Water-insoluble pigment components

Abstract

The purpose of the present invention is to provide: a water-insoluble dye composition that is a complex of a natural dye, a dehydration condensation compound of a fatty acid and an amino acid, and an inorganic material; and a food product, cosmetic product, lipstick cosmetic, eye-surrounding cosmetic, nail cosmetic, hair cosmetic, cosmetic for base makeup, medicine, coating material for agrochemicals, printing marker, stationery, writing material, printing ink, inkjet ink, metal ink, coating material, plastic-coloring agent, color toner, fluorescent labeling agent, fluorescent probe, or chemical sensor that contains the water-insoluble dye composition.　The present invention was completed through a finding that a water-insoluble dye composition is obtained by forming a complex of a natural dye, a dehydration condensation compound of a fatty acid and an amino acid, and an inorganic material.

Description

[Technical Field]

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

[0002] There are a wide variety of natural colorants, including red, yellow, and blue pigments. However, in recent years, synthetic colorants have come into question due to concerns about carcinogenicity and other issues, and expectations are growing for natural colorants, which are thought to be safer.

[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 pigments dissolving in water and fading, i.e., improving water solubility. They found a description of a method for extracting natural pigments, including oral cosmetics, dairy products, and pet foods using the extract (Reference 1). Furthermore, there is a description of dry-blending a carotenoid pigment with sodium tartrate, alum, and sodium carbonate, and dissolving this mixed powder in water to obtain an aqueous solution, with the aim of stabilizing the hue (Reference 2). There is also a description of a powder composition containing a carotenoid, an oily component, and sugar (Reference 3).

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

[0006] [Patent Document 1] Special Publication No. 2009-508505 [Patent Document 2] Special Publication No. 59-050264 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-185023 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[0008] As a result of intensive research to solve the above problems, the present inventors have found that a water-insoluble dye composition can be obtained by combining a natural dye, a dehydration condensation compound of a fatty acid and an amino acid, and an inorganic material, and have thus completed the present invention.

[0009] That is, the present invention includes the following aspects. [1] A water-insoluble dye composition comprising a complex of a natural dye, a dehydration condensation compound of a fatty acid and an amino acid, and an inorganic material. [2] 2. The water-insoluble dye composition according to 1, wherein the water-insoluble dye composition contains, by mass, 0.1 to 70% of a natural dye, 5 to 60% of a dehydrated condensation compound of a fatty acid and an amino acid, and 30 to 80% of an inorganic material, and the total mass of the natural dye, the dehydrated condensation compound of a fatty acid and an amino acid, and the inorganic material is 100%. [3] 3. The water-insoluble dye composition according to 1 or 2, wherein the inorganic material is at least one selected from the group consisting of boron nitride, titanium oxide, pearl pigments, clay minerals, and hydroxyapatite. [4] 3. The water-insoluble dye composition according to 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. [5] 3. The water-insoluble pigment composition according to 1 or 2, wherein the natural pigment is at least one selected from the group consisting of carotenoid pigments, porphyrin pigments, flavonoid pigments, and pigment proteins. [6] 3. The water-insoluble pigment composition according to 1 or 2, wherein the natural pigment is at least one selected from the group consisting of annatto pigment, chlorophyll pigment, safflower yellow pigment, and phycocyanin pigment. [7] 3. The water-insoluble dye composition according to 1 or 2, wherein the dehydrated condensation compound of a fatty acid and an amino acid is at least one selected from lauroyl lysine and N-capryloyl lysine. [8] 7. A food, cosmetic, lipstick cosmetic, eye cosmetic, nail cosmetic, hair cosmetic, base makeup cosmetic, pharmaceutical, agricultural chemical coating material, printing marker, stationery, writing implement, printing ink, inkjet ink, metal 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 6. [Effects of the Invention]

[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, and therefore, 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. DETAILED DESCRIPTION OF THE INVENTION

[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 there are more than 20,000 known compounds. 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 used in a wide range of applications, including optoelectronic functional materials, metal complex catalysts, and molecular conductive materials, and are known to exhibit a wide variety of functionalities 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] (chromoprotein) 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. Widely found in nature are hemoglobin, myoglobin, cytochromes, 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) The most preferred chromoprotein used in the present invention is phycocyanin, which 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 genera Spirulina, Arthrospira, ApHanizomenon, Fisherella, Anabaena, Nostoc, Synechocystis, Synechococcus, Tolypothrix, ApHanothece, Mastigoclaus, and Pleurocapsa. Among these, cyanobacteria of the genera 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) is a first step of extracting phycocyanin from cyanobacteria into a water suspension to obtain an extract; The method comprises 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, and a third step of removing the cyanobacterial residues and 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) is a first step of extracting phycocyanin from cyanobacteria into a water 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 residues and adsorbed substances of blue-green algae from the extract; The method includes 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 (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 complexed with a dehydration condensation compound of a fatty acid and an amino acid and an inorganic material, or a single natural colorant may be complexed with a dehydration condensation compound of a fatty acid and an amino acid and an inorganic material, and then the resulting complexed water-insoluble colorant compositions may be mixed.

[0035] (Dehydrated condensation compound of fatty acids and amino acids) Compounds produced by dehydration condensation of the carboxyl group of a fatty acid and the amino group of an amino acid are commonly used in surfactants and other applications. Amino acids and fatty acids are constituents of living organisms, and are highly biodegradable and have little adverse effect on the living body. Therefore, dehydration condensation products of fatty acids and amino acids produced using these substances as raw materials are expected to be safe and biodegradable. Examples of dehydration condensation compounds of fatty acids and amino acids used in the present invention include lauroyl lysine and N-capryloyl lysine.

[0036] Lauroyl lysine is an amide compound formed by dehydration condensation between the carboxyl group of lauric acid and the amino group of lysine. It is a widely used ingredient in makeup cosmetics, including foundations and lipsticks. It is a highly transparent and safe compound that is used for texture improvement and surface treatment, which can bring quality to cosmetics. It is also characterized by being almost insoluble in solvents and water. However, it is easily soluble in alkaline aqueous solutions.

[0037] (Inorganic materials) In the present invention, any inorganic material can be used, but it is preferable to use at least one selected from boron nitride, titanium oxide, pearl pigments, clay minerals, and hydroxyapatite.

[0038] Boron nitride is a solid compound composed of nitrogen and boron. It exists in a hexagonal, normal-pressure phase and a cubic, high-pressure phase, and either crystal system can be used. In normal-pressure phase boron nitride, the atoms are tightly interlocked, forming hexagonal mesh planes that overlap at wide intervals. The layers are held together by weak van der Waals forces, allowing them to slide easily over each other. For this reason, it is also known as white graphite. Because of its tight mesh planes, heat is transmitted well through lattice vibrations, giving it the highest thermal conductivity of any electrical insulator and a low thermal expansion coefficient, about one-tenth that of alumina. It is an electrical insulator and does not absorb visible light, making it white.

[0039] 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.

[0040] 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. Also, those with spherical or plate-like particle sizes are preferred.

[0041] (pearl pigment) Pearlescent 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 commonly used powders 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, making it suitable for a variety of applications in cosmetics, paints, inks, plastics, and other fields. Recently, the use of synthetic flake base materials and advances in metal oxide coating technology have led to the development of pearlescent pigments with new designs. For example, titanium mica, iron oxide coated titanium mica, carmine coated titanium mica, carmine and konjo coated titanium mica, iron oxide and carmine treated titanium mica, konjo treated titanium mica, iron oxide and konjo 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, fish scale foil, etc.

[0042] (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 to gray to black when exposed to ultraviolet light or hydrogen sulfide. It is generally used to impart a pearlescent luster to cosmetics and to create beautiful skin color and facial expressions 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.

[0043] Any pearlescent pigment can be used in the present invention, but it is preferable to use a pigment in which particles of one or more selected from mica, talc, or glass are coated with titanium oxide, or bismuth oxychloride. Furthermore, the 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.

[0044] (Titanium oxide) Titanium dioxide, also known as titanium dioxide, simply titanium oxide, or titania, is a colorless, solid, photoelectrically active metal oxide that occurs naturally as the main component of rutile (tetragonal crystal system), anatase (tetragonal crystal system), and brookite (orthorhombic crystal system). Known crystal structures include anatase (tetragonal crystal system), rutile (tetragonal crystal system), and brookite (orthorhombic crystal system). Its applications include pigments and colorants, photocatalysis, decomposition of chemicals and microorganisms, offset printing, catalysts, cosmetics such as sunscreen, and dye-sensitized solar cells.

[0045] Any titanium oxide can be used in the present invention, but the particle size is preferably 0.1 μm to 100 μm, more preferably 0.1 μm to 50 μm, and even more preferably 0.1 μm to 30 μm.

[0046] (clay minerals) Clay minerals are the minerals that make up clay, and their main component is layered silicate minerals (phyllosilicate minerals). They are formed by layers of metal ions (aluminum, sodium, calcium, etc.) linked with silicic acid. Because they easily absorb and release water, metal ions, and even organic matter in the gaps between these layers, they are used in a variety of fields, including everyday items, as functional materials for humidity control, ion exchange, and as catalysts. They are also used as raw materials for ceramic materials and pottery.

[0047] Clay minerals that can be used in the present invention include bentonite, hectorite, smectite, kaolinite, montmorillonite, sericite, illite, glauconite, chlorite, talc, and zeolite.

[0048] Among these, bentonite, hectorite, and smectite are desirable clay minerals for the present invention because they have high affinity with dyes, are highly water-insoluble, and have excellent color development properties.

[0049] The crystalline phases of bentonite, hectorite, and smectite are negatively charged. The layers of the sheet structure contain cations between them to compensate for the charge imbalance, and the layer surface area is large relative to the thickness of the sheet.

[0050] Organization treatment refers to a process in which metal cations contained in clay minerals are replaced with hydrophobic organic ions. The surfaces of organized bentonite, organized hectorite, and organized smectite that have been subjected to the organization treatment each become hydrophobic, which strengthens the hydrophobic interaction with the hydrophobic moieties in the chemical structure of natural pigments such as annatto pigment, chlorophyll pigment, safflower yellow pigment, and phycocyanin pigment, making the pigments more easily adsorbed. From the standpoints of ease of pigment adsorption and the amount of adsorption, it is preferable to use an organized clay mineral in the present invention.

[0051] The particle size of the clay mineral used is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 5 μm to 30 μm.

[0052] (hydroxyapatite) The hydroxyapatite used in the present invention is a type of calcium phosphate and is the main component of teeth and bones. Hydroxyapatite exists in nature as a mineral and a biological component. Due to its high biocompatibility, it is widely used as a synthetic component in medical devices and dental materials, such as implant coatings, bone formation materials, and artificial dental roots. Hydroxyapatite also has a unique property: its crystalline structure can be maintained even if some of the ions in the crystal are replaced. As a result, by delicately controlling the ions and crystal shape in the crystal, various functions can be imparted, such as selective protein adsorption and catalytic activity, making it a substance widely used in the chemical industry.

[0053] The particle size of the hydroxyapatite used is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 5 μm to 30 μm.

[0054] (Water-insoluble pigment composition) While most of the natural colorants used in the present invention are in the form of dyes and therefore water-soluble, the present invention has discovered that the natural colorant, the dehydration condensation compound of fatty acids and amino acids, and the inorganic material are strongly complexed through the action modes of coating, impregnation, and adsorption, resulting in a water-insoluble colorant composition. The term "complexed" here is not limited to the action modes of coating, impregnation, adsorption, etc., and is defined as not being a simple mixture but as being made water-insoluble through physical or chemical adsorption of the natural colorant, the dehydration condensation compound of fatty acids and amino acids, and the inorganic material interacting with each other.

[0055] When a composite is formed using only an inorganic material and a natural dye, the interaction between the inorganic material and the natural dye is weak, resulting in a small amount of natural dye adsorbed and insufficient color development. On the other hand, natural dyes interact strongly with dehydrated condensation compounds of fatty acids and amino acids, allowing for the adsorption of large amounts of natural dye. Furthermore, since the dehydrated condensation compounds of fatty acids and amino acids are adsorbed onto the surface of the inorganic material, a water-insoluble dye composition can be obtained that combines the color development and other properties inherent to natural dyes, the smooth feel and other properties of the dehydrated condensation compounds of fatty acids and amino acids, and the hiding power and other properties inherent to inorganic materials.

[0056] 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.

[0057] The composition of the water-insoluble dye composition of the present invention, including the natural dye, the dehydrated condensation compound of fatty acids and amino acids, and the inorganic material, is not particularly limited, but the composition of the natural dye, the dehydrated condensation compound of fatty acids and amino acids, and the inorganic material is preferably set to a total of 100% by mass, such that the natural dye, the dehydrated condensation compound of fatty acids and amino acids, and the inorganic material are in the ranges of 0.1% to 90%, 1% to 70%, and 15% to 90%, respectively. More preferably, the composition is set to a range of 0.1% to 70%, 5% to 60%, and 30% to 80%, and even more preferably, the natural dye, the dehydrated condensation compound of fatty acids and amino acids, and the inorganic material are in the ranges of 1% to 40%, 10% to 50%, and 40% to 60%.

[0058] The average particle size of the water-insoluble dye composition of the present invention is preferably from 0.1 μm to 100 μm, more preferably from 1 μm to 50 μm.

[0059] In the water-insoluble dye composition of the present invention, the content of elements derived from the inorganic material used is preferably 90% or less, more preferably 80% or less, compared to the inorganic material itself.

[0060] (Method of producing a water-insoluble dye composition) Methods for producing the water-insoluble dye composition of the present invention include a method (Method 1) in which a natural dye, a dehydrated condensation compound of fatty acids and amino acids, and an inorganic material are mixed in a solvent, and a water-insoluble dye composition is obtained by wet processing; and a method (Method 2) in which a natural dye and a dehydrated condensation compound of fatty acids and amino acids are mixed in a solvent, and a composite composition of the natural dye and the dehydrated condensation compound of fatty acids and amino acids obtained by wet processing is then combined with an inorganic material by dry processing.

[0061] (Method 1, compounding by wet processing) Methods for obtaining a water-insoluble pigment composition by mixing a natural pigment, a dehydrated condensation compound of fatty acids and amino acids, and an inorganic material in a solvent include: 1) preparing a dispersion or solution of the dehydrated condensation compound of fatty acids and amino acids. The solution is prepared by dissolving the dehydrated condensation compound of fatty acids and amino acids using sodium hydroxide or the like. The dispersion may be prepared by dispersing the dehydrated condensation compound of fatty acids and amino acids in a solvent, or by reprecipitating the dehydrated condensation compound of fatty acids and amino acids by adjusting the pH of the solution. 2) Meanwhile, a natural pigment is dissolved in a solvent to prepare a natural pigment solution. 3) A dispersion of the inorganic material is prepared. When preparing the dispersion or solution of 1 to 3, alcohol or a mixed solvent of water and alcohol may be used. 4) A dispersion or solution of a dehydrated condensation compound of fatty acids and amino acids and a natural colorant solution are added to and mixed with a dispersion solution of an inorganic material to prepare a water-insoluble colorant composition. The method and order of mixing of the dispersion or solution of the dehydrated condensation compound of fatty acids and amino acids, the natural colorant solution, and the dispersion solution of the inorganic material may be any method or order. The mixing temperature may be room temperature or heated. Taking into account the decomposition temperature of the natural colorant alone, mixing is preferably carried out at 10 to 60°C, more preferably 20 to 50°C. The pH of each dispersion or solution during mixing is adjusted taking into account the decomposition of the natural colorant. 5) The pH of the mixture is adjusted to complex the natural colorant, the dehydrated condensation compound of fatty acids and amino acids, and the inorganic material to prepare a water-insoluble colorant composition.

[0062] 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, the dehydrated condensation compound of fatty acids and amino acids, and the inorganic material have been complexed. Furthermore, when the wet cake of the water-insoluble dye composition is repeatedly washed with water, the filtrate becomes colorless and transparent, confirming that the dye components have not leaked out. The water-containing wet cake of the resulting 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. The drying method and dryer may be any conventional method and device, and are not limited thereto.

[0063] (Method 2: Combining wet and dry processing) A method for dry-composite-treating a composite composition of a natural pigment and a dehydrated condensation compound of a fatty acid and an amino acid, obtained by mixing the natural pigment and the dehydrated condensation compound of a fatty acid and an amino acid in a solvent, with an inorganic material includes the following steps: 1) First, a dispersion or solution of the dehydrated condensation compound of a fatty acid and an amino acid is prepared. The solution is prepared by dissolving the dehydrated condensation compound of a fatty acid and an amino acid using an aqueous sodium hydroxide solution or the like. The dispersion may be prepared by dispersing the dehydrated condensation compound of a fatty acid and an amino acid in water, or by adjusting the pH of the solution to reprecipitate the dehydrated condensation compound of a fatty acid and an amino acid. 2) Meanwhile, a natural pigment is dissolved in a solvent to prepare a natural pigment solution. When preparing the dispersion or solution of steps 1 and 2, alcohol or a mixed solvent of water and alcohol may be used. 3) Next, the two liquids are mixed to prepare a water-insoluble pigment composition. The natural pigment solution may be mixed with a dispersion or solution of the dehydrated condensation compound of fatty acids and amino acids, or vice versa, the natural pigment solution may be mixed with a dispersion or solution of the dehydrated condensation compound of fatty acids and amino acids, or the two liquids may be mixed little by little to prepare the composition. The mixing temperature may be room temperature or heated. Taking into account the decomposition temperature of the natural pigment alone, mixing is preferably carried out at 10 to 60°C, more preferably 20 to 50°C. The pH of each dispersion or solution during mixing is adjusted taking into account the decomposition of the natural pigment. 4) The pH of the mixed liquid is adjusted to complex the natural pigment with the dehydrated condensation compound of fatty acids and amino acids to prepare a water-insoluble pigment composition.

[0064] The resulting mixture is filtered and dried to obtain a complex composition of a natural colorant and a dehydrated condensation compound of a fatty acid and an amino acid. When the mixture is filtered through a filter such as a Nutsche filter, a wet cake colored with the natural colorant is obtained on the filter paper, confirming that the natural colorant and the dehydrated condensation compound of a fatty acid and an amino acid have been complexed. Furthermore, when the wet cake of the complex composition of a natural colorant and a dehydrated condensation compound of a fatty acid and an amino acid is repeatedly washed with water, the filtrate becomes colorless and transparent, confirming that the colorant components have not been washed out. The resulting water-containing wet cake of the complex composition of a natural colorant and a dehydrated condensation compound of a fatty acid and an amino acid is dried at room temperature, by heating, vacuum drying, reduced-pressure drying, or the like, to obtain a dry complex composition of a natural colorant and a dehydrated condensation compound of a fatty acid and an amino acid. Any conventional method and device can be used for the drying method and dryer, and there are no limitations.

[0065] Furthermore, the water-insoluble dye composition of the present invention can be obtained by compounding a natural dye, a compound composition of a dehydrated condensation compound of a fatty acid and an amino acid, and an inorganic material through a dry compounding treatment using mechanical energy such as impact, compression, shear, shear stress, or friction.

[0066] 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.

[0067] (stabilizers, additives) It is of course possible to mix other organic pigments, inorganic pigments, dyes, and coloring matters in any ratio with the water-insoluble colorant 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 may be added.

[0068] The stabilizer and additives may be added to all or each of the solution of the dehydrated condensation compound of a fatty acid and an amino acid, the dispersion of an inorganic material, and the natural colorant solution, or may be added to the prepared water-insoluble colorant composition.

[0069] 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.

[0070] (Cosmetic use) The water-insoluble dye composition of the present invention can be used as a cosmetic product. There are no particular limitations on the type of cosmetic product to be used, and the water-insoluble dye composition of the present invention can be used in various types of cosmetic products.

[0071] 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 products such as face washes, makeup removers, toners, serums, packs, protective emulsions, protective creams, whitening cosmetics, and UV protection cosmetics; makeup products such as foundations, face powders, makeup bases, lipsticks, eye makeup, blushers, and nail enamel; hair care products such as shampoos, hair rinses, hair treatments, hair styling products, permanent wave agents, hair dyes, and hair growth agents; and body care products such as body cleansers, deodorants, and bath additives.

[0072] The amount of the water-insoluble dye composition of the present invention used in the cosmetic product can be appropriately set depending on the type of cosmetic product. The content in the cosmetic product 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 product is within the above range, it can effectively exhibit functions such as coloring ability while maintaining the functions required of cosmetics.

[0073] 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.

[0074] 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.

[0075] (Ink and paint applications) The water-insoluble dye composition of the present invention can be used as an ink or a paint. The uses and compositions of the ink and paint will be described below, but the present invention is not limited thereto. The water-insoluble dye composition of the present invention may be dispersed in a thermoplastic resin alone, or it can be dispersed in a printing ink vehicle, a paint vehicle, or the like, which contains a thermoplastic resin as an essential component.

[0076] 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.

[0077] 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 aromatics, and a few% (by mass) of other additives such as solubilizers and gelling agents.

[0078] 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, etc., and 30 to 80% (by mass) of a solvent such as alcohols, toluene, n-hexane, ethyl acetate, cellosolve, or butyl acetate cellosolve.

[0079] Paint vehicles are produced from raw materials such as 20 to 80 (by mass) % of resins such as alkyd resins, epoxy resins, acrylic resins, polyurethane resins, polyester resins, melamine resins, urea resins, and water-soluble resins, and 10 to 60 (by mass) % of solvents such as hydrocarbons, alcohols, ketones, and water.

[0080] (Plastic applications) 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.

[0081] (Toner use) 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.

[0082] The toner for developing electrostatic images produced using the water-insoluble dye composition of the present invention as a constituent component 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 mixed with a carrier (color toner for two-component development).

[0083] 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, just like those commonly used.

[0084] 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 per 100 parts by mass of the binder resin, and more preferably 4 to 10 parts by mass per 100 parts by mass of the binder resin in order to further enhance the charging performance of the colorant itself.

[0085] As the binder resin used in the toner for developing electrostatic images, any of the known and commonly used resins exemplified as the thermoplastic resins can be used, but any of synthetic resins, natural resins, natural rubbers, synthetic rubbers, synthetic waxes, etc. that exhibit adhesive properties under application of heat or pressure can also be used. [Example]

[0086] 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.

[0087] Example 1 19.8 g of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 100 g of ethanol were added to a 3 L beaker and thoroughly mixed. Next, 1000 g of ion-exchanged water was added and stirred at room temperature for 5 minutes using a glass stirring blade connected to a Three-One motor to prepare a boron nitride dispersion. 10.5 g of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), 50 g of ethanol, 200 g of ion-exchanged water, and 5 g of 48% aqueous sodium hydroxide solution (special grade, Kanto Chemical Co., Ltd.) were added to a 1 L beaker and thoroughly dissolved to prepare a lauroyl lysine solution. 9.01 g of annatto colorant (Kanto Chemical Co., Ltd.), 300 mL of ion-exchanged water, and a stir bar were added to a 500 mL beaker and stirred at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto colorant solution. The lauroyl lysine solution and annatto colorant solution were added sequentially to the boron nitride dispersion and stirred at room temperature for 15 minutes. Next, dilute hydrochloric acid (hydrochloric acid grade 1, manufactured by Kanto Chemical Co., Inc.) diluted 10 times with ion-exchanged water was slowly added dropwise using a dropper to adjust the pH to 4.0, and then the mixture was 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 33.9 g of powder (1). The composition ratio of boron nitride, lauroyl lysine, and annatto pigment in powder (1) was 50:27:23 in terms of the amount charged. The resulting powder exhibited an orange color similar to that of annatto pigment. Dispersion (1) was prepared by adding 100 mg of powder (1), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (1) was placed on filter paper, the area where the drop was placed turned orange in a circular pattern, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The orange-colored area was powder (1) insoluble in water, and the area where the transparent liquid spread in concentric circles was water, confirming that powder (1) was insoluble in water.

[0088] Example 2 10 g of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 100 g of ethanol were added to a 3 L beaker and thoroughly mixed. Next, 1000 g of ion-exchanged water was added and stirred at room temperature for 5 minutes using a glass stirring blade connected to a Three-One motor to prepare a boron nitride dispersion. 10 g of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), 50 g of ethanol, 200 g of ion-exchanged water, and 5 g of 48% aqueous sodium hydroxide solution (Kanto Chemical Co., Ltd., special grade) were added to a 1 L beaker and thoroughly dissolved to prepare a lauroyl lysine solution. 1.0 g of safflower yellow (Safflower Y1500, 85% safflower pigment, 15% dextrin, Daiwa Kasei Co., Ltd.), 300 mL of ion-exchanged water, and a stirring bar were added to a 500 mL beaker and stirred at room temperature for 15 minutes using a magnetic stirrer to prepare a safflower yellow solution. The lauroyl lysine solution was added to the boron nitride dispersion, and dilute hydrochloric acid (hydrochloric acid grade 1, manufactured by Kanto Chemical Co., Inc.) was diluted 10-fold with ion-exchanged water. The pH was adjusted to 7.0 by slowly adding dilute hydrochloric acid dropwise using a dropper. The entire safflower yellow solution was then added, and dilute hydrochloric acid was added dropwise using a dropper to adjust the pH to 4.0. The mixture was then stirred at room temperature for 2 hours. The 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 18.8 g of powder (2). The composition ratio of boron nitride, lauroyl lysine, and safflower yellow in powder (2) was 200:200:17 in terms of the amount charged. The resulting powder exhibited a yellow color similar to that of safflower yellow. Dispersion (2) was prepared by adding 104.3 mg of powder (2), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (2) was placed on filter paper, a yellow circle appeared where the drop was placed, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The yellow area was powder (2) insoluble in water, and the area where the transparent liquid subsequently spread in concentric circles was water, confirming that powder (2) was insoluble in water.

[0089] Example 3 18.8 g of powder (3) was obtained in the same manner as in Example 2, except that copper chlorophyllin sodium (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of the safflower yellow pigment used in Example 2. The composition ratio of boron nitride, lauroyl lysine, and copper chlorophyllin sodium in powder (3) was 10:10:1 in terms of the charge ratio. The obtained powder exhibited the same green color as copper chlorophyllin sodium. Dispersion (3) was prepared by adding 105 mg of powder (3), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (3) was placed on filter paper, the area where the drop was placed turned green in a circular pattern, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The green-colored area was powder (3) insoluble in water, and the area where the transparent liquid subsequently spread in concentric circles was water, confirming that powder (3) was insoluble in water.

[0090] Example 4 An experiment was conducted in the same manner as in Example 2, except that Linablue G1 (manufactured by DIC Lifetech Co., Ltd., trehalose 55%, spirulina extract 40%, trisodium citrate 5%) was used instead of the safflower yellow pigment used in Example 2, and 20.4 g of powder (4) was obtained. The composition ratio of boron nitride, lauroyl lysine, and spirulina extract in powder (4) was 25:25:1 in terms of the amount charged. The obtained powder exhibited a blue color similar to that of phycocyanin pigment. Dispersion (4) was prepared by adding 102 mg of powder (4), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (4) was placed on filter paper, a blue circle appeared where the drop was placed, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The blue-colored area was powder (4) insoluble in water, and the area where the clear liquid spread in concentric circles was water, confirming that powder (4) was insoluble in water.

[0091] Example 5 20 g of pearl pigment (SunSHINE Spectral Red, manufactured by Sun Chemical) and 100 g of ethanol were added to a 3 L beaker and thoroughly mixed. Next, 1000 g of ion-exchanged water was added and stirred at room temperature for 5 minutes using a glass stirring blade connected to a three-one motor to prepare a pearl pigment dispersion. 5 g of lauroyl lysine (N-lauroyl-L-lysine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 50 g of ethanol, 200 g of ion-exchanged water, and 5 g of 48% aqueous sodium hydroxide solution (special grade, manufactured by Kanto Chemical Co., Ltd.) were added to a 1 L beaker and thoroughly dissolved to prepare a lauroyl lysine solution. 15 g of annatto colorant (Kanto Chemical Co., Ltd.), 300 mL of ion-exchanged water, and a stir bar were added to a 500 mL beaker and stirred at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto colorant solution. 33.8 g of powder (5) was obtained using the same procedure as in Example 1. The composition ratio of the pearl pigment, lauroyl lysine, and annatto colorant in powder (5) was 4:1:3 in terms of the amount of ingredients charged. The resulting powder had the same orange color as the annatto colorant. Dispersion (5) was prepared by adding 120 mg of powder (5), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (5) was placed on filter paper, the area where the drop was placed turned orange in a circular pattern, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The orange-colored area was powder (5) insoluble in water, and the area where the transparent liquid spread in concentric circles was water, confirming that powder (5) was insoluble in water.

[0092] Example 6 19.8 g of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 100 g of ethanol were added to a 3 L beaker and thoroughly mixed. Next, 1000 g of ion-exchanged water was added and stirred at room temperature for 5 minutes using a glass stirring blade connected to a Three-One motor to prepare a boron nitride dispersion. 10.5 g of N-capryloyl lysine (n6-(1-Oxooctyl)-L-lysine, Alfa Chemistry), 50 g of ethanol, 200 g of ion-exchanged water, and 5 g of 48% aqueous sodium hydroxide (special grade, Kanto Chemical Co., Ltd.) were added to a 1 L beaker and thoroughly dissolved to prepare an N-capryloyl lysine solution. 9.01 g of annatto color (Kanto Chemical Co., Ltd.), 300 mL of ion-exchanged water, and a stir bar were added to a 500 mL beaker and stirred at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto color solution. The N-capryloyl lysine solution and the annatto pigment solution were added sequentially to the boron nitride dispersion and stirred at room temperature for 15 minutes. Subsequently, dilute hydrochloric acid (hydrochloric acid grade 1, manufactured by Kanto Chemical Co., Inc.) diluted 10 times 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. The 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 34.0 g of powder (6). The composition ratio of boron nitride, N-capryloyl lysine, and annatto pigment in powder (6) was 50:27:23 in terms of the amount charged. The resulting powder exhibited an orange color similar to that of annatto pigment. Dispersion (6) was prepared by adding 100 mg of powder (6), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (6) was placed on filter paper, the area where the drop was placed turned orange in a circular pattern, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The orange-colored area was powder (6) insoluble in water, and the area where the transparent liquid subsequently spread in concentric circles was water, confirming that powder (6) was insoluble in water.

[0093] Example 7 A lauroyl lysine solution was prepared by adding 27 g of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), 50 g of ethanol, 200 g of ion-exchanged water, and 10 g of 48% aqueous sodium hydroxide (special grade, Kanto Chemical Co., Ltd.) to a 1 L beaker and dissolving thoroughly. A 500 mL beaker was also prepared by adding 23.0 g of annatto colorant (Kanto Chemical Co., Ltd.), 300 mL of ion-exchanged water, and a stir bar. The mixture was stirred at room temperature for 15 minutes using a magnetic stirrer to prepare an annatto colorant solution. The lauroyl lysine solution and the annatto colorant solution were then added sequentially to 1000 g of ion-exchanged water in a 3 L beaker and stirred at room temperature for 15 minutes. Next, dilute hydrochloric acid (first-grade hydrochloric acid, Kanto Chemical Co., Ltd.) diluted 10-fold 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 funnel, and the resulting solid was dried in a vacuum dryer (740 mmHg) at 30°C for 14 hours to obtain 47.0 g of powder (7). The composition ratio of lauroyl lysine to annatto pigment in powder (7) was 27:23 in terms of the amount charged. The resulting powder had the same orange color as annatto pigment.

[0094] 20 g of powder (7) and 20 g of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.) were premixed. Subsequently, the mixture was processed at 4000 rpm for 3 minutes using a dry particle compositing device (Nobilta (registered trademark), Hosokawa Micron Corporation) (using a Φ=86 mm blade) and then removed to obtain 37.0 g of powder (8). The composition ratio of boron nitride, lauroyl lysine, and annatto color in powder (8) was 50:27:23 in terms of the amount charged. The obtained powder had an orange color similar to that of annatto color. Dispersion (7) was prepared by adding 100 mg of powder (8), 1.0 g of ion-exchanged water, and a stirring bar to a 10 mL vial and stirring for 5 minutes with a magnetic stirrer. When a drop of dispersion (7) was placed on filter paper, the area where the drop was placed turned orange in a circular pattern, followed by the appearance of a colorless, transparent liquid spreading in concentric circles. The orange-colored area was powder (8) insoluble in water, and the area where the transparent liquid spread in concentric circles was water, confirming that powder (8) was insoluble in water.

[0095] (Comparative Example 1) 10 mg of annatto color (Kanto Chemical Co., Inc.) and 1.0 g of water were added to a 10 mL vial, and a stir bar was added and the mixture was stirred for 5 minutes to prepare dispersion (8). When one drop of dispersion (8) was placed on filter paper, an orange liquid was observed to spread uniformly in a concentric pattern around the drop. This confirmed that the annatto color was dissolved in water in dispersion (8).

[0096] (Comparative Example 2) A 10 mL vial was charged with 23 mg of annatto colorant (Kanto Chemical Co., Ltd.), 50 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), 27 mg of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water. A stir bar was then added and the mixture was stirred for 5 minutes to produce dispersion (9). When a drop of dispersion (9) was placed on filter paper, an orange liquid was observed to spread uniformly in a concentric pattern around the drop. It was confirmed that the annatto colorant was dissolved in water in dispersion (9).

[0097] (Comparative Example 3) 10 mg of safflower yellow (safflower Y1500, 85% safflower pigment, 15% dextrin) and 1.0 g of water were added to a 10 mL vial, and a stir bar was added and the mixture was stirred for 5 minutes to prepare dispersion (10). When one drop of dispersion (10) was placed on filter paper, it was observed that the yellow liquid spread uniformly in a concentric pattern around the drop. This confirmed that safflower yellow had dissolved in water in dispersion (10).

[0098] Comparative Example 4 5 mg of safflower yellow (safflower Y1500, 85% safflower pigment, 15% dextrin), 50 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), 50 mg of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water were added to a 10 mL vial, and a stir bar was added and the mixture was stirred for 5 minutes to produce dispersion (11). When a drop of dispersion (11) was placed on filter paper, a uniform yellow liquid was observed spreading concentrically around the drop. It was confirmed that safflower yellow had dissolved in water in dispersion (11).

[0099] (Comparative Example 5) 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 stir bar was added and the mixture was stirred for 5 minutes to produce dispersion (12). When one drop of dispersion (12) was placed on filter paper, a green liquid was observed to spread uniformly in a concentric pattern around the drop. It was confirmed that copper chlorophyllin sodium was dissolved in water in dispersion (12).

[0100] (Comparative Example 6) A 10 mL vial was charged with 5 mg of copper chlorophyllin sodium (Fujifilm Wako Pure Chemical Industries, Ltd.), 50 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), 50 mg of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water. A stir bar was added and the mixture was stirred for 5 minutes to produce dispersion (13). When a drop of dispersion (13) was placed on filter paper, a green liquid was observed to spread uniformly in a concentric pattern around the drop. It was confirmed that copper chlorophyllin sodium was dissolved in water in dispersion (13).

[0101] (Comparative Example 7) 10 mg of Linablue G1 (DIC Lifetech, Inc., 55% trehalose, 40% spirulina extract, 5% trisodium citrate) and 1.0 g of water were added to a 10 mL vial, and a stir bar was added and the mixture was stirred for 5 minutes to produce dispersion (14). When one drop of dispersion (14) was placed on filter paper, it was observed that the blue liquid spread uniformly in a concentric pattern around the drop. This confirmed that the phycocyanin pigment in dispersion (14) was dissolved in water.

[0102] (Comparative Example 8) 5 mg of Linablue G1 (DIC Lifetech Co., Ltd., 55% trehalose, 40% spirulina extract, 5% trisodium citrate), 50 mg of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), 50 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 stir bar was added and the mixture was stirred for 5 minutes to produce dispersion (15). When a drop of dispersion (15) was placed on filter paper, a blue liquid was observed to spread uniformly in a concentric pattern around the drop. It was confirmed that phycocyanin pigment was dissolved in water in dispersion (15).

[0103] Comparative Example 9 A 10 mL vial was charged with 45 mg of annatto dye (Kanto Chemical Co., Ltd.), 60 mg of pearl pigment (Sun Chemical, SunSHINE Spectral Red), 15 mg of lauroyl lysine (N-lauroyl-L-lysine, Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.0 g of water. A stir bar was then added and the mixture was stirred for 5 minutes to produce dispersion (16). When a drop of dispersion (16) was placed on filter paper, an orange liquid was observed to spread uniformly in a concentric pattern around the drop. This confirmed that the annatto dye had dissolved in water in dispersion (16).

[0104] (Comparative Example 10) A 10 mL vial was charged with 23 mg of annatto colorant (Kanto Chemical Co., Ltd.), 50 mg of boron nitride (Fujifilm Wako Pure Chemical Industries, Ltd.), 27 mg of N-capryloyl lysine (n6-(1-Oxooctyl)-L-lysine, Alfa Chemistry), and 1.0 g of water. A stir bar was then added and the mixture was stirred for 5 minutes to produce dispersion (17). When a drop of dispersion (17) was placed on filter paper, it was observed that an orange liquid spread uniformly in a concentric pattern around the drop. This confirmed that the annatto colorant was dissolved in water in dispersion (17).

[0105] The results obtained so far are shown in Table 1. Water resistance was evaluated as ◯ if the dye was insoluble in water, and × if it was soluble.

[0106] [Table 1]

[0107] From Table 1, it is clear that the water-insoluble dye composition of the present invention has high water resistance.

[0108] The water-insoluble dye composition of the present invention exhibits better color development than a simple mixture of a natural dye, a dehydrated condensation compound of a fatty acid and an amino acid, and an inorganic material, or a simple mixture of a composite composition of a natural dye, a dehydrated condensation compound of a fatty acid and an amino acid, and an inorganic material.

[0109] (Preparation of powder (9)) 15 g of annatto color (Kanto Chemical Co., Ltd.), 5 g of lauroyl lysine, and 20 g of boron nitride (Kanto Chemical Co., Ltd.) were added in powder form to a 45 L plastic bag and thoroughly mixed to prepare powder (9).

[0110] (Preparation of powder (10)) 20 g of powder (7) and 20 g of boron nitride were added in powder form to a 45 L plastic bag and thoroughly mixed to prepare powder (10).

[0111] (Method for measuring powder color) An integrating sphere unit (JASCO Corporation, ISN-923) was attached to a spectrophotometer (JASCO Corporation, V-770DS). Next, a powder cell (JASCO Corporation, PSH-002) was filled with enough powder to fully cover the color measurement area. The powder cell was attached to the spectrophotometer, and color measurement was performed. L* was calculated using the L*a*b* color system from the measured reflectance spectrum from 380 to 780 nm. The measured reflectance is the relative reflectance measured using a standard white plate for the integrating sphere as a reference.

[0112] Powder (1), powder (8), powder (9), and powder (10) were measured in powder form. The color measurement results are shown in Table 2.

[0113] [Table 2]

[0114] From Table 2, it is clear that Evaluation Examples 1 and 2 have smaller L* values ​​than Comparative Evaluation Examples 1 and 2, and have better color development.

[0115] The coloring materials of the Examples and Comparative Examples were evaluated as lipstick cosmetics, eye cosmetics, nail cosmetics, and hair cosmetics.

[0116] (Production and evaluation of lipstick cosmetics) Balm cream base (manufactured by Orange Flower Co., Ltd.) and castor oil (manufactured by Orange Flower Co., Ltd.) were weighed into a pudding cup and mixed while heating in a water bath at 70°C to 80°C. Powder (1) prepared in Example 1, powder (5) prepared in Example 5, or the annatto colorant used in Comparative Example 1 was added and mixed while heating. The mixed liquid was poured 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 introduced, and the cylinder was gradually lowered and placed inside the cylinder, yielding a lipstick cosmetic. Table 3 summarizes the lipstick cosmetics prepared.

[0117] [Table 3]

[0118] Each lipstick was evaluated for water resistance, coarse particles in appearance, usability, color unevenness, and makeup retention. Water resistance was evaluated by applying the lipstick 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. Usability and color unevenness were evaluated by applying the lipstick to the wrist. Makeup retention was evaluated by rubbing the lipstick applied to the wrist with tissue paper three times and visually checking color fading. The evaluation results are summarized in Table 2. Water resistance was evaluated as ◯ if it did not smudge, and × if it smudged. Coarse particles in appearance were evaluated as ◯ if there were no coarse particles, and × if there were coarse particles. Usability was evaluated as ◯ if it was good, and × if it was poor. Color unevenness was evaluated as ◯ if there was no color unevenness, and × if there was color unevenness. Makeup retention was evaluated as ◯ if there was no color fading, and × if there was color fading.

[0119] [Table 4]

[0120] As is clear from Table 4, 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.

[0121] (Production and evaluation of eye cosmetics) 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 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 powder (5) prepared in the Examples or the annatto colorant used in Comparative Example 1 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 5 summarizes the eye cosmetics prepared.

[0122] [Table 5]

[0123] 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 with 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 6. For water resistance, ◯ was given if there was no bleeding, and × if there was bleeding. For roughness, ◯ was given if there was no roughness, and × if there was roughness. For color unevenness, ◯ was given if there was no unevenness in the color, and × if there was unevenness in the color. For makeup retention, ◯ was given if there was no color fading, and × if there was color fading.

[0124] [Table 6]

[0125] As is clear from Table 6, the eye cosmetics using the water-insoluble pigment composition of the present invention showed superiority in terms of water resistance, roughness, uneven color, and makeup durability compared to eye cosmetics using natural pigments themselves.

[0126] (Preparation and evaluation of nail cosmetics) The powder or natural 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. Each nail cosmetic used powder (1) or powder (5) prepared in the Examples or the annatto pigment used in Comparative Example 1 as a coloring material. Table 7 summarizes the prepared nail cosmetics.

[0127] [Table 7]

[0128] 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 8. 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.

[0129] [Table 8]

[0130] As is clear from Table 8, 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.

[0131] (Preparation and evaluation of hair color cream) A hair color cream was prepared and evaluated as a hair cosmetic. 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 powder (5) prepared in the Examples or the annatto colorant used in Comparative Example 1 was added 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, producing a hair color cream. Table 9 summarizes the hair color creams prepared.

[0132] [Table 9]

[0133] (Hair color evaluation method) (Color evaluation) <Color development when applied to blonde human hair> The hair color cream was applied and spread by hand on blonde human hair, and the color development was evaluated visually. The color development on blonde hair was evaluated as ◯ if the color development was good, and x if the color development was poor. <Color development when applied to black human hair> The hair color cream was applied and spread by hand on black human hair, and the color development was evaluated visually. When the color development on the black hair was good, it was rated as ◯, and when it was poor, it was rated as ×. <Color development when applied to artificial skin> The hair color cream was spread on the artificial skin in a circular motion with the fingers, and the color development was evaluated visually. If the color development on the artificial skin was good, it was marked as ◯, and if it was poor, it was marked as ×.

[0134] (Water resistance evaluation) The hair color cream was spread on filter paper in a circular motion with a finger and allowed to dry at room temperature for approximately 10 minutes. Next, 1 mL of tap water was dropped into the center of the colored area using a dropper. If the dropped area remained colored the same as before the drop was dropped, and if a colorless, transparent solution was observed spreading concentrically from the colored area, it was evaluated as not bleeding into the water. Water resistance was evaluated as ◯ if the cream did not bleed, and × if it bleeded.

[0135] (Evaluation of pigmentation) The 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 then hand-washed using half a pump of shampoo (LUX Super Rich Shine Damage Repair Moisture Repair Shampoo, manufactured by Unilever Japan Co., Ltd.), and the shampoo was thoroughly rinsed out with room-temperature tap water. Furthermore, half a pump of conditioner (LUX Super Rich Shine Damage Repair Moisture Repair Conditioner, manufactured by Unilever Japan Co., Ltd.) was applied, and the shampoo was then rinsed out with room-temperature tap water. After washing, the blonde human hair was dried with hot air from a hair dryer for approximately 2 minutes, and then checked for the presence or absence of pigmentation. If no pigmentation was observed, it was marked with a ◯, and if pigmentation was observed, it was marked with an ×. The evaluation results of the prepared hair cosmetics are summarized in Table 10.

[0136] [Table 10]

[0137] As is clear from Table 10, 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.

[0138] 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. The water-insoluble dye composition of the present invention exhibited superior performance due to the complexation of the natural dye, the dehydrated condensation compound of a fatty acid and an amino acid, and the inorganic material, and the powder described in the Examples exhibited superior performance as a cosmetic.

Claims

1. The water-insoluble pigment composition is a composite of a natural pigment, a dehydration condensation compound of a fatty acid and an amino acid, and an inorganic material, the natural colorant is contained in an amount of 0.1 to 70% by mass, the dehydrated condensation compound of a fatty acid and an amino acid is contained in an amount of 5 to 60% by mass, and the inorganic material is contained in an amount of 30 to 80% by mass, and the total of the natural colorant, the dehydrated condensation compound of a fatty acid and an amino acid, and the inorganic material is contained in an amount of 100% by mass, The natural pigment is at least one selected from a carotenoid pigment, a porphyrin pigment, a pigment protein, an annatto pigment, a chlorophyll pigment, and a phycocyanin pigment; the dehydrated condensation compound of a fatty acid and an amino acid is at least one selected from lauroyl lysine and N-capryloyl lysine, the inorganic material is at least one selected from the group consisting of boron nitride, titanium oxide, pearl pigments, clay minerals, and hydroxyapatite; Complexed water-insoluble dye compositions.

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

3. 3. A food, cosmetic, lipstick cosmetic, eye cosmetic, nail cosmetic, base makeup cosmetic, coating material or printing marker for pharmaceuticals or pesticides, stationery, writing implement, printing ink, inkjet ink, metal ink, paint, plastic colorant, color toner, fluorescent labeling agent, fluorescent probe, or chemical sensor, comprising the water-insoluble dye composition according to claim 1 or 2.

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