Classifications

• • 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)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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Citations (7)

• 2022
  • 2022-09-15 WO PCT/JP2022/034504 patent/WO2023053981A1/ja not_active Ceased
  • 2022-09-15 JP JP2023551301A patent/JP7552925B2/ja active Active

Patent Citations (7)

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