Colorant, coloring composition, method for producing the same, paint and coating film

Abstract

An object of the present invention is to provide a colorant that can form a blue coating film that has high transparency and a vivid color tone, with large angle dependence of lightness (dark flop) and small angle dependence of hue (color flop). [Solution] A colorant represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3. Condition 1: The average primary particle diameter as photographed with a transmission electron microscope is 20 nm or more and 300 nm or less. Condition 2: The average value of major axis / minor axis, which is the ratio of the major axis to the minor axis of primary particles photographed with a transmission electron microscope, is 1 or more and 2.5 or less. Condition 3: In a powder X-ray diffraction spectrum shown by the diffraction intensity versus diffraction angle 2θ measured using CuKα radiation, the powder has a peak in the range of 2θ from 25.55° to 25.95°.

Description

[Technical Field]

[0001] The present invention relates to a colorant and a coating film using the same. [Background technology]

[0002] In industrial product fields such as automotive coatings, the market demands a wide variety of colors and designs. For example, copper phthalocyanine pigments are used as colorants for blue hues because of their high tinting strength, vividness, and fastness. Depending on the hue, copper phthalocyanine pigments are used in three varieties: CI Pigment Blue 15:3, CI Pigment Blue 15:1, and CI Pigment Blue 15:6. In addition, paints are required to not only have higher transparency and vivid colors, but also flip-flop properties. This means that paints with high angle dependence of brightness (dark flop) and low angle dependence of hue (color flop) are required.

[0003] For example, Patent Document 1 discloses a paint containing a metallic pigment and CI Pigment Blue 15:1. Furthermore, Patent Document 2 discloses a multilayer coating film in which a color clear coating film containing a color pigment is laminated on a coating film containing a luster material and / or a color pigment. This multilayer coating film allows the color and / or reflected light of the coating film below to be seen through the color clear coating film provided on the upper layer, resulting in a multilayer coating film with excellent color depth. For example, a coating film in which a color clear coating film containing a color pigment is laminated on a metallic base coating film containing a luster material is known as a "candy color" coating film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-75946 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-167720 [Patent Document 3] Japanese Patent Application Laid-Open No. 1999-106671 [Patent Document 4] Japanese Patent Application Publication No. 2023-091898 Summary of the Invention [Problem to be solved by the invention]

[0005] One trend in blue colors is a reddish blue with less color flop, but this has not been achieved with conventional methods. In particular, when used on three-dimensional objects such as the exteriors of automobiles, good flip-flop properties (high angle dependence of lightness (dark flop) and low angle dependence of hue (color flop)) are preferred. CI Pigment Blue 15:6 is used as a colorant to produce a reddish blue, but it has the problem of high color flop. Therefore, Patent Document 3 discloses an indanthrene pigment composition with little color flop using a δ-type indanthrene blue pigment. However, the hue of the coating film with δ-type indanthrene blue is too reddish, resulting in a problem of insufficient clarity. Patent Document 4 discloses an inkjet ink with high coloring strength that uses an α-type indanthrene blue pigment. However, when the inkjet ink is used in paint applications, there are problems such as insufficient flip-flop properties and clarity.

[0006] The present invention aims to provide a colorant that can form a blue coating film that has a high degree of angle dependency of lightness (dark flop), a low degree of angle dependency of hue (color flop), and a high transparency and a vivid color tone (hereinafter referred to as vividness). [Means for solving the problem]

[0007] A colorant represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3: Condition 1: The average primary particle diameter as photographed with a transmission electron microscope is 20 nm or more and 300 nm or less. Condition 2: The average value of major axis / minor axis, which is the ratio of the major axis to the minor axis of primary particles photographed with a transmission electron microscope, is 1 or more and 2.5 or less. Condition 3: In a powder X-ray diffraction spectrum shown by the diffraction intensity versus diffraction angle 2θ measured using CuKα radiation, the powder has a peak in the range of 2θ from 25.55° to 25.95°. Chemical formula (1) [ka] [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a colorant capable of forming a coating film having high color transparency and vivid color tone (hereinafter referred to as vividness), with large angle dependence of lightness (dark flop) and small angle dependence of hue (color flop).The present invention also provides a colorant composition, a colorant dispersion, a coating film, a multi-layer coating film, a coated article for vehicle exteriors, and a method for producing a colorant composition. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing the measurement angle when measuring the color of a coated plate in a flip-flop test. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, the embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following embodiments, and various modifications may be made within the scope of solving the problems, and various embodiments are included. First, let us explain the terms used in this specification. "CI" stands for Color Index number. "Coated material" has the same meaning as "printed material," "image-formed material," and "coated material." "Colorant" is a term that includes pigments and dyes.

[0011] <1> coloring agent One embodiment of the present invention is a colorant represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3: Condition 1: The average primary particle diameter as photographed with a transmission electron microscope is 20 nm or more and 300 nm or less. Condition 2: The average value of major axis / minor axis, which is the ratio of the major axis to the minor axis of primary particles photographed with a transmission electron microscope, is 1 or more and 2.5 or less. Condition 3: In a powder X-ray diffraction spectrum shown by the diffraction intensity versus diffraction angle 2θ measured using CuKα radiation, the powder has a peak in the range of 2θ from 25.55° to 25.95°. Chemical formula (1) [ka]

[0012] The mechanism by which the colorant of the present invention can solve the problems is presumed to be as follows. The transparency of a colorant depends on the size of its primary particle diameter, and therefore, the smaller the primary particle diameter, the more transparent the coating film obtained. Furthermore, the smaller the ratio of the major axis to the minor axis of the primary particle (hereinafter referred to as the aspect ratio), the more effectively the aggregation of pigment particles can be suppressed. Therefore, a coating film containing the colorant of the present invention is less likely to cause diffuse reflection of light, has high dark flop properties, and can suppress color flop properties. The colorant represented by chemical formula (1) is called indanthrene, also known as CI Pigment Blue 60. As shown in Patent Document 3, the hue changes depending on the crystal system. The colorant represented by chemical formula (1) of the present invention can obtain a coating film with the desired vivid blue hue by adjusting the crystal system to form crystals that have a peak in the 2θ range of 25.55° or more and 25.95° or less in a powder X-ray diffraction spectrum, which is shown as the diffraction intensity versus diffraction angle 2θ measured with CuKα radiation.

[0013] The average primary particle diameter of the colorant of the present invention is the average value of the major axis of the primary particles, and is 20 nm to 300 nm. From the viewpoint of transparency, it is preferably 200 nm or less, and from the viewpoint of ease of pigment dispersion, it is preferably 25 nm or more. The average primary particle diameter is more preferably 30 nm to 150 nm, and even more preferably 35 nm to 100 nm.

[0014] The colorant of the present invention has an average value of the ratio of the major axis to the minor axis (hereinafter referred to as the "aspect ratio") of 1 to 2.5. The aspect ratio is preferably 1 to 2.3, more preferably 1 to 2. When the aspect ratio is 1 to 2.5, the colorant particle shape is close to spherical and the distance between each particle is uniform, thereby suppressing particle aggregation. When the aspect ratio is within the above range, the number of aggregated particles in the coating film is reduced, suppressing light scattering and resulting in a coating film with high dark flop and low color flop. Note that the aspect ratio of all particles does not need to be within the above range; it is sufficient that the average value of the ratio of the major axis to the minor axis is within the above range. Details of the method for measuring the major axis and minor axis of primary particles and the method for calculating the average value are shown in the Examples.

[0015] The colorant of the present invention preferably has a coefficient of variation (hereinafter sometimes referred to as CV value) of primary particle diameters of particles in an image taken with a transmission electron microscope of 0 to 0.29, more preferably 0 to 0.28, and even more preferably 0 to 0.25. The coefficient of variation of primary particle diameters is the value obtained by dividing the standard deviation of the major diameters of the primary particles by the average major diameter. When the coefficient of variation of primary particle diameters is 0 to 0.29, the primary particles have a uniform size, and a coating film with higher clarity and particularly reduced color flop can be obtained.

[0016] The colorant of the present invention can be used in combination with other pigments in addition to the colorant represented by chemical formula (1). While known pigments can be used, blue, purple, and black pigments, which result in minimal loss of clarity when mixed with the colorant of the present invention, are preferred. Phthalocyanine pigments, dioxazine pigments, and carbon black pigments, which have high color flop properties, are particularly preferred. Examples of other pigments include phthalocyanine pigments such as CI Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, and Pigment Blue 15:6. Examples of dioxazine pigments include Pigment Violet 23. Depending on the manufacturing method and raw materials, carbon black can be thermal black, acetylene black, lamp black, furnace black, etc.

[0017] The colorant composition of the present invention preferably contains a colorant and at least one additive selected from a dye derivative (A) and a resin (B). When controlling the primary particle size of the colorant, the dye derivative (A) and the resin (B) contribute to reducing the primary particle size, the aspect ratio, and the coefficient of variation of the primary particle size of the colorant. Furthermore, the dye derivative (A) and the resin (B) act to suppress growth of the primary particle size and secondary aggregation during dispersion preparation and coating preparation.

[0018] <Dye derivative (A)> The dye derivative (A) is a compound represented by the structure AXB. A represents an organic pigment residue or an aromatic compound residue having three or more rings. A is preferably a group having a heterocycle. Examples of the organic pigment residue include a phthalocyanine pigment residue, a quinacridone pigment residue, an anthraquinone pigment residue, an indanthrene pigment residue, a diketopyrrolopyrrole pigment residue, a dioxazine pigment residue, and an azo pigment residue. Examples of compounds that form an aromatic compound residue having three or more rings include polycyclic structures in which ring structures share each side, such as anthracene, phenanthrene, phenalene, and acenaphthylene, and linked ring structures in which rings are bonded directly or via a linking group, such as triphenylmethane and terphenyl. B represents an acidic group, a basic group, or an optionally substituted phthalimidomethyl group. Examples of B include a sulfone group, a carboxyl group, a phosphate group, a primary amino group, a secondary amino group, a tertiary amino group, and a phthalimidomethyl group. Examples of the optionally substituted phthalimidomethyl group include phthalimidomethyl groups substituted with an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, or a phthalimidomethyl group. X represents a direct bond or any linking group. Examples of the linking group include an alkylene group having 1 to 8 carbon atoms, an amide bond, a sulfonamide bond, an ester bond, an imino group, a triazine ring, a phenylene group which may have a substituent, and combinations thereof. The dye derivative (A) is oriented on the surface of the colorant, suppressing particle growth of the colorant, thereby making it possible to make the average primary particle size fine and reduce the CV value.

[0019] The content of the dye derivative (A) is preferably 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the colorant. From the viewpoint of miniaturizing the primary particle diameter, the content of the dye derivative (A) is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more. From the viewpoint of coloring power, the content is more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0020] <Resin (B)> The resin (B) is preferably a resin that is soluble in water or a water-soluble organic solvent, or has a softening point or glass transition point of not more than 105° C. The resin (B) is preferably a resin-type dispersant. Examples of the resin (B) include (meth)acrylic resins, polyester resins, polyurethane resins, and polyol resins. The resin (B) can contain a hydroxyl group or a carboxyl group. Commercially available products of the resin (B) include the Dianal series (manufactured by Mitsubishi Chemical Corporation), the DEGALAN series (manufactured by Evonik Industries) including Dianal BR-605, Dianal MB-7922, and Dianal BR-116 (all manufactured by Mitsubishi Chemical Corporation), DEGALAN LP64 / 11, DEGALAN LP64 / 12, DEGALAN LP63 / 11, DEGALAN LP67 / 11, DEGALAN PM381N, and DEGALAN 64 / 12N (all manufactured by Evonik Industries).

[0021] Examples of the molecular structure of resin-type dispersants include random polymers, comb polymers, and block polymers. Among these, comb polymers and block polymers are preferred. Resin-type dispersants have adsorption sites that have high affinity for colorants and relaxation sites that have affinity for solvents, binders, etc. and contribute to the dispersion and dispersion stability of colorants. Examples of monomers that can be used to form adsorption sites include styrene, α-olefins, (meth)acrylic acid alkyl esters, and (meth)acrylic acid aryl esters. Examples of monomers that can form relaxation sites include acidic polymers having acidic groups such as carboxy groups, sulfonic groups, and phosphate groups; basic monomers having basic groups such as amino groups and pyridyl groups; and hydrophilic monomers having polyoxyalkylene groups. Resin-type dispersants preferably have one or more of an acid value and an amine value, and the sum of the acid value and the amine value is preferably 10 mgKOH / g to 250 mgKOH / g.

[0022] Commercially available resin-type dispersants include, for example, the SOLSPERSE series (manufactured by Lubrizol), the Joncryl series (manufactured by BASF), the BYK series (manufactured by BYK-Chemie), the Efka series (manufactured by BASF), and the Hi-Loss-X series (manufactured by Seiko PMC). Specifically, SOLSPERSE 26000, SOLSPERSE 36000, SOLSPERSE 41000, SOLSPERSE 85000, SOLSPERSE J180, SOLSPERSE J200, SOLSPERSE V320, SOLSPERSE X300, SOLSPERSE 32000, SOLSPERSE 33000, SOLSPERSE 45000, SOLSPERSE 24000GR, SOLSPERSE 28000, SOLSPERSE 35000, SOLSPERSE 39000 (all manufactured by Lubrizol), JONCRYL 67, JONCRYL 678, JONCRYL 690, JONCRYL 693, DispexUltra PA4560, DispexUltra PA4580, DispexUltra PX4585, EFKA PX4780 (all manufactured by BASF), DISPERBYK-190, DISPERBYK-191, DISPERBYK-194N, DISPERBYK-2013, DISPERBYK-2015, DISPERBYK-2055 (all manufactured by BYK-Chemie), Hi-Loss X-200, Hi-Loss X-210 (all manufactured by Seiko PMC Co., Ltd.), and the like.

[0023] Resin (B) adsorbs to the surface of the colorant to suppress secondary aggregation of the colorant, and also controls the kneading intensity in the primary particle control step described below, thereby reducing the primary particle size of the colorant.

[0024] The content of resin (B) is preferably 1 part by mass or more and 25 parts by mass or less relative to 100 parts by mass of the colorant. From the viewpoint of reducing the primary particle size, the content of resin (B) is more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more. From the viewpoint of kneading strength, the content is more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

[0025] <1> Method for producing colorant and coloring composition The colorant represented by chemical formula (1) that satisfies conditions 1, 2, and 3 of the present invention may be prepared by any method as long as it satisfies conditions 1 to 3. A preferred embodiment for preparing the colorant represented by chemical formula (1) that satisfies conditions 1, 2, and 3 will be described below.

[0026] The colorant of the present invention has a crystal system with a peak at 25.75±0.2° in the powder X-ray diffraction spectrum measured with CuKα radiation. To obtain an indanthrene compound having this crystal system, the indanthrene compound is first dissolved in a solvent with good solubility and then added to a poor solvent to precipitate an indanthrene compound with an unstable crystal system. Furthermore, an organic solvent is added to this indanthrene compound to obtain an indanthrene compound with the desired crystal system. For example, the following method can be used. An indanthrene compound is dissolved in 98% sulfuric acid to obtain a sulfuric acid solution. The sulfuric acid solution is added to water to precipitate the indanthrene compound. The precipitate is filtered and washed with water. The residue is reslurried in water, and then an organic solvent is added and the mixture is heated and stirred at 80°C or higher for at least 3 hours. Further filtration, washing with water, drying, and pulverization are performed sequentially to obtain an indanthrene compound having a peak at 25.75±0.2°C. The 98% sulfuric acid must be in an amount sufficient to dissolve the indanthrene compound; for example, approximately 8 times the amount by mass is sufficient. Furthermore, the amount of water used to precipitate the indanthrene compound is preferably 5 times or more the mass of the sulfuric acid solution. Cold water or ice water is preferred. The organic solvent used during heating is preferably a water-soluble organic solvent or a solvent emulsion containing a hydrophobic organic solvent and a surfactant. Examples of water-soluble organic solvents that can be used include isopropanol, butanol, isobutanol, methyl ethyl ketone, tetrahydrofuran, and N-methylpyrrolidone. Examples of hydrophobic organic solvents that can be used include xylene, toluene, ethylbenzene, chlorobenzene, and nitrobenzene. The surfactant is preferably a compound that can form an emulsion in combination with an organic solvent and water, for example, a nonionic or anionic surfactant.

[0027] The colorant of the present invention is preferably subjected to primary particle control. Examples of primary particle control include a solution precipitation method in which a colorant is dissolved in a good solvent such as sulfuric acid and then reprecipitated by releasing it into a poor solvent such as water; a mechanical pulverization method in which a colorant is impacted with hard media such as iron, zirconia, or glass; a high-pressure pulverization method in which a pigment composition is pulverized by spraying and impacting it under high pressure; and wet kneading in which a pigment is mixed with a water-soluble inorganic salt and a water-soluble organic solvent, kneaded, and then milled. These methods may also be combined. Among these, wet kneading is preferred. Examples of kneading machines include a kneader, a trimix, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, a vertical sand mill, and an annular bead mill. Among these, a kneader or a trimix is ​​preferred.

[0028] The colored composition of the present invention can be obtained by mixing a colorant with at least one additive selected from a dye derivative (A) or a resin (B). The mixing is preferably carried out, for example, when controlling the primary particle size of the colorant.

[0029] The wet kneading method mechanically kneads a mixture containing a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent (hereinafter referred to as "dough") to adjust the colorant to a desired primary particle size, aspect ratio, and coefficient of variation. Primary particle control by wet kneading involves repeated cycles of particle crushing by kneading with a water-soluble inorganic salt, primary particle refinement by grinding, and primary particle growth using a water-soluble organic solvent and heat. This allows the primary particle size to converge within an appropriate range, resulting in primary particles with the desired particle size and coefficient of variation. Furthermore, when indanthrene compounds undergo crystal growth without external force, large particles grow in a specific direction, resulting in needle-like crystals with a high aspect ratio. However, simultaneous refinement and crystal growth can produce particles with a small aspect ratio. To obtain the desired primary particles, it is preferable to use a water-soluble inorganic salt in an amount 10 times by weight or more, more preferably 15 times by weight or more, relative to the colorant, and further add a dye derivative (A) or resin (B). Among these, adding a dye derivative (A) or a resin (B) during kneading is preferred because it can reduce the aspect ratio and coefficient of variation. The dye derivative (A) has the effect of suppressing the growth of primary particle size by orienting on the surface of the colorant, while the resin (B) not only orients on the surface of the colorant but also increases the viscosity of the dough, thereby strengthening the force applied to the primary particles during kneading and making the primary particles finer. Examples of water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of water-soluble inorganic salt used is not particularly limited as long as a colorant having the desired average primary particle size and aspect ratio can be obtained. From the viewpoints of both processing efficiency and production efficiency, the amount used is preferably 300 to 3,000 parts by mass, more preferably 500 to 2,500 parts by mass, and even more preferably 1,000 to 2,000 parts by mass, per 100 parts by mass of colorant. Note that, by adding an appropriate amount of the dye derivative (A) and resin (B) during kneading, the amount of water-soluble inorganic salt required can be reduced, which is advantageous in terms of production efficiency.

[0030] The water-soluble organic solvent is a solvent that dissolves or is miscible in water, and examples thereof include glycerin, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, and 2-butyl-2-ethyl-1,3-propanediol. The water-soluble organic solvents can be used alone or in combination. The amount of the water-soluble organic solvent used is preferably 50 to 500 parts by mass, more preferably 75 to 300 parts by mass, per 100 parts by mass of the colorant. The temperature during the kneading can be set depending on the desired average particle size of the colorant, and is preferably 40 to 120°C, more preferably 50 to 100°C.

[0031] After the kneading, the dough is poured into water and stirred to obtain a suspension. The mass of water added is not limited as long as it is an amount sufficient to obtain a suspension. The suspension may be heated as needed. For example, water is added in an amount 4 to 20 times the total mass of the water-soluble inorganic salt and the water-soluble organic solvent, and the mixture is mixed and stirred. The mixing and stirring conditions are not limited, and a temperature of 15 to 90°C is preferred, for example. The water-soluble organic solvent and water-soluble inorganic salt can then be removed by removing the filtrate through operations such as filtration and washing. If necessary, the mixture can be reslurried in water and washed again. The water used for purification is preferably tap water or purified water such as ion-exchanged water or distilled water, with purified water being more preferred. The wet cake of the colorant or colorant composition obtained after filtration and washing with water can be dried and pulverized in a dryer or the like to produce a powder colorant or colorant composition. Alternatively, the wet cake can be used to produce a colorant dispersion without drying.

[0032] <3> Colorant Dispersion The colorant dispersion of the present invention contains the colorant or colorant composition of the present invention and a dispersion medium. The dispersion medium may be any medium capable of dispersing the colorant or colorant composition, and examples thereof include solvents.

[0033] The solvent is selected from organic solvents and water. Examples of organic solvents include hydrocarbon solvents such as toluene and xylene, ester solvents such as butyl acetate and methyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, monoalcohol solvents such as ethanol, n-propanol, isopropanol, n-butanol, and isobutanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol, polyhydric alcohol solvents such as glycerin, and glycol ether solvents such as methoxypropanol, methoxybutanol, butyl glycol, and butyl diglycol. Other examples include solvents commonly used in the fields of inks and paints.

[0034] The colorant dispersion of the present invention may contain a resin-type dispersant, such as the pigment dispersants listed for the resin (B).

[0035] The dispersion can be carried out using a disperser such as a horizontal sand mill, a vertical sand mill, an annular bead mill, a microfluidizer, a high-speed mixer, a homomixer, a homogenizer, a high-pressure homogenizer, a paint shaker, a roll mill, a stone mill, an ultrasonic disperser, a high-pressure disperser, a counter-impingement type disperser, or an oblique collision type disperser. A plurality of dispersers can also be used for dispersion.

[0036] The colorant dispersion of the present invention can contain, in 100% by mass, the colorant or colorant composition of the present invention in an amount of 1 to 70% by mass calculated as nonvolatile matter, and a resin-type dispersant in an amount of 10 to 200% by mass relative to 100% by mass of the colorant or colorant composition. The remainder includes the dispersion medium, and if necessary, part of the dispersion medium may be replaced with additives such as antifoaming agents and preservatives.

[0037] <4> paint The coating material of the present invention contains a colorant dispersion, a binder resin, and a curing agent. The binder resin is not particularly limited as long as it is a resin that can be generally used in coating materials, and examples thereof include acrylic resins, polyurethane resins, alkyd resins, amino resins, epoxy resins, and modified resins thereof. When aluminum is used in the bright coating material, the binder resin is preferably a phosphate group-containing resin. A curing agent for curing the coating film can also be contained. The curing agent is not particularly limited as long as it can react with the binder resin to form a coating film, and examples include epoxy compounds, isocyanate compounds, blocked isocyanate compounds, polyamine compounds, polyamide resins, and melamine compounds. The coating material of the present invention can contain, based on 100% by mass, 60 to 96% by mass of binder resin, 3 to 40% by mass of curing agent, and 1 to 50% by mass of colorant dispersion.

[0038] The coating material of the present invention may contain a lustrous material. Examples of lustrous materials include metal flakes, mica, and coated glass flakes. Metal flakes are preferred when obtaining a particularly vivid hue. Examples of metal flakes include flakes of aluminum, zinc, copper, iron, nickel, titanium, stainless steel, and gold. Among these, aluminum flakes are preferred from the viewpoints of lustrousness, cost, and specific gravity. The average particle diameter of the metal flakes is preferably 1 to 100 μm, more preferably 5 to 50 μm. The metal flakes may be surface-treated with fatty acids, resins, etc. to prevent oxidation. Examples of mica include ordinary mica and coated mica coated with a metal oxide such as titanium oxide. Examples of coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide. The average particle diameter of the mica and glass flakes is preferably 1 to 200 μm, more preferably 10 to 150 μm. The content of the luster material is preferably 10 to 4000 parts by mass, and more preferably 10 to 1000 parts by mass, relative to 100 parts by mass of the colorant or coloring composition. The average particle size of the luster material can be measured in the same manner as the average particle size of the pigment composition, except that an optical microscope is used.

[0039] The coating material of the present invention may contain other known additives such as viscosity modifiers, preservatives, surfactants, ultraviolet absorbers, and light stabilizers.

[0040] The coating material of the present invention can be produced by mixing a colorant dispersion with a binder resin and a curing agent. Alternatively, the coating material can be produced by dispersing a colorant or colorant composition in a dispersion medium and a binder resin, and then mixing with a curing agent. Dispersion or mixing can be performed using the dispersers and mixers exemplified in the description of the colorant dispersion above.

[0041] <5> coating The coating film of the present invention can be obtained by applying a coating material containing the colorant of the present invention or the colorant composition of the present invention onto a substrate to form a coating film.

[0042] Examples of substrates on which a coating film is formed include metals, resins, wood, concrete, stone, etc. Among these, metals and resins are preferred. Examples of metals include iron, aluminum, stainless steel, silver, copper, gold, and alloys thereof. Examples of metal shapes include three-dimensional shapes such as flat or curved plates, rods, cylinders, and spheres. Examples of resin shapes include sheets and molded three-dimensional objects. Examples of resin types include polyolefin resins, polymethyl methacrylate resins, polycarbonate resins, polystyrene resins, acrylonitrile-styrene copolymer resins, polyvinyl chloride resins, acetate resins, ABS resins, polyester resins, and polyamide resins. It is preferable that the surface of the substrate is coated with a primer paint.

[0043] Examples of coating methods include roll coating, brush coating, spray coating, etc. Among these, spray coating is preferred. The thickness of the coating film is preferably 15 μm or more and 150 μm or less. When the thickness is 15 μm or more, the protective function and flip-flop property of the coated object are improved. When the thickness is 150 μm or less, a coating film with higher transparency is obtained.

[0044] The coating film is preferably a curable coating film that is cured by light, heat or oxidation.

[0045] The coating film of the present invention can contain pigments other than indanthrene compounds. Examples of such pigments include phthalocyanine pigments, dioxazine pigments, and carbon black (hereinafter referred to as high-color-flop pigments). Specific examples of phthalocyanine pigments include CI Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, and Pigment Blue 15:6. Examples of dioxazine pigments include Pigment Violet 23. Depending on the manufacturing method and raw materials, carbon black can be used as thermal black, acetylene black, lamp black, furnace black, and the like. While these pigments exhibit high color flop when used alone, using them in combination with the colorant of the present invention reduces color flop, resulting in a coating film that retains the original color of the pigment regardless of the viewing angle. Examples of methods for using high color flop pigments in combination include mixing them during primary particle control, mixing them during the production of a colorant dispersion, preparing separate colorant dispersions and mixing them, and preparing separate coating materials and mixing them. Any of these methods may be used.

[0046] The multilayer coating film of the present invention preferably has a first coating film that does not contain a colorant represented by chemical formula (1), and a coating film according to claim 5 as a second coating film on the first coating film. The coating film of the present invention may be in an embodiment in which a single layer of the coating film contains a high color flop pigment and a colorant represented by chemical formula (1). However, in another embodiment, when a multilayer coating film is formed in which a first coating film contains a high color flop pigment and the coating film of the present invention is used as a second coating film, diffused reflection of light is unlikely to occur, and a hue with high dark flop and suppressed color flop is easily obtained.

[0047] The thickness of the first coating film is preferably 15 μm or more and 135 μm or less, and more preferably 20 μm or more and 80 μm or less. The thickness of the second coating film is preferably 15 μm or more and 135 μm or less, and more preferably 20 μm or more and 80 μm or less. The total thickness of the first coating film and the second coating film is preferably 30 μm or more and 150 μm or less.

[0048] The multilayer coating film of the present invention provides a highly decorative coating film with a unique color tone as follows. For example, if a phthalocyanine pigment is used in the first coating film, the multilayer coating film will have a reddish blue color. Similarly, if a dioxazine pigment is used in the first coating film, the multilayer coating film will have a bluish purple color. Similarly, if carbon black is used, the multilayer coating film will have a bluish black color.

[0049] The coated article for vehicle exterior of the present invention has the coating film of the present invention. The coating film may be the multi-layer coating film of the present invention. The coated article for vehicle exterior of the present invention is excellent in transparency, clarity, and brilliance, and has durability that can withstand outdoor use, so it is preferably used for automobiles, motorcycles, etc.

[0050] [Example of embodiment] Examples of embodiments of the present invention are given below: The present invention is not limited to the following.

[0051] <1> The colorant of the present invention is a colorant represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3. Condition 1: The average primary particle diameter as photographed with a transmission electron microscope is 20 nm or more and 300 nm or less. Condition 2: The average value of major axis / minor axis, which is the ratio of the major axis to the minor axis of primary particles photographed with a transmission electron microscope, is 1 or more and 2.5 or less. Condition 3: In a powder X-ray diffraction spectrum shown by the diffraction intensity versus diffraction angle 2θ measured using CuKα radiation, the powder has a peak in the range of 2θ from 25.55° to 25.95°. Chemical formula (1) [ka] <2> The colorant has a coefficient of variation of primary particle diameter of particles in an image taken with a transmission electron microscope of 0 or more and 0.29 or less. <1> Coloring agent. <3> <1> or <2> and at least one additive selected from a dye derivative (A) and a resin (B). <4> <1> or <2> coloring agent, or <3> and a dispersion medium. <5> <4> a colorant dispersion of the formula (I), a binder resin, and a hardener. <6> <1> or <2> coloring agent, or <3> A coating film comprising the colorant composition of claim 1. <7> Further, pigments other than the compound of formula (1) are included. <6> Coating film. <8> A first coating film that does not contain a colorant represented by chemical formula (1), and a second coating film on the first coating film. <6> A multi-layer coating film having the coating film. <9> <6> A vehicle exterior coating having a coating film of the formula: <10> <3> A method for producing a colorant composition according to the present invention, comprising the steps of: A method for producing a colorant composition, comprising a step of kneading a mixture containing at least one additive selected from a dye derivative (A) and a resin (B), a colorant represented by chemical formula (1), a water-soluble inorganic salt, and a water-soluble organic solvent. [Example]

[0052] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

[0053] The abbreviations and product names used in the following examples have the following meanings. <Colorants, pigments> PB60: Indanthrene compound having a peak at 25.75±0.2° (Production Example 9) PB15:1:CI Pigment Blue 15:1 (Toyocolor LIONOL BLUE 7189-PM) PB15:3: CI Pigment Blue 15:3 (Toyo Color LIONOL BLUE FG-7330) PB15:6: CI Pigment Blue 15:6 (Toyo Color LIONOL BLUE ESP-S) PV23: CI Pigment Violet 23 (Toyocolor Lionogen Violet FG-6150) PBk7: CI Pigment Black 7 (Birla Carbon Raven 5000 Ultra 3)

[0054] <Dye derivative (A)> Dye derivative (A)-1: A mixture of compounds represented by the following general formula (2), where n=1 to 3. General formula (2) [ka]

[0055] Dye derivative (A)-2: A mixture of compounds represented by the following general formula (3), where n=1 to 3. General formula (3) [ka]

[0056] Dye derivative (A)-3: A mixture of compounds represented by the following general formula (4), where n=1 to 3. General formula (4) [ka]

[0057] Dye derivative (A)-4: A mixture of compounds represented by the following general formula (5), where n=1 to 3. General formula (5) [ka]

[0058] Dye derivative (A)-5: A compound represented by the following chemical formula (6). Chemical formula (6) [ka]

[0059] Dye derivative (A)-6: A compound represented by the following general formula (7). General formula (7) [ka]

[0060] Dye derivative (A)-7: A mixture of compounds represented by the following general formula (8), where n=1 to 3. General formula (8) [ka]

[0061] <Resin (B)> SOLSPERSE 36000 (Lubrizol Corporation, resin-type dispersant, comb polymer, acid value 45 mg KOH / g, amine value 13 mg KOH / g) SOLSPERSE J200 (Lubrizol Corporation, resin-type dispersant, comb polymer, acid value 10.5 mg KOH / g, amine value 33 mg KOH / g) SOLSPERSE 35000 (Lubrizol Corporation, resin-type dispersant, comb polymer, acid value 15.8 mg KOH / g, amine value 32 mg KOH / g) Joncryl 690 (BASF, resin-type dispersant, acid value 240 mg KOH / g) DISPERBYK-191 (BYK, resin-type dispersant, acid value 30 mg KOH / g, amine value 20 mg KOH / g) DISPERBYK-2013 (BYK, resin-type dispersant, acid value 8 mg KOH / g, amine value 18 mg KOH / g) DISPERBYK-2055 (BYK, resin-type dispersant, amine value 40 mg KOH / g) Hiros X-210 (Seiko PMC, resin-type dispersant, acid value 220 mg KOH / g) Dispex Ultra PX4585 (BASF, resin-type dispersant, block polymer, amine value 20 mg KOH / g) EFKA PX4780 (BASF, resin-type dispersant, amine value 20 mg KOH / g)

[0062] [Measurement of average primary particle size and aspect ratio] The average primary particle diameter of the obtained colorant composition was determined by observation with a transmission electron microscope (TEM) as follows. Approximately 50 primary particles of the colorant composition were randomly selected from a photograph taken with a transmission electron microscope at a magnification of 10,000 times. A rectangle with the smallest area circumscribing the image of the particle was drawn for each particle. The length of the long side of the rectangle was taken as the major axis, and the length of the short side was taken as the minor axis, and the average values ​​for each were calculated. The average value of the major axes was taken as the average primary particle diameter, and the average value of the major axis / minor axis was taken as the aspect ratio. The standard deviation of the major axes / the average primary particle diameter was taken as the coefficient of variation.

[0063] [X-ray diffraction spectrum measurement] The X-ray diffraction spectrum was measured by the following method. Equipment: Rigaku X-ray diffractometer SmartLab (wide-angle X-ray diffraction measurement mode) X-ray source:CuKα Voltage: 45kV Current: 200mA Measurement range: 3.0° to 35.0° Step angle: 0.01° From the X-ray diffraction spectrum obtained under these conditions, a diffraction peak was confirmed at 2θ=25.75±0.2°.

[0064] [Dark flop and color flop evaluation] The following performance tests were carried out on the prepared coated panels to determine their dark flop and color flop properties. Because the color tone of the color clear and metallic paint colors varies depending on the viewing angle or the angle of incidence of light, a multi-angle colorimeter (X-Rite, MA94) was used for color measurement. Figure 1 shows a side view of the color measurement test. Incident light 101 was irradiated onto a painted panel 100 at a 45-degree angle. The specularly reflected light 102, which reflects at a 90-degree angle from the incident light, is reflected at a 15-degree angle toward the incident light 101, and this light is designated as highlight 103. Highlight 103 is the color tone of a bright area with a high amount of reflected light, as observed visually. Reflected light at a 110-degree angle toward the incident light 101 from specularly reflected light 102 is designated as shade 104. Shade 104 is the color tone of a dark area with a low amount of reflected light, as observed visually. The resulting shade and highlight brightness (L * ) absolute value of the difference |ΔL * |=|L * (110°)-L * The larger the (15°)|, the greater the change in lightness with respect to the angle change, meaning that it can be said that the dark flop properties are high. Also, painted panels that appear to have high dark flop properties when visually inspected have low shade lightness (L*(110°)). The DF value below, which combines these, was used as an index of dark flop properties. The higher the DF value, the higher and more favorable the dark flop properties. DF value=|L*(110°)-L*(15°)| / L*(110°) Also, the resulting shade and highlight hue (H * The absolute value of the difference between the values ​​of the CF and the CF values ​​is taken as the CF value. The smaller the CF value, the smaller the change in hue with respect to the change in angle, i.e., the better the color flop. CF value = |H * (110°)-H * (15°)|

[0065] [Preparation of dye derivative (A)] (Production Example 1) Production of dye derivative (A)-1 The dye derivative (A)-1 was produced based on Comparative Production Example 1 of JP 2023-159499 A. 70 parts of PB15:3, 26 parts of phthalimide, and 10 parts of paraformaldehyde were added to 400 parts of 98% sulfuric acid, stirred to dissolve, and then reacted at 80 ° C. for 3 hours to obtain a reaction solution. The resulting reaction solution was poured into 8,000 parts of ice water, and the resulting precipitate was filtered, washed with water, dried, and pulverized in this order to obtain the dye derivative (A)-1 represented by general formula (2).

[0066] (Production Example 2) Production of dye derivative (A)-2 While stirring 100 parts by mass of 98% sulfuric acid, 10 parts by mass of Hostaperm Red E5B 02 (CI Pigment Violet 19 manufactured by Heubach) was added. 11.3 parts by mass of N-hydroxymethylphthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was then added little by little, and the mixture was stirred at 40°C for 2 hours. This reaction solution was dropped into 1,000 parts of ice water, and the precipitate was filtered, washed with water, dried, and pulverized, yielding the dye derivative (A)-2 represented by general formula (3).

[0067] (Production Example 3) Production of dye derivative (A)-3 Dye derivative (A)-3 was produced based on Example 1 of JP-A No. 52-132031. 100 parts of chlorosulfonic acid was dissolved in 10 parts of PB15:3. After dissolution, 7 parts of thionyl chloride was added, the mixture was heated, and stirred at 112-113°C for 4 hours. After cooling, the mixture was poured onto ice, filtered, and washed with ice water. This paste was reslurried in 100 parts of water, and 8 parts of N,N-diethylaminopropylamine was added. The mixture was stirred at 25°C for 12 hours, then heated to 60°C and stirred for 1 hour. The slurry was filtered, washed with water, dried, and pulverized, yielding the dye derivative (A)-3 represented by general formula (4).

[0068] (Production Example 4) Production of dye derivative (A)-4 Dye derivative (A)-4 was prepared based on Production Example 1 in JP-A-56-118462. 100 parts by weight of chlorosulfonic acid was added to 10 parts by weight of Hostaperm Red E5B 02 at 10-20°C, stirred at 40-50°C for 3 hours, poured into 1,000 parts of ice water, filtered, and washed with water to obtain a water cake of chlorosulfonated quinacridone. This water cake of chlorosulfonated quinacridone was added to 300 parts by weight of ice water and reslurried, and 28 parts by weight of N,N-dibutylaminopropylamine was added and stirred at 10°C or below for 4 hours, filtered, and washed with water. This water cake was then added to 300 parts by weight of 0.5% aqueous sodium carbonate solution, stirred for 1 hour, filtered, washed with water until neutral, dried, and pulverized, to obtain dye derivative (A)-4 represented by general formula (5).

[0069] (Production Example 5) Production of dye derivative (A)-5 Dye derivative (A)-5 was produced based on Production Example 5 in JP-A 2016-132693. To 800 parts of dimethylacetamide, 44 parts of Cinilex Red SR4C (CI Pigment Red 177 manufactured by CINIC) and 37 parts of cyanuric chloride were added, and the mixture was stirred at 100-110°C for 5 hours. After cooling, 104 parts of 3-diethylaminopropylamine was added, and the mixture was reacted at 130-140°C for 3 hours. After cooling, the mixture was filtered and washed with methanol and water. The mixture was dried at 60°C and further pulverized to obtain dye derivative (A)-5 represented by chemical formula (6).

[0070] (Production Example 6) Production of dye derivative (A)-6 Dye derivative (A)-6 was produced based on Production Example 1 in JP-A No. 4-209660. 10 parts of crude indanthrene blue was added to 150 parts of 12% fuming sulfuric acid at 30°C or below and stirred to dissolve. Next, 9 parts of paraformaldehyde and 20 parts of monochloroacetic acid amide were added at 30°C or below, and the mixture was stirred at 25°C for 50 hours, then poured into ice water, filtered, and washed with water to obtain a blue wet cake. This wet cake was reslurried in 200 parts of water, and 10.6 parts of dibutylamine was added. The mixture was heated to reflux for 2 hours, then filtered, washed with water, dried, and pulverized to obtain the dye derivative (A)-6 represented by general formula (7).

[0071] (Production Example 7) Production of dye derivative (A)-7 10 parts of copper phthalocyanine was added to 80 parts of 101% sulfuric acid, and the mixture was stirred at 90°C for 2 hours, then added to 500 parts of ice water to precipitate. The resulting precipitate was washed with 1% hydrochloric acid, dried, and pulverized, yielding the dye derivative (A)-7 represented by general formula (8).

[0072] (Production Example 8) Production of Comparative Resin (B)-1 Resin (B)-1 was produced in accordance with Resin A-12 of JP-A 2023-091898. [First Reaction] A reaction vessel equipped with a gas inlet tube, thermometer, condenser, dropping funnel, and stirrer was charged with the following monomer mixture: 61.3 parts (60 mol%) of maleic anhydride, 62.4 parts (3 mol%) of Unilube PKA-5013 (NOF Corporation, polyethylene glycol-polypropylene glycol-allyl ether: number average molecular weight 2,000), 7.4 parts (37 mol%) of 1-hexadecene as an α-olefin, 100 parts of MEK, and 0.5 parts of octyl thioglycolate as a chain transfer agent. After nitrogen substitution, the mixture was heated to 105°C with stirring. A mixture of 2.0 parts of dimethyl isobutyrate (Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-601) as a radical polymerization initiator and 5 parts of MEK was added dropwise over 1 hour. Thereafter, while stirring at a temperature of 85°C, a mixture of 5 parts of V-601 and 12 parts of MEK was added dropwise over 6 hours, and the mixture was allowed to react for 1 hour while maintaining the temperature at 85°C, yielding a polymer having maleic anhydride as an acid anhydride group. [Second Reaction] Subsequently, 81.3 parts of isopropyl alcohol (82% equivalent ratio relative to the acid anhydride groups in the maleic anhydride monomer) and 0.1 parts of diazabicycloundecene as a catalyst were added, and the mixture was stirred for 6 hours while maintaining the temperature at 85°C to cause a reaction, resulting in ring-opening and half-esterification of the maleic anhydride. The solvent in the resulting product was completely removed by concentration under reduced pressure, producing Comparative Resin (B)-1 (number average molecular weight (Mn): 13,200, acid value 125 mgKOH / g).

[0073] (Production Example 9) Production of indanthrene compound PB60 having a peak at 25.75±0.2° 120 parts of Vat Blue RSN (an indanthrene compound manufactured by Hangzhou Emperor Chemical Co., Ltd.) was gradually added to 1,000 parts of 98% sulfuric acid and dissolved, followed by stirring at 25°C for 1 hour to obtain a sulfuric acid solution. Next, the sulfuric acid solution was poured into 7,000 parts of stirred ice water. After stirring for 10 minutes, the mixture was filtered and washed with water to obtain a blue wet cake. This wet cake was added to 900 parts of water, and the pH was adjusted to 7-8 with 25% aqueous sodium hydroxide. 100 parts of isobutanol was added, and the mixture was refluxed and stirred at 90-95°C for 4 hours, followed by stirring at 95°C or higher for 1 hour to distill off the isobutanol. Water was added until the temperature reached 70°C or below, followed by filtration and washing with water to obtain a wet cake of PB60. This wet cake was dried at 80°C for 24 hours and pulverized to obtain an indanthrene compound PB60, which has a peak at 2θ = 25.75 ± 0.2° in its powder X-ray diffraction spectrum.

[0074] <1> Production of colorants and colorant compositions (Example A-1) Preparation of Colorant Composition a-1 100 parts of PB60 as a colorant, 10 parts of dye derivative (A)-1 as a dye derivative (A), 10 parts of Joncryl 690 as a resin (B), 500 parts of sodium chloride as a water-soluble inorganic salt, and 85 parts of diethylene glycol as a water-soluble organic solvent were charged into a 3-L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60° C. This mixture was added to 5,000 parts of ion-exchanged water and stirred in a high-speed mixer for 2 hours to form a slurry, which was then filtered and repeatedly washed with ion-exchanged water to remove the sodium chloride and diethylene glycol, yielding a wet cake of colorant composition a-1.

[0075] (Examples A-2 to A-26) Preparation of colorants or colorant compositions a-2 to a-26 Wet cakes of colorants or colorant compositions a-2 to a-26 were obtained in the same manner as in Example A-1, except that the types and amounts of the dye derivative (A), resin (B), sodium chloride, and diethylene glycol were changed as shown in Table 1.

[0076] (Comparative Example A-1) Preparation of Colorant a-101 100 parts of PB60 as a colorant, 500 parts of sodium chloride as a water-soluble inorganic salt, and 85 parts of diethylene glycol as a water-soluble organic solvent were charged into a 3-liter stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60°C. This mixture was poured into 9,000 parts of ion-exchanged water and stirred for 2 hours in a high-speed mixer to form a slurry, which was then filtered and washed repeatedly with ion-exchanged water to remove the sodium chloride and diethylene glycol, yielding a wet cake of colorant a-101.

[0077] (Comparative Example A-2) Preparation of Colorant Composition a-102 A wet cake of colorant composition a-102 was obtained in the same manner as in Comparative Example A-1, except that 28 parts (as nonvolatile content) of Comparative Resin (B)-1 prepared in Production Example 8 was added as Resin (B) and the kneading temperature was changed to 75°C.

[0078] (Comparative Example A-3) Preparation of Colorant a-103 The wet cake of PB60 in Production Example 9 was used as colorant a-103.

[0079] (Comparative Example A-4) Preparation of Colorant a-104 Colorant a-104 was prepared according to WO 96 / 05255. A reaction vessel was charged with 600 parts of water and heated to 60°C while stirring. Next, 54.4 parts of 48% aqueous sodium hydroxide solution and 18.8 parts of hydrosulfite were added to the reaction vessel, followed by 12.0 parts of Indanthrene Blue crude. A reduction reaction was carried out at 60°C for 15 minutes with stirring to obtain a reduced solution of Indanthrene Blue. The reduction potential at this time was -1060 mV. Separately, 400 parts of water and 25.0 parts of 30% aqueous hydrogen peroxide were charged to a separate reaction vessel and kept at 20°C with stirring to prepare an oxidized solution. Next, the reduced solution of Indanthrene Blue was pumped into the stirred oxidized solution at a rate of 500 ml per minute to carry out an oxidation reaction. After completion of the oxidation reaction, stirring was continued for another hour, followed by filtration and washing with water until the filtrate became neutral, yielding a wet cake of colorant a-104.

[0080] (Examples B-1 to B-26) Preparation of colorants or colorant compositions b-1 to b-26 The wet cakes of the colorants or colorant compositions obtained in Examples A-1 to A-26 were dried at 80° C. for 24 hours and then pulverized with a hammer mill to obtain colorants or colorant compositions b-1 to b-26.

[0081] (Comparative Examples B-1 to B-4) Preparation of Colorants or Colorant Compositions b-101 to b-104 The wet cakes of the colorants or colorant compositions obtained in Comparative Examples A-1 to A-4 were dried at 80°C for 24 hours and then pulverized with a hammer mill to obtain colorants or colorant compositions b-101 to b-104.

[0082] For the colorants or colorant compositions obtained in Examples B-1 to B-26 and Comparative Examples B-1 to B-4, the peaks in the X-ray diffraction spectrum, the average primary particle size, the aspect ratio, and the CV value were determined according to the above-mentioned methods. The results are shown in Tables 1-1 to 1-3 and 2. In Tables 1-1 to 1-3 and 2, the "composition ratio" refers to the content of the colorant, the dye derivative (A), and the resin (B) in a total of 100% by mass of the colorant, the dye derivative (A), and the resin (B).

[0083] [Table 1-1] [Table 1-2] [Table 1-3] [Table 2]

[0084] <2> Paint manufacturing and evaluation Below are specific examples of paints containing a colorant or colorant composition. In the examples, the pigment content indicates the mass ratio of the colorant or colorant composition in the colorant dispersion or paint, and the nonvolatile content indicates the mass ratio of the raw materials, colorant dispersion, or paint other than the volatile components. PWC is an abbreviation for "pigment weight concentration" and indicates the mass ratio of the pigment in the nonvolatile content (coating film components) of the paint. The pigment content, nonvolatile content, and PWC are values ​​calculated from the charged masses.

[0085] <c>Colorant Dispersion (C1) Preparation of colorant dispersion (Example C-1) Preparation of Colorant Dispersion c-1 The following raw materials and 70 parts of zirconia beads with a diameter of 1.25 mm were placed in a 70 ml glass bottle and dispersed for 180 minutes using a Candex SK450 manufactured by Fast & Fluid Management to obtain a dispersion with a pigment content of 20% and a nonvolatile content of 30.5%. Wet cake of colorant composition a-1: 6.3 parts in terms of nonvolatile content Pigment dispersant (BASF acrylic block copolymer, Dispex UltraPX 4585, non-volatile content 50%): 6.3 parts Antifoaming agent (BASF FoamStar ST 2400, non-volatile content 100%): 0.16 parts Ion-exchanged water: balance (31.5 parts total) Next, the zirconia beads were removed from the dispersion to obtain colorant dispersion c-1.

[0086] (Examples C-2 to C-14, Examples C-23 to C-26, Comparative Examples C-1 to C-8) Preparation of Colorant Dispersions c-2 to c-14, c-23 to c-26, c-101 to c-108 Colorant dispersions c-2 to c-14, c-23 to c-26, and c-101 to c-108 were prepared in the same manner as in Example C-1, except that the wet cake of colorant composition a-1 in Example C-1 was changed as shown in Table 3. In Comparative Examples C-5 to C-8, the pigments listed in Table 3 were used instead of the wet cake.

[0087] [Table 3]

[0088] <d>Water-based color clear paint (D1) Preparation of water-based clear paint The following raw materials were mixed using a mixer to obtain a water-based clear paint with a non-volatile content of 31.1%. Alkali-swellable acrylic dispersion (Setaqua 6802 manufactured by Allnex, non-volatile content 24%): 15 parts Thermosetting water-based acrylic emulsion (Setaqua 6169 manufactured by Allnex, non-volatile content 45%): 9 parts Aliphatic polyester polyurethane emulsion (Daotan TW6466 / 36WA, non-volatile content 36%, manufactured by Allnex): 52 parts Methylated monomer melamine crosslinker (Cymel 303LF, non-volatile content 98% or more, manufactured by Allnex): 4.8 parts Base (dimethylethanolamine): Add as needed to achieve a pH range of 8.0 to 8.5 Ion-exchanged water and ethylene glycol monobutyl ether: balance (total 100 parts) The amounts of ion-exchanged water and ethylene glycol monobutyl ether were adjusted appropriately to achieve a viscosity suitable for spray coating (Stormer viscosity 58 to 60 KU).

[0089] (D2) Preparation of water-based color clear paint and coated board (Example D-1) Preparation of water-based color clear paint d-1 and preparation of coated board The following raw materials were mixed using a mixer to obtain a water-based color clear paint d-1 with a pigment content of 0.5% and a non-volatile content of 31.1%. Colorant dispersion c-1: 1 part Water-based clear paint: 39 parts Dimethylethanolamine, ion-exchanged water, and ethylene glycol monobutyl ether were then added as needed to achieve a pH of 8.0-8.5 and a Stormer viscosity of 58-60 KU. This water-based color clear paint was sprayed onto a mirror-finished stainless steel plate using a spray gun. The coating was applied in nine coats, then allowed to stand at 25°C for at least two hours and then dried at 80°C for 15 minutes. A second water-based clear paint was similarly applied using a spray gun. The coating was applied in six coats, allowed to stand at 25°C for at least two hours, and then baked at 140°C for 20 minutes to obtain a water-based color clear-coated plate. The PWC of the color clear coating film was 1.6%, the color clear coating film thickness was approximately 35 μm, and the clear coating film thickness was approximately 20 μm.

[0090] (Examples D-2 to D-14, Examples D-23 to D-26, Comparative Examples D-1 to D-8) Preparation of Water-Based Color Clear Coatings d-2 to d-14, d-23 to d-26, d-101 to d-108 and Preparation of Coated Plates) The same procedure as in Example D-1 was carried out except that the colorant dispersion c-1 in Example D-1 was changed as shown in Table 4, and water-based color clear coatings d-2 to d-14, d-23 to d-26, d-101 to d-108 and their coated plates were obtained.

[0091] (D3) Evaluation of painted panels The resulting coated plates were evaluated for the following items, with the coated plate of Comparative Example D-1 as the standard. Note that Comparative Examples D-5 to D-8 used colorants other than indanthrene and had different color characteristics, so they were not evaluated for coloring strength, vividness, or brilliance. <Coloring power> The coated panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 4. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for coloring strength) 4: Extremely strong coloring power compared to standard painted boards 3: Higher coloring strength than standard painted board 2: Slightly stronger coloring than the standard painted board 1: Tinting strength is equivalent to that of the standard painted board

[0092] <Clarity> The coated panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 4. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Slightly more vivid than the standard painted board 1: Clarity is equal to or lower than the standard painted board

[0093] <Transparency> The coated panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 4. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. (Transparency evaluation criteria) 4: Extremely high transparency compared to the standard painted board, with extremely strong metallic luster of the base 3: Higher transparency than the standard painted board, with a stronger metallic luster of the base 2: Slightly more transparent than the standard painted board, with a slightly stronger metallic luster of the base 1: Transparency is the same or lower than that of the standard painted board, and the metallic luster of the base is also the same or weaker

[0094] <Dark flop> The coated panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 4. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. 4: DF value is 7 or more times higher than the standard painted board (dark flop is significantly higher than the standard) 3: DF value is 4 or more but less than 7 compared to the standard painted board (higher dark flop than the standard) 2: DF value is 1 or more but less than 4 compared to the standard painted board (dark flop tendency is slightly higher than the standard) 1: DF value is less than 1 higher than the standard painted board, or is equal to or lower than the standard (dark flop property is equal to or lower than the standard)

[0095] <Color flop> The coated panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 4. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. 4:4>CF value (very low color flop, very good) 3:6>CF value ≧4 (low color flop, good) 2:8>CF value≧6 (slightly low color flop, usable) 1: CF value ≧ 8 (high color flop, poor)

[0096] [Table 4]

[0097] <e>Water-based metallic paint (E1) Preparation of aqueous metallic base The following raw materials were mixed using a mixer to obtain an aqueous metallic base with an aluminum content of 6.5% and a non-volatile content of 23.1%. Aluminum paste (Toyo Aluminum Co., Ltd. aluminum paste, EMR-D5422, aluminum content 60%, non-volatile content 65%): 10 parts Pigment wetting agent (Additol XL250 manufactured by Allnex, non-volatile content 55%): 2 parts Water-based clear paint (non-volatile content 31.1%) prepared with D1: 50 parts Ion-exchanged water: 27 parts Ethylene glycol monobutyl ether: 11 parts

[0098] (E2) Preparation of water-based metallic paint and coated board (Example E-1) Preparation of water-based metallic paint e-1 and coated plate The following raw materials were mixed using a mixer to obtain a water-based metallic paint e-1 with a pigment content of 2.1%, an aluminum content of 2.2%, and a non-volatile content of 28.3%. Colorant dispersion c-1: 8.5 parts Water-based metallic base: 28.3 parts Water-based clear paint: 45 parts Dimethylethanolamine, ion-exchanged water, and ethylene glycol monobutyl ether were then added as needed to adjust the pH to 8.0-8.5 and the Stormer viscosity to 55-58 KU. This water-based metallic paint was sprayed onto a steel plate using a spray gun. The coating was applied in nine coats, then allowed to stand at 25°C for at least two hours and then dried at 80°C for 15 minutes. A water-based clear paint was then similarly applied using a spray gun. The coating was applied in six coats, allowed to stand at 25°C for at least two hours, and then baked at 140°C for 20 minutes to obtain a water-based metallic-coated plate. The PWC of the metallic coating was 7.4%, the metallic coating thickness was approximately 40 μm, and the clear coating thickness was approximately 20 μm.

[0099] (Examples E-2 to E-14, Examples E-23 to E-26, Comparative Examples E-1 to E-8) Preparation of water-based metallic paints e-2 to e-14, e-23 to e-26, e-101 to e-108 and preparation of coated plates) The same procedure as in Example E-1 was carried out except that the colorant dispersion c-1 in Example E-1 was changed as shown in Table 5, and water-based metallic paints e-2 to e-14, e-23 to e-26, and e-101 to e-108 and their coated plates were obtained.

[0100] (E3) Preparation of water-based mixed paint and painted board (Examples E-27 to E-28, Comparative Examples E-9 to E-10) Preparation of mixed paints e-27 to e-28, e-109 to e-110, and preparation of coated plates Using a mixer, paints were mixed in the combinations and blending ratios shown in Table 6 to obtain mixed paints e-27 to e-28 and e-109 to e-110. These mixed paints were spray painted in the same manner as in Example E-1 to obtain metallic-coated panels.

[0101] (E4) Preparation of water-based multi-layer coated panels (Examples E-29 to E-32, Comparative Examples E-11 to E-14) Preparation of multilayer coated boards e-29 to e-32, e-111 to e-114 The paint (1) listed in Table 7 was sprayed onto the steel plate using a spray gun. The coating was applied in nine coats, and then the plate was left to stand at 25°C for at least two hours. The paint (2) listed in Table 7 was then applied in seven coats using a spray gun, and the plate was left to stand at 25°C for at least two hours, after which it was dried at 80°C for 15 minutes. A water-based clear paint was then applied in the same manner using a spray gun. The coating was applied in six coats, and the plate was left to stand at 25°C for at least two hours, after which it was baked at 140°C for 20 minutes, to obtain metallic multilayer coated plates e-29 to e-32 and e-111 to e-114.

[0102] (E5) Evaluation of painted panels The resulting coated plates were evaluated for the following items. For Examples E-1 to E-14, Examples E-23 to E-26, and Comparative Examples E-2 to E-8, the coated plate of Comparative Example E-1 was used as the standard, and for Examples E-27 to E-32, the coated plate of the corresponding Comparative Example listed in Tables 6 and 7 was used as the standard. Note that Comparative Examples E-5 to E-8 used colorants other than indanthrene and had different color characteristics, so clarity and brilliance were not evaluated.

[0103] <Clarity> The coated panels were visually observed and evaluated according to the following criteria. The results are shown in Tables 5 to 7. According to the following criteria, "4", "3" and "2" are at practically acceptable levels. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Slightly more vivid than the standard painted board 1: Clarity is equal to or lower than the standard painted board

[0104] <Shining feeling> The coated panels were visually observed and evaluated according to the following criteria. The results are shown in Tables 5 to 7. According to the following criteria, "4", "3" and "2" are at practically acceptable levels. (Evaluation criteria for brightness) 4: Significantly brighter than the standard painted board 3: Higher brightness than the standard painted board 2: Slightly brighter than the standard painted board 1: The brightness is the same or lower than the standard painted board

[0105] <Dark flop> The coated panels were measured with a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 5 to 7. According to the following criteria, "4," "3," and "2" are considered to be at practically acceptable levels. 4: DF value is 7 or more times higher than the standard painted board (dark flop is significantly higher than the standard) 3: DF value is 4 or more but less than 7 compared to the standard painted board (higher dark flop than the standard) 2: DF value is 1 or more but less than 4 compared to the standard painted board (dark flop tendency is slightly higher than the standard) 1: DF value is less than 1 higher than the standard painted board, or is equal to or lower than the standard (dark flop property is equal to or lower than the standard)

[0106] <Color flop> The coated panels were measured with a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 5 to 7. According to the following criteria, "4," "3," and "2" are considered to be at practically acceptable levels. 4:4>CF value (very low color flop, very good) 3:6>CF value ≧4 (low color flop, good) 2:8>CF value≧6 (slightly low color flop, usable) 1: CF value ≧ 8 (high color flop, poor)

[0107] <Weather resistance> For the weather resistance test, the above painted panels were subjected to an accelerated weather resistance test using an ultra-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151) at 90 mW / cm 2 The test was conducted for 96 hours (four cycles of 12 hours day and night), and the color difference (ΔE * ) was evaluated using a Konica Minolta color difference meter CM-700d. The results are shown in Tables 5 to 7. A rating of "3" or "2" on the following scale is considered to be at a practical level. (Weather resistance evaluation criteria) 3: Color change before and after the test (ΔE * ) is less than 2.5, good 2: Color change before and after the test (ΔE * ) is between 2.5 and 3, suitable for practical use 1: Color change before and after the test (ΔE * ) 3 or more, poor

[0108] [Table 5]

[0109] Table 6

[0110] Table 7

[0111] <f>Preparation and evaluation of solvent-based paints (F1) Preparation of solvent-based paint (Example F-6) Preparation of solvent-based paint f-6 Colorant composition b-6 9 parts 7.7 parts acrylic resin (DIC Corporation, Acrydic 47-712) Dispersion medium (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150FLUID manufactured by ENEOS Corporation in a mass ratio of 3:3:2:2) 40.7 parts The above materials and 230 parts of steel beads were placed in a sealable glass container, sealed, and dispersed for 60 minutes using a Red Devil paint shaker. 75.4 parts of Acrydic 47-712 and 17.2 parts of melamine resin (DIC Amidair L-117-60) were then added and dispersed for another 10 minutes. The steel beads were then removed to obtain dark paint f-6.

[0112] (Examples F-7 to F-26, Comparative Examples F-1 to F-9) Preparation of solvent-based paints f-7 to f-26 and f-101 to f-109 The same procedure as in Example F-6 was carried out except that the colorant composition b-6 of Example F-6 was changed as shown in Table 8, to obtain solvent-based paints f-7 to f-26 and f-101 to f-109.

[0113] [Table 8]

[0114] <g>Preparation and evaluation of solvent-based color clear paints and painted panels (G1) Preparation of solvent-based clear paint Acrylic resin (DIC, Acrydic 44-179) 120 parts Melamine resin (DIC, Amidia L117-60) 30 parts Dilution solvent (a mixed solvent of toluene, xylene, T-SOL150FLUID manufactured by ENEOS Corporation, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2) 50 parts The above materials were mixed and stirred with a high-speed mixer to obtain a solvent-based clear coating material.

[0115] (G2) Preparation of solvent-based color clear paint and painted board (Example G-6) Preparation of solvent-based color clear paint g-6 and coated plate One part of the solvent-based paint f-6 prepared in Example F-6 was mixed with 9 parts of the solvent-based clear paint prepared in Example G1 to prepare solvent-based color clear paint g-6. This solvent-based color clear paint was sprayed with a spray gun onto a mirror-finished stainless steel plate. To adjust the viscosity to facilitate spraying, a dilution solvent (a mixed solvent consisting of toluene, xylene, ENEOS T-SOL150FLUID, 3-ethoxypropionate ethyl, and ethyl acetate in a mass ratio of 3:2:2:1:2) was appropriately mixed with the color clear paint at a ratio of approximately 10 to 20% by mass, and the viscosity was adjusted to a value suitable for spray coating (Stormer viscosity 58 to 60 KU). The painting was done in nine separate coats, followed by six coats of solvent-based clear paint sprayed on. After drying at 25°C for 1 hour, the coating was dried at 140°C for 30 minutes to obtain a solvent-based color clear coated plate. The PWC of the color clear coating film was 1.5%, the thickness of the color clear coating film was approximately 35 μm, and the thickness of the clear coating film was approximately 20 μm.

[0116] (Examples G-7 to G-26, Comparative Examples G-1 to G-8) Preparation of solvent-based color clear coatings g-7 to g-26, g-101 to g-108 and coated plates The same procedure as in Example G-6 was carried out except that the solvent-based paint f-6 in Example G-6 was changed as shown in Table 9, and solvent-based color clear paints g-7 to g-26, g-101 to g-108 and their coated plates were obtained.

[0117] (G3) Evaluation of solvent-based color clear coated panels The resulting coated plates were evaluated for the following items. The coated plate of Comparative Example G-1 was used as the standard. Note that Comparative Examples G-5 to G-8 used colorants other than indanthrene and had different color characteristics, so they were not evaluated for coloring strength, vividness, or brilliance. <Coloring power> The coated panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 9. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for coloring strength) 4: Extremely strong coloring power compared to standard painted boards 3: Higher coloring strength than standard painted board 2: Slightly stronger coloring than the standard painted board 1: Tinting strength is equivalent to that of the standard painted board

[0118] <Clarity> The coated panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 9. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Slightly more vivid than the standard painted board 1: Clarity is equal to or lower than the standard painted board

[0119] <Transparency> The coated panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 9. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. (Transparency evaluation criteria) 4: Extremely high transparency compared to the standard painted board, with extremely strong metallic luster of the base 3: Higher transparency than the standard painted board, with a stronger metallic luster of the base 2: Slightly more transparent than the standard painted board, with a slightly stronger metallic luster of the base 1: Transparency is the same or lower than that of the standard painted board, and the metallic luster of the base is also the same or weaker

[0120] <Dark flop> The coated panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 9. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. 4: DF value is 7 or more times higher than the standard painted board (dark flop is significantly higher than the standard) 3: DF value is 4 or more but less than 7 compared to the standard painted board (higher dark flop than the standard) 2: DF value is 1 or more but less than 4 compared to the standard painted board (dark flop tendency is slightly higher than the standard) 1: DF value is less than 1 higher than the standard painted board, or is equal to or lower than the standard (dark flop property is equal to or lower than the standard)

[0121] <Color flop> The coated panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 9. A rating of "4," "3," or "2" on the following criteria is considered to be at a practical level. 4:4>CF value (very low color flop, very good) 3:6>CF value ≧4 (low color flop, good) 2:8>CF value≧6 (slightly low color flop, usable) 1: CF value ≧ 8 (high color flop, poor)

[0122] [Table 9]

[0123] <h>Preparation and evaluation of solvent-based metallic paints and painted panels (H1) Preparation of solvent-based metallic base paint 10 parts aluminum flake paste (Toyo Aluminum Co., Ltd. Aluminum Paste 5620NS) Acrylic resin (DIC Corporation, Acrydic 47-712) 101.7 parts Melamine resin (DIC Corporation, Amidia L-117-60) 21.3 parts Dispersion solvent (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150FLUID manufactured by ENEOS Corporation in a mass ratio of 3:3:2:2) 20.9 parts The above materials were stirred and mixed with a high-speed stirrer to obtain a solvent-based metallic base paint.

[0124] (H2) Preparation of solvent-based metallic paint and fabrication of painted panels (Example H-6) Preparation of solvent-based metallic coated plate h-6 and production of coated plate 20 parts of the solvent-based paint f-6 prepared in Example F-6 and 18.5 parts of the solvent-based metallic base paint were mixed and stirred using a high-speed mixer to obtain solvent-based metallic paint h-6. This solvent-based metallic paint was sprayed onto a steel plate using a spray gun. To adjust the viscosity for easy spraying, a dilution solvent (a mixture of toluene, xylene, ENEOS T-SOL150FLUID, 3-ethoxypropionate ethyl acetate, and a mass ratio of 3:2:2:1:2) was appropriately mixed with the metallic paint in an amount roughly equivalent to the metallic paint, and the viscosity was adjusted to a suitable viscosity for spray coating (Stormer viscosity 58-60 KU). The coating was performed in nine passes, followed by six sprays of the solvent-based clear paint. The mixture was dried at 25°C for 1 hour and then at 140°C for 30 minutes to obtain a solvent-based metallic-coated plate. The PWC of the metallic coating was 7.2%, the thickness of the metallic coating was approximately 40 μm, and the thickness of the clear coating was approximately 20 μm.

[0125] (Examples H-7 to H-26, Comparative Examples H-1 to H-9) Preparation of solvent-based metallic paints h-7 to h-26, h-101 to h-109 and their coated plates Solvent-based metallic paints h-7 to h-26, h-101 to h-109 and their coated plates were obtained in the same manner as in Example H-6, except that the solvent-based paint f-6 in Example H-6 was changed as shown in Table 10. However, only the solvent-based metallic paint h-109 in Comparative Example H-9 had the mixing ratio of the solvent-based paint to the solvent-based metallic base paint changed from 20:18.5 to 3:1.

[0126] (H3) Preparation of solvent-based mixed paint and painted board (Examples H-27 to H-30, Comparative Examples H-10 to H-13) Preparation of mixed paints h-27 to h-30, h-110 to h-113 and preparation of coated plates Using a mixer, the paints were mixed in the combinations and blending ratios shown in Table 11 to obtain mixed paints h-27 to h-30 and h-110 to h-113. Using these mixed paints, spray coating was performed in the same manner as in Example H-6 to obtain metallic-coated panels.

[0127] (H4) Preparation of solvent-based multi-layer coated panels (Examples H-31 to H-33, Comparative Examples H-14 to H-16) Preparation of multilayer coated boards h-31 to h-33, h-114 to h-116 The paint (1) listed in Table 12 was sprayed onto the steel plate using a spray gun. The coating was carried out in nine separate applications. Furthermore, the paint (2) listed in Table 12 was applied in seven separate applications using a spray gun. Furthermore, a solvent-based clear paint was similarly applied using a spray gun. The coating was carried out in six separate applications, and after leaving the coatings at 25°C for at least one hour, they were baked at 140°C for 30 minutes to obtain metallic multilayer coated panels h-31 to h-33 and h-114 to h-116.

[0128] (H5) Evaluation of solvent-based metallic painted panels The resulting coated plates were evaluated for the following items. For Examples H-6 to H-26 and Comparative Examples H-2 to H-9, the coated plate of Comparative Example H-1 was used as the standard, and for Examples H-27 to H-33, the coated plates of the corresponding Comparative Examples listed in Tables 11 and 12 were used as the standard. Note that Comparative Examples H-5 to H-9 used a colorant with a structure other than indanthrene, resulting in different color characteristics, and Example H-33 and Comparative Example H-16 were black, so evaluations of clarity and brilliance were not performed. <Clarity> The coated panels were visually observed and evaluated according to the following criteria. The results are shown in Tables 10 to 12. According to the following criteria, "4," "3," and "2" are at practically acceptable levels. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Slightly more vivid than the standard painted board 1: Clarity is equal to or lower than the standard painted board

[0129] <Shining feeling> The coated panels were visually observed and evaluated according to the following criteria. The results are shown in Tables 10 to 12. According to the following criteria, "4," "3," and "2" are at practically acceptable levels. (Evaluation criteria for brightness) 4: Significantly brighter than the standard painted board 3: Higher brightness than the standard painted board 2: Slightly brighter than the standard painted board 1: The brightness is the same or lower than the standard painted board

[0130] <Dark flop> The coated panels were measured with a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 10 to 12. According to the following criteria, a rating of "4," "3," or "2" is considered to be at a practical level. 4: DF value is 7 or more times higher than the standard painted board (dark flop is significantly higher than the standard) 3: DF value is 4 or more but less than 7 compared to the standard painted board (higher dark flop than the standard) 2: DF value is 1 or more but less than 4 compared to the standard painted board (dark flop tendency is slightly higher than the standard) 1: DF value is less than 1 higher than the standard painted board, or is equal to or lower than the standard (dark flop property is equal to or lower than the standard)

[0131] <Color flop> The coated panels were measured with a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 10 to 12. According to the following criteria, a rating of "4," "3," or "2" is considered to be at a practical level. 4:4>CF value (very low color flop, very good) 3:6>CF value ≧4 (low color flop, good) 2:8>CF value≧6 (slightly low color flop, usable) 1: CF value ≧ 8 (high color flop, poor)

[0132] <Weather resistance> For the weather resistance test, the above painted panels were subjected to an accelerated weather resistance test using an ultra-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151) at 90 mW / cm 2 The test was conducted for 96 hours (four cycles of 12 hours day and night), and the color difference (ΔE * ) was evaluated using a Konica Minolta color difference meter CM-700d. The results are shown in Tables 10 to 12. A rating of "3" or "2" on the following scale is considered to be at a practical level. (Weather resistance evaluation criteria) 3: Color change before and after the test (ΔE * ) is less than 2.5, good 2: Color change before and after the test (ΔE * ) is between 2.5 and 3, suitable for practical use 1: Color change before and after the test (ΔE * ) 3 or more, poor

[0133] [Table 10]

[0134] [Table 11]

[0135] [Table 12]

[0136] A coating material using the colorant or colorant composition of the present invention has high clarity and transparency, and when applied to a metal plate or when used in combination with a luster material, it can provide excellent metallic luster, brilliance, dark flop properties, and color flop properties, making it suitable for coating vehicle exteriors, electrical products, etc. Furthermore, by mixing the paint of the present invention with a paint with high color flop properties, or by forming a multi-layer paint film consisting of the paint film of the present invention and a paint film with high color flop properties, it is possible to obtain a paint film with low color flop properties while controlling the hue, which is suitable for painting vehicle exteriors, electrical products, etc. On the other hand, colorants having an aspect ratio of primary particle size of 2.5 or more, colorants not having a peak at a specified angle (having a crystal system different from that of the present invention), and paints and coated boards using these colorants did not yield paints and coated boards that were excellent in the desired transparency, clarity, brilliance, and flip-flop properties. [Explanation of symbols]

[0137] 100: Painted board 101: Light source 102: Specular reflection light 103: Highlight 104: Shade< / h> < / g> < / f> < / e> < / d> < / c>

Claims

1. A colorant represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3: Condition 1: The average primary particle diameter as photographed with a transmission electron microscope is 20 nm or more and 300 nm or less. Condition 2: The average value of major axis / minor axis, which is the ratio of the major axis to the minor axis of primary particles photographed with a transmission electron microscope, is 1 or more and 2.5 or less. Condition 3: In a powder X-ray diffraction spectrum shown by the diffraction intensity versus diffraction angle 2θ measured with CuKα rays, the powder has a peak in the 2θ range of 25.55° or more and 25.95° or less. Chemical formula (1) 【Chemistry 11】

2. The colorant according to claim 1 , wherein the coefficient of variation of the primary particle diameter of the particles in an image taken with a transmission electron microscope is 0 to 0.

29.

3. A colorant composition comprising the colorant according to claim 1 and at least one additive selected from a dye derivative (A) and a resin (B).

4. A colorant dispersion comprising the colorant according to claim 1 or 2, or the colorant composition according to claim 3, and a dispersion medium.

5. A paint comprising the colorant dispersion of claim 4, a binder resin, and a curing agent.

6. A coating film comprising the colorant according to claim 1 or 2, or the colorant composition according to claim 3.

7. The coating film according to claim 6, further comprising a pigment other than the compound of formula (1).

8. A multi-layer coating film comprising a first coating film that does not contain a colorant represented by chemical formula (1), and the coating film of claim 6 as a second coating film on the first coating film.

9. A vehicle exterior coating having the coating film of claim 6.

10. A method for producing the colorant composition according to claim 3, comprising the steps of: A method for producing a colorant composition, comprising a step of kneading a mixture containing at least one additive selected from a dye derivative (A) and a resin (B), a colorant represented by chemical formula (1), a water-soluble inorganic salt, and a water-soluble organic solvent.

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