Water-insoluble pigment composition

Abstract

The purpose of the present invention is to provide: a water-insoluble pigment composition in which a natural pigment and one or more substances selected from pearl pigments or boron nitride are compounded; and a food, a cosmetic, a lipstick cosmetic, an eye cosmetic, a nail cosmetic, a base makeup cosmetic, a hair cosmetic, a pharmaceutical, an agrochemical coating material, a printing marker, stationery, a writing instrument, a printing ink, an inkjet ink, a metal ink, a coating material, a plastic coloring agent, a color toner, a fluorescent labeling agent, a fluorescent probe, or a chemical sensor containing the water-insoluble pigment composition.　The present invention was completed once it was discovered that compounding a natural pigment and one or more substances selected from pearl pigments or boron nitride yields a water-insoluble pigment composition.

Description

Water-insoluble pigment composition

[0001] The present invention relates to a water-insoluble dye composition.

[0002] There are a wide variety of natural dyes, including red, yellow, and blue dyes, but in recent years, expectations have grown for natural dyes, which are thought to be safer than synthetic coloring agents.

[0003] Furthermore, with business activities that place a strong emphasis on sustainability in mind, there is a demand for environmentally friendly colorants. Under these circumstances, many natural colorants are easily soluble in water, so when used in cosmetics or food coloring, they can leach into the water and cause color fading. Furthermore, when used in flexographic printing, they can cause problems such as migration and plate staining. For these reasons, they are currently only used in very limited applications.

[0004] The inventors conducted a search for literature describing solutions to the problems of natural pigment leaching and discoloration in water, i.e., improving water solubility. The literature found a description of a method for extracting natural pigments, including oral cosmetics, dairy products, and pet foods using the extract (Patent Document 1). Furthermore, a description of dry-blending a carotenoid pigment with sodium tartrate, alum, and sodium carbonate, and dissolving the resulting powder mixture in water to obtain an aqueous solution, with the aim of stabilizing the color (Patent Document 2). Another description of a powder composition containing a carotenoid, an oily component, and sugar (Patent Document 3).

[0005] However, these documents do not improve the water solubility of natural dyes, which is a desired issue.

[0006] JP-T-2009-508505A JP-B-59-050264A JP-A-2009-185023A

[0007] An object of the present invention is to provide a water-insoluble dye composition, and a coating material for foods, cosmetics, pharmaceuticals, or agricultural chemicals, or a printing marker, stationery, writing implement, printing ink, inkjet ink, metallic ink, paint, plastic colorant, color toner, fluorescent labeling agent, fluorescent probe, or chemical sensor containing the water-insoluble dye composition.

[0008] As a result of extensive research into solving the above problems, the present inventors have found that a water-insoluble dye composition can be obtained by combining a natural dye with one or more substances selected from boron nitride and pearl pigments, and have thus completed the present invention.

[0009] That is, the present invention encompasses the following aspects. [1] A water-insoluble pigment composition comprising a complex of a natural pigment and one or more substances selected from a pearl pigment or boron nitride. [2] The water-insoluble pigment composition according to 1, wherein the natural pigment and at least one substance selected from a pearl pigment or boron nitride are present in a mass ratio of natural pigment:one or more substances selected from a pearl pigment or boron nitride of 0.1:99.9 to 90:10. [3] The water-insoluble pigment composition according to 1 or 2, wherein the pearl pigment is at least one selected from a pigment in which one or more particles selected from mica, talc, or glass are coated with titanium oxide, and bismuth oxychloride. [4] The water-insoluble pigment composition according to 1 or 2, wherein the natural pigment is at least one selected from a carotenoid pigment, a porphyrin pigment, a flavonoid pigment, and a chromoprotein. [5] The water-insoluble pigment composition according to 1 or 2, wherein the natural pigment is at least one selected from an annatto pigment, a chlorophyll pigment, a safflower yellow pigment, and a phycocyanin pigment. [6] A food, cosmetic, lipstick cosmetic, eye cosmetic, nail cosmetic, base makeup cosmetic, hair cosmetic, pharmaceutical, agricultural chemical coating material, printing marker, stationery, writing instrument, printing ink, inkjet ink, metallic ink, paint, plastic colorant, color toner, fluorescent labeling agent, fluorescent probe, or chemical sensor, characterized by containing the water-insoluble dye composition according to any one of [1] to [5].

[0010] According to the present invention, a water-insoluble dye composition can be provided. The water-insoluble dye composition of the present invention has high water resistance, so that when used in cosmetics or food, it is less likely to dissolve in water and the resulting color fading. Furthermore, when used in flexographic printing, migration and plate staining are reduced.

[0011] The water-insoluble dye composition of the present invention will be described in detail below. However, the following description of the constituent elements is an example of one embodiment of the present invention, and the present invention is not limited to these contents.

[0012] (Natural Pigments) The natural pigments used in the present invention include red cabbage pigment, red radish pigment, annatto pigment, squid ink pigment, turmeric pigment, cacao pigment, carotene pigment, carotenoid pigment, gardenia red pigment, gardenia blue pigment, gardenia yellow pigment, chlorophyll pigment, sorghum pigment, cochineal pigment, saffron pigment, perilla pigment, rosewood pigment, spirulina pigment, phycocyanin pigment, onion pigment, tamarind pigment, butterfly pea pigment, chili pepper pigment, tomato pigment, hibiscus pigment, beet red pigment, grape skin pigment, Haematococcus pigment, Monascus pigment, safflower red pigment, safflower yellow pigment, berry pigment, marigold pigment, purple sweet potato pigment, purple corn pigment, purple yam pigment, caramel pigment, and plant charcoal powder pigment, so long as they are naturally derived pigments. Furthermore, these dyes may also be used in the same manner as above, if they are biosynthesized, enzymatically synthesized, or chemically synthesized.

[0013] Among these, pigments that can be suitably used in the present invention include carotenoid pigments, porphyrin pigments, flavonoid pigments, and pigment proteins.

[0014] Carotenoid pigments are known to be red pigments extracted from carrots, tomatoes, and chili peppers, and yellow pigments extracted from citrus fruits, gardenia, annatto, and marigolds. Green leafy vegetables also contain large amounts of carotenoid pigments.

[0015] Carotenoids are substances belonging to the tetraterpene group of terpene compounds. Terpenes are important compounds for plants, and more than 20,000 compounds are known. Carotenoid pigments include hydrocarbon pigments such as β-carotene and lycopene, xanthophyll pigments such as astaxanthin, capsanthin, and lutein, and others such as bixin, norbixin, and crocin.

[0016] Porphyrin pigments have four pyrrole rings, and their metal complexes are found in chlorophyll, which absorbs light and transfers electrons during photosynthesis, and in the heme of hemoglobin, which transports oxygen in the blood. Porphyrin metal complexes are widely used as optoelectronic functional materials, metal complex catalysts, and molecular conductive materials, and are known to exhibit a wide range of functionality by changing the peripheral substituents, central metal, and axial ligands of the porphyrin.

[0017] Flavonoids are one of the major categories of polyphenols. Flavonoids are a general term for compounds with a specific chemical structure found in plant leaves, stems, and trunks. They are substances that plants produce to protect themselves from ultraviolet rays and pests, and are the source of pigments and bitter compounds. Flavonoids are further divided into flavonols, flavones, catechins, flavanones, anthocyanins, isoflavones, etc., depending on their structure.

[0018] Flavonoid pigments include flavonols, anthocyanin pigments that exhibit a variety of colors, and pigments such as chalcones and aurones that exhibit a deep yellow color.

[0019] (Chromoproteins) Chromoproteins are a general term for proteins that are naturally complexed with pigments. They exist in the cells and body fluids of animals and plants, and express various colors and physiological functions depending on the prosthetic group containing the pigment. Hemoproteins are complexes of iron-porphyrin complexes and proteins, with binding ratios of protein to heme of 1:1, 1:2, 1:4, etc. They are widely present in nature and include hemoglobin, myoglobin, cytochrome, catalase, and peroxidase.

[0020] Metal complex compounds are complexes of metal ions and proteins, including copper proteins such as hemocyanin and iron proteins such as ferritin. Ferritin is found in the spleen, small intestinal mucosa, liver, etc. and is thought to be involved in iron storage in the body and iron absorption during digestion.

[0021] Phycoproteins are conjugates of pyrrole derivatives and proteins, such as phycoerythrin, which gives red color to red algae, and phycocyanin, which gives blue-green algae their blue color. These are contained in chloroplasts along with chlorophyll and carotenoids, and are thought to be auxiliary pigments for photosynthesis.

[0022] Flavoproteins have flavin mononucleotide or flavin adenine dinucleotide as a prosthetic group. They all function as oxidoreductases and are also called flavoenzymes. Examples include amino acid oxidase and xanthine oxidase.

[0023] Carotenoid proteins are complexes of carotenoids and proteins, such as complexes of vitamin A and proteins, including rhodopsin.

[0024] (Phycocyanin) As the chromoprotein used in the present invention, phycocyanin is the most preferred because it produces a vivid blue color. Phycocyanin is a chromoprotein that contains phycocyanobilin as a chromophore. Phycocyanin has a structure in which phycocyanobilin and protein are bound together.

[0025] Examples of phycocyanins of the present invention include phycocyanins derived from algae, such as phycocyanins derived from cyanobacteria, phycocyanins derived from red algae, and phycocyanins derived from cryptophytes. Of these, phycocyanins derived from cyanobacteria are preferred because they can be harvested in large quantities.

[0026] Examples of cyanobacteria include those of the genus Spirulina, Arthrospira, Aphanizomenon, Fisherella, Anabaena, Nostoc, Synechocystis, Synechococcus, Tolypothrix, Aphanothece, Mastigoclaus, and Pleurocapsa. Among these, cyanobacteria of the genus Spirulina and Arthrospira are preferred, as they are produced on an industrial scale and their safety has been confirmed, and cyanobacteria of the genus Spirulina are more preferred.

[0027] Furthermore, as a raw material for preparing phycocyanin, either fresh or dried cyanobacteria can be used. As for the dried product of cyanobacteria, fresh cyanobacteria can be dried according to a conventional method, or commercially available dried products can be used.

[0028] Phycocyanin can be obtained, for example, by suspending blue-green algae in water or a buffer solution such as a phosphate buffer or a citrate buffer, and extracting the phycocyanin from the blue-green algae.

[0029] The method for extracting phycocyanin is not particularly limited, and any commonly known method can be used.

[0030] A preferred embodiment of the extraction method is, for example, the extraction method described in JP 2006-230272 A. Specifically, the extraction method described in the following extraction method (i) can be mentioned. By this extraction method (i), phycocyanin with high purity and vivid color can be obtained.

[0031] <Extraction method (i)> Extraction method (i) comprises the following steps: a first step of extracting phycocyanin from cyanobacteria into an aqueous suspension to obtain an extract; a second step of reacting a calcium salt with a phosphate salt in the extract to produce calcium phosphate and adsorbing impurities of phycocyanin onto the calcium phosphate to obtain an adsorbate; and a third step of removing cyanobacterial residues and the adsorbate from the extract.

[0032] Furthermore, it is more preferable that the above extraction method (i) is the following extraction method (ii). <Extraction method (ii)> Extraction method (ii) comprises the following steps: a first step of extracting phycocyanin from cyanobacteria into an aqueous suspension to obtain an extract; a second step of reacting a calcium salt with a phosphate salt in the extract to produce calcium phosphate and adsorbing phycocyanin impurities onto the calcium phosphate to obtain an adsorbate; a third step of removing cyanobacteria residues and the adsorbate from the extract; and a step of adding a chelating agent to the extract prior to the third step.

[0033] The phycocyanin used in this invention was a commercially available product, Linablue G1 (manufactured by DIC Lifetech Co., Ltd., trehalose 55%, spirulina extract 40%, trisodium citrate 5%), mixed with a stabilizer. As described in JP-A-11-299450, trehalose is used to increase thermal stability, and citric acid is used as a pH adjuster. Phycocyanin pigment is contained as the main component of spirulina extract.

[0034] In the present invention, one type of natural colorant may be used alone, or several types of natural colorants may be used simultaneously. Depending on the application, in order to achieve a desired hue, the natural colorants may be mixed in advance and then composited with one or more substances selected from pearl pigments or boron nitride, or a single natural colorant may be composited with one or more substances selected from pearl pigments or boron nitride, and then the composited water-insoluble colorant compositions may be mixed.

[0035] (Boron Nitride) The boron nitride used in this invention is a solid compound composed of nitrogen and boron. It exists in a hexagonal, atmospheric-pressure phase and a cubic, high-pressure phase. Either crystal system can be used. In the atmospheric-pressure phase, boron nitride has widely spaced hexagonal meshes of tightly interlocking atoms, which are held together by weak van der Waals forces, allowing the layers to slide easily against each other. For this reason, it is also known as white graphite. Because of its tight mesh, heat is transmitted well through lattice vibrations. It has the highest thermal conductivity of any electrical insulator and a low thermal expansion coefficient, approximately one-tenth that of alumina. It is also white because it does not absorb visible light.

[0036] Common uses include as a solid lubricant for ceramics, alloys, resins, rubber, etc., as a release agent for molds used to cast automobile engines and glass molding molds, and as a fine powder in cosmetics, etc.

[0037] Any boron nitride can be used in the present invention, but those with an average particle size of 0.1 μm to 100 μm are preferred, more preferably 1 μm to 50 μm, and even more preferably 5 μm to 30 μm. Spherical or plate-shaped particles are also preferred.

[0038] (Pearl pigments) Pearl pigments are substances that produce a deep, pearl-like luster by utilizing the phenomenon of multiple reflection and interference of light in a thin film, and are a versatile powder used in paints and cosmetics. The current mainstream is titanium dioxide-coated mica (mica), which uses mica flake particles as a base material and is coated with titanium dioxide microcrystals on its surface. This titanium dioxide-coated mica is highly safe and has stable physical properties, so it has been used in a variety of applications in fields such as cosmetics, paints, inks, and plastics. Recently, the use of synthetic flake base materials and advances in metal oxide coating technology have led to the development of pearl pigments with new designs. Examples include titanium mica, iron oxide-coated titanium mica, carmine-coated titanium mica, carmine- and konjou-coated titanium mica, iron oxide- and carmine-treated titanium mica, konjou-treated titanium mica, iron oxide- and konjou-treated titanium mica, chromium oxide-treated titanium mica, black titanium oxide-treated titanium mica, acrylic resin-coated aluminum powder, titanium oxide-coated mica, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, colored titanium oxide-coated mica, bismuth oxychloride, and fish scale foil.

[0039] (Bismuth oxychloride) Bismuth oxychloride is a pearlescent pigment, an inorganic material with the chemical formula BiClO. It can be obtained by reacting bismuth chloride with water or by mixing and heating bismuth chloride with cadmium oxide. It was developed as a pearlescent pigment with a pearlescent luster, and is white to dull yellow in color. It is tasteless and odorless, and comes in two types: crystalline powder and amorphous powder. It has poor lightfastness and discolors from gray to black when exposed to ultraviolet light or hydrogen sulfide. It is generally used to impart a pearlescent luster to cosmetics and to impart beautiful skin color and expression in makeup. Due to its high specific gravity and tendency to settle in liquid, it is suitable for solid products such as lipstick and eye shadow.

[0040] Any pearl pigment can be used in the present invention, but it is preferable to use a pearl pigment in which particles of one or more materials selected from mica, talc, or glass are coated with titanium oxide. Furthermore, the average particle size is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 5 μm to 30 μm. Furthermore, spherical or plate-like particle shapes are preferred.

[0041] (Water-insoluble dye composition) Most of the natural dyes used in the present invention are in the form of dyes and are therefore water-soluble, but the present invention has discovered that the natural dye is firmly complexed with at least one substance selected from pearl pigments or boron nitride through the action forms of coating, impregnation, and adsorption, and becomes insoluble in water as a water-insoluble dye composition. The complexation referred to here is not limited to action forms such as coating, impregnation, and adsorption, and is defined as not being a simple mixture but as being a composition in which the natural dye interacts with at least one substance selected from pearl pigments or boron nitride through physical or chemical adsorption, thereby achieving water insolubility.

[0042] The water-insoluble nature of the natural dye obtained by the present invention has improved the resistance of the natural dye to the extent that it can be used as a coloring material equivalent to ordinary pigments in applications such as coating materials for foods, cosmetics, pharmaceuticals, or agricultural chemicals, or as printing markers, stationery, writing implements, printing inks, inkjet inks, metallic inks, paints, plastic colorants, color toners, fluorescent labeling agents, fluorescent probes, and chemical sensors. Furthermore, the insolubilization is expected to result in improved properties such as heat resistance and light resistance. However, the uses of the water-insoluble dye composition of the present invention are not limited to those described above.

[0043] The water-insoluble dye composition of the present invention can be used by setting the mass ratio of the natural dye to at least one substance selected from pearl pigments or boron nitride at natural dye: at least one substance selected from pearl pigments or boron nitride = 0.1:99.9 to 90:10, preferably natural dye: at least one substance selected from pearl pigments or boron nitride = 1:99 to 70:30.

[0044] The average particle size of the water-insoluble dye composition of the present invention is preferably from 0.1 to 100 μm, more preferably from 1 to 50 μm.

[0045] In the water-insoluble dye composition of the present invention, the content of elements derived from at least one substance selected from the group consisting of pearl pigments and boron nitride is preferably 99% or less, more preferably 90% or less, compared to the content of at least one substance selected from the group consisting of pearl pigments and boron nitride.

[0046] (Method for Producing Water-Insoluble Dye Composition) As a method for producing the water-insoluble dye composition of the present invention, a method of mixing a natural dye with at least one substance selected from pearl pigments and boron nitride in a solvent is preferred because it allows the production of the most uniform water-insoluble dye composition.

[0047] A method for producing a water-insoluble dye composition by mixing each substance in a solvent includes: 1) first preparing a dispersion of one or more substances selected from pearl pigments or boron nitride; 2) separately dissolving a natural dye in a solvent to prepare a natural dye solution; 3) the two liquids are then mixed to prepare a water-insoluble dye composition. The natural dye solution may be mixed with a dispersion of at least one substance selected from pearl pigments or boron nitride, or conversely, a dispersion of at least one substance selected from pearl pigments or boron nitride may be mixed with a natural dye solution; or the two liquids may be mixed in small amounts to prepare the composition. The mixing temperature may be room temperature or heated. Taking into account the decomposition temperature of the natural dye alone, mixing is preferably performed at 10 to 60°C, more preferably 20 to 50°C. The pH of the dispersion or solution during mixing is adjusted to take into account the decomposition of the natural dye. 4) The pH of the mixture is adjusted to combine the natural dye with the supporting material to form a water-insoluble dye composition.

[0048] The resulting mixture is filtered and dried to obtain a water-insoluble dye composition. When the mixture is filtered through a filter such as a Nutsche filter, a wet cake colored with the natural dye is obtained on the filter paper, confirming that the natural dye and at least one substance selected from pearl pigments and boron nitride are complexed. Furthermore, when the wet cake of the water-insoluble dye composition is further washed with water, the filtrate becomes colorless and transparent, confirming that no dye components have been washed out. The resulting water-containing wet cake of the water-insoluble dye composition is dried at room temperature, by heating, vacuum drying, reduced-pressure drying, or the like, to obtain a dry water-insoluble dye composition. Any conventional method and device can be used for the drying method and dryer, and there are no limitations.

[0049] The water-insoluble dye composition of the present invention can be used in either the form of a wet cake containing water or a dry, dried water-insoluble dye composition depending on the application. When used in an aqueous dispersion or ink, the wet cake can be used as is, and when used in a solvent-based dispersion, the wet cake can be used after replacing the aqueous system with a solvent-based system. The dry water-insoluble dye composition can be used as is, or can be redispersed in water, an organic solvent, a resin solution, or the like and used.

[0050] (Stabilizers, Additives) It is of course possible to mix other organic pigments, inorganic pigments, dyes, and coloring matter in any ratio with the water-insoluble dye composition of the present invention, thereby achieving the desired hue. In order to further impart light resistance and heat resistance to the water-insoluble dye composition of the present invention, stabilizers and additives can also be added.

[0051] The stabilizer and additives may be added to either or both of the dispersion of at least one substance selected from the group consisting of pearl pigments and boron nitride and the natural dye solution, or may be added to the prepared water-insoluble dye composition.

[0052] The water-insoluble dye composition of the present invention is mixed with other resins, rubbers, additives, pigments, dyes, etc., as needed, and is prepared and used as a coating material for food, cosmetics, medicines, or agricultural chemicals, or as a printing marker, stationery, writing implement, printing ink, inkjet ink, metal ink, paint, plastic colorant, color toner, fluorescent labeling agent, fluorescent probe, chemical sensor, etc. Examples of the above uses are shown below.

[0053] (Use in cosmetics) The water-insoluble colorant composition of the present invention can be used as a cosmetic. There are no particular limitations on the type of cosmetic to be used, and the water-insoluble colorant composition of the present invention can be used in various types of cosmetics.

[0054] The cosmetic product may be of any type as long as it can effectively exhibit its function. The cosmetic product may be a lotion, cream gel, spray, etc. Examples of the cosmetic product include skin care cosmetics such as face washes, makeup removers, toners, serums, packs, protective emulsions, protective creams, whitening cosmetics, and UV protection cosmetics; makeup cosmetics such as foundations, face powders, makeup bases, lipsticks, eye makeup, blushers, and nail enamel; hair care cosmetics such as shampoos, hair rinses, hair treatments, hair styling products, permanent wave agents, hair dyes, and hair growth agents; and body care cosmetics such as body cleansing cosmetics, deodorant cosmetics, and bath additives.

[0055] The amount of the water-insoluble dye composition of the present invention used in the cosmetic can be appropriately set depending on the type of cosmetic. The content in the cosmetic is usually in the range of 0.1 to 99% by mass, and generally, it is preferable that the content be in the range of 0.1 to 10% by mass. On the other hand, in makeup cosmetics intended for coloring, the content 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. When the amount of the water-insoluble dye composition of the present invention contained in the cosmetic is in the above range, it can effectively exhibit functions such as coloring ability and can also maintain the functions required of cosmetics.

[0056] The cosmetic may contain, depending on the type of cosmetic, in addition to the water-insoluble dye composition of the present invention, a carrier, pigment, oil, sterol, amino acid, moisturizer, powder, colorant, pH adjuster, fragrance, essential oil, cosmetic active ingredient, vitamin, essential fatty acid, sphingolipid, self-tanning agent, excipient, filler, emulsifier, antioxidant, surfactant, chelating agent, gelling agent, thickener, emollient, humectant, moisturizer, mineral, viscosity adjuster, flow adjuster, keratolytic agent, These may include retinoids, hormonal compounds, alpha hydroxy acids, alpha keto acids, antimycobacterial agents, antifungal agents, antibacterial agents, antiviral agents, analgesics, antiallergic agents, antihistamines, anti-inflammatory agents, anti-irritants, antitumor agents, immune system boosters, immune system suppressants, anti-acne agents, anesthetics, disinfectants, insect repellents, skin cooling compounds, skin protectants, skin penetration enhancers, exfoliants, lubricants, fragrances, dyes, bleaching agents, hypopigmenting agents, preservatives, stabilizers, pharmaceuticals, light stabilizers, and spherical powders.

[0057] The cosmetic can be produced by mixing the water-insoluble colorant composition of the present invention with other cosmetic ingredients. The cosmetic containing the water-insoluble colorant composition of the present invention can be used in the same manner as ordinary cosmetics, depending on the type of the cosmetic, etc.

[0058] (Ink and Paint Uses) The water-insoluble dye composition of the present invention can be used as ink or paint. However, although the uses and compositions of ink and paint will be described, the present invention is not limited thereto. Furthermore, the water-insoluble dye composition of the present invention may be dispersed in a thermoplastic resin alone, but can also be dispersed in a printing ink vehicle, a paint vehicle, or the like containing a thermoplastic resin as an essential component.

[0059] Examples of thermoplastic resins that can be used as dispersion resins include polyester resins, polyamide resins, styrene resins, acrylic resins, polyolefins, polyalkylene terephthalates, and polyvinyl chloride resins.

[0060] For example, a vehicle for lithographic printing ink is produced from raw materials such as 20 to 50 (by mass) % of a resin such as rosin-modified phenolic resin, petroleum resin, or alkyd resin, 0 to 30 (by mass) % of an animal or vegetable oil such as linseed oil, tung oil, or soybean oil, 10 to 60 (by mass) % of a solvent such as n-paraffin, isoparaffin, naphthene, α-olefin, or aromatic, and a few (by mass) % of other additives such as solubilizers and gelling agents.

[0061] Vehicles for gravure printing inks and flexographic printing inks are produced from raw materials such as 10 to 50 (by mass) of one or more resins selected from rosins, maleic acid resins, polyamide resins, vinyl resins, cyclized rubbers, chlorinated rubbers, ethylene-vinyl acetate copolymer resins, urethane resins, polyester resins, alkyd resins, nitrocellulose, cellulose acetate, and the like, and 30 to 80 (by mass) of a solvent such as an alcohol, toluene, n-hexane, ethyl acetate, cellosolve, or butyl cellosolve acetate.

[0062] Vehicles for paints are produced from raw materials such as 20 to 80 (by mass) % of a resin such as an alkyd resin, epoxy resin, acrylic resin, polyurethane resin, polyester resin, melamine resin, urea resin, or water-soluble resin, and 10 to 60 (by mass) % of a solvent such as a hydrocarbon, alcohol, ketone, or water.

[0063] (Plastic Use) The water-insoluble dye composition of the present invention can also be used for coloring plastics. When obtaining colored plastic molded products, thermoplastic resins (plastics) for thermoforming such as injection molding and press molding, such as polyolefins (e.g., polyethylene and polypropylene) and polyvinyl chloride resins, are used. The water-insoluble dye composition of the present invention can be kneaded into these resins by a conventionally known method.

[0064] The water-insoluble dye composition of the present invention can also be used for toner coloring. When preparing a toner for developing electrostatic images, a film-forming thermoplastic resin that is solid at room temperature, such as a polyester resin, a polyamide resin, a styrene resin, or an acrylic resin, is used as a dispersing resin.

[0065] The toner for developing electrostatic images, which is produced using the water-insoluble dye composition of the present invention as a constituent, can be used as a one-component magnetic toner containing a magnetic material in the toner (color toner for magnetic one-component development), a non-magnetic one-component color toner not containing a magnetic material (color toner for non-magnetic one-component development), or a color toner for a two-component color developer containing a carrier (color toner for two-component development).

[0066] The one-component color magnetic toner can be composed of, for example, a colorant, a binder resin, a magnetic powder, and other additives such as a charge control agent (CCA) and a release agent, as is the case with commonly used toners.

[0067] The amount of the water-insoluble dye composition used in the toner for developing electrostatic images is not particularly limited, but is preferably 0.5 to 25 parts by mass relative to 100 parts by mass of the binder resin, and more preferably 4 to 10 parts by mass relative to 100 parts by mass of the binder resin in order to further enhance the charging performance of the colorant itself.

[0068] As the binder resin used in the toner for developing electrostatic images, any of the known and commonly used resins exemplified above as the thermoplastic resin can be used, but any of synthetic resins, natural resins, natural rubber, synthetic rubber, synthetic wax, etc. that exhibit adhesiveness under application of heat or pressure can also be used.

[0069] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples.

[0070] Example 1: 20.0 g of boron nitride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 100 g of ethanol were added to a 3 L beaker and thoroughly mixed. Next, 1,000 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 5 minutes using a glass stirring blade connected to a three-one motor to prepare a boron nitride dispersion. 2.0 g of annatto pigment (manufactured by Kanto Chemical Co., Ltd.), 300 mL of ion-exchanged water, and a stir bar were added to a 500 mL beaker, and the mixture was stirred at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto pigment solution. The annatto pigment solution was added to the boron nitride dispersion, and the mixture was stirred at room temperature for 15 minutes. Next, dilute hydrochloric acid (first-class hydrochloric acid, manufactured by Kanto Chemical Co., Ltd.) prepared by diluting it 10 times with ion-exchanged water was slowly added dropwise using a dropper to adjust the pH to 4.0, and the mixture was then stirred at room temperature for 2 hours. This solution was filtered through a Nutsche filter, and the resulting solid was dried in a vacuum dryer (740 mmHg) at 30°C for 14 hours to obtain 19.9 g of powder (1). The composition ratio of boron nitride to annatto pigment in powder (1) was 10:1 in terms of the amount charged. The resulting powder exhibited the same orange color as the annatto pigment.

[0071] 110 mg of powder (1), 1.0 g of ion-exchanged water, and a stirring bar were added to a 10 mL vial and stirred with a magnetic stirrer for 5 minutes to prepare dispersion (1). When one drop of dispersion (1) was dropped onto filter paper, the area where the drop was dropped turned orange in a circular pattern, and then a colorless, transparent liquid was observed to spread concentrically. The orange-colored area was powder (1) insoluble in water, and the area where the transparent liquid spread concentrically was water, confirming that powder (1) was insoluble in water.

[0072] Example 2 An experiment was conducted in the same manner as in Example 1, except that copper chlorophyllin sodium (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of the annatto pigment used in Example 1, to obtain 18.7 g of powder (2). The composition ratio of boron nitride to copper chlorophyllin sodium in powder (2) was 10:1 in terms of the charged amount. The obtained powder exhibited the same green color as copper chlorophyllin sodium.

[0073] 110 mg of powder (2), 1.0 g of ion-exchanged water, and a stirring bar were added to a 10 mL vial and stirred for 5 minutes with a magnetic stirrer to prepare dispersion (2). When one drop of dispersion (2) was dropped onto filter paper, the area where the drop was dropped turned green in a circular pattern, and then a colorless, transparent liquid was observed to spread concentrically. The green-colored area was powder (2) insoluble in water, and the area where the transparent liquid subsequently spread concentrically was water, confirming that powder (2) was insoluble in water.

[0074] Example 3 An experiment was conducted in the same manner as in Example 1, except that 2.0 g of red cabbage pigment (manufactured by Kanto Chemical Co., Inc.) was used instead of the annatto pigment used in Example 1, to obtain 18.7 g of powder (3). The composition ratio of boron nitride to red cabbage pigment in powder (3) was 10:1 in terms of the amount charged. The obtained powder exhibited the same red color as the red cabbage pigment.

[0075] 110 mg of powder (3), 1.0 g of ion-exchanged water, and a stirring bar were added to a 10 mL vial and stirred with a magnetic stirrer for 5 minutes to prepare dispersion (3). When one drop of dispersion (3) was dropped onto filter paper, the area where the drop was dropped turned red in a circular pattern, and then a colorless, transparent liquid was observed to spread concentrically. The red-colored area was powder (3) insoluble in water, and the area where the transparent liquid spread concentrically was water, confirming that powder (3) was insoluble in water.

[0076] Example 4 An experiment was conducted in the same manner as in Example 1, except that Linablue G1 (manufactured by DIC Lifetech Corporation, trehalose 55%, spirulina extract 40%, trisodium citrate 5%) was used instead of the annatto pigment used in Example 1, to obtain 19.5 g of powder (4). The composition ratio of boron nitride to spirulina extract in powder (4) was 25:1 in terms of the amount charged. The obtained powder exhibited the same blue color as the phycocyanin pigment.

[0077] 104 mg of powder (4), 1.0 g of ion-exchanged water, and a stirring bar were added to a 10 mL vial and stirred with a magnetic stirrer for 5 minutes to prepare dispersion (4). When one drop of dispersion (4) was dropped onto filter paper, the area where the drop was dropped turned blue in a circular pattern, and then a colorless, transparent liquid was observed to spread concentrically. The blue-colored area was powder (4) insoluble in water, and the area where the transparent liquid spread concentrically was water, confirming that powder (4) was insoluble in water.

[0078] Example 5 An experiment was conducted in the same manner as in Example 1, except that a pearl pigment (SunSHINE Spectral Red, manufactured by Sun Chemical) was used instead of the boron nitride used in Example 1, to obtain 19.9 g of powder (5). The composition ratio of the pearl pigment to the annatto dye in powder (5) was 10:1 in terms of the amount charged. The obtained powder exhibited the same orange color as the annatto dye.

[0079] 110 mg of powder (5), 1.0 g of ion-exchanged water, and a stirring bar were added to a 10 mL vial and stirred for 5 minutes with a magnetic stirrer to prepare dispersion (5). When one drop of dispersion (5) was dropped onto filter paper, the area where the drop was dropped turned orange in a circular pattern, and then a colorless, transparent liquid was observed to spread concentrically. The orange-colored area was powder (5) insoluble in water, and the area where the transparent liquid spread concentrically was water, confirming that powder (5) was insoluble in water.

[0080] Comparative Example 1: 10 mg of annatto colorant (Kanto Chemical Co., Inc.) and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (6). When one drop of dispersion (6) was dropped onto filter paper, it was observed that a yellow liquid spread uniformly in a concentric pattern around the drop. It was confirmed that the annatto colorant was dissolved in water in dispersion (6).

[0081] Comparative Example 2: 10 mg of annatto pigment (Kanto Chemical Co., Ltd.), 100 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (7). When one drop of dispersion (7) was dropped onto filter paper, it was observed that a yellow liquid spread uniformly in a concentric pattern around the drop. It was confirmed that the annatto pigment was dissolved in water in dispersion (7).

[0082] (Comparative Example 3) 10 mg of copper chlorophyllin sodium (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (8). When one drop of dispersion (8) was dropped onto filter paper, it was observed that a green liquid spread uniformly in a concentric pattern around the drop. Here, it was confirmed that copper chlorophyllin sodium was dissolved in water in dispersion (8).

[0083] (Comparative Example 4) 10 mg of copper chlorophyllin sodium (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 100 mg of boron nitride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (9). When one drop of dispersion (9) was dropped onto filter paper, it was observed that a green liquid spread uniformly in a concentric pattern around the drop. Here, it was confirmed that copper chlorophyllin sodium was dissolved in water in dispersion (9).

[0084] (Comparative Example 5) 10 mg of red cabbage pigment (manufactured by Kanto Chemical Co., Inc.) and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (10). When one drop of dispersion (10) was dropped onto filter paper, it was observed that a red liquid spread uniformly in a concentric pattern around the drop. It was then confirmed that the red cabbage pigment was dissolved in water in dispersion (10).

[0085] (Comparative Example 6) 10 mg of red cabbage pigment (Kanto Chemical Co., Ltd.), 100 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (11). When one drop of dispersion (11) was dropped onto filter paper, it was observed that a red liquid spread uniformly in a concentric pattern around the drop. It was confirmed that the red cabbage pigment was dissolved in water in dispersion (11).

[0086] (Comparative Example 7) 10 mg of Linablue G1 (DIC Lifetech Corporation, trehalose 55%, spirulina extract 40%, trisodium citrate 5%) and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and stirred for 5 minutes to prepare dispersion (12). When one drop of dispersion (12) was dropped onto filter paper, it was observed that the blue liquid spread uniformly in a concentric pattern around the drop. Here, it was confirmed that the phycocyanin pigment was dissolved in water in dispersion (12).

[0087] (Comparative Example 8) 10 mg of Linablue G1 (DIC Lifetech Co., Ltd., trehalose 55%, spirulina extract 40%, trisodium citrate 5%), 100 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (13). When one drop of dispersion (13) was dropped onto filter paper, it was observed that the blue liquid spread uniformly in a concentric circle around the drop. Here, it was confirmed that the phycocyanin pigment was dissolved in water in dispersion (13).

[0088] Comparative Example 9: 10 mg of annatto dye (Kanto Chemical Co., Ltd.), 100 mg of pearlescent pigment (SunSHINE Spectral Red, DIC Corporation), and 1.0 g of water were added to a 10 mL vial, and a stirrer was added and the mixture was stirred for 5 minutes to prepare dispersion (14). When one drop of dispersion (14) was dropped onto filter paper, a yellow liquid was observed to spread uniformly in a concentric pattern around the drop. This confirmed that the annatto dye was dissolved in water in dispersion (14).

[0089] The coloring materials of the Examples and Comparative Examples were evaluated as lipstick cosmetics, eye cosmetics, nail cosmetics, and hair cosmetics.

[0090] (Evaluation Examples, Comparative Evaluation Examples) (Preparation and Evaluation of Lipstick Cosmetics) Balm cream base (manufactured by Orange Flower Co., Ltd.) and castor oil (manufactured by Orange Flower Co., Ltd.) were measured into a pudding cup and mixed while heating in a water bath at 70°C to 80°C. Powder (1) prepared in Example 1 or the annatto colorant used in Comparative Example 1 was added and mixed while heating. The mixed liquid was filled into a silicone mold with a ring, left to stand for 10 minutes, and then cooled in a refrigerator at 10°C for approximately 10 minutes. Any lipstick cosmetic that protruded from the ring was scraped off with a spatula, and after removing the ring, a lipstick cylinder was inserted. The bottom of the silicone mold was pinched, a small amount of air was let in, and the cylinder was gradually lowered and placed inside the cylinder to obtain a lipstick cosmetic. Table 1 summarizes the lipstick cosmetics prepared.

[0091]

[0092] Each lipstick cosmetic was evaluated for water resistance, coarse particles in appearance, usability, color unevenness, and makeup retention. Water resistance was evaluated by applying the lipstick cosmetic to filter paper and visually checking the degree of bleeding when 1 mL of water was dropped onto the colored area with a dropper. Coarse particles in appearance were evaluated by visually inspecting the lipstick cosmetic. Usability and color unevenness were evaluated by applying the lipstick cosmetic to the wrist. Coarse particles in appearance were evaluated by rubbing the lipstick cosmetic applied to the wrist three times with tissue paper and visually checking color fading. The evaluation results are summarized in Table 2. Water resistance was evaluated as ◯ if there was no bleeding, and × if there was bleeding. Coarse particles in appearance were evaluated as ◯ if there were no coarse particles, and × if there were coarse particles. Usability was evaluated as ◯ if there was good, and × if there was poor. Color unevenness was evaluated as ◯ if there was no color unevenness, and × if there was color unevenness. Coarse particles were evaluated as ◯ if there was no color fading, and × if there was color fading.

[0093]

[0094] As is clear from Table 2, the lipstick cosmetic using the water-insoluble colorant composition of the present invention exhibited superiority in terms of water resistance, coarse grain appearance, feel during use, color unevenness, and cosmetic durability, compared to the lipstick cosmetic using the natural colorant itself.

[0095] (Preparation and Evaluation of Eye Cosmetics) 14.1 g of talc (Yamaguchi Mica Co., Ltd.), 0.02 g of methylparaben (Maruzen Pharmaceuticals Co., Ltd.), 0.02 g of propylparaben (Maruzen Pharmaceuticals Co., Ltd.), and 1.88 g of trihydroxystearin (Matsumoto Trading Co., Ltd.) were weighed into a coffee grinder and stirred for 10 seconds three times to prepare a dispersion base. The dispersion base and powder (1) or annatto pigment prepared in the Examples were added to the coffee grinder and stirred for 5 seconds twice to prepare an eye cosmetic powder. The eye cosmetic powder was placed on a metal plate and pressed to prepare an eye cosmetic. Table 3 summarizes the prepared eye cosmetics.

[0096]

[0097] Each eye cosmetic was evaluated for water resistance, roughness, color unevenness, and makeup retention. Water resistance was evaluated by applying the eye cosmetic to filter paper and visually checking the degree of bleeding when 0.5 mL of water was dropped onto the colored area using a dropper. Roughness and color unevenness were evaluated by applying the eye cosmetic to the wrist. Makeup retention was evaluated by rubbing the eye cosmetic applied to the wrist three times and then evaluating the color. The evaluation results are summarized in Table 4. Water resistance was evaluated as ◯ if it did not bleed, and × if it bleed. Roughness was evaluated as ◯ if there was no roughness, and × if there was roughness. Color unevenness was evaluated as ◯ if there was no unevenness in the color, and × if there was unevenness in the color. Makeup retention was evaluated as ◯ if there was no color fading, and × if there was color fading.

[0098]

[0099] As is clear from Table 4, the eye cosmetics using the water-insoluble pigment composition of the present invention showed superiority in terms of water resistance, roughness, uneven color, and cosmetic durability compared to eye cosmetics using natural pigments themselves.

[0100] (Preparation and Evaluation of Nail Cosmetics) Powder (1) or annatto pigment prepared in the Examples and 1.7 g of Nailholic Base Coat (color: SP030, manufactured by Kose Corporation) were added to a 20 mL plastic bottle and mixed with a dropper. Nailholic Base Coat was then added to the bottle to prepare nail cosmetics. Table 5 summarizes the prepared nail cosmetics.​

[0101]

[0102] Each nail cosmetic was evaluated for water resistance, unevenness of the applied surface, and color unevenness. Water resistance was evaluated by applying the nail cosmetic to filter paper and visually checking the degree of bleeding when 1 mL of water was dropped onto the colored area using a dropper. Color unevenness and unevenness of the applied surface were evaluated by applying the nail cosmetic to a nail tip, allowing it to dry, and then checking the appearance and feel of the applied surface. The evaluation results are summarized in Table 6. Water resistance was evaluated as ◯ if there was no bleeding, and × if there was bleeding. Application surface unevenness was evaluated as ◯ if there was no unevenness, and × if there was unevenness. Color unevenness was evaluated as ◯ if there was no unevenness in the coloring, and × if there was unevenness in the coloring.

[0103]

[0104] As is clear from Table 6, the nail cosmetics using the water-insoluble dye composition of the present invention showed superiority in terms of water resistance, unevenness of the applied surface, and color unevenness compared to nail cosmetics using natural dyes themselves.

[0105] (Preparation and Evaluation of Hair Color Cream) A hair color cream was prepared as a hair cosmetic and evaluated. Distilled water, propylene glycol (manufactured by Koyo Fine Chemical Co., Ltd.), polyquaternium-37 dicaprylyl carbonate lauryl glucoside (manufactured by BASF Japan Ltd.), and 0.016 g of EDTA-2Na (manufactured by BASF Japan Ltd.) were weighed into a 50 mL beaker and mixed with a stirrer until uniform. Powder (1) or annatto pigment prepared in the Examples was added to the mixture and mixed with a spatula until uniform. Next, methylparaben (manufactured by Maruzen Pharmaceuticals Co., Ltd.) and propylparaben (manufactured by Maruzen Pharmaceuticals Co., Ltd.) were added and mixed with a spatula until uniform, thereby preparing a hair color cream. The hair color creams prepared are summarized in Table 7.

[0106]

[0107] (Hair Color Evaluation Method) (Color Development Evaluation) <Color Development When Applied to Blonde Human Hair> The hair color cream was spread by hand onto blonde human hair, and the color development was evaluated visually. Good color development on blonde hair was rated ◯, and poor color development was rated ×. <Color Development When Applied to Black Human Hair> The hair color cream was spread by hand onto black human hair, and the color development was evaluated visually. Good color development on black hair was rated ◯, and poor color development was rated ×. <Color Development When Applied to Artificial Skin> The hair color cream was spread on artificial skin in a circular motion with the fingers, and the color development was evaluated visually. Good color development on the artificial skin was rated ◯, and poor color development was rated ×.

[0108] (Evaluation of Water Resistance) The hair color cream was spread on filter paper in a circular motion with a finger and allowed to dry at room temperature for about 10 minutes. Subsequently, 1 mL of tap water was dropped onto the center of the colored area using a dropper. At this time, if the dropped area remained colored the same as before the drop, and if a colorless, transparent solution was observed to spread concentrically from the colored area, it was evaluated that the hair color cream did not bleed into water. The water resistance was evaluated as ◯ if there was no bleeding, and × if there was bleeding.

[0109] (Evaluation of Pigmentation) A hair color cream was applied evenly to blonde human hair and allowed to dry at room temperature for approximately 10 minutes. The blonde human hair was hand-washed using half a pump of shampoo (LUX super rich shine Damage Repair Moist Repair Shampoo, manufactured by Unilever Japan Co., Ltd.), and the shampoo was thoroughly rinsed off with tap water at room temperature. Furthermore, half a pump of conditioner (LUX super rich shine Damage Repair Moist Repair Conditioner, manufactured by Unilever Japan Co., Ltd.) was applied, and the shampoo was then rinsed off with tap water at room temperature. After washing, the blonde human hair was dried with hot air from a hair dryer for approximately 2 minutes, and the presence or absence of pigmentation was checked. If no pigmentation was observed, it was marked with ◯, and if pigmentation was observed, it was marked with ×. Table 8 summarizes the evaluation results of the prepared hair cosmetics.

[0110]

[0111] As is clear from Table 8, the hair cosmetic preparations using the water-insoluble dye composition of the present invention were superior to hair cosmetic preparations using natural dyes themselves in terms of color development on black hair, color development on artificial skin, water resistance, and pigmentation.

[0112] As described above, lipstick cosmetics, eye cosmetics, nail cosmetics, and hair cosmetics containing the water-insoluble dye composition of the present invention exhibited superior performance compared to cosmetics containing natural dyes themselves. It is believed that the water-insoluble dye composition of the present invention exhibits superior performance by combining the natural dye with one or more substances selected from pearl pigments and boron nitride, and the powders described in the examples exhibited superior performance as cosmetics.

Claims

1. A water-insoluble dye composition comprising a complex of a natural dye and one or more substances selected from a pearl pigment or boron nitride.

2. The water-insoluble dye composition according to claim 1, wherein the mass ratio of the natural dye to the one or more substances selected from the group consisting of pearl pigments and boron nitride is natural dye:one or more substances selected from the group consisting of pearl pigments and boron nitride=0.1:99.9 to 90:

10.

3. The water-insoluble dye composition according to claim 1 or 2, wherein the pearl pigment is at least one selected from the group consisting of a pigment in which one or more particles selected from mica, talc, and glass are coated with titanium oxide, and bismuth oxychloride.

4. The water-insoluble dye composition according to claim 1 or 2, wherein the natural dye is at least one selected from the group consisting of carotenoid dyes, porphyrin dyes, flavonoid dyes, and pigment proteins.

5. The water-insoluble dye composition according to claim 1 or 2, wherein the natural dye is at least one selected from the group consisting of annatto dye, chlorophyll dye, safflower yellow dye, and phycocyanin dye.

6. Food, cosmetics, lipstick cosmetics, eye cosmetics, nail cosmetics, base makeup cosmetics, hair cosmetics, medicines, agricultural chemical coating materials, printing markers, stationery, writing implements, printing inks, inkjet inks, metal inks, paints, plastic colorants, color toners, fluorescent markers, fluorescent probes, or chemical sensors, characterized by containing the water-insoluble dye composition according to claim 1 or 2.

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