Water-insoluble pigment composition

Abstract

The purpose of the present invention is to provide: a water-insoluble pigment composition; and a food product, a cosmetic product, a lipstick cosmetic product, a periorbital cosmetic product, a nail cosmetic product, a base cosmetic product, a pharmaceutical product, an agricultural chemical coating material, a printing mark, a stationary material, a writing instrument, a printing ink, an inkjet ink, a metallic ink, and a coating material containing the water-insoluble pigment composition. The present invention relates to a non-water-soluble pigment composition, a plastic colorant, a color toner, a fluorescent marker, a fluorescent probe or a chemical sensor, the non-water-soluble pigment composition being obtained by compounding a natural pigment and at least one selected from hydroxyapatite and clay minerals. It has been found that a water-insoluble pigment composition is obtained by complexing a natural pigment with hydroxyapatite or a clay mineral, and the present invention has been completed.

Description

Technical Field

[0001] The present invention relates to a pigment composition. Background Art

[0002] As natural pigments, there are various red pigments, yellow pigments, and blue pigments. However, in recent years, due to problems such as carcinogenicity, synthetic colorants have been suspected, and the expectation for natural pigments, which are considered to be safer, has increased.

[0003] In addition, there is a strong awareness that sustainable business activities are attracting attention, and there is a demand for environmentally friendly color materials. Under such circumstances, most natural pigments are easily soluble in water. Therefore, when used in cosmetics or food colorants, there are problems such as dissolution in water and accompanying color fading. In addition, when used in flexographic printing, problems such as migration and plate contamination occur. Therefore, at present, they can only be used in very limited applications.

[0004] The inventors investigated the literature that describes solutions to the problems of dissolution and color fading of natural pigments in water, that is, improvement of water solubility. As a result, there are descriptions of extraction methods of natural pigments, and descriptions of oral administration cosmetics, dairy products, and pet foods using the extracts (Patent Document 1). In addition, there is a description of dry-mixing carotenoid-based pigments with sodium tartrate, alum, and sodium carbonate for the purpose of stabilizing the hue, and dissolving the mixed powder in water to obtain an aqueous solution (Patent Document 2). In addition, there is a description of a powder composition containing carotenoids, an oily component, and sugar (Patent Document 3).

[0005] However, these documents cannot improve the water solubility of natural pigments. There are no examples where the water solubility of natural pigments has been improved, which is a desired subject.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-508505

[0009] Patent Document 2: Japanese Patent Publication No. 59-050264

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2009-185023 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] An object of the present invention is to provide a water-insoluble pigment composition, and a food, a cosmetic, a lip cosmetic, a periocular cosmetic, a nail cosmetic, a base makeup cosmetic, a pharmaceutical, a coating material for pesticides, a printing marker, a stationery, a writing instrument, a printing ink, an inkjet ink, a metal ink, a paint, a plastic colorant, a color toner, a fluorescent marker, a fluorescent probe or a chemical sensor containing the water-insoluble pigment composition.

[0013] Means for solving the problem

[0014] The inventors of the present invention repeatedly conducted in-depth research to solve the above problems, and as a result, found that by compounding a natural pigment with hydroxyapatite or clay mineral, a water-insoluble pigment composition is obtained, and thus the present invention was completed.

[0015] That is, the present invention includes the following aspects. [1]

[0017] A water-insoluble pigment composition obtained by compounding a natural pigment with at least one selected from hydroxyapatite and clay mineral. [2]

[0019] The water-insoluble pigment composition according to 1, wherein the composition of the natural pigment and at least one selected from hydroxyapatite and clay mineral is such that the mass ratio of natural pigment:hydroxyapatite or clay mineral = 0.1:99.9 to 90:10. [3]

[0021] The water-insoluble pigment composition according to 1 or 2, wherein the clay mineral is at least one selected from bentonite, hectorite, and smectite. [4]

[0023] The water-insoluble pigment composition according to any one of 1 to 3, wherein the clay mineral is at least one selected from organically treated bentonite, hectorite, and smectite. [5]

[0025] The water-insoluble pigment composition according to any one of 1 to 4, wherein the natural pigment is at least one selected from carotenoid pigments, porphyrin pigments, flavonoid pigments, and pigment proteins. [6]

[0027] The water-insoluble pigment composition according to any one of 1 to 4, wherein the natural pigment is at least one selected from annatto pigment, chlorophyll pigment, safflower yellow pigment, and phycocyanin pigment. [7]

[0029] A coating material for foods, cosmetics, lip cosmetics, eye cosmetics, nail cosmetics, base makeup cosmetics, pharmaceuticals, pesticides, printing markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, coatings, plastic colorants, color toners, fluorescent markers, fluorescent probes or chemical sensors, characterized by containing the water-insoluble pigment composition according to any one of 1 to 6.

[0030] Advantages of the Invention

[0031] According to the present invention, a water-insoluble pigment composition can be provided. Detailed Description of the Invention

[0032] Hereinafter, the water-insoluble pigment composition of the present invention will be described in detail. However, the description of the constituent elements described below is an example of one embodiment of the present invention and is not limited to these contents.

[0033] (Natural Pigments)

[0034] The natural pigments used in the present invention can be used as long as they are pigments of natural origin such as red cabbage pigment, radish red pigment, annatto pigment, squid melanin, curcumin, cocoa pigment, carotenoid pigment, carotenoid pigment, gardenia red pigment, gardenia blue pigment, gardenia yellow pigment, chlorophyll pigment, sorghum pigment, cochineal pigment, saffron pigment, perilla pigment, red sandalwood pigment, spirulina pigment, phycocyanin pigment, onion pigment, tamarind pigment, butterfly pea pigment, capsanthin, 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, vegetable carbon black pigment, etc. In addition, substances obtained by biosynthesis, enzyme synthesis, or chemical synthesis of these pigments can also be used.

[0035] Among them, as the pigments that can be preferably used in the present invention, there are carotenoid pigments, porphyrin pigments, flavonoid pigments, and pigment proteins.

[0036] Regarding carotenoid pigments, it is known that red pigments extracted from carrots, tomatoes, and peppers, and yellow pigments extracted from citrus fruits, gardenias, annatto, and marigolds, etc. are also abundantly contained in green leafy vegetables.

[0037] Carotenoids are substances belonging to the tetraterpenes among terpenoid compounds. Terpenoids are important compounds for plants, and more than 20,000 compounds are known. As carotenoid pigments, hydrocarbon pigments such as β-carotene and lycopene are known; xanthophyll pigments such as astaxanthin, capsanthin, and lutein; and other carminic acid, norcarminic acid, and crocin.

[0038] Porphyrin-based pigments have four pyrrole rings, and their metal complexes are included in chlorophyll that plays a role in light absorption and photoelectron transfer in photosynthesis, heme of hemoglobin that transports oxygen in the blood, etc., and are compounds that play important roles in organisms. Porphyrin metal complexes are used in many aspects as optoelectronic functional materials, metal complex catalysts, and molecular conductive materials, and it is known that various functions are actually exhibited by changing the peripheral substituents, central metal, and axial ligands of porphyrin.

[0039] Flavonoids are one of the major classifications of polyphenols. Flavonoids are a general term for components with a certain chemical structure, are contained in the leaves, stems, trunks, etc. of plants, and are substances produced by plants to protect themselves from ultraviolet rays, pests, etc., and become the sources of pigments and bitter components. In addition, flavonoids are classified into flavonols, flavones, catechins, flavanones, anthocyanins, isoflavones, etc. according to their structures.

[0040] As flavonoid-based pigments, flavonols, anthocyanin pigments showing various hues, chalcones showing deep yellow color, aurones, etc. can be cited.

[0041] (Pigment protein)

[0042] Pigment proteins are a general term for proteins complexed with pigments in their natural state. Through prosthetic groups containing pigments present in the cells and body fluids of animals and plants, various hues and physiological functions are expressed. Hemoprotein is a combination of iron-porphyrin complex salt and protein, and the binding ratio of protein to heme is 1:1, 1:2, 1:4, etc. It is widely present in nature, and there are hemoglobin, myoglobin, cytochrome, catalase, peroxidase, etc.

[0043] Metal complexes are combinations of metal complex ions and proteins, and there are copper proteins such as hemocyanin and iron proteins such as ferritin. Ferritin is present in the spleen, small intestinal mucosa, liver, etc., and is considered to be related to the storage of iron in the body and the absorption of iron during digestion.

[0044] Phycobiliproteins are combinations of pyrrole derivatives and proteins, and there are phycoerythrin showing red color in red algae plants, phycocyanin showing blue color in cyanobacteria plants, etc. They are contained in chloroplasts along with chlorophyll and carotenoids, and are considered to be auxiliary pigments for photosynthesis.

[0045] Flavoproteins have flavin mononucleotide or flavin adenine dinucleotide as prosthetic groups. All have the function of oxidoreductase and are also called flavoenzymes. There are amino acid oxidase, xanthine oxidase, etc.

[0046] Carotenoid proteins are combinations of carotenoids and proteins. Examples include combinations of vitamin A and proteins, and rhodopsin is one of them.

[0047] (Phycocyanin)

[0048] As the pigment protein used in the present invention, starting from the vivid blue color development, phycocyanin is most preferred. Phycocyanin is a pigment protein and has phycocyanobilin as a chromophore. Phycocyanin has a structure formed by the combination of phycocyanobilin and protein.

[0049] Examples of the phycocyanin related to the present invention include phycocyanin from cyanobacteria, phycocyanin from red algae, phycocyanin from cryptophytes, etc., among which, starting from the ability to be collected in large quantities, phycocyanin from cyanobacteria is preferred.

[0050] Examples of cyanobacteria include, for example: genera such as Spirulina, Arthrospira, Aphanizomenon, Fisherella, Anabaena, Nostoc, Synechocystis, Synechococcus, Tolypothrix, Aphanothece, Mastigocladus, Pleurocapsa, etc. Among them, cyanobacteria of the genera Spirulina and Arthrospira that are produced on an industrial scale and whose safety has been confirmed are preferred, and cyanobacteria of the genus Spirulina are more preferred.

[0051] In addition, as a raw material for preparing phycocyanin, live cyanobacteria can be used, or dried cyanobacteria can be used. The dried product of cyanobacteria can be prepared from live cyanobacteria by a conventional method, or a commercially available dried product can be used.

[0052] Phycocyanin can be obtained, for example, by suspending cyanobacteria in a buffer such as water, phosphate buffer, or citrate buffer and extracting phycocyanin from the cyanobacteria.

[0053] As a method for extracting phycocyanin, there is no particular limitation, and a generally known method can be used.

[0054] As a preferred embodiment of the extraction method, for example, the extraction method described in Japanese Patent Laid-Open No. 2006-230272 can be cited. Specifically, the extraction method described in the following extraction method (i) can be cited. By this extraction method (i), phycocyanin with high purity and vivid color tone can be obtained.

[0055] <Extraction method (i)>

[0056] The extraction method (i) has the following steps:

[0057] The first step is to obtain an extract in which phycocyanin in cyanobacteria is extracted into an aqueous suspension; the second step is to react a calcium salt with a phosphate in the extract to form calcium phosphate, and to adsorb the inclusion of phycocyanin to the calcium phosphate to obtain an adsorbate; and the third step is to remove the residue of cyanobacteria and the adsorbate from the extract.

[0058] Furthermore, it is more preferable that the above extraction method (i) is the following extraction method (ii).

[0059] <Extraction method (ii)>

[0060] The extraction method (ii) has the following steps:

[0061] The first step is to obtain an extract in which phycocyanin in cyanobacteria is extracted into an aqueous suspension; the second step is to react a calcium salt with a phosphate in the extract to form calcium phosphate, and to adsorb the inclusion of phycocyanin to the calcium phosphate to obtain an adsorbate; the third step is to remove the residue of cyanobacteria and the adsorbate from the extract; and before the third step, a step of making the extract contain a chelating agent.

[0062] The phycocyanin used in the present invention is used from LINABLUE G1 (manufactured by DIC Life Science Co., Ltd., 55% trehalose, 40% spirulina extract, 5% trisodium citrate) which is a commercially available product mixed with a stabilizer. As described in Japanese Patent Laid-Open No. 11-299450, trehalose is used to improve thermal stability, and citric acid is used as a pH regulator. It should be noted that the phycocyanin pigment is contained as the main component in the spirulina extract.

[0063] In the present invention, a single natural pigment can be used alone, or multiple natural pigments can be used simultaneously. Depending on the application, in order to adjust the color to a desired hue, the natural pigments can be premixed and compounded with a carrier substance, or after compounding a single natural pigment and a carrier substance, the non-water-soluble pigment compositions compounded respectively can be mixed.

[0064] In the present invention, a single natural pigment can be used alone, or multiple natural pigments can be used simultaneously. Depending on the application, in order to adjust the color to a desired hue, the natural pigments can be premixed and compounded with hydroxyapatite and clay minerals, or after compounding a single natural pigment with hydroxyapatite and clay minerals, the non-water-soluble pigment compositions compounded respectively can be mixed.

[0065] (Hydroxyapatite)

[0066] The hydroxyapatite used in the present invention is a kind of calcium phosphate and is the main component of teeth and bones. Since hydroxyapatite existing as a mineral or a constituent of organisms in nature has high biocompatibility, it is widely used as a synthetic component in medical devices and dental materials (such as coatings for implants, bone-forming materials, artificial tooth roots, etc.). In addition, hydroxyapatite has unique properties. Even if a part of the ions in the crystal are replaced, its crystal structure can be maintained. As a result, by subtly controlling the ions and crystal shape in the crystal, various functions such as selective adsorption function and catalytic function for expressing proteins can be achieved, so it is also a substance widely used in the chemical industry field.

[0067] Regarding hydroxyapatite, there is a tendency that the lower the crystallinity, the larger the specific surface area and the higher the adsorption capacity. From this viewpoint, the hydroxyapatite used in the present invention preferably uses low-crystalline hydroxyapatite with a Ca / P (molar ratio) of 1.4 to 1.8 as the carrier substance. Similarly, from the viewpoint of the adsorption amount, the specific surface area measured by the nitrogen adsorption method is preferably 10 m 2 / g or more (more preferably 40 m 2 / g or more). Regarding the adsorption amount, there is a tendency that the larger the volume of hydroxyapatite, the greater the adsorption amount. The volume is preferably 500 mL / 100 g or more (more preferably 900 mL / 100 g or more). The average particle size is preferably 0.1 to 40 μm, more preferably 10 to 30 μm.

[0068] (Clay minerals)

[0069] Clay minerals are the minerals that make up clay, and the main component is layered silicate minerals (phyllosilicate minerals). Sheets formed by the connection of metal ions (such as aluminum, sodium, calcium, etc.) and silicic acid are in a layered form. Water, metal ions are easily absorbed and released in the gaps of the sheets, and in some cases, organic substances are also easily absorbed and released. Therefore, as functional materials such as humidity adjustment, ion exchangeability, and catalysts, they are used in a variety of fields represented by daily necessities. In addition, they are used as raw materials for ceramics and pottery.

[0070] As the clay minerals used in the present invention, bentonite, lithium montmorillonite, smectite, kaolinite (kaolin), montmorillonite, sericite, illite, glauconite, chlorite, talc, zeolite, etc. can be cited.

[0071] Among them, bentonite, lithium montmorillonite, and smectite have high affinity with pigments, high non-water-soluble performance, and excellent color development performance, so they are preferably used as the clay minerals of the present invention.

[0072] The crystal phases of bentonite, hectorite, and smectite carry negative charges. Cations that maintain the deviation of the compensating charge are present between the layers of the sheet-like structure and have a large expansion in the plane relative to the thickness of the sheet.

[0073] Organic treatment refers to the treatment of allowing organic compounds to enter the interlayers of clay minerals or adsorb on their surfaces. In the present invention, the organic compounds used in the organic treatment are not particularly limited, and examples include organic compounds having a cationic group, and particularly preferably organic compounds having an ammonium group. The molecular weight of the above organic compounds is not particularly limited, and the number of carbon atoms is preferably 10 to 500, more preferably 20 to 100. In addition, as the organic treatment agent, in addition to the compound itself, its salts are also included. Regarding organic compounds, specific examples include quaternary ammonium such as dialkyldimethylammonium, alkyltrimethylammonium, alkyldimethylammonium, and alkyldimethylbenzylammonium; phosphonium, sulfonium, imidazolium, and pyridinium, and among them, quaternary ammonium is particularly preferred. The quaternary ammonium is not particularly limited, and preferably dimethyldidecylammonium, dimethyldistearylammonium, cetyltrimethylammonium, etc. are used.

[0074] The surfaces of the organically treated organobentonite, organohectorite, and organosmectite become hydrophobic, and thus the hydrophobic interaction with the hydrophobic parts in the chemical structures of natural pigments such as bixin pigment, chlorophyll pigment, safflower yellow pigment, and phycocyanin pigment becomes stronger, and the pigments are more easily adsorbed. From the viewpoints of the ease of pigment adsorption and the adsorption amount, in the present invention, clay minerals after organic treatment are preferably used.

[0075] The particle shape of the clay mineral used preferably has a secondary particle size of 0.1 to 100 μm, more preferably 5 to 50 μm.

[0076] (Water-insoluble pigment composition)

[0077] Most of the natural pigments used in the present invention are derived from nature, and thus are basically in the form of dyes and are water-soluble. However, in the present invention, it has been found that natural pigments are firmly complexed with hydroxyapatite or clay minerals due to the forms of coating, impregnation, and adsorption, and are insoluble in water as a water-insoluble pigment composition. The complexation mentioned here is not limited to the modes of action such as coating, impregnation, and adsorption, and is defined not only as a mixture, but also as a substance that can form water-insolubility through physical adsorption or chemical adsorption, in which natural pigments have an interaction with hydroxyapatite and clay minerals.

[0078] Through the water-insolubilization obtained by the present invention, the natural pigment can be improved to be used as a coloring material equivalent to ordinary pigments in applications such as coating materials or printing marks for foods, cosmetics, lip cosmetics, eye cosmetics, nail cosmetics, base makeup cosmetics, pharmaceuticals or pesticides, stationery, writing tools, printing inks, inkjet inks, metal inks, coatings, plastic colorants, color toners, fluorescent markers, fluorescent probes or chemical sensors, etc. In addition, with insolubilization, it is also possible to expect improvement in properties such as heat resistance and light resistance. In addition, the use of the water-insoluble pigment composition of the present invention is not limited to the above applications.

[0079] As the water-insoluble pigment composition of the present invention, the composition of the natural pigment and hydroxyapatite or clay mineral can be set to natural pigment:hydroxyapatite or clay mineral = 0.1:99.9 to 90:10 by mass ratio for use. Preferably, natural pigment:hydroxyapatite or clay mineral = 1:99 to 70:30.

[0080] The average particle size of the water-insoluble pigment composition of the present invention is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm.

[0081] In the water-insoluble pigment composition of the present invention, the content rate of the elements derived from the hydroxyapatite or clay mineral used is preferably 99% or less, more preferably 90% or less, and further preferably 85% or less compared to the hydroxyapatite or clay mineral itself.

[0082] (Method for manufacturing water-insoluble pigment composition)

[0083] As a method for manufacturing the water-insoluble pigment composition of the present invention, a method of mixing a natural pigment and hydroxyapatite or clay mineral in a solvent can manufacture the most uniform water-insoluble pigment composition, and thus is preferred.

[0084] As a method for manufacturing a water-insoluble pigment composition by mixing each substance in a solvent, 1) First, a dispersion of hydroxyapatite or clay mineral is prepared. 2) On the other hand, the natural pigment is dissolved in water to prepare an aqueous solution. 3) Then, the above two liquids are mixed to prepare a water-insoluble pigment composition. However, it is also possible to mix the natural pigment aqueous solution in the dispersion of hydroxyapatite or clay mineral. On the contrary, it is also possible to mix the dispersion of hydroxyapatite or clay mineral in the natural pigment aqueous solution, or it is also possible to prepare it by mixing these two liquids little by little each time. The mixing temperature can be room temperature or heating mixing. Considering the decomposition temperature of the natural pigment monomer, it is preferably mixed at 10 to 60 °C, more preferably 20 to 50 °C. 4) The pH of the mixed solution is adjusted to complex the natural pigment with the carrier substance to form a water-insoluble pigment composition.

[0085] The obtained mixture is filtered and dried to obtain a water-insoluble pigment composition. When filtering the mixture with a filter such as a Nutsche filter, the filtrate is not colored, so it can be confirmed that the natural pigment is complexed with hydroxyapatite or clay mineral. In addition, the wet filter cake of the water-insoluble pigment composition is further repeatedly washed with water. Similarly, the filtrate is colorless and transparent, and it can be confirmed that the pigment component does not flow out. The obtained water-containing wet filter cake of the water-insoluble pigment composition can be dried by methods such as room temperature drying, heating drying, vacuum drying, and reduced-pressure drying to obtain a dried water-insoluble pigment composition. The drying method and dryer can be ordinary methods and devices without limitation.

[0086] The water-insoluble pigment composition of the present invention can be separately used according to the use, whether it is the above-mentioned wet filter cake containing water or the dried water-insoluble pigment composition after drying. In the case of being used in an aqueous dispersion or ink, the wet filter cake can be directly used. In the case of a solvent dispersion system, it can be used after being replaced from an aqueous system to a solvent system. The dried water-insoluble pigment composition can be directly used or can be redispersed in water, an organic solvent, a resin solution, etc. for use.

[0087] (Stabilizers, additives)

[0088] Of course, other organic pigments, inorganic pigments, dyes, and pigments can also be mixed in the water-insoluble pigment composition of the present invention in any proportion to meet the required hue.

[0089] In order to further impart light resistance and heat resistance to the water-insoluble pigment composition of the present invention, stabilizers and additives can also be added.

[0090] The stabilizers and additives can be added to the dispersion of hydroxyapatite or clay mineral and the aqueous solution of natural pigment respectively, or added to both of them, or added to the prepared water-insoluble pigment composition.

[0091] The water-insoluble pigment composition of the present invention can be mixed with other resins, rubbers, additives, pigments, dyes, etc. as needed to be prepared into final food, cosmetics, lip cosmetics, eye cosmetics, nail cosmetics, base makeup cosmetics, pharmaceuticals, coating materials for pesticides, printing marks, stationery, writing tools, printing inks, inkjet inks, metal inks, coatings, plastic colorants, color toners, fluorescent markers, fluorescent probes or chemical sensors for use. Hereinafter, an example of the above uses is shown.

[0092] (Cosmetic uses)

[0093] The water-insoluble pigment composition of the present invention can be used as a cosmetic. The cosmetics used are not particularly limited, and the water-insoluble pigment composition of the present invention can be used in various types of cosmetics such as powders, liquids, gels, and solids.

[0094] As long as the above-mentioned cosmetics can effectively exhibit their functions, they can be any type of cosmetics. The above-mentioned cosmetics can be lotions, creams, gels, sprays, etc. Examples of the above-mentioned cosmetics include skin care cosmetics such as facial cleansers, makeup removers, lotions, essences, masks, protective lotions, protective creams, whitening cosmetics, anti-UV cosmetics, etc.; color cosmetics such as foundations, face powders, makeup bases, lip cosmetics, eye makeup, blushes, nail polishes, etc.; hair care cosmetics such as shampoos, conditioners, hair masks, hair styling agents, hair perming agents, hair dyes, hair growth agents, etc.; body care cosmetics such as body cleansing cosmetics, deodorant cosmetics, bath agents, etc.

[0095] The amount of the water-insoluble pigment composition of the present invention used in the above-mentioned cosmetics can be appropriately set according to the type of the cosmetics. The content in the above-mentioned cosmetics is usually in the range of 0.1 to 99% by mass, and is usually preferably in the range of 0.1 to 10% by mass. On the other hand, for makeup cosmetics for the purpose of coloring, the amount is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and most preferably 20 to 60% by mass. If the amount of the water-insoluble pigment composition of the present invention contained in the cosmetics is within the above range, functions such as coloring can be effectively exhibited, and the functions required for the cosmetics can also be maintained.

[0096] According to the type of the cosmetics, the above-mentioned cosmetics may contain, in addition to the water-insoluble pigment composition of the present invention, carriers, pigments, oils, sterols, amino acids, humectants, powders, colorants, pH regulators, fragrances, essential oils, cosmetic active ingredients, vitamins, essential fatty acids, sphingolipids, self-tanners, excipients, fillers, emulsifiers, antioxidants, surfactants, chelating agents, gelling agents, thickeners, emollients, wetting agents, humectants, minerals, viscosity regulators, flow regulators, keratolytic agents, retinoids, hormone compounds, α-hydroxy acids, α-keto acids, anti-mycobacterial agents, anti-fungal agents, antibacterial agents, antiviral agents, analgesics, anti-allergy agents, antihistamines, anti-inflammatory agents, anti-irritants, anti-tumor agents, immune system enhancers, immune system inhibitors, anti-acne agents, anesthetics, disinfectants, insect repellents, skin cooling compounds, skin protectants, skin penetration enhancers, exfoliants, lubricants, fragrances, dyes, decolorants, hypopigmenting agents, preservatives, stabilizers, pharmaceuticals, light stabilizers, and spherical powders, etc. which are permissible as cosmetic ingredients.

[0097] In order to adjust the tone of the cosmetic, one or more pigments and dyes other than the water-insoluble pigment composition may also be added. Examples of the pigments and dyes include white pigments, colored pigments, extender pigments, pearlescent pigments, etc. Examples of the white pigments include titanium oxide and zinc oxide. Examples of the colored pigments include inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as iron oxide yellow and loess; inorganic black pigments such as iron oxide black and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide, and cobalt titanate; inorganic blue pigments such as Prussian blue and ultramarine; substances obtained by lake-forming tar-based pigments (dyes) (Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 228, Yellow No. 401, Blue No. 404, Orange No. 203, Orange No. 204, etc.), red tar-based pigments (dyes) (Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 226, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Blue No. 1, Blue No. 2, Blue No. 201, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 206, Orange No. 207, carminic acid, laccaic acid, etc.), and synthetic resin powders obtained by compounding these powders. Examples of the extender pigments include silicic acids such as silica and hydrous silicic acid; silicates such as aluminum silicate and magnesium silicate; clay minerals such as talc, kaolin, bentonite, mica, and sericite; phosphate minerals such as hydroxyapatite; metal oxides such as aluminum oxide and magnesium oxide; carbonates of alkaline earth metals such as light calcium carbonate, heavy calcium carbonate, light magnesium carbonate, and heavy magnesium carbonate; sulfates of alkaline earth metals such as magnesium sulfate and barium sulfate (plate-shaped barium sulfate, butterfly-shaped barium sulfate, etc.); boron nitride; organic powders such as lauroyl lysine and metal soaps; plate-shaped synthetic powders such as synthetic mica; resin powders such as nylon beads, nylon powder, and silicone beads. Furthermore, surface treatments such as silicone treatment, fluorine compound treatment, silane coupling agent treatment, silane treatment, organic titanate treatment, acylated lysine treatment, fatty acid treatment, metal soap treatment, oil treatment, and amino acid treatment may be performed on these powders. Examples of the pearlescent pigments include mica coated with titanium oxide, mica coated with titanium oxide, bismuth oxychloride, bismuth oxychloride coated with titanium oxide, talc coated with titanium oxide, fish scale foil, and colored mica coated with titanium oxide.

[0098] The above-mentioned cosmetics can be manufactured by mixing the water-insoluble pigment composition of the present invention and other cosmetic ingredients. In addition, the cosmetics containing the water-insoluble pigment composition of the present invention can be used in the same manner as ordinary cosmetics according to the type of the cosmetics, etc.

[0099] (For use in inks and coatings)

[0100] The water-insoluble pigment composition of the present invention can be used as an ink or a coating. However, the uses and compositions of the ink and the coating are described, but not limited thereto. In addition, the water-insoluble pigment composition of the present invention can be dispersed only in a thermoplastic resin, or can be dispersed in a color carrier for printing ink, a color carrier for coating, etc. containing a thermoplastic resin as an essential component.

[0101] As the thermoplastic resin, for example, polyester resin, polyamide resin, styrene resin, acrylic resin, polyolefin, alkylene terephthalate, polyvinyl chloride resin and other resins can be used as the resin for dispersion.

[0102] For example, the color carrier for offset printing ink is manufactured from raw materials such as 20 - 50 (mass)% of resins such as rosin-modified phenolic resin, petroleum resin, alkyd resin, 0 - 30 (mass)% of animal and vegetable oils such as linseed oil, tung oil, soybean oil, 10 - 60 (mass)% of solvents such as n-paraffin, iso-paraffin, naphthene, α-olefin, aromatic hydrocarbon, and several (mass)% of other additives such as solubilizers and gelling agents.

[0103] In addition, in the case of the color carrier for gravure printing ink and flexographic printing ink, for example, it is manufactured from raw materials such as 10 - 50 (mass)% of one or more resins selected from rosin, maleic resin, polyamide resin, vinyl resin, cyclized rubber, chlorinated rubber, ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin, alkyd resin, nitrocellulose, cellulose acetate, etc., and 30 - 80 (mass)% of solvents such as alcohols, toluene, n-hexane, ethyl acetate, cellosolve, butyl cellosolve.

[0104] The color carrier for coating is manufactured from raw materials such as 20 - 80 (mass)% of resins such as alkyd resin, epoxy resin, acrylic resin, polyurethane resin, polyester resin, melamine resin, urea resin, water-soluble resin, and 10 - 60 (mass)% of solvents such as hydrocarbons, alcohols, ketones, water.

[0105] (Plastic use)

[0106] The water-insoluble pigment composition of the present invention can also be used for plastic coloring. When obtaining a colored plastic molded article, for example, polyolefins such as polyethylene and polypropylene; thermoplastic resins (plastics) for thermoforming such as injection molding and compression molding of polyvinyl chloride resin can be used, and the water-insoluble pigment composition of the present invention can be kneaded into these resins by a conventionally known method for use.

[0107] (Toner use)

[0108] The water-insoluble pigment composition of the present invention can also be used for toner coloring applications. When obtaining a toner for electrostatic image development, a film-forming thermoplastic resin that is solid at room temperature, such as a polyester resin, polyamide resin, styrene resin, or acrylic resin, is used as the dispersion resin.

[0109] The toner for electrostatic image development manufactured using the water-insoluble pigment composition of the present invention can be used as a one-component color magnetic toner containing a magnetic body in the toner (color toner for magnetic one-component development), a non-magnetic one-component color toner not containing a magnetic body (color toner for non-magnetic one-component development), or a color toner for two-component development mixed with a carrier (color toner for two-component development).

[0110] The one-component color magnetic toner, like the commonly used toner, can be composed of, for example, a colorant, a binder resin, magnetic powder, a charge control agent (CCA), a release agent, and other additives.

[0111] The amount of the water-insoluble pigment composition used in the toner for electrostatic image development is not particularly limited, and it is preferably used in a proportion of 0.5 to 25 parts by mass relative to 100 parts by mass of the binder resin. From the aspect of making the charging performance of the colorant itself more significant, it is further preferably 4 to 10 parts by mass relative to 100 parts by mass of the binder resin.

[0112] As the binder resin used in the toner for electrostatic image development, any of the well-known and commonly used binder resins exemplified as the above thermoplastic resins can be used, and any of the synthetic resins, natural resins, natural rubbers, synthetic rubbers, synthetic waxes, etc. that exhibit adhesiveness under the application of heat or pressure can be used.

[0113] Examples

[0114] The following examples are given to further elaborate the present invention, but the scope of the present invention is not limited to these examples.

[0115] (Example 1)

[0116] Add 20.0 g of hydroxyapatite (manufactured by Fujifilm Wako Pure Chemical Corporation) and 1000 g of ion-exchanged water to a 3 L beaker, and stir with a glass stirring blade connected to a Three-One Motor at room temperature for 5 minutes to prepare an aqueous dispersion of hydroxyapatite. Add 2.0 g of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar to a 500 mL beaker, and stir with a magnetic stirrer at room temperature for 15 minutes to prepare an annatto pigment solution. Add the annatto pigment solution to the aqueous dispersion of hydroxyapatite, and stir at room temperature for 15 minutes. Then, slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water, adjust the pH to 4.0, and stir at room temperature for 2 hours. Drop 1 drop of this slurry onto filter paper. As a result, it was observed that the dropped portion was colored orange in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry with a Nutsche filter, wash it with 2000 g of ion-exchanged water to obtain a solid, dry this solid with a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice crushing to obtain 19.9 g of powder (1). The composition ratio of hydroxyapatite to annatto pigment in powder (1) was 91:9 based on the feeding amount ratio. The obtained powder exhibited an orange color similar to that of the annatto pigment.

[0117] Add 10 mg of the above-obtained powder (1), 1.0 g of ion-exchanged water, and a magnetic stir bar to a 10 mL vial, and stir with a magnetic stirrer for 5 minutes to prepare dispersion (1). Drop 1 drop of dispersion (1) onto filter paper. As a result, it was observed that the dropped portion was colored orange in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. The orange-colored portion was the water-insoluble powder (1), and the portion where the transparent liquid spread in a concentric circle pattern later was water. Therefore, it was confirmed that powder (1) was insoluble in water.

[0118] (Example 2)

[0119] Add 20.0 g of hydroxyapatite (manufactured by Fujifilm Wako Pure Chemical Corporation) and 1000 g of ion-exchanged water to a 3 L beaker, and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of hydroxyapatite. Add 6.0 g of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar to a 500 mL beaker, and stir at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto pigment solution. Add the annatto pigment solution to the aqueous dispersion of hydroxyapatite, and stir at room temperature for 15 minutes. Then, slowly add dropwise a dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water, adjust the pH to 4.0, and stir at room temperature for 2 hours. Add 1 drop of this slurry to a filter paper. As a result, it was observed that the dropped portion was colored orange in a circular shape, and then the colorless and transparent liquid spread in a concentric circle shape. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry with a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid in a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice extraction and pulverization to obtain 18.3 g of powder (2).

[0120] The composition ratio of hydroxyapatite to annatto pigment in the obtained powder (2) is 77:23 in terms of the feeding amount ratio. The obtained powder exhibits an orange color homologous to annatto pigment. Add 10 mg of powder (2), 1.0 g of ion-exchanged water, and a magnetic stir bar to a 10 mL vial, and stir for 5 minutes using a magnetic stirrer to prepare dispersion (2). Add 1 drop of dispersion (2) to a filter paper. As a result, it was observed that the dropped portion was colored orange in a circular shape, and then the colorless and transparent liquid spread in a concentric circle shape. The orange-colored portion is the water-insoluble powder (2), and the portion where the transparent liquid spreads in a concentric circle shape later is water. Therefore, it was confirmed that powder (2) is insoluble in water.

[0121] (Example 3)

[0122] In 3L beaker, add hydroxyapatite (Fuji Film & Wako Pure Chemical Industries, Ltd. system) 20.0g and ion exchange water 1000g, with the glass stirring blade being connected with Three-One Motor, stirring at room temperature for 5 minutes, prepare the aqueous dispersion of hydroxyapatite.In 500mL beaker, add sodium copper chlorophyllin (Fuji Film & Wako Pure Chemical Industries, Ltd.) 2.0g, ion exchange water 300mL, stirrer, use magnetic stirring apparatus, stirring at room temperature for 15 minutes, prepare pigment solution.Pigment solution is joined in the hydroxyapatite aqueous dispersion, stirring at room temperature for 15 minutes.Then, with dropper, slowly drip the dilute hydrochloric acid that hydrochloric acid (deer 1 grade, Kanto Chemical Co., Ltd. system) is diluted 10 times with ion exchange water and modulated, after pH is adjusted to 4.0, stirring at room temperature for 2 hours. One drop of the slurry was dripped onto the filter paper. The dripped portion was observed to be green in color in a circular shape, and then the colorless transparent liquid expanded in a concentric circle shape, thus confirming that the pigment was insoluble in water. Next, the slurry was filtered with a Nutsche filter, washed with 2000 g of ion exchange water to obtain a solid, which was dried at 30° C. for 14 hours in a vacuum dryer (740 mmHg), and then crushed by squeezing to obtain 20.2 g of powder (3).

[0123] The composition ratio of hydroxyapatite and sodium copper chlorophyllin in the powder (3) obtained above is 91:9 in terms of feed ratio. The obtained powder exhibits a green color that is the same as that of sodium copper chlorophyllin. 10 mg of powder (3), 1.0 g of ion exchange water, and a stirrer were added to a 10 mL small glass bottle, and stirred with a magnetic stirrer for 5 minutes to prepare a dispersion (3). One drop of dispersion (3) was added to the filter paper, and it was observed that the added part turned green in a circular shape, and then the colorless and transparent liquid expanded in concentric circles. The green part is the powder (3) that is insoluble in water, and the part where the transparent liquid expanded in concentric circles is water, so it was confirmed that the powder (3) is insoluble in water.

[0124] (Example 4)

[0125] In a 3 L beaker, add 20.0 g of organophilic bentonite (MOISTNITE-WO, manufactured by KUNIMINE INDUSTRIES CO., LTD.) treated with quaternary ammonium and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.), and wet thoroughly. Then, add 1000 g of ion-exchanged water, and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare a dispersion of organophilic bentonite. In a 500 mL beaker, add 2.0 g of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar, and stir at room temperature for 15 minutes using a magnetic stirrer to prepare a pigment solution. Add the pigment solution to the aqueous dispersion, stir at room temperature for 15 minutes, and then slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water to adjust the pH to 4.0, and stir at room temperature for 2 hours. Drop 1 drop of this slurry onto filter paper. As a result, it was observed that the dropped portion was colored orange in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry using a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid using a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice extraction and pulverization to obtain 18.1 g of powder (4).

[0126] The composition ratio of the organophilic bentonite and annatto pigment in the powder (4) obtained above was 91:9 in terms of the feeding amount ratio. The obtained powder exhibited an orange color similar to that of the annatto pigment. In a 10 mL vial, add 10 mg of powder (4), 1.0 g of ion-exchanged water, and a magnetic stir bar, and stir for 5 minutes using a magnetic stirrer to prepare dispersion (4). Drop 1 drop of dispersion (4) onto filter paper. As a result, it was observed that the dropped portion was colored orange in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. The portion colored orange was the powder (4) insoluble in water, and the portion where the transparent liquid spread in a concentric circle pattern later was water. Therefore, it was confirmed that powder (4) was insoluble in water.

[0127] (Example 5)

[0128] Add 20.0 g of organophilic bentonite (MOISTNITE-WO, manufactured by KUNIMINE INDUSTRIES CO., LTD.) treated with quaternary ammonium and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.) to a 3 L beaker and wet thoroughly. Then, add 1000 g of ion-exchanged water and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of organophilic bentonite. Add 5.0 g of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar to a 500 mL beaker and stir at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto pigment solution. Add the pigment solution to the aqueous dispersion, stir at room temperature for 15 minutes, and then slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water to adjust the pH to 4.0 and stir at room temperature for 2 hours. Add 1 drop of this slurry to filter paper. As a result, it was observed that the dropped portion was circularly colored orange, and then the colorless and transparent liquid spread concentrically. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry using a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid using a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice crushing to obtain 18.5 g of powder (5).

[0129] The composition ratio of the organophilic bentonite to the annatto pigment in the obtained powder (5) is 80:20 in terms of the feeding amount ratio. The obtained powder exhibits an orange color similar to that of the annatto pigment. Add 10 mg, 1.0 g of ion-exchanged water, and a magnetic stir bar to a 10 mL vial and stir for 5 minutes using a magnetic stirrer to prepare dispersion (5). Add 1 drop of dispersion (5) to filter paper. As a result, it was observed that the dropped portion was circularly colored orange, and then the colorless and transparent liquid spread concentrically. The orange-colored portion is the water-insoluble powder (5), and the portion where the subsequent transparent liquid spread concentrically is water. Therefore, it was confirmed that powder (5) is insoluble in water.

[0130] (Example 6)

[0131] In a 3 L beaker, add 20.0 g of organophilic bentonite (MOISTNITE-WO, manufactured by KUNIMINE INDUSTRIES CO., LTD.) treated with quaternary ammonium and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.) and wet thoroughly. Then, add 1000 g of ion-exchanged water and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of organophilic bentonite. In a 500 mL beaker, add 2.0 g of sodium copper chlorophyllin (FUJIFILM Wako Pure Chemical Corporation), 300 mL of ion-exchanged water, and a magnetic stir bar, and stir at room temperature for 15 minutes using a magnetic stirrer to prepare a pigment solution. Add the pigment solution to the aqueous dispersion, stir at room temperature for 15 minutes, and then slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water to adjust the pH to 4.0, and stir at room temperature for 2 hours. Drop 1 drop of this slurry onto filter paper. As a result, it was observed that the dropped portion showed a circular green coloration, and then the colorless and transparent liquid spread in a concentric circle pattern. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry using a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid using a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juicing and pulverization to obtain 18.1 g of powder (6).

[0132] The composition ratio of organophilic bentonite to sodium copper chlorophyllin in the obtained powder (6) is 91:9 in terms of the feeding amount ratio. The obtained powder exhibits a green color similar to that of sodium copper chlorophyllin. Add 10 mg of powder (6), 1.0 g of ion-exchanged water, and a magnetic stir bar to a 10 mL vial, and stir for 5 minutes using a magnetic stirrer to prepare dispersion (6). Drop 1 drop of dispersion (6) onto filter paper. As a result, it was observed that the dropped portion showed a circular green coloration, and then the colorless and transparent liquid spread in a concentric circle pattern. The green-colored portion is the powder (6) insoluble in water, and the later transparent liquid spreading in a concentric circle pattern is water. Therefore, it was confirmed that powder (6) is insoluble in water.

[0133] (Example 7)

[0134] Add 30.0 g of organophilic saponite treated with quaternary ammonium (SUMECTON-SAN-P, manufactured by Kunimine Industries Co., Ltd.) and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.) to a 3 L beaker and moisten well. Then, add 1000 g of ion-exchanged water and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of organophilic saponite. Add 3.0 g of achiote pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar to a 500 mL beaker and stir at room temperature for 15 minutes using a magnetic stirrer to prepare a pigment solution. Add the pigment solution to the aqueous dispersion and stir at room temperature for 15 minutes. Then, slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water to adjust the pH to 4.0 and stir at room temperature for 2 hours. Add 1 drop of this slurry to filter paper. As a result, it was observed that the dropped portion showed an orange color in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry with a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid with a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice crushing to obtain 29.8 g of powder (7).

[0135] The composition ratio of the organophilic saponite to the achiote pigment in the powder (7) obtained above was 91:9 in terms of the feeding amount ratio. The obtained powder exhibited an orange color similar to that of the achiote pigment. Add 10 mg of powder (7), 1.0 g of ion-exchanged water, and a magnetic stir bar to a 10 mL vial and stir for 5 minutes using a magnetic stirrer to prepare dispersion (7). Add 1 drop of dispersion (7) to filter paper. As a result, it was observed that the dropped portion showed an orange color in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. The orange-colored portion was the powder (7) insoluble in water, and the portion where the transparent liquid spread in a concentric circle pattern later was water. Therefore, it was confirmed that the powder (7) was insoluble in water.

[0136] (Example 8)

[0137] In a 3 L beaker, add 20.0 g of organophilic bentonite (MOISTNITE-WO, manufactured by KUNIMINE INDUSTRIES CO., LTD.) treated with quaternary ammonium and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.), and wet thoroughly. Then, add 1000 g of ion-exchanged water, and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of organophilic bentonite. In a 500 mL beaker, add 6.0 g of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar, and stir at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto pigment solution. Add the pigment solution to the aqueous dispersion, stir at room temperature for 15 minutes, and then slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water to adjust the pH to 4.0, and stir at room temperature for 2 hours. Drop 1 drop of this slurry onto filter paper. As a result, it was observed that the dropped part showed a circular orange color, and then the colorless and transparent liquid spread in a concentric circle pattern. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry using a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid using a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice crushing to obtain 19.5 g of powder (8).

[0138] The composition ratio of the organophilic bentonite to the annatto pigment in the obtained powder (8) is 77:23 in terms of the feeding amount ratio. The obtained powder exhibits an orange color similar to that of the annatto pigment. In a 10 mL vial, add 10 mg of powder (8), 1.0 g of ion-exchanged water, and a magnetic stir bar, and stir for 5 minutes using a magnetic stirrer to prepare dispersion (8). Drop 1 drop of dispersion (8) onto filter paper. As a result, it was observed that the dropped part showed a circular orange color, and then the colorless and transparent liquid spread in a concentric circle pattern. The orange-colored part is the water-insoluble powder (8), and the part where the transparent liquid spread in a concentric circle pattern later is water. Therefore, it was confirmed that powder (8) is insoluble in water.

[0139] (Example 9)

[0140] In a 3L beaker, add 20.0g of organic bentonite (MOISTNITE-WO, manufactured by KUNIMINE Industries) treated with quaternary ammonium and 100g of ethanol (Deer Grade 1, manufactured by Kanto Chemical Co., Ltd.) to fully wet. Next, add 1000g of ion exchange water and stir at room temperature for 5 minutes with a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of the organic bentonite. In a 500mL beaker, add 1.0g of safflower Y1500 (Yamato Chemicals Co., Ltd., safflower yellow pigment 85%, dextrin 15%), 300mL of ion exchange water, and a stirring bar, and stir at room temperature for 15 minutes using a magnetic stirrer to prepare a safflower yellow pigment solution. The pigment solution was added to the aqueous dispersion and stirred at room temperature for 15 minutes. Then, the diluted hydrochloric acid (Deer Grade 1, manufactured by Kanto Chemical Co., Ltd.) was slowly added dropwise with a dropper and diluted 10 times with ion exchange water to adjust the pH to 4.0. The mixture was stirred at room temperature for 2 hours. One drop of the slurry was added dropwise to the filter paper. As a result, it was observed that the added portion was circularly colored yellow, and then the colorless transparent liquid expanded in concentric circles, thus confirming that the pigment was insoluble in water. Next, the slurry was filtered with a Nutsche filter, washed with 2000 g of ion exchange water to obtain a solid. The solid was dried at 30° C. for 14 hours with a vacuum dryer (740 mmHg), and then crushed by squeezing to obtain 18.7 g of powder (9).

[0141] The composition ratio of the organic bentonite and safflower yellow in the powder (9) obtained above is 96:4 in terms of the added amount ratio. The obtained powder exhibits a yellow color that is the same as safflower yellow. 10 mg of powder (9), 1.0 g of ion exchange water, and a stirrer were added to a 10 mL vial, and stirred with a magnetic stirrer for 5 minutes to prepare a dispersion (9). One drop of dispersion (9) was added to the filter paper, and it was observed that the added part turned yellow in a circular shape, and then the colorless and transparent liquid expanded in concentric circles. The part that turned yellow was the powder (9) that was insoluble in water, and the part where the transparent liquid expanded in concentric circles was water, so it was confirmed that the powder (9) was insoluble in water.

[0142] (Example 10)

[0143] In a 3 L beaker, add 20.0 g of organophilic bentonite (MOISTNITE-WO, manufactured by KUNIMINE INDUSTRIES CO., LTD.) treated with quaternary ammonium and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.), and wet thoroughly. Then, add 1000 g of ion-exchanged water, and stir at room temperature for 5 minutes using a glass stirring blade connected to a Three-One Motor to prepare an aqueous dispersion of organophilic bentonite. In a 500 mL beaker, add 2.0 g of caramel I pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar, and stir at room temperature for 15 minutes using a magnetic stirrer to prepare a caramel pigment solution. Add the pigment solution to the aqueous dispersion, stir at room temperature for 15 minutes, and then slowly add dropwise dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water to adjust the pH to 4.0, and stir at room temperature for 2 hours. Drop 1 drop of this slurry onto filter paper. As a result, it was observed that the dropped portion was circularly colored brown, and then the colorless and transparent liquid spread concentrically. Therefore, it was confirmed that the pigment was insoluble in water. Next, filter this slurry using a Nutsche filter, wash with 2000 g of ion-exchanged water to obtain a solid, dry this solid in a vacuum dryer (740 mmHg) at 30 °C for 14 hours, and then perform juice crushing to obtain 18.5 g of powder (10).

[0144] The composition ratio of the organophilic bentonite to the caramel I pigment in the powder (10) obtained above was 91:9 in terms of the feeding amount ratio. The obtained powder was brownish in color similar to the caramel pigment. Add 10 mg of powder (10), 1.0 g of ion-exchanged water, and a magnetic stir bar to a 10 mL vial, and stir for 5 minutes using a magnetic stirrer to prepare dispersion (10). Drop 1 drop of dispersion (10) onto filter paper. As a result, it was observed that the dropped portion was circularly colored brown, and then the colorless and transparent liquid spread concentrically. The brownish-colored portion was the powder (10) insoluble in water, and the portion where the subsequent transparent liquid spread concentrically was water. Therefore, it was confirmed that the powder (10) was insoluble in water.

[0145] (Example 11)

[0146] In 3L beaker, add hydroxyapatite (Fuji Film Wako Pure Chemical Industries, Ltd. system) 20.0g and ion exchange water 1000g, with the glass stirring blade being connected with Three-One Motor, stirring at room temperature 5 minutes, prepare the aqueous dispersion of hydroxyapatite.In 500mL beaker, add caramel I pigment (Kanto Chemical Co., Ltd. system) 2.0g, ion exchange water 300mL, stirrer, use magnetic stirring apparatus, stirring at room temperature 15 minutes, prepare pigment solution.Pigment solution is joined in the hydroxyapatite aqueous dispersion, stirring at room temperature 15 minutes.Then, with dropper, slowly drip the dilute hydrochloric acid that hydrochloric acid (deer 1 grade, Kanto Chemical Co., Ltd. system) is diluted 10 times and modulated with ion exchange water, after pH is adjusted to 4.0, stirring at room temperature 2 hours. One drop of the slurry was dripped onto the filter paper. The dripped portion was observed to be brown in color in a circular shape, and then the colorless transparent liquid expanded in a concentric circle shape, thus confirming that the pigment was insoluble in water. Next, the slurry was filtered with a Nutsche filter, washed with 2000 g of ion exchange water to obtain a solid, which was dried at 30° C. for 14 hours in a vacuum dryer (740 mmHg), and then crushed by squeezing to obtain 19.0 g of powder (11).

[0147] The composition ratio of hydroxyapatite and caramel I pigment in the powder (11) obtained above is 91:9 in terms of feed ratio. The obtained powder exhibits a brown color similar to that of caramel I pigment. 10 mg of powder (11), 1.0 g of ion exchange water and a stirrer were added to a 10 mL small glass bottle, and stirred with a magnetic stirrer for 5 minutes to prepare a dispersion (11). One drop of dispersion (11) was dripped onto filter paper, and it was observed that the dripped part turned brown in a circular shape, and then the colorless and transparent liquid expanded in concentric circles. The part that turned brown was the powder (11) that was insoluble in water, and the part where the transparent liquid expanded in concentric circles was water, so it was confirmed that the powder (11) was insoluble in water.

[0148] (Example 12)

[0149] In a 3 L beaker, 20.0 g of saponite (SUMECTON-SWN, manufactured by Kunimine Industries Co., Ltd.) and 100 g of ethanol (Grade 1, manufactured by Kanto Chemical Co., Inc.) were added and thoroughly wetted. Subsequently, 1000 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 an aqueous dispersion of saponite. In a 500 mL beaker, 2.0 g of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 300 mL of ion-exchanged water, and a magnetic stir bar were added, and the mixture was stirred at room temperature for 15 minutes using a magnetic stirrer to prepare a pigment solution. The pigment solution was added to the aqueous dispersion, and after stirring at room temperature for 15 minutes, dilute hydrochloric acid prepared by diluting hydrochloric acid (Grade 1, manufactured by Kanto Chemical Co., Inc.) 10-fold with ion-exchanged water was slowly added dropwise using a dropper to adjust the pH to 4.0, and the mixture was stirred at room temperature for 2 hours. One drop of this slurry was added dropwise onto filter paper, and as a result, it was observed that the added portion developed an orange color in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. Therefore, it was confirmed that the pigment was insoluble in water. Subsequently, this slurry was filtered using a Nutsche filter, washed with 2000 g of ion-exchanged water to obtain a solid, and the solid was dried at 30 °C for 14 hours using a vacuum dryer (740 mmHg), followed by juicing and pulverization to obtain 18.8 g of a powder (12).

[0150] The composition ratio of saponite to annatto pigment in the powder (12) obtained above was 91:9 in terms of the feeding amount ratio. The obtained powder exhibited an orange color similar to that of annatto pigment. In a 10 mL vial, 10 mg of the powder (12), 1.0 g of ion-exchanged water, and a magnetic stir bar were added, and the mixture was stirred for 5 minutes using a magnetic stirrer to prepare a dispersion (12). One drop of the dispersion (12) was added dropwise onto filter paper, and as a result, it was observed that the added portion developed an orange color in a circular shape, and then the colorless and transparent liquid spread in a concentric circle pattern. The portion that developed an orange color was the powder (12) insoluble in water, and the portion where the transparent liquid spread in a concentric circle pattern afterwards was water. Therefore, it was confirmed that the powder (12) was insoluble in water.

[0151] (Comparative Example 1)

[0152] After adding 10 mg of annatto pigment (manufactured by Kanto Chemical Co., Inc.) and 1.0 g of ion-exchanged water to a 10 mL vial, a magnetic stir bar was added and the mixture was stirred for 5 minutes to prepare a dispersion (13). One drop of the dispersion (13) was added dropwise onto filter paper, and as a result, it was observed that the orange liquid spread uniformly in a concentric circle pattern centered on the added portion.

[0153] (Comparative Example 2)

[0154] After adding 10 mg of sodium copper chlorophyllin (manufactured by FUJIFILM Wako Pure Chemical Corporation) and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (14). When 1 drop of the dispersion (14) was dropped onto filter paper, it was observed that the green liquid uniformly spread concentrically with the dropped portion as the center.

[0155] (Comparative Example 3)

[0156] After adding 0.9 mg of bixin (manufactured by Kanto Chemical Co., Inc.), 9.1 mg of hydroxyapatite (FL-HAP(SC), manufactured by Taihei Chemical Industry Co., Ltd.), and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (15). When 1 drop of the dispersion (15) was dropped onto filter paper, it was observed that the orange liquid uniformly spread concentrically with the dropped portion as the center.

[0157] (Comparative Example 4)

[0158] After adding 2.3 mg of bixin (manufactured by Kanto Chemical Co., Inc.), 7.7 mg of hydroxyapatite (FL-HAP(SC), manufactured by Taihei Chemical Industry Co., Ltd.), and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (16). When 1 drop of the dispersion (16) was dropped onto filter paper, it was observed that the orange liquid uniformly spread concentrically with the dropped portion as the center.

[0159] (Comparative Example 5)

[0160] After adding 0.9 mg of sodium copper chlorophyllin (manufactured by FUJIFILM Wako Pure Chemical Corporation), 9.1 mg of hydroxyapatite (FL-HAP(SC), manufactured by Taihei Chemical Industry Co., Ltd.), and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (17). When 1 drop of the dispersion (17) was dropped onto filter paper, it was observed that the green liquid uniformly spread concentrically with the dropped portion as the center.

[0161] (Comparative Example 6)

[0162] After adding 0.9 mg of bixin (manufactured by Kanto Chemical Co., Inc.), 9.1 mg of quaternary ammonium-treated organophilic bentonite (MOISTNITE-WO, manufactured by Kunimine Industries Co., Ltd.), and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (18). When 1 drop of the dispersion (18) was dropped onto filter paper, it was observed that the orange liquid uniformly spread concentrically with the dropped portion as the center.

[0163] (Comparative Example 7)

[0164] 2.0 mg of annatto pigment (manufactured by Kanto Chemical Co., Inc.) and 8.0 mg of quaternary ammonium-treated organophilic bentonite (MOISTNITE-WO, manufactured by Kunimine Industries Co., Ltd.) and 1.0 g of ion-exchanged water were added to a 10 mL vial, and then a stir bar was added and stirred for 5 minutes to prepare a dispersion (19). One drop of the dispersion (19) was dropped onto filter paper, and as a result, it was observed that the orange liquid spread uniformly in a concentric circle centered on the dropped portion.

[0165] (Comparative Example 8)

[0166] 0.9 mg of sodium copper chlorophyllin (manufactured by Fujifilm Wako Pure Chemical Corporation) and 9.1 mg of quaternary ammonium-treated organophilic bentonite (MOISTNITE-WO, manufactured by Kunimine Industries Co., Ltd.) and 1.0 g of ion-exchanged water were added to a 10 mL vial, and then a stir bar was added and stirred for 5 minutes to prepare a dispersion (20). One drop of the dispersion (20) was dropped onto filter paper, and as a result, it was observed that the green liquid spread uniformly in a concentric circle centered on the dropped portion.

[0167] (Comparative Example 9)

[0168] 0.9 mg of annatto pigment (manufactured by Kanto Chemical Co., Inc.) and 9.1 mg of quaternary ammonium-treated organophilic smectite (SUMECTON-SAN-P, manufactured by Kunimine Industries Co., Ltd.) and 1.0 g of ion-exchanged water were added to a 10 mL vial, and then a stir bar was added and stirred for 5 minutes to prepare a dispersion (21). One drop of the dispersion (21) was dropped onto filter paper, and as a result, it was observed that the orange liquid spread uniformly in a concentric circle centered on the dropped portion.

[0169] (Comparative Example 10)

[0170] 2.3 mg of annatto pigment (manufactured by Kanto Chemical Co., Inc.) and 7.7 mg of quaternary ammonium-treated organophilic bentonite (MOISTNITE-WO, manufactured by Kunimine Industries Co., Ltd.) and 1.0 g of ion-exchanged water were added to a 10 mL vial, and then a stir bar was added and stirred for 5 minutes to prepare a dispersion (22). One drop of the dispersion (22) was dropped onto filter paper, and as a result, it was observed that the orange liquid spread uniformly in a concentric circle centered on the dropped portion.

[0171] (Comparative Example 11)

[0172] After adding 10 mg of safflower Y1500 (manufactured by Daiwa Kasei Co., Ltd., 85% safflower yellow pigment, 15% dextrin) and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (23). One drop of the dispersion (23) was dropped onto a filter paper, and as a result, it was observed that the yellow liquid spread evenly in a concentric circle centered on the dropped portion.

[0173] (Comparative Example 12)

[0174] After adding 10 mg of caramel I pigment (manufactured by Kanto Chemical Co., Inc.) and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (24). One drop of the dispersion (24) was dropped onto a filter paper, and as a result, it was observed that the brown liquid spread evenly in a concentric circle centered on the dropped portion.

[0175] (Comparative Example 13)

[0176] After adding 0.5 mg of safflower Y1500 (manufactured by Daiwa Kasei Co., Ltd., 85% safflower yellow pigment, 15% dextrin) and 9.5 mg of quaternary ammonium-treated organophilic bentonite (MOISTNITE-WO, manufactured by Kunimine Industries Co., Ltd.) and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (25). One drop of the dispersion (25) was dropped onto a filter paper, and as a result, it was observed that the orange liquid spread evenly in a concentric circle centered on the dropped portion.

[0177] (Comparative Example 14)

[0178] After adding 2.3 mg of caramel I pigment (manufactured by Kanto Chemical Co., Inc.) and 7.7 mg of quaternary ammonium-treated organophilic bentonite (MOISTNITE-WO, manufactured by Kunimine Industries Co., Ltd.) and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (26). One drop of the dispersion (26) was dropped onto a filter paper, and as a result, it was observed that the brown liquid spread evenly in a concentric circle centered on the dropped portion.

[0179] (Comparative Example 15)

[0180] After adding 0.9 mg of caramel I pigment (manufactured by Kanto Chemical Co., Inc.) and 9.1 mg of hydroxyapatite (manufactured by Fujifilm Wako Pure Chemical Corporation) and 1.0 g of ion-exchanged water to a 10 mL vial, a stir bar was added and stirred for 5 minutes to prepare a dispersion (27). One drop of the dispersion (27) was dropped onto a filter paper, and as a result, it was observed that the orange liquid spread evenly in a concentric circle centered on the dropped portion.

[0181] (Comparative Example 16)

[0182] 0.9 mg of annatto pigment (manufactured by Kanto Chemical Co., Inc.), 9.1 mg of untreated saponite (SUMECTON - SWN, manufactured by Kunimine Industries Co., Ltd.), and 1.0 g of ion - exchanged water were added to a 10 - mL vial. After adding a stir bar and stirring for 5 minutes, a dispersion (28) was prepared. When 1 drop of the dispersion (28) was dropped onto filter paper, it was observed that the orange liquid spread evenly in a concentric - circle pattern centered on the dropped - part.

[0183] Cosmetics such as lipsticks, eye - area cosmetics, and nail cosmetics containing the water - insoluble pigment composition of the present invention have advantageous properties compared to cosmetics containing natural pigments themselves.

[0184] (Evaluation Example)

[0185] (Production and Evaluation of Lipstick Cosmetics)

[0186] The cream base (manufactured by Orange Blossom Co., Ltd.) and castor oil (manufactured by Orange Blossom Co., Ltd.) were weighed into a pudding cup and mixed while heating in a hot - water bath at 70°C to 80°C. The powder or natural pigment prepared in the examples was added and mixed while heating. The mixed liquid was filled into a silicon mold with a ring. After standing for 10 minutes, it was cooled in a refrigerator at 10°C for about 10 minutes. The lipstick cosmetic exposed from the ring was cut with a spatula. After removing the ring, it was inserted into a lipstick tube. By grasping the lower part of the silicon mold, slightly introducing air, and lowering the tube little by little, it was stored in the tube to obtain a lipstick cosmetic. The powder or natural pigment prepared in the examples was used as a colorant in each lipstick cosmetic. As the natural pigments, annatto pigment (manufactured by Kanto Chemical Co., Inc.), sodium copper chlorophyllin (manufactured by Fujifilm Wako Pure Chemical Corporation), and safflower Y1500 (manufactured by Daiwa Kasei Co., Ltd., 85% safflower yellow pigment, 15% dextrin) were used. In addition, the addition amount of the colorant was added in combination with the mass parts of the pigment in the preparation. The lipstick cosmetics produced are summarized in Table 1.

[0187] [Table 1]

[0188]

[0189] Evaluate the water resistance, appearance of coarse particles, usability, color unevenness, and makeup persistence of each lipstick cosmetic. For water resistance, apply the lipstick cosmetic on filter paper, and use a dropper to drip 1 mL of water onto the colored part, and visually confirm the bleeding degree at this time. Evaluate the appearance of coarse particles by visually confirming the lipstick cosmetic. Evaluate the usability and color unevenness by applying the lipstick cosmetic on the wrist. Makeup persistence is evaluated by wiping the lipstick cosmetic applied on the wrist 3 times with a tissue paper and visually confirming the color fading at this time. Summarize the evaluation results in Table 2. For water resistance, set it as ○ when there is no bleeding, and set it as × when there is bleeding. For the appearance of coarse particles, set it as ○ when there are no coarse particles, and set it as × when there are coarse particles. For usability, set it as ○ when it is good, and set it as × when it is bad. For color unevenness, set it as ○ when there is no uneven coloring, and set it as × when there is uneven coloring. For makeup persistence, set it as ○ when there is no color fading, and set it as × when there is color fading.

[0190] [Table 2]

[0191]

[0192] As can be seen from Table 2, compared with the lipstick cosmetic using the natural pigment itself, the lipstick cosmetic using the water-insoluble pigment composition of the present invention shows superiority in terms of water insolubility, appearance of coarse particles, usability, color unevenness, and makeup persistence.

[0193] (Production and Evaluation of Periocular Cosmetics)

[0194] Weigh 14.1 g of talc (Yamaguchi Mica Co., Ltd.), 0.02 g of methylparaben (Maruzen Pharmaceutical Co., Ltd.), 0.02 g of propylparaben (Maruzen Pharmaceutical Co., Ltd.), and 1.88 g of trihydroxystearate (Matsumoto Koshō Co., Ltd.) into a coffee grinder, and perform stirring for 3 times for 10 seconds each to prepare a dispersion base. Add the dispersion base and the powder or natural pigment prepared in the examples into the coffee grinder, and perform stirring for 2 times for 5 seconds each to prepare the periocular cosmetic powder. Place the periocular cosmetic powder in a metal dish and press it to prepare the periocular cosmetic. In each periocular cosmetic, use the powder prepared in the examples as the colorant. In addition, for the periocular cosmetics using annatto pigment (manufactured by Kanto Chemical Co., Inc.), sodium copper chlorophyllin (manufactured by Fujifilm Wako Pure Chemical Corporation), and safflower Y1500 (manufactured by Daiwa Kasei Co., Ltd., 85% safflower yellow pigment, 15% dextrin), they are also prepared as comparison objects. In addition, the addition amount of the colorant is added in combination with the mass parts of the pigment in the preparation. Table 3 summarizes the prepared periocular cosmetics.

[0195] [Table 3]

[0196]

[0197] Evaluate the water resistance, uneven smoothness, uneven color, and makeup persistence of each periorbital cosmetic. For water resistance, apply the periorbital cosmetic on filter paper, and use a dropper to add 0.5 mL of water to the colored part, and visually confirm the bleeding degree at this time. The uneven smoothness and uneven color are evaluated by applying the periorbital cosmetic on the wrist. The makeup persistence is to evaluate the coloring after wiping the periorbital cosmetic applied on the wrist three times. Summarize the evaluation results in Table 4. For water resistance, it is set as ○ when there is no bleeding, and set as × when there is bleeding. For uneven smoothness, it is set as ○ when there is no uneven smoothness, and set as × when there is uneven smoothness. For uneven color, it is set as ○ when there is no uneven coloring, and set as × when there is uneven coloring. For makeup persistence, it is set as ○ when there is no color fading, and set as × when there is color fading.

[0198] [Table 4]

[0199]

[0200] As can be seen from Table 4, compared with the periorbital cosmetic using the natural pigment itself, the periorbital cosmetic using the water-insoluble pigment composition of the present invention shows superiority in terms of water resistance, uneven smoothness, uneven color, and makeup persistence.

[0201] (Production and Evaluation of Nail Cosmetics)

[0202] Add the powder prepared in the examples, or natural pigment and 1.7 g of Nail holic base coat (Color: SP030, manufactured by Kose Corporation) to a 20 mL plastic bottle, and mix with a dropper. Add Nail holic base coat additionally here to produce nail cosmetics. Use the powder prepared in the examples as the colorant in each nail cosmetic. In addition, for nail cosmetics using annatto pigment (manufactured by Kanto Chemical Co., Ltd.), sodium copper chlorophyllin (manufactured by Fujifilm Wako Pure Chemical Corporation), and safflower Y1500 (manufactured by Daiwa Kasei Co., Ltd., 85% safflower yellow pigment, 15% dextrin), they are also produced as comparison objects. It should be noted that the addition amounts of the colorant and Nail holic base coat are added in combination with the mass parts of the pigment in the preparation. The produced nail cosmetics are summarized in Table 5.

[0203] [Table 5]

[0204]

[0205] The water resistance, unevenness of the coated surface, and color unevenness of each nail cosmetic were evaluated. For water resistance, the nail cosmetic was applied on filter paper, and 1 mL of water was dropped onto the colored part with a dropper, and the bleeding degree at this time was visually confirmed. For color unevenness and unevenness of the coated surface, the nail cosmetic was applied on a nail patch, and after drying, the appearance and feel of the coated surface were confirmed for evaluation. The evaluation results are summarized in Table 6. For water resistance, ○ was set when there was no bleeding, and × was set when there was bleeding. For unevenness of the coated surface, ○ was set when there was no unevenness, and × was set when there was unevenness. For color unevenness, ○ was set when there was no color unevenness, and × was set when there was color unevenness.

[0206] [Table 6]

[0207]

[0208] As can be seen from Table 6, the nail cosmetic using the water-insoluble pigment composition of the present invention showed superiority in terms of water resistance, unevenness of the coated surface, and color unevenness compared with the nail cosmetic using the natural pigment itself.

Claims

1. A water-insoluble pigment composition, which is obtained by complexing a natural pigment with at least one selected from hydroxyapatite and clay minerals.

2. The water-insoluble pigment composition according to claim 1, wherein, The composition of the natural pigment and at least one selected from hydroxyapatite and clay minerals is such that the mass ratio of natural pigment: hydroxyapatite or clay mineral = 0.1:99.9 to 90:

10.

3. The water-insoluble pigment composition according to claim 1 or 2, wherein, The clay mineral is at least one selected from bentonite, hectorite, and smectite.

4. The water-insoluble pigment composition according to claim 1 or 2, wherein, The clay mineral is at least one selected from organically treated bentonite, hectorite, and smectite.

5. The water-insoluble pigment composition according to claim 1 or 2, wherein, The natural pigment is at least one selected from carotenoid pigments, porphyrin pigments, flavonoid pigments, and pigment proteins.

6. The water-insoluble pigment composition according to claim 1 or 2, wherein, The natural pigment is at least one selected from annatto pigment, chlorophyll pigment, safflower yellow pigment, and phycocyanin pigment.

7. A coating material for food, cosmetics, lip cosmetics, periorbital cosmetics, nail cosmetics, base makeup cosmetics, pharmaceuticals, pesticides, printing markers, stationery, writing instruments, printing inks, inkjet inks, metal inks, paints, plastic colorants, color toners, fluorescent markers, fluorescent probes or chemical sensors, characterized in that Contains the water-insoluble pigment composition according to claim 1 or 2.

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