. The water-insoluble and oil-insoluble pigment composition according to 1 or 2, wherein the chlorophyll pigment is copper chlorophyll or copper chlorophyllin sodium.
[4]
4. The water-insoluble and oil-insoluble dye composition according to any one of 1 to 3, wherein the metal compound is a metal hydroxide or metal oxide.
[5]
4. The water-insoluble and oil-insoluble dye composition according to any one of 1 to 4, wherein the metal element of the metal or metal compound is aluminum.
[6]
Food, cosmetics, pharmaceuticals or agricultural chemicals coating materials or printing markers, stationery, writing instruments, printing inks, characterized by containing the water-insoluble and oil-insoluble dye composition according to any one of 1 to 5, Inkjet inks, metallic inks, paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.
［１］
金属または金属化合物に、クロロフィル系色素が被覆、含浸、複合化、あるいは吸着された非水溶性且つ、非油溶性色素組成物。
［２］
前記クロロフィル系色素と、金属または金属化合物が質量比で、クロロフィル系色素：金属または金属化合物＝０．１：９９．９～９０：１０である１記載の非水溶性且つ、非油溶性色素組成物。
［３］
前記クロロフィル系色素が銅クロロフィル、または銅クロロフィリンナトリウムである１または２に記載の非水溶性且つ、非油溶性色素組成物。
［４］
前記金属化合物が金属水酸化物または金属酸化物である１～３いずれか１つに記載の非水溶性且つ、非油溶性色素組成物。
［５］
前記金属または金属化合物の金属元素がアルミニウムである１～４いずれか１つに記載の非水溶性且つ、非油溶性色素組成物。
［６］
１～５いずれか１つに記載の非水溶性且つ、非油溶性色素組成物を含有することを特徴とする食品、化粧品、医薬品または農薬のコーティング材または印字マーカー、文房具、筆記具、印刷インキ、インクジェットインキ、金属インキ、塗料、プラスチック着色剤、カラートナー、蛍光標識剤、蛍光プローブ、または化学センサー。 That is, the present invention includes the following aspects.
[1]
A water-insoluble and oil-insoluble dye composition in which a chlorophyll-based dye is coated, impregnated, complexed, or adsorbed onto a metal or metal compound.
[2]
2. The water-insoluble and oil-insoluble dye composition according to 1, wherein the mass ratio of the chlorophyll-based dye to the metal or metal compound is chlorophyll-based dye:metal or metal compound=0.1:99.9 to 90:10. thing.
[3]
3. The water-insoluble and oil-insoluble pigment composition according to 1 or 2, wherein the chlorophyll pigment is copper chlorophyll or copper chlorophyllin sodium.
[4]
4. The water-insoluble and oil-insoluble dye composition according to any one of 1 to 3, wherein the metal compound is a metal hydroxide or metal oxide.
[5]
4. The water-insoluble and oil-insoluble dye composition according to any one of 1 to 4, wherein the metal element of the metal or metal compound is aluminum.
[6]
Food, cosmetics, pharmaceuticals or agricultural chemicals coating materials or printing markers, stationery, writing instruments, printing inks, characterized by containing the water-insoluble and oil-insoluble dye composition according to any one of 1 to 5, Inkjet inks, metallic inks, paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.
本発明によれば、着色剤として、安定性、分散性に優れた色素組成物を提供することができる。
According to the present invention, it is possible to provide a pigment composition excellent in stability and dispersibility as a coloring agent.
以下、本発明の非水溶性且つ、非油溶性色素組成物について詳細に説明するが、以下に記載する構成要件の説明は、本発明の一実施態様としての一例であり、これらの内容に特定されるものではない。
Hereinafter, the water-insoluble and oil-insoluble dye composition of the present invention will be described in detail. not to be
（クロロフィル系色素）
本発明で使用するクロロフィル系色素は、葉緑素とも呼ばれている。４つのピロールが環を巻いた構造であるテトラピロールに、フィトールと呼ばれる長鎖アルコールがエステル結合した基本構造を有する。天然に存在するものは一般にマグネシウムがテトラピロール環中心に配位した構造を有する。マグネシウム以外では、亜鉛が配位した例が紅色光合成細菌において報告されている。金属がはずれ、2つの水素で置換された物質はフェオフィチンと呼ばれる。クロロフィルは水に不溶、アルコールに可溶、油脂に易溶な緑色色素で、着色料として認められている天然色素としては、単独で緑色を呈する唯一の色素である。上記で述べたように、テトラピロール環の中のマグネシウムが酸や光で簡単に離脱して不安定化してしまうため、耐熱・耐光性があまり強くなく、またｐＨ５以下で褐変する性質がある。抽出されたクロロフィルでは、化学反応によって中心元素を人工的に置換することができる。特に銅が配位したものはマグネシウムのものよりも光や酸に対して安定であり、化粧品や食品への添加物として利用される。 (chlorophyll pigment)
The chlorophyll pigment used in the present invention is also called chlorophyll. It has a basic structure in which a long-chain alcohol called phytol is ester-bonded to tetrapyrrole, which is a structure in which four pyrroles are wound around a ring. Naturally occurring compounds generally have a structure in which magnesium is coordinated to the tetrapyrrole ring center. Besides magnesium, examples of zinc coordination have been reported in red photosynthetic bacteria. The substance with the metal removed and replaced with two hydrogens is called pheophytin. Chlorophyll is a green pigment that is insoluble in water, soluble in alcohol, and readily soluble in fats and oils, and is the only natural pigment recognized as a coloring agent that exhibits a green color by itself. As described above, the magnesium in the tetrapyrrole ring is easily detached by acid or light and destabilized. In the extracted chlorophyll, the central element can be artificially substituted by chemical reaction. In particular, those with copper coordination are more stable to light and acid than those with magnesium, and are used as additives for cosmetics and foods.
本発明で使用するクロロフィル系色素は、葉緑素とも呼ばれている。４つのピロールが環を巻いた構造であるテトラピロールに、フィトールと呼ばれる長鎖アルコールがエステル結合した基本構造を有する。天然に存在するものは一般にマグネシウムがテトラピロール環中心に配位した構造を有する。マグネシウム以外では、亜鉛が配位した例が紅色光合成細菌において報告されている。金属がはずれ、2つの水素で置換された物質はフェオフィチンと呼ばれる。クロロフィルは水に不溶、アルコールに可溶、油脂に易溶な緑色色素で、着色料として認められている天然色素としては、単独で緑色を呈する唯一の色素である。上記で述べたように、テトラピロール環の中のマグネシウムが酸や光で簡単に離脱して不安定化してしまうため、耐熱・耐光性があまり強くなく、またｐＨ５以下で褐変する性質がある。抽出されたクロロフィルでは、化学反応によって中心元素を人工的に置換することができる。特に銅が配位したものはマグネシウムのものよりも光や酸に対して安定であり、化粧品や食品への添加物として利用される。 (chlorophyll pigment)
The chlorophyll pigment used in the present invention is also called chlorophyll. It has a basic structure in which a long-chain alcohol called phytol is ester-bonded to tetrapyrrole, which is a structure in which four pyrroles are wound around a ring. Naturally occurring compounds generally have a structure in which magnesium is coordinated to the tetrapyrrole ring center. Besides magnesium, examples of zinc coordination have been reported in red photosynthetic bacteria. The substance with the metal removed and replaced with two hydrogens is called pheophytin. Chlorophyll is a green pigment that is insoluble in water, soluble in alcohol, and readily soluble in fats and oils, and is the only natural pigment recognized as a coloring agent that exhibits a green color by itself. As described above, the magnesium in the tetrapyrrole ring is easily detached by acid or light and destabilized. In the extracted chlorophyll, the central element can be artificially substituted by chemical reaction. In particular, those with copper coordination are more stable to light and acid than those with magnesium, and are used as additives for cosmetics and foods.
（銅クロロフィル系色素）
銅クロロフィルと銅クロロフィリンナトリウムは食品衛生法で指定添加物に分類され、着色料として用いられる。天然クロロフィルは光や空気中の酸素に対して不安定で、これを改善するために銅（Cu）と反応させたものが銅クロロフィルである。銅クロロフィリンナトリウムは銅クロロフィルの末端エステルを加水分解したナトリウム塩であり、水溶性且つ、安定で鮮やかな緑色となる。 (copper chlorophyll pigment)
Copper chlorophyll and copper chlorophyllin sodium are classified as designated additives under the Food Sanitation Act and used as coloring agents. Natural chlorophyll is unstable against light and oxygen in the air, and copper chlorophyll is made by reacting with copper (Cu) to improve this. Sodium copper chlorophyllin is a sodium salt obtained by hydrolyzing a terminal ester of copper chlorophyll, which is water-soluble, stable, and bright green.
銅クロロフィルと銅クロロフィリンナトリウムは食品衛生法で指定添加物に分類され、着色料として用いられる。天然クロロフィルは光や空気中の酸素に対して不安定で、これを改善するために銅（Cu）と反応させたものが銅クロロフィルである。銅クロロフィリンナトリウムは銅クロロフィルの末端エステルを加水分解したナトリウム塩であり、水溶性且つ、安定で鮮やかな緑色となる。 (copper chlorophyll pigment)
Copper chlorophyll and copper chlorophyllin sodium are classified as designated additives under the Food Sanitation Act and used as coloring agents. Natural chlorophyll is unstable against light and oxygen in the air, and copper chlorophyll is made by reacting with copper (Cu) to improve this. Sodium copper chlorophyllin is a sodium salt obtained by hydrolyzing a terminal ester of copper chlorophyll, which is water-soluble, stable, and bright green.
本発明に係るクロロフィル系色素としては、クロロフィル系全般の色素を使用することができるが、銅クロロフィル、または銅クロロフィリンナトリウムが、発色、不溶性に関して好ましい。
As the chlorophyll pigment according to the present invention, general chlorophyll pigments can be used, but copper chlorophyll or copper chlorophyllin sodium is preferable in terms of color development and insolubility.
金属、金属化合物）
本発明で使用する金属および金属化合物は、クロロフィル系色素を不溶化するための担持作用を有するものであれば、如何なるものでも使用することができる。金属単体、金属酸化物、金属水酸化物等であり、特にアルミニウム、アルミニウム水酸化物が好適に使用できる。本発明で使用する金属または金属化合物中の金属元素としては、元素の周期表１～１５族に属するもののうち、第１周期及び第２周期のものを除いたものが挙げられる。中でも鉄、コバルト、ニッケル、亜鉛、アルミニウム、チタン等の金属元素の使用が可能であり、それらから選択される１種類以上の金属元素を使用することができる。特に食品、化粧品用途として人体に影響のない金属または金属化合物が好ましく、本発明の実施形態においては、特にアルミニウム、チタン、亜鉛が好ましい。本発明の実施形態において、クロロフィル系色素と金属または金属化合物の物理的吸着をより強固にするために、金属または金属化合物として金属の水酸化物や酸化物が好適に用いられ、特に水酸化アルミニウム、酸化チタン及び酸化亜鉛が好適に用いられる。塩化アルミニウムや４塩化チタン、塩化亜鉛等の塩化物にアルカリを添加し、水酸化アルミニウムや酸化チタン、水酸化亜鉛等のスラリーとしたものを使用したほうが、クロロフィル系色素との物理的吸着がより強くなり、好ましい。さらに、物理的吸着をより強固にするために、金属または金属化合物の表面にクロロフィル系色素が被覆されている状態がより好ましい。被覆の定義として、クロロフィル系色素が金属表面に一部または均一に存在し覆っている状態を示す。金属または金属化合物の粒子の粒径は、用途によって好適な粒径が異なり、金属または金属化合物の粒子の粒子サイズによって色相も異なる。一例として、食品、化粧品用途では１００ｎｍ～２０μｍ、その他用途では５０～５００ｎｍが好ましい。 metals, metal compounds)
Any metal or metal compound can be used as long as it has a supporting action for insolubilizing the chlorophyll 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 strengthen the physical adsorption of chlorophyll-based dyes and metals or metal compounds, particularly aluminum hydroxide. , titanium oxide and zinc oxide are preferably used. Add alkali to chlorides such as aluminum chloride, titanium tetrachloride, zinc chloride, etc., and use aluminum hydroxide, titanium oxide, zinc hydroxide, etc. as a slurry for better physical adsorption with chlorophyll dyes. Be strong and be favorable. Furthermore, in order to make the physical adsorption stronger, it is more preferable that the surface of the metal or metal compound is coated with a chlorophyll-based dye. As the definition of coating, it indicates a state in which a chlorophyll-based dye 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.
本発明で使用する金属および金属化合物は、クロロフィル系色素を不溶化するための担持作用を有するものであれば、如何なるものでも使用することができる。金属単体、金属酸化物、金属水酸化物等であり、特にアルミニウム、アルミニウム水酸化物が好適に使用できる。本発明で使用する金属または金属化合物中の金属元素としては、元素の周期表１～１５族に属するもののうち、第１周期及び第２周期のものを除いたものが挙げられる。中でも鉄、コバルト、ニッケル、亜鉛、アルミニウム、チタン等の金属元素の使用が可能であり、それらから選択される１種類以上の金属元素を使用することができる。特に食品、化粧品用途として人体に影響のない金属または金属化合物が好ましく、本発明の実施形態においては、特にアルミニウム、チタン、亜鉛が好ましい。本発明の実施形態において、クロロフィル系色素と金属または金属化合物の物理的吸着をより強固にするために、金属または金属化合物として金属の水酸化物や酸化物が好適に用いられ、特に水酸化アルミニウム、酸化チタン及び酸化亜鉛が好適に用いられる。塩化アルミニウムや４塩化チタン、塩化亜鉛等の塩化物にアルカリを添加し、水酸化アルミニウムや酸化チタン、水酸化亜鉛等のスラリーとしたものを使用したほうが、クロロフィル系色素との物理的吸着がより強くなり、好ましい。さらに、物理的吸着をより強固にするために、金属または金属化合物の表面にクロロフィル系色素が被覆されている状態がより好ましい。被覆の定義として、クロロフィル系色素が金属表面に一部または均一に存在し覆っている状態を示す。金属または金属化合物の粒子の粒径は、用途によって好適な粒径が異なり、金属または金属化合物の粒子の粒子サイズによって色相も異なる。一例として、食品、化粧品用途では１００ｎｍ～２０μｍ、その他用途では５０～５００ｎｍが好ましい。 metals, metal compounds)
Any metal or metal compound can be used as long as it has a supporting action for insolubilizing the chlorophyll 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 strengthen the physical adsorption of chlorophyll-based dyes and metals or metal compounds, particularly aluminum hydroxide. , titanium oxide and zinc oxide are preferably used. Add alkali to chlorides such as aluminum chloride, titanium tetrachloride, zinc chloride, etc., and use aluminum hydroxide, titanium oxide, zinc hydroxide, etc. as a slurry for better physical adsorption with chlorophyll dyes. Be strong and be favorable. Furthermore, in order to make the physical adsorption stronger, it is more preferable that the surface of the metal or metal compound is coated with a chlorophyll-based dye. As the definition of coating, it indicates a state in which a chlorophyll-based dye 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.
（非水溶性且つ非油溶性色素組成物）
クロロフィル系色素単体は染料の形態であるため油溶性、または水溶性である。本発明では、強固に金属または金属化合物に、クロロフィル系色素が被覆、含浸、複合化、あるいは吸着された非水溶性且つ非油溶性色素組成物とすることで、水と溶剤に不溶となることを見出したものである。不溶化のメカニズムとしては、下記に一例を示しているが、これに限定されるものではない。
クロロフィル系色素は、構造中にカルボニル基、エステル、カルボン酸をはじめとした酸素官能基が数多く存在する。そのため、クロロフィル系色素は、水溶液のｐＨを変化させたときの分子電荷が大きく変化する。同様に、金属化合物も水溶液中でのｐＨ変化における粒子電荷の変化が大きい。そのため、これら二つの物質の水分散液のｐＨを調整することにより、金属化合物とクロロフィル系色素が電気的な相互作用により物理吸着し、複合体として析出、水と溶剤にに不溶化した、と考えている。 (Water-insoluble and oil-insoluble dye composition)
Since the chlorophyll-based dye alone is in the form of a dye, it is oil-soluble or water-soluble. In the present invention, by forming a water-insoluble and oil-insoluble dye composition in which a chlorophyll-based dye is firmly coated, impregnated, complexed, or adsorbed on a metal or metal compound, it becomes insoluble in water and solvents. This is what I found. An example of the insolubilization mechanism is shown below, but it is not limited to this.
Chlorophyll dyes have many oxygen functional groups such as carbonyl groups, esters, and carboxylic acids in their structures. Therefore, the chlorophyll-based pigment undergoes a large change in molecular charge when the pH of the aqueous solution is changed. 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 chlorophyll pigment physically adsorbed through electrical interaction, precipitated as a complex, and became insoluble in water and solvents. ing.
クロロフィル系色素単体は染料の形態であるため油溶性、または水溶性である。本発明では、強固に金属または金属化合物に、クロロフィル系色素が被覆、含浸、複合化、あるいは吸着された非水溶性且つ非油溶性色素組成物とすることで、水と溶剤に不溶となることを見出したものである。不溶化のメカニズムとしては、下記に一例を示しているが、これに限定されるものではない。
クロロフィル系色素は、構造中にカルボニル基、エステル、カルボン酸をはじめとした酸素官能基が数多く存在する。そのため、クロロフィル系色素は、水溶液のｐＨを変化させたときの分子電荷が大きく変化する。同様に、金属化合物も水溶液中でのｐＨ変化における粒子電荷の変化が大きい。そのため、これら二つの物質の水分散液のｐＨを調整することにより、金属化合物とクロロフィル系色素が電気的な相互作用により物理吸着し、複合体として析出、水と溶剤にに不溶化した、と考えている。 (Water-insoluble and oil-insoluble dye composition)
Since the chlorophyll-based dye alone is in the form of a dye, it is oil-soluble or water-soluble. In the present invention, by forming a water-insoluble and oil-insoluble dye composition in which a chlorophyll-based dye is firmly coated, impregnated, complexed, or adsorbed on a metal or metal compound, it becomes insoluble in water and solvents. This is what I found. An example of the insolubilization mechanism is shown below, but it is not limited to this.
Chlorophyll dyes have many oxygen functional groups such as carbonyl groups, esters, and carboxylic acids in their structures. Therefore, the chlorophyll-based pigment undergoes a large change in molecular charge when the pH of the aqueous solution is changed. 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 chlorophyll pigment physically adsorbed through electrical interaction, precipitated as a complex, and became insoluble in water and solvents. ing.
本発明によって得られた不溶化により、食品や化粧品用途に限定されていたクロロフィル系色素を、通常の顔料と同等の着色材として、食品、化粧品、医薬品または農薬のコーティング材または印字マーカー、文房具、筆記具、印刷インキ、インクジェットインキ、金属インキ、塗料、プラスチック着色剤、カラートナー、蛍光標識剤、蛍光プローブ、または化学センサー等の用途に使用できうる耐性まで向上することができたものである。また、不溶化に伴い、耐熱性、耐光性等の特性向上も期待できる。なお、本発明の非水溶性且つ非油溶性色素組成物の用途は、上記の用途に限定されるものではない。
Due to the insolubilization obtained by the present invention, chlorophyll-based 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 and oil-insoluble dye composition of the present invention are not limited to the above uses.
本発明の非水溶性且つ非油溶性色素組成物として、クロロフィル系色素と金属または金属化合物の組成の質量比は、任意に設計が可能であり、クロロフィル系色素：金属または金属化合物＝０．１：９９．９～９９．９：０．１の割合で設定して使用することができる。好ましくは、クロロフィル系色素：金属または金属化合物＝０．１：９９．９～９０：１０である。
As the water-insoluble and oil-insoluble dye composition of the present invention, the mass ratio of the composition of the chlorophyll dye and the metal or metal compound can be arbitrarily designed, and the chlorophyll dye: metal or metal compound = 0.1. :99.9 to 99.9:0.1. Preferably, the chlorophyll-based pigment:metal or metal compound=0.1:99.9 to 90:10.
（非水溶性且つ非油溶性色素組成物の製造方法）
本発明の非水溶性色かつ非油溶性素組成物を製造する方法としては、溶媒中でクロロフィル系色素と金属または金属化合物を混合する方法が、最も均一な非水溶性且つ非油溶性色素組成物を製造できるため好ましい。 (Method for producing water-insoluble and oil-insoluble dye composition)
As a method for producing the water-insoluble color and oil-insoluble pigment composition of the present invention, a method of mixing a chlorophyll-based pigment and a metal or a metal compound in a solvent is the most uniform water-insoluble and oil-insoluble pigment composition. It is preferable because it can manufacture things.
本発明の非水溶性色かつ非油溶性素組成物を製造する方法としては、溶媒中でクロロフィル系色素と金属または金属化合物を混合する方法が、最も均一な非水溶性且つ非油溶性色素組成物を製造できるため好ましい。 (Method for producing water-insoluble and oil-insoluble dye composition)
As a method for producing the water-insoluble color and oil-insoluble pigment composition of the present invention, a method of mixing a chlorophyll-based pigment and a metal or a metal compound in a solvent is the most uniform water-insoluble and oil-insoluble pigment composition. It is preferable because it can manufacture things.
溶媒中で各物質を混合する非水溶性且つ非油溶性色素組成物の製造方法としては、１）まず金属または金属化合物を酸や塩基の希釈水溶液に溶解し、溶液を作成する。２）一方でクロロフィル系色素または、クロロフィル系色素を含有する調剤を水に溶解、又は分散させ、水溶液又は水分散液を作成する。３）次に上記２つの液を混合して混合液を作成する。４）さらに混合液にｐＨ調整剤を添加しｐＨを調整することで非水溶性且つ非油溶性色素組成物を含む混合液を作成する。５）得られた非水溶性且つ非油溶性色素組成物を含む混合液を濾過、乾燥する方法が挙げられる。
As a method for producing a water-insoluble and oil-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 chlorophyll-based dye or a preparation containing a chlorophyll-based dye is dissolved or dispersed in water to prepare an aqueous solution or aqueous dispersion. 3) Next, the above two liquids are mixed to prepare a mixed liquid. 4) Further, a pH adjuster is added to the mixture to adjust the pH, thereby preparing a mixture containing the water-insoluble and oil-insoluble dye composition. 5) A method of filtering and drying the resulting mixture containing the water-insoluble and oil-insoluble dye composition.
金属または金属化合物溶液とクロロフィル系色素含有水溶液、又は水分散液を混合する方法としては、金属または金属化合物溶液にクロロフィル系色素含有水溶液又は水分散液を混合しても良いし、クロロフィル系色素を粉体のまま加えて混合しても良いし、その逆にクロロフィル系色素含有水溶液又は水分散液に金属または金属化合物溶液を混合しても良いし、これら２つの液を少量ずつ混合しながら作成しても構わない。また、金属または金属化合物溶液は、金属または金属化合物が液中に完全溶解していてもよいし、金属または金属化合物が液中に一部のみ溶解し一部は液中に分散している状態でもよい。混合する温度は、室温でもよいし加熱してもよい。クロロフィル系色素の分解温度を考慮し、１０～６０℃で混合するのが好ましく、２０～５０℃がより好ましい。また、金属または金属化合物溶液とクロロフィル系色素含有水溶液又は水分散液を混合する際のｐＨの範囲は、２．０～６．０が好ましく、３．０～５．０に調整することがさらに好ましい。
As a method for mixing the metal or metal compound solution and the chlorophyll dye-containing aqueous solution or aqueous dispersion, the metal or metal compound solution may be mixed with the chlorophyll dye-containing aqueous solution or aqueous dispersion, or the chlorophyll dye may be mixed. The powder may be added and mixed as it is, or conversely, the metal or metal compound solution may be mixed with the chlorophyll pigment-containing aqueous solution or aqueous dispersion, or these two liquids may be mixed little by little. I don't mind. 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. The temperature for mixing may be room temperature or may be heated. Considering the decomposition temperature of the chlorophyll pigment, the mixing temperature is preferably 10 to 60°C, more preferably 20 to 50°C. Further, the pH range when mixing the metal or metal compound solution and the chlorophyll dye-containing aqueous solution or aqueous dispersion is preferably 2.0 to 6.0, and more preferably adjusted to 3.0 to 5.0. preferable.
ｐＨを調整する際のｐＨ調整剤としては、水酸化ナトリウム、水酸化カリウムなどの水溶液が挙げられる。ｐＨ調整剤を添加したときの混合液のｐＨの範囲は、混合液中で金属または金属化合物と、クロロフィル系色素を効率的に吸着させ不溶化させる観点から６．０～８．５が好ましく、６．５～８．０に調整することがさらに好ましい。
Aqueous solutions such as sodium hydroxide and potassium hydroxide can be used as pH adjusters when adjusting the pH. 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 chlorophyll-based dye in the mixed solution. It is more preferable to adjust to 0.5 to 8.0.
得られた非水溶性且つ非油溶性色素組成物を含む混合液を濾過、乾燥し、非水溶性且つ非油溶性色素組成物を得ることができる。混合液をヌッチェ等のろ過器でろ過したとき、ろ液に着色がないことから、クロロフィル系色素と金属または金属化合物が吸着していることを確認できる。また、得られた非水溶性且つ非油溶性色素組成物の水含有ウェットケーキは、室温や加熱、真空、減圧乾燥等により乾燥し、ドライの非水溶性且つ非油溶性色素組成物を得ることができる。乾燥方法、乾燥機は、通常の方法、装置であればいかなるものでも可能であり、限定されるものではない。
The resulting mixture containing the water-insoluble and oil-insoluble dye composition is filtered and dried to obtain the water-insoluble and oil-insoluble dye composition. When the mixed liquid was filtered with a filter such as Nutsche, the filtrate was not colored, so it was confirmed that the chlorophyll-based pigment and the metal or metal compound were adsorbed. In addition, the water-containing wet cake of the obtained water-insoluble and oil-insoluble dye composition is dried at room temperature, by heating, in vacuum, by drying under reduced pressure, etc., to obtain a dry water-insoluble and oil-insoluble dye composition. can be done. The drying method and the dryer are not limited as long as they are ordinary methods and devices.
本発明の非水溶性且つ非油溶性色素組成物は、上記の水が含有したウェットケーキであっても乾燥したドライの非水溶性且つ非油溶性色素組成物であっても、用途によって使い分けが可能である。水系の分散液、インキに使用する場合は、ウェットケーキをそのまま使用が可能であり、溶剤分散系で使用する場合は、水系から溶剤系に置換し、使用が可能である。ドライの非水溶性且つ非油溶性色素組成物は、そのままでも使用可能であるし、水、または有機溶媒、樹脂溶液等に再分散させて使用することももちろん可能である。
The water-insoluble and oil-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 and oil-insoluble dye composition. It is possible. When used in water-based dispersions and inks, the wet cake can be used as it is, and when used in solvent-dispersed systems, it can be used after replacing the water-based with solvent-based. The dry water-insoluble and oil-insoluble dye composition can be used as it is, or can of course be used after being redispersed in water, an organic solvent, a resin solution, or the like.
（安定化剤、添加剤）
本発明の非水溶性且つ非油溶性色素組成物に、他の有機顔料、無機顔料、染料、色素を任意の割合で混合することももちろん可能であり、所望の要求される色相を満たすことができる。
本発明の非水溶性且つ非油溶性色素組成物を更に耐光性、耐熱性を付与するために、安定化剤や添加剤を添加することもできる。 (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 and oil-insoluble dye composition of the present invention, and the desired hue can be satisfied. can.
Stabilizers and additives can also be added to the water-insoluble and oil-insoluble dye composition of the present invention in order to further impart light resistance and heat resistance.
本発明の非水溶性且つ非油溶性色素組成物に、他の有機顔料、無機顔料、染料、色素を任意の割合で混合することももちろん可能であり、所望の要求される色相を満たすことができる。
本発明の非水溶性且つ非油溶性色素組成物を更に耐光性、耐熱性を付与するために、安定化剤や添加剤を添加することもできる。 (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 and oil-insoluble dye composition of the present invention, and the desired hue can be satisfied. can.
Stabilizers and additives can also be added to the water-insoluble and oil-insoluble dye composition of the present invention in order to further impart light resistance and heat resistance.
安定化剤、添加剤は、金属水酸化物の水溶液または、クロロフィル系色素含有水溶液各々または両方に添加することも可能であるし、作成された非水溶性且つ非油溶性色素組成物に添加しても良い。
Stabilizers and additives can be added to each or both of the aqueous solution of the metal hydroxide and the aqueous solution containing the chlorophyll dye, or added to the prepared water-insoluble and oil-insoluble dye composition. can be
本発明の非水溶性且つ非油溶性色素組成物は、必要に応じて、他の樹脂、ゴム、添加剤、顔料や染料等と混合され最終的な食品、化粧品、医薬品または農薬のコーティング材または印字マーカー、文房具、筆記具、印刷インキ、インクジェットインキ、金属インキ、塗料、プラスチック着色剤、カラートナー、蛍光標識剤、蛍光プローブ、または化学センサー等に調整され使用される。以下、上記用途の一例を示す。
The water-insoluble and oil-insoluble dye composition of the present invention is optionally mixed with other resins, rubbers, additives, pigments, dyes, etc., and is used as the final coating material for food, cosmetics, pharmaceuticals, or agricultural chemicals. It can be adjusted and used for printing markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, paints, plastic coloring agents, color toners, fluorescent labeling agents, fluorescent probes, chemical sensors, and the like. An example of the above application is shown below.
（化粧品用途）
本発明の非水溶性且つ非油溶性色素組成物は、化粧品として使用できる。使用される化粧品には特に制限はなく、本発明の非水溶性且つ非油溶性色素組成物は、様々なタイプの化粧品に使用することができる。 (Cosmetics use)
The water-insoluble and oil-insoluble dye composition of the present invention can be used as cosmetics. The cosmetics used are not particularly limited, and the water-insoluble and oil-insoluble dye composition of the present invention can be used in various types of cosmetics.
本発明の非水溶性且つ非油溶性色素組成物は、化粧品として使用できる。使用される化粧品には特に制限はなく、本発明の非水溶性且つ非油溶性色素組成物は、様々なタイプの化粧品に使用することができる。 (Cosmetics use)
The water-insoluble and oil-insoluble dye composition of the present invention can be used as cosmetics. The cosmetics used are not particularly limited, and the water-insoluble and oil-insoluble dye composition of the present invention can be used in various types of cosmetics.
前記化粧品は、機能を有効に発現することができる限り、いかなるタイプの化粧品であってもよい。前記化粧品は、ローション、クリームゲル、スプレー等であってよい。前記化粧品としては、洗顔料、メーク落とし、化粧水、美容液、パック、保護用乳液、保護用クリーム、美白化粧品、紫外線防止化粧品等のスキンケア化粧品、ファンデーション、白粉、化粧下地、口紅、アイメークアップ、頬紅、ネイルエナメル等のメークアップ化粧品、シャンプー、ヘアリンス、ヘアトリートメント、整髪剤、パーマネント・ウェーブ剤、染毛剤、育毛剤等のヘアケア化粧品、身体洗浄用化粧品、デオドラント化粧品、浴用剤等のボディケア化粧品などを挙げることができる。
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.
前記化粧品に使用される本発明の非水溶性且つ非油溶性色素組成物の量は、化粧品の種類に応じて適宜設定することができる。前記化粧品中の含有量が通常０．１～９９質量％の範囲であり、一般的には、０．１～１０質量％の範囲となるような量であることが好ましい。一方で、着色が目的のメークアップ化粧品では、好ましくは５～８０質量％の範囲、さらに好ましくは１０～７０質量％の範囲、最も好ましくは２０～６０質量％の範囲となるような量であることが好ましい。前記化粧品に含まれる本発明の非水溶性且つ非油溶性色素組成物の量が前記範囲であると、着色性等の機能を有効に発現することができ、かつ化粧品に要求される機能も保持することができる。
The amount of the water-insoluble and oil-insoluble dye composition of the present invention used in the cosmetics can be appropriately set according to the type of the 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 and oil-insoluble dye composition of the present invention contained in the cosmetic product is within the above range, it is possible to effectively express functions such as coloring properties, and to retain the functions required for the cosmetic product. can do.
前記化粧品は、化粧品の種類に応じて、本発明の非水溶性且つ非油溶性色素組成物の他、化粧品成分として許容可能な、担体、顔料、油、ステロール、アミノ酸、保湿剤、粉体、着色剤、ｐＨ調整剤、香料、精油、化粧品活性成分、ビタミン、必須脂肪酸、スフィンゴ脂質、セルフタンニング剤、賦形剤、充填剤、乳化剤、酸化防止剤、界面活性剤、キレート剤、ゲル化剤、濃厚剤、エモリエント剤、湿潤剤、保湿剤、鉱物、粘度調整剤、流動調整剤、角質溶解剤、レチノイド、ホルモン化合物、アルファヒドロキシ酸、アルファケト酸、抗マイコバクテリア剤、抗真菌剤、抗菌剤、抗ウイルス剤、鎮痛剤、抗アレルギー剤、抗ヒスタミン剤、抗炎症剤、抗刺激剤、抗腫瘍剤、免疫系ブースト剤、免疫系抑制剤、抗アクネ剤、麻酔剤、消毒剤、防虫剤、皮膚冷却化合物、皮膚保護剤、皮膚浸透増強剤、剥脱剤（ｅｘｆｏｌｉａｎｔ）、潤滑剤、芳香剤、染色剤、脱色剤、色素沈着低下剤（ｈｙｐｏｐｉｇｍｅｎｔｉｎｇ ａｇｅｎｔ）、防腐剤、安定剤、医薬品、光安定化剤、及び球形粉末等を含むことができる。
Depending on the type of cosmetic, the cosmetic may include the water-insoluble and oil-insoluble dye composition of the present invention, as well as carriers, pigments, oils, sterols, amino acids, moisturizers, powders, and other ingredients acceptable as cosmetic ingredients. Colorants, pH adjusters, 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, Humectants, Minerals, Viscosity Modifiers, Flow Control Agents, Keratolytics, Retinoids, Hormonal Compounds, Alpha Hydroxy Acids, Alpha Keto Acids, Antimycobacterials, Antifungals, Antimicrobials antiviral agents, analgesics, antiallergic agents, antihistamines, antiinflammatory agents, antiirritants, antitumor agents, immune system boosters, immune system suppressants, antiacne agents, anesthetics, disinfectants, insect repellents, Skin cooling compounds, skin protectants, skin penetration enhancers, exfoliants, lubricants, fragrances, dyes, bleaching agents, hypopigmenting agents, preservatives, stabilizers, pharmaceuticals, photostabilizers agents, spherical powders, and the like.
前記化粧品は、本発明の非水溶性且つ非油溶性色素組成物およびその他の化粧品成分を混合することによって製造することができる。
また、本発明の非水溶性且つ非油溶性色素組成物を含む化粧品は、該化粧品のタイプ等に応じて、通常の化粧品と同様に使用することができる。 The cosmetics can be produced by mixing the water-insoluble and oil-insoluble pigment composition of the present invention and other cosmetic ingredients.
Cosmetics containing the water-insoluble and oil-insoluble dye composition of the present invention can be used in the same manner as ordinary cosmetics, depending on the type of the cosmetic.
また、本発明の非水溶性且つ非油溶性色素組成物を含む化粧品は、該化粧品のタイプ等に応じて、通常の化粧品と同様に使用することができる。 The cosmetics can be produced by mixing the water-insoluble and oil-insoluble pigment composition of the present invention and other cosmetic ingredients.
Cosmetics containing the water-insoluble and oil-insoluble dye composition of the present invention can be used in the same manner as ordinary cosmetics, depending on the type of the cosmetic.
（インキ、塗料用途）
本発明の非水溶性且つ非油溶性色素組成物は、インキ、塗料として使用できる。ただし、インキ、塗料の用途、組成について記述するが、これらに限定されるものではない。
また本発明の非水溶性且つ非油溶性色素組成物は、熱可塑性樹脂のみに分散させてもよいが、熱可塑性樹脂を必須成分として含有する印刷インキ用ビヒクルや塗料用ビヒクル等に分散させることも出来る。 (For ink and paint applications)
The water-insoluble and oil-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 and oil-insoluble dye composition of the present invention may be dispersed only in a thermoplastic resin, but may be dispersed in a vehicle for printing ink, a vehicle for paint, etc. containing a thermoplastic resin as an essential component. can also
本発明の非水溶性且つ非油溶性色素組成物は、インキ、塗料として使用できる。ただし、インキ、塗料の用途、組成について記述するが、これらに限定されるものではない。
また本発明の非水溶性且つ非油溶性色素組成物は、熱可塑性樹脂のみに分散させてもよいが、熱可塑性樹脂を必須成分として含有する印刷インキ用ビヒクルや塗料用ビヒクル等に分散させることも出来る。 (For ink and paint applications)
The water-insoluble and oil-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 and oil-insoluble dye composition of the present invention may be dispersed only in a thermoplastic resin, but may be dispersed in a vehicle for printing ink, a vehicle for paint, etc. containing a thermoplastic resin as an essential component. can also
熱可塑性樹脂としては、たとえばポリエステル樹脂、ポリアミド樹脂、スチレン樹脂、アクリル樹脂、ポリオレフィン、ポリアルキレンテレフタレートやポリ塩化ビニル樹脂等の樹脂が分散用樹脂として使用できる。
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.
たとえば平版印刷用インキのビヒクルは、たとえばロジン変性フェノール樹脂、石油樹脂、アルキッド樹脂等の樹脂を２０～５０（質量）％、アマニ油、桐油、大豆油等の動植物油を０～３０（質量）％、ｎ－パラフィン、イソパラフィン、ナフテン、α－オレフィン、アロマティック等の溶剤を１０～６０（質量）％、その他可溶化剤、ゲル化剤等の添加剤を数（質量）％の原料から製造される。
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 at 10-60% (mass), and other additives such as solubilizers and gelling agents at several (mass)%. be done.
またグラビア印刷インキ、フレキソ印刷インキ用ビヒクルの場合は、たとえばロジン類、マレイン酸樹脂、ポリアミド樹脂、ビニル樹脂、環化ゴム、塩化ゴム、エチレン－酢酸ビニル共重合体樹脂、ウレタン樹脂、ポリエステル樹脂、アルキド樹脂、ニトロセルロース、酢酸セルロース等から選ばれる一種以上の樹脂を１０～５０（質量）％、アルコール類、トルエン、ｎ－ヘキサン、酢酸エチル、セロソルブ、酢酸ブチルセロソルブ等の溶剤３０～８０（質量）％の原料等から製造される。
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.
塗料用のビヒクルでは、たとえばアルキド樹脂、エポキシ樹脂、アクリル樹脂、ポリウレタン樹脂、ポリエステル樹脂、メラミン樹脂、ユリア樹脂、水溶性樹脂等の樹脂２０～８０（質量）％、炭化水素類、アルコール類、ケトン類、水等の溶剤１０～６０（質量）％の原料等から製造される。
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.
（プラスチック用途）
本発明の非水溶性且つ非油溶性色素組成物はプラスチック着色用途にも使用できる。着色プラスチック成形品を得る場合には、たとえばポリエチレン、ポリプロピレン等のポリオレフィンやポリ塩化ビニル樹脂等の、射出成形やプレス成形等の熱成形用の熱可塑性樹脂（プラスチック）が用いられるが、本発明の非水溶性且つ非油溶性色素組成物はこれらの樹脂に従来公知の方法で練り込んで使用することができる。 (for plastics)
The water-insoluble and oil-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 and oil-insoluble dye composition can be used by kneading into these resins by a conventionally known method.
本発明の非水溶性且つ非油溶性色素組成物はプラスチック着色用途にも使用できる。着色プラスチック成形品を得る場合には、たとえばポリエチレン、ポリプロピレン等のポリオレフィンやポリ塩化ビニル樹脂等の、射出成形やプレス成形等の熱成形用の熱可塑性樹脂（プラスチック）が用いられるが、本発明の非水溶性且つ非油溶性色素組成物はこれらの樹脂に従来公知の方法で練り込んで使用することができる。 (for plastics)
The water-insoluble and oil-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 and oil-insoluble dye composition can be used by kneading into these resins by a conventionally known method.
（トナー用途）
本発明の非水溶性且つ非油溶性色素組成物はトナー着色用途にも使用できる。
静電荷像現像用トナーを得る場合には、たとえばポリエステル樹脂、ポリアミド樹脂、スチレン樹脂、アクリル樹脂等の常温で固形の皮膜形成性の熱可塑性樹脂が分散用樹脂として使用される。 (for toner)
The water-insoluble and oil-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.
本発明の非水溶性且つ非油溶性色素組成物はトナー着色用途にも使用できる。
静電荷像現像用トナーを得る場合には、たとえばポリエステル樹脂、ポリアミド樹脂、スチレン樹脂、アクリル樹脂等の常温で固形の皮膜形成性の熱可塑性樹脂が分散用樹脂として使用される。 (for toner)
The water-insoluble and oil-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.
本発明の非水溶性且つ非油溶性色素組成物を構成成分として製造される静電荷像現像用トナーは、トナー中に磁性体を含有する１成分色磁性トナー（磁性一成分現像用カラートナー）、磁性体を含有しない非磁性１成分色カラートナー（非磁性一成分現像用カラートナー）、又は、キャリアーを混合した２成分色現像剤用カラートナー（二成分現像用カラートナー）として用いることができる。
The electrostatic charge image developing toner produced using the water-insoluble and oil-insoluble dye composition of the present invention as a constituent component is a one-component color magnetic toner (color toner for magnetic one-component development) containing a magnetic substance in the toner. 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 magnetic substance, or a color toner for a two-component color developer mixed with a carrier (color toner for two-component development). can.
１成分色磁性トナーは、通常使用されているものと同様に、例えば着色剤、結着樹脂、磁性粉、電荷制御剤（ＣＣＡ）や離型剤に代表されるその他添加剤等から構成出来る。
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.
静電荷像現像用トナー中に占める非水溶性且つ非油溶性色素組成物の使用量は特に限定されないが、結着樹脂１００質量部に対し０．５～２５質量部の割合で使用することが好ましく、着色剤自身の有する帯電性能を一層顕著ならしめる点から結着樹脂１００質量部に対し４～１０質量部であることが更に好ましい。
The amount of the water-insoluble and oil-insoluble dye composition used in the toner for electrostatic charge image development is not particularly limited, but it can be used at a rate of 0.5 to 25 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, the amount is from 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 colorant itself more remarkable.
静電荷像現像用トナーに用いられる結着樹脂としては、前記熱可塑性樹脂として例示した公知慣用のものがいずれも使用できるが、熱又は圧力の適用下で接着性を示す合成樹脂、天然樹脂、天然ゴム、合成ゴム、合成ワックス等がいずれも使用できる。
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.
（蛍光標識剤、蛍光プローブ用途）
クロロフィル系色素は赤色蛍光性を有することが知られている。本発明のクロロフィル系色素組成物において、クロロフィル系色素はその構造は維持されることから、蛍光性を利用した用途、例えば蛍光標識剤、蛍光プローブ等に使用することができる。 (for fluorescent labeling agents and fluorescent probes)
Chlorophyll pigments are known to have red fluorescence. In the chlorophyll-based dye composition of the present invention, since the chlorophyll-based dye composition maintains its structure, it can be used for applications utilizing fluorescence, such as fluorescent labeling agents and fluorescent probes.
クロロフィル系色素は赤色蛍光性を有することが知られている。本発明のクロロフィル系色素組成物において、クロロフィル系色素はその構造は維持されることから、蛍光性を利用した用途、例えば蛍光標識剤、蛍光プローブ等に使用することができる。 (for fluorescent labeling agents and fluorescent probes)
Chlorophyll pigments are known to have red fluorescence. In the chlorophyll-based dye composition of the present invention, since the chlorophyll-based dye composition maintains its structure, it can be used for applications utilizing fluorescence, such as fluorescent labeling agents and fluorescent probes.
例えば、本発明のクロロフィル系色素組成物における金属または金属化合物に、さらに所望の標的生体分子を分子認識する物質を表面に結合もしくは吸着させることによって蛍光標識剤とすることができる。具体的には検体（例えば、任意の細胞抽出液、溶菌液、培地・培養液、溶液、バッファー）中の標的生体分子（生理活性物質を含む。）を蛍光標識付けすることができる。前記標的生体分子を分子認識する物質としては、抗体、抗原、ペプチド、ＤＮＡ、ＲＮＡ、糖鎖、リガンド、受容体、化学物質等が挙げられる。前記標的生体分子との分子認識が、抗原－抗体反応である場合は、免疫染色用試薬とすることも可能である。
For example, the metal or metal compound in the chlorophyll-based 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.
（化学センサー用途）
クロロフィル系色素はｐＨがにより色相が変化する。よって、ｐＨを検出するための化学センサーとして使用することもできる。 (for chemical sensors)
The hue of chlorophyll-based dyes changes depending on the pH. Therefore, it can also be used as a chemical sensor for detecting pH.
クロロフィル系色素はｐＨがにより色相が変化する。よって、ｐＨを検出するための化学センサーとして使用することもできる。 (for chemical sensors)
The hue of chlorophyll-based dyes changes depending on the pH. Therefore, it can also be used as a chemical sensor for detecting pH.
例えば、環境河川水、地下水、産業排水中に含まれるイオンを簡便に検出することができる。日常的な環境モニタリングや工場排水の管理等において、その手段として、大型の測定機器による機器分析を使用するには、時間、コスト、及び労力の点で問題が多いが、本発明のクロロフィル系色素組成物を用いることで、測定の現場で、簡便にｐＨ変化を観測でき、また、非水溶性であることより、濾別等で回収できるため、水性媒体に色素を流出させることもなく工程管理に使用することも可能である。
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 large-sized measuring instruments as a means, but the chlorophyll-based 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
以下に実施例を挙げて本発明を更に詳述するが、本発明の範囲はこれらの実施例に限定されるものではない。
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.
（実施例１）
２Ｌビーカーに塩化アルミニウム（III）六水和物（関東化学株式会社製）４６．４ｇをイオン交換水１０００ｍＬに溶解した。続いて、４８％水酸化ナトリウム水溶液（関東化学株式会社製）より希釈調製した４．８％水酸化ナトリウム水溶液を加え、ｐＨを４．０とし、水酸化アルミニウムのスラリーとした。この溶液に、銅クロロフィル粉末４．５０ｇを加え、室温で１時間後、４．８％水酸化ナトリウム水溶液を加え、ｐＨを７．０とし、３０分攪拌した。濾過後の固体を真空乾燥機（７４０ｍｍＨｇ）で３０℃、１４時間乾燥し、粉体（１）１７．１ｇを得た。粉体（１）の収量から、仕込んだクロロフィル色素分を差し引いて求めた、粉体（１）中の水酸化アルミニウムとクロロフィル色素の組成比率は、質量比で、水酸化アルミニウム：クロロフィル色素＝７４：２６だった。得られた粉体（１）はクロロフィル色素と同系の緑色を呈した。１０ｍＬバイヤルに粉体（１）１０ｍｇと水１．０ｇを添加後、５分間攪拌し、分散液（１）を作製した。分散液（１）をろ紙上に１滴滴下したところ、滴下部分は円状に緑色に呈色し、その後同心円状に無色透明の液が広がっていく様子が観察された。初めに円状に緑色に呈色した部分は水に不溶化した粉体（１）、その後同心円状に透明の液が広がった部分は水であり、粉体（１）は水に不溶であったことが分かった。次に、１０ｍＬバイヤルに粉体（１）１０ｍｇとエタノール１．０ｇを添加後、５分間攪拌し、分散液（２）を作製した。分散液（２）をろ紙上に１滴滴下したところ、滴下部分は円状に緑色に呈色し、その後同心円状に無色透明の液が広がっていく様子が観察された。初めに円状に緑色に呈色した部分はエタノールに不溶化した粉体（２）、その後同心円状に透明の液が広がった部分はエタノールであり、粉体（２）はエタノールに不溶であったことが分かった。 (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, 4.50 g of copper chlorophyll powder was added, and after 1 hour at room temperature, a 4.8% sodium hydroxide aqueous solution was added to adjust the pH to 7.0, and the mixture was stirred for 30 minutes. The filtered solid was dried in a vacuum dryer (740 mmHg) at 30° C. for 14 hours to obtain 17.1 g of powder (1). The composition ratio of aluminum hydroxide and chlorophyll pigment in powder (1), which is obtained by subtracting the chlorophyll pigment charged from the yield of powder (1), is aluminum hydroxide:chlorophyll pigment = 74 in mass ratio. : was 26. The powder (1) thus obtained exhibited a green color similar to that of chlorophyll pigments. 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 green in a circular shape, and then the colorless and transparent liquid spread concentrically. The green circular portion at first was the water-insoluble powder (1), and the portion where the transparent liquid spread concentrically was water, and the powder (1) was insoluble in water. I found out. Next, after adding 10 mg of powder (1) and 1.0 g of ethanol 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 turned green in a circular shape, and then it was observed that the colorless and transparent liquid spread concentrically. The green circular portion at first was the powder (2) insoluble in ethanol, and the portion where the transparent liquid spread concentrically was ethanol, and the powder (2) was insoluble in ethanol. I found out.
２Ｌビーカーに塩化アルミニウム（III）六水和物（関東化学株式会社製）４６．４ｇをイオン交換水１０００ｍＬに溶解した。続いて、４８％水酸化ナトリウム水溶液（関東化学株式会社製）より希釈調製した４．８％水酸化ナトリウム水溶液を加え、ｐＨを４．０とし、水酸化アルミニウムのスラリーとした。この溶液に、銅クロロフィル粉末４．５０ｇを加え、室温で１時間後、４．８％水酸化ナトリウム水溶液を加え、ｐＨを７．０とし、３０分攪拌した。濾過後の固体を真空乾燥機（７４０ｍｍＨｇ）で３０℃、１４時間乾燥し、粉体（１）１７．１ｇを得た。粉体（１）の収量から、仕込んだクロロフィル色素分を差し引いて求めた、粉体（１）中の水酸化アルミニウムとクロロフィル色素の組成比率は、質量比で、水酸化アルミニウム：クロロフィル色素＝７４：２６だった。得られた粉体（１）はクロロフィル色素と同系の緑色を呈した。１０ｍＬバイヤルに粉体（１）１０ｍｇと水１．０ｇを添加後、５分間攪拌し、分散液（１）を作製した。分散液（１）をろ紙上に１滴滴下したところ、滴下部分は円状に緑色に呈色し、その後同心円状に無色透明の液が広がっていく様子が観察された。初めに円状に緑色に呈色した部分は水に不溶化した粉体（１）、その後同心円状に透明の液が広がった部分は水であり、粉体（１）は水に不溶であったことが分かった。次に、１０ｍＬバイヤルに粉体（１）１０ｍｇとエタノール１．０ｇを添加後、５分間攪拌し、分散液（２）を作製した。分散液（２）をろ紙上に１滴滴下したところ、滴下部分は円状に緑色に呈色し、その後同心円状に無色透明の液が広がっていく様子が観察された。初めに円状に緑色に呈色した部分はエタノールに不溶化した粉体（２）、その後同心円状に透明の液が広がった部分はエタノールであり、粉体（２）はエタノールに不溶であったことが分かった。 (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, 4.50 g of copper chlorophyll powder was added, and after 1 hour at room temperature, a 4.8% sodium hydroxide aqueous solution was added to adjust the pH to 7.0, and the mixture was stirred for 30 minutes. The filtered solid was dried in a vacuum dryer (740 mmHg) at 30° C. for 14 hours to obtain 17.1 g of powder (1). The composition ratio of aluminum hydroxide and chlorophyll pigment in powder (1), which is obtained by subtracting the chlorophyll pigment charged from the yield of powder (1), is aluminum hydroxide:chlorophyll pigment = 74 in mass ratio. : was 26. The powder (1) thus obtained exhibited a green color similar to that of chlorophyll pigments. 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 green in a circular shape, and then the colorless and transparent liquid spread concentrically. The green circular portion at first was the water-insoluble powder (1), and the portion where the transparent liquid spread concentrically was water, and the powder (1) was insoluble in water. I found out. Next, after adding 10 mg of powder (1) and 1.0 g of ethanol 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 turned green in a circular shape, and then it was observed that the colorless and transparent liquid spread concentrically. The green circular portion at first was the powder (2) insoluble in ethanol, and the portion where the transparent liquid spread concentrically was ethanol, and the powder (2) was insoluble in ethanol. I found out.
＜比較例１＞
１０ｍＬバイアルにクロロフィル色素１０ｍｇと水１．０ｇ添加後、５分間攪拌し、分散液（３）を作製した。分散液（３） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（３）において、クロロフィル色素が水に溶解していることを示している。 <Comparative Example 1>
After adding 10 mg of chlorophyll pigment and 1.0 g of water to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (3). When one drop of Dispersion (3) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in water in dispersion (3).
１０ｍＬバイアルにクロロフィル色素１０ｍｇと水１．０ｇ添加後、５分間攪拌し、分散液（３）を作製した。分散液（３） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（３）において、クロロフィル色素が水に溶解していることを示している。 <Comparative Example 1>
After adding 10 mg of chlorophyll pigment and 1.0 g of water to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (3). When one drop of Dispersion (3) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in water in dispersion (3).
＜比較例２＞
１０ｍＬバイアルにクロロフィル色素２．６ｍｇと、実施例１と同様の方法で色素を加えずに作製した水酸化アルミニウム７．４ｍｇ、水１．０ｇ添加後、５分間攪拌し、分散液（４）を作製した。分散液（４） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（４）において、クロロフィル色素が水に溶解していることを示している。 <Comparative Example 2>
After adding 2.6 mg of chlorophyll pigment, 7.4 mg of aluminum hydroxide prepared without adding pigment in a 10 mL vial, and 1.0 g of water in the same manner as in Example 1, the mixture was stirred for 5 minutes to give dispersion (4). made. When one drop of Dispersion (4) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in water in dispersion (4).
１０ｍＬバイアルにクロロフィル色素２．６ｍｇと、実施例１と同様の方法で色素を加えずに作製した水酸化アルミニウム７．４ｍｇ、水１．０ｇ添加後、５分間攪拌し、分散液（４）を作製した。分散液（４） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（４）において、クロロフィル色素が水に溶解していることを示している。 <Comparative Example 2>
After adding 2.6 mg of chlorophyll pigment, 7.4 mg of aluminum hydroxide prepared without adding pigment in a 10 mL vial, and 1.0 g of water in the same manner as in Example 1, the mixture was stirred for 5 minutes to give dispersion (4). made. When one drop of Dispersion (4) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in water in dispersion (4).
＜比較例３＞
１０ｍＬバイアルにクロロフィル色素１０ｍｇとエタノール１．０ｇ添加後、５分間攪拌し、分散液（５）を作製した。分散液（５） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（５）において、クロロフィル色素がエタノールに溶解していることを示している。 <Comparative Example 3>
After adding 10 mg of chlorophyll pigment and 1.0 g of ethanol to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (5). When one drop of Dispersion (5) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in ethanol in dispersion (5).
１０ｍＬバイアルにクロロフィル色素１０ｍｇとエタノール１．０ｇ添加後、５分間攪拌し、分散液（５）を作製した。分散液（５） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（５）において、クロロフィル色素がエタノールに溶解していることを示している。 <Comparative Example 3>
After adding 10 mg of chlorophyll pigment and 1.0 g of ethanol to a 10 mL vial, the mixture was stirred for 5 minutes to prepare dispersion liquid (5). When one drop of Dispersion (5) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in ethanol in dispersion (5).
＜比較例４＞
１０ｍＬバイアルにクロロフィル色素２．６ｍｇと、実施例１と同様の方法で色素を加えずに作製した水酸化アルミニウム７．４ｍｇ、エタノール１．０ｇ添加後、５分間攪拌し、分散液（６）を作製した。分散液（６） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（６）において、クロロフィル色素がエタノールに溶解していることを示している。 <Comparative Example 4>
After adding 2.6 mg of chlorophyll pigment, 7.4 mg of aluminum hydroxide prepared without adding pigment in a 10 mL vial, and 1.0 g of ethanol in the same manner as in Example 1, the mixture was stirred for 5 minutes to give dispersion (6). made. When one drop of Dispersion (6) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in ethanol in dispersion (6).
１０ｍＬバイアルにクロロフィル色素２．６ｍｇと、実施例１と同様の方法で色素を加えずに作製した水酸化アルミニウム７．４ｍｇ、エタノール１．０ｇ添加後、５分間攪拌し、分散液（６）を作製した。分散液（６） をろ紙上に１滴滴下したところ、滴下部分を中心に同心円状に緑色の液が均一に広がっていく様子が観察された。これは分散液（６）において、クロロフィル色素がエタノールに溶解していることを示している。 <Comparative Example 4>
After adding 2.6 mg of chlorophyll pigment, 7.4 mg of aluminum hydroxide prepared without adding pigment in a 10 mL vial, and 1.0 g of ethanol in the same manner as in Example 1, the mixture was stirred for 5 minutes to give dispersion (6). made. When one drop of Dispersion (6) was dropped onto the filter paper, it was observed that the green liquid spread uniformly concentrically around the dropped portion. This indicates that the chlorophyll pigment is dissolved in ethanol in dispersion (6).
Claims (6)
- 金属または金属化合物に、クロロフィル系色素が被覆、含浸、複合化、あるいは吸着された非水溶性且つ、非油溶性色素組成物。 A water-insoluble and oil-insoluble dye composition in which a chlorophyll-based dye is coated, impregnated, complexed, or adsorbed onto a metal or metal compound.
- 前記クロロフィル系色素と、金属または金属化合物が質量比で、クロロフィル系色素：金属または金属化合物＝０．１：９９．９～９０：１０である請求項１記載の非水溶性且つ、非油溶性色素組成物。 The water-insoluble and oil-insoluble according to claim 1, wherein the mass ratio of the chlorophyll-based dye and the metal or metal compound is chlorophyll-based dye: metal or metal compound = 0.1:99.9 to 90:10. pigment composition.
- 前記クロロフィル系色素が銅クロロフィル、または銅クロロフィリンナトリウムである請求項１または２に記載の非水溶性且つ、非油溶性色素組成物。 3. The water-insoluble and oil-insoluble pigment composition according to claim 1, wherein the chlorophyll pigment is copper chlorophyll or copper chlorophyllin sodium.
- 前記金属化合物が金属水酸化物または金属酸化物である請求項１または２に記載の非水溶性且つ、非油溶性色素組成物。 3. The water-insoluble and oil-insoluble dye composition according to claim 1, wherein said metal compound is a metal hydroxide or metal oxide.
- 前記金属または金属化合物の金属元素がアルミニウムである請求項１または２に記載の非水溶性且つ、非油溶性色素組成物。 3. The water-insoluble and oil-insoluble dye composition according to claim 1, wherein the metal element of said metal or metal compound is aluminum.
- 請求項１または２に記載の非水溶性且つ、非油溶性色素組成物を含有することを特徴とする食品、化粧品、医薬品または農薬のコーティング材または印字マーカー、文房具、筆記具、印刷インキ、インクジェットインキ、金属インキ、塗料、プラスチック着色剤、カラートナー、蛍光標識剤、蛍光プローブ、または化学センサー。 Coating materials for foods, cosmetics, pharmaceuticals, or agricultural chemicals, or printing markers, stationery, writing instruments, printing inks, and inkjet inks, which contain the water-insoluble and oil-insoluble dye composition according to claim 1 or 2. , metallic inks, paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, or chemical sensors.
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Citations (7)
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|---|---|---|---|---|
| JPS63258957A (en) * | 1986-10-10 | 1988-10-26 | ローヌープーラン・シミ | Colored pigment based on silica, alumina, titanium oxide or zirconium oxide type mineral oxide and production thereof |
| JPH01230676A (en) * | 1986-12-23 | 1989-09-14 | Kao Corp | Spherical microparticulate pigment and its production |
| JPH02204751A (en) * | 1989-02-02 | 1990-08-14 | Ishihara Sangyo Kaisha Ltd | Electrophotographic sensitive body |
| WO2001055262A1 (en) * | 2000-01-28 | 2001-08-02 | Carlo Ghisalberti | New pigments and compositions containing them |
| JP2006070175A (en) * | 2004-09-02 | 2006-03-16 | Shiseido Co Ltd | Phenolic compound fixing carrier and method of fixing phenolic compound |
| EP1798262A1 (en) * | 2005-12-15 | 2007-06-20 | Lcw - Les Colorants Wackherr | Blue lakes comprising natural dyestuff |
| WO2012124785A1 (en) * | 2011-03-15 | 2012-09-20 | 国立大学法人大阪大学 | Organic-inorganic composite coloring composition and method for producing same |
-
2022
- 2022-09-15 WO PCT/JP2022/034504 patent/WO2023053981A1/en active Application Filing
- 2022-09-15 JP JP2023551301A patent/JP7552925B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63258957A (en) * | 1986-10-10 | 1988-10-26 | ローヌープーラン・シミ | Colored pigment based on silica, alumina, titanium oxide or zirconium oxide type mineral oxide and production thereof |
| JPH01230676A (en) * | 1986-12-23 | 1989-09-14 | Kao Corp | Spherical microparticulate pigment and its production |
| JPH02204751A (en) * | 1989-02-02 | 1990-08-14 | Ishihara Sangyo Kaisha Ltd | Electrophotographic sensitive body |
| WO2001055262A1 (en) * | 2000-01-28 | 2001-08-02 | Carlo Ghisalberti | New pigments and compositions containing them |
| JP2006070175A (en) * | 2004-09-02 | 2006-03-16 | Shiseido Co Ltd | Phenolic compound fixing carrier and method of fixing phenolic compound |
| EP1798262A1 (en) * | 2005-12-15 | 2007-06-20 | Lcw - Les Colorants Wackherr | Blue lakes comprising natural dyestuff |
| WO2012124785A1 (en) * | 2011-03-15 | 2012-09-20 | 国立大学法人大阪大学 | Organic-inorganic composite coloring composition and method for producing same |
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| JPWO2023053981A1 (en) | 2023-04-06 |
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