Colorants, colored compositions, methods for producing the same, paints, and coating films.

Abstract

The present invention aims to provide a colorant that can form a blue coating film with high brightness angle dependence (dark flop property) and low hue angle dependence (color flop property), as well as high transparency and a vivid color tone. [Solution] A coloring agent represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3. Condition 1: The average primary particle diameter captured by a transmission microscope is between 20 nm and 300 nm. Condition 2: The average ratio of the major axis to the minor axis of primary particles photographed with a transmission microscope is between 1 and 2.5. Condition 3: The powder X-ray diffraction spectrum, expressed as the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays, has a peak in the range where 2θ is between 25.55° and 25.95°.

Description

[Technical Field]

[0001] This invention relates to a coloring agent and a coating film using the same. [Background technology]

[0002] Industrial products such as automotive paints are in demand for a wide range of colors and designs from the market. For example, copper phthalocyanine pigments are used as blue colorants due to their high coloring power, vividness, and durability. Depending on the hue, copper phthalocyanine pigments are used in CI Pigment Blue 15:3, CI Pigment Blue 15:1, and CI Pigment Blue 15:6 ratios. In addition, paints are required to have higher transparency and vivid colors, as well as flip-flop properties. That is, paints with high angle dependence of brightness (dark-flop property) and low angle dependence of hue (color-flop property) are in demand.

[0003] For example, Patent Document 1 discloses a paint containing a metallic pigment and CI pigment blue in a 15:1 ratio. Furthermore, Patent Document 2 discloses a multilayer coating in which a color clear coating containing a color pigment is laminated on a coating film containing a glossy material and / or a color pigment. This multilayer coating allows the color and / or reflected light of the lower coating film to be seen through the color clear coating on the upper layer, resulting in a multilayer coating with excellent depth of color. For example, a coating in which a color clear coating containing a color pigment is laminated on a metallic base coating film containing a glossy material is called a so-called "candy color" coating. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-75946 [Patent Document 2] Japanese Patent Publication No. 2007-167720 [Patent Document 3] Japanese Patent Publication No. 1999-106671 [Patent Document 4] Japanese Patent Publication No. 2023-091898 [Overview of the project] [Problems that the invention aims to solve]

[0005] One trend in blue color is the use of reddish-blue with less color flop, but this has not been achievable with conventional methods. In particular, when used on three-dimensional painted surfaces 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 coloring agent that exhibits reddish-blue, but it has the problem of high color flop properties. Therefore, Patent Document 3 discloses an indanthrene pigment composition with low color flop properties using a δ-type indanthrene blue pigment. However, δ-type indanthrene blue has the problem of the color of the coating film being too reddish, resulting in insufficient clarity. Furthermore, Patent Document 4 discloses a highly coloring inkjet ink using α-type indanthrene blue pigment. However, when this inkjet ink is repurposed for paint applications, it suffers from insufficient flip-flop properties and sharpness.

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

[0007] A coloring agent represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3. Condition 1: The average primary particle diameter captured by a transmission microscope is between 20 nm and 300 nm. Condition 2: The average value of the major axis / minor axis, which is the ratio of the major axis to the minor axis of the primary particles photographed with a transmission microscope, is 1 or more and 2.5 or less. Condition 3: In the powder X-ray diffraction spectrum represented by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays, it has a peak in the range where 2θ is 25.55° or more and 25.95° or less. Chemical formula (1)

Chemical formula

Advantages of the Invention

[0008] [[ID=十七]]According to the present invention, it is possible to provide a colorant that can form a coating film having high color transparency, a clear color tone (hereinafter referred to as clarity), a large angular dependence of lightness (dark flop property), and a small angular dependence of hue (color flop property). Further, the present invention can provide a colorant composition, a colorant dispersion, a coating film, a multilayer coating film, a vehicle exterior coating, and a method for producing a colorant composition.

Brief Description of the Drawings

[0009] [Figure 1] [[ID=2十五]]Figure 1 is a schematic diagram showing the measurement angles when measuring the color of a coated plate in a flip flop property test. [[ID=2十八]]

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present invention will be described more specifically. However, the present invention is not limited to the following embodiments, and may be variously modified within the range that can solve the problems, and various embodiments are included. [[ID=三十四]] First, the terms used in this specification will be described. "C.I." represents a Color Index number. "Coating" has the same meaning as "printed matter", "image forming matter", and "coated object". A colorant is a term including pigments and dyes.

[0011] <1> Colorant 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 photographed with a transmission microscope is 20 nm or more and 300 nm or less. Condition 2: The average value of the major axis / minor axis ratio (hereinafter referred to as the aspect ratio) of the primary particles photographed with a transmission microscope is 1 or more and 2.5 or less. Condition 3: In the powder X-ray diffraction spectrum shown by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays, 2θ has a peak in the range of 25.55° or more and 25.95° or less. Chemical formula (1)

Chemical formula

[0012] The mechanism by which the colorant of the present invention can solve the problem is speculated as follows. Since the transparency of the colorant depends on the size of the primary particle diameter, a thinner coating film can be obtained as the primary particle diameter is smaller. Moreover, the smaller the ratio of the major axis to the minor axis of the primary particles (hereinafter referred to as the aspect ratio), the more the aggregation of the pigment particles can be suppressed. Therefore, in the coating film containing the colorant of the present invention, diffuse reflection of light hardly occurs, and the dark flop property is high and the color flop property can be suppressed. The colorant represented by Chemical formula (1) is called indanthrene and is also referred to as C.I. Pigment Blue 60. As shown in Patent Document 3, the hue changes according to the crystal system. The colorant represented by Chemical formula (1) of the present invention adjusts the crystal system and has a peak in the range of 25.55° or more and 25.95° or less in the powder X-ray diffraction spectrum shown by the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays, so that a coating film with a desired vivid blue hue can be obtained.

[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 or more and 300 nm or less. 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. Further, the average primary particle diameter is more preferably 30 nm or more and 150 nm or less, and even more preferably 35 nm or more and 100 nm or less.

[0014] The colorant of the present invention has an average aspect ratio (the ratio of the major axis to the minor axis of the primary particles) of 1 to 2.5. The aspect ratio is preferably 1 to 2.3, and more preferably 1 to 2. When the aspect ratio is 1 to 2.5, the particle shape of the colorant is close to spherical, and the distance between each particle is uniform, thus suppressing particle aggregation. By having an aspect ratio within the above range, aggregated particles in the coating film are reduced, and scattered light is suppressed, resulting in a coating film with high dark flop properties and low color flop properties. Note that the aspect ratio of all particles does not need to be within the above range; it is sufficient if the average value of the ratio of the major axis to the minor axis is within the above range. Details of the measurement method for the major axis and minor axis of the primary particles and the calculation method for 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 the primary particle diameter in images captured by a transmission 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 the primary particle diameter is the value obtained by dividing the standard deviation of the major axis of the primary particle by the average of the major axis. When the coefficient of variation of the primary particle diameter is 0 to 0.29, the size of the primary particles is uniform, and a coating film with higher clarity and particularly low 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, it is preferable to use blue, purple, or black pigments that do not significantly reduce clarity when mixed with the colorant of the present invention. In particular, it is preferable to use phthalocyanine pigments, dioxazine pigments, and carbon black pigments that exhibit high color flop. Other pigments include phthalocyanine pigments such as CIPigmentBlue15, PigmentBlue15:1, PigmentBlue15:2, PigmentBlue15:3, PigmentBlue15:4, and PigmentBlue15:6. An example of a dioxazine pigment is PigmentViolet23. Carbon black can be thermal black, acetylene black, lamp black, furnace black, etc., depending on the manufacturing method and raw materials.

[0017] The colorant composition of the present invention preferably contains a colorant and at least one additive selected from a pigment derivative (A) and a resin (B). The pigment derivative (A) and resin (B) contribute to controlling the primary particle size of the colorant by refining the primary particle size, reducing the aspect ratio, and lowering the coefficient of variation of the primary particle size. Furthermore, the pigment derivative (A) and resin (B) act to suppress the growth of primary particle size and secondary aggregation when preparing dispersions and paints.

[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. Preferably, A is a group having a heterocyclic ring. Examples of organic pigment residues include phthalocyanine pigment residues, quinacridone pigment residues, anthraquinone pigment residues, indanthrene pigment residues, diketopyrrolopyrrole pigment residues, dioxazine pigment residues, and azo pigment residues. Compounds that form aromatic compound residues having three or more rings include, for example, polycyclic structures in which the ring structures share their respective sides, such as anthracene, phenanthrene, phenalene, and acenaphthylene, as well as linked-ring structures in which the rings are directly or via linking groups, 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. Optionally substituted phthalimidomethyl groups include phthalimidomethyl groups substituted with C1-C4 alkyl groups, nitro groups, chlorine groups, and phthalimidomethyl groups. X represents a direct bond or any linking group. Examples of linking groups include alkylene groups having 1 to 8 carbon atoms, amide bonds, sulfonamide bonds, ester bonds, imino groups, triazine rings, and phenylene groups which may have substituents, as well as combinations thereof. The pigment derivative (A) is oriented on the surface of the colorant, suppressing particle growth of the colorant, thereby making the average primary particle size finer and reducing the CV value.

[0019] The content of the pigment derivative (A) is preferably 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the colorant. From the viewpoint of miniaturizing the primary particle size, the content of the pigment 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, it is more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0020] <Resin (B)> Resin (B) is preferably soluble in water or a water-soluble organic solvent, or has a softening point or glass transition point of 105°C or lower. Resin (B) is also preferably a resin-type dispersant. Examples of resin (B) include (meth)acrylic resin, polyester resin, polyurethane resin, and polyol resin. Resin (B) can contain hydroxyl groups and carboxyl groups. Examples of commercially available resins (B) include the Dianaal series (manufactured by Mitsubishi Chemical Corporation) and the DEGALAN series (manufactured by Evonik Industries), such as Dianaal BR-605, Dianaal MB-7922, Dianaal 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] The molecular structure of the resin-type dispersant can be, for example, random polymers, comb-type polymers, or block polymers. Among these, comb-type polymers and block polymers are preferred. The resin-type dispersant has adsorption sites that have a high affinity for colorants and relaxation sites that have an affinity for solvents, binders, etc., and contribute to the dispersion and dispersion stability of the colorant. Monomers that can be used to form the adsorption sites can be, for example, styrene, α-olefins, alkyl (meth)acrylates, and aryl (meth)acrylates. Monomers that can form relaxation sites can be, for example, acidic polymers having acidic groups such as carboxyl groups, sulfone groups, and phosphate groups, basic monomers having basic groups such as amino groups and pyridyl groups, and hydrophilic monomers having polyoxyalkylene groups. The resin-type dispersant preferably has one or more of the acid value and amine value, and the sum of the acid value and amine value is preferably 10 mg KOH / g to 250 mg KOH / g.

[0022] Examples of commercially available resin-type dispersants include the SOLSPERSE series (manufactured by Lubrizol), the Joncryl series (manufactured by BASF), the BYK series (manufactured by Bic Chemie), the Efka series (manufactured by BASF), and the Hyros-X series (manufactured by Seikoh 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 Examples include the PX4585, EFKA PX4780 (both manufactured by BASF), DISPERBYK-190, DISPERBYK-191, DISPERBYK-194N, DISPERBYK-2013, DISPERBYK-2015, DISPERBYK-2055 (all manufactured by Big Chemie), and the Hi-Loss X-200, Hi-Loss X-210 (both manufactured by Seikoh PMC).

[0023] Resin (B) adsorbs onto the surface of the colorant, suppressing secondary aggregation of the colorant. In addition, it can control the kneading strength in the primary particle control process described later, 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 per 100 parts by mass of colorant. From the viewpoint of primary particle size refinement, 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, it is more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

[0025] <1> Method for producing colorants and colored compositions The coloring agent represented by chemical formula (1) that satisfies conditions 1, 2, and 3 of the present invention only needs to satisfy conditions 1 to 3, and the method of preparation is not limited. A preferred embodiment for preparing the coloring agent 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 crystalline system having a peak at 25.75 ± 0.2° in the powder X-ray diffraction spectrum measured by CuKα rays. To obtain an indanthrene compound having this crystalline system, an indanthrene compound is first dissolved in a well-dissolving solvent and added to a poor solvent to precipitate an unstable crystalline indanthrene compound. Furthermore, by reacting this crystalline indanthrene compound with an organic solvent, the desired crystalline indanthrene compound can be obtained. For example, the following method can be used. An indanthrene compound is dissolved in 98% sulfuric acid to obtain a sulfuric acid solution. The indanthrene compound is precipitated by adding the sulfuric acid solution to water. The precipitate is filtered and washed with water, the residue is rinsed in water, and then an organic solvent is added and the mixture is heated and stirred at 80°C or higher for 3 hours or more. Further filtering, washing with water, drying, and grinding are performed sequentially to obtain an indanthrene compound having a peak at 25.75±0.2°. Here, the amount of 98% sulfuric acid must be sufficient to dissolve the indanthrene compound; for example, using about 8 times the mass is sufficient. Also, 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 using a hydrophobic organic solvent and a surfactant in combination. For example, water-soluble organic solvents that can be used include isopropanol, butanol, isobutanol, methyl ethyl ketone, tetrahydrofuran, N-methylpyrrolidone, etc. Hydrophobic organic solvents that can be used include xylene, toluene, ethylbenzene, chlorobenzene, nitrobenzene, etc. The surfactant is preferably a compound that can form an emulsion when combined with an organic solvent and water. For example, nonionic and anionic surfactants are preferably used.

[0027] The colorant of the present invention preferably undergoes primary particle control. Primary particle control includes, for example, a dissolution-deposition method in which the colorant is dissolved in a good solvent such as sulfuric acid and released into a poor solvent such as water for reprecipitation; a mechanical grinding method in which the colorant is impacted with a hard media such as iron, zirconia, or glass; a high-pressure grinding method in which the pigment composition is sprayed and impacted under high pressure to pulverize it; and a wet kneading method in which the colorant is mixed with a water-soluble inorganic salt or a water-soluble organic solvent, kneaded, and ground. These methods may be combined. Among these, the wet kneading method is preferred. Examples of kneaders include kneaders, trimixes, two-roll mills, three-roll mills, ball mills, attritors, horizontal sand mills, vertical sand mills, and annular bead mills. Among these, kneaders or trimixes are preferred.

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

[0029] The wet kneading method allows for the adjustment of the colorant to a preferred primary particle size, aspect ratio, and coefficient of variation by mechanically kneading a mixture (hereinafter referred to as "dough") containing a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent. In primary particle control by wet kneading, the crushing and grinding of primary particles by kneading with the water-soluble inorganic salt, and the growth of primary particles by the water-soluble organic solvent and heat are repeated. By converging the primary particle size within an appropriate range, primary particles with the desired particle size and coefficient of variation can be obtained. Furthermore, when indanthrene compounds undergo crystal growth without external force, the particles grow large in a specific direction, resulting in needle-shaped crystals with a large aspect ratio. However, by performing refinement and crystal growth simultaneously, particles with a small aspect ratio can be obtained. To obtain the desired primary particles, it is preferable to use a water-soluble inorganic salt at least 10 times, more preferably 15 times, the amount of the colorant, and to further add a dye derivative (A) or resin (B). Among these, adding a pigment derivative (A) or a resin (B) during kneading is preferable because it can further reduce the aspect ratio and coefficient of variation. Pigment derivative (A) has the effect of suppressing the growth of primary particle size by orienting itself on the surface of the colorant, while resin (B) not only orients itself on the surface of the colorant but also improves the viscosity of the dough, thereby increasing 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 standpoint of cost. The amount of water-soluble inorganic salt used is not limited as long as a colorant with the desired average primary particle size and aspect ratio can be obtained. From the perspective 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. Furthermore, by adding an appropriate amount of dye derivative (A) or resin (B) during kneading, the amount of water-soluble inorganic salt required can be reduced, which also has advantages in terms of production efficiency.

[0030] Water-soluble organic solvents are solvents that dissolve or are miscible in water, and examples 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, trippropionine, triptyline, and 2-butyl-2-ethyl-1,3-propanediol. Water-soluble organic solvents can be used individually or in combination. The amount of water-soluble organic solvent used is preferably 50 to 500 parts by mass, and more preferably 75 to 300 parts by mass, per 100 parts by mass of colorant. The temperature during the mixing process can be set according to the average particle size of the desired coloring agent. The temperature is preferably 40 to 120°C, and more preferably 50 to 100°C.

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

[0032] <3> Colorant dispersion The colorant dispersion of the present invention comprises 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, such as a solvent.

[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 solvents commonly used in the ink and paint fields are also included.

[0034] The colorant dispersion of the present invention may contain a resin-type dispersant. For example, the pigment dispersant listed as resin (B) can be used as the resin-type dispersant.

[0035] For the aforementioned dispersion, dispersants such as horizontal sand mills, vertical sand mills, annular bead mills, microfluitizers, high-speed mixers, homomixers, homogenizers, high-pressure homogenizers, paint shakers, roll mills, stone mills, ultrasonic dispersers, high-pressure dispersers, opposing impact dispersers, and oblique impact dispersers can be used. Furthermore, multiple dispersants can be used for dispersion.

[0036] The colorant dispersion of the present invention may contain 1 to 70% by mass of the colorant or colorant composition of the present invention (on a non-volatile content basis) and 10 to 200% by mass of the resin-type dispersant (based on 100% by mass of the colorant or colorant composition). The remainder consists of a dispersion medium, but a portion of the dispersion medium may be replaced with additives such as defoamers and preservatives as needed.

[0037] <4> paint The paint 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 used in paints in general, and examples include acrylic resins, polyurethane resins, alkyd resins, amino resins, epoxy resins, and modified resins thereof. When aluminum is used as a glossy coating material, a phosphate group-containing resin is preferred as the binder resin. The paint may also contain a curing agent for curing the coating film. 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, melamine compounds, and the like. The paint of the present invention may contain 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, per 100% by mass.

[0038] The paint of the present invention may contain a luminous material. Examples of luminous materials include metal flakes, mica, and coated glass flakes. Metal flakes are particularly preferred when obtaining vivid hues. Examples of metal flakes include aluminum, zinc, copper, iron, nickel, titanium, stainless steel, and gold flakes. Among these, aluminum flakes are preferred from the viewpoint of luminosity, cost, and specific gravity. The average particle size of the metal flakes is preferably 1 to 100 μm, and more preferably 5 to 50 μm. From the viewpoint of oxidation prevention, the metal flakes may be surface-treated with fatty acids, resins, etc. Examples of mica include ordinary mica and coated mica coated with metal oxides such as titanium dioxide. Examples of coated glass flakes include glass flakes coated with metal oxides such as titanium dioxide. The average particle size of mica and glass flakes is preferably 1 to 200 μm, and more preferably 10 to 150 μm. The content of the luminescent material is preferably 10 to 4000 parts by mass, and more preferably 10 to 1000 parts by mass, per 100 parts by mass of the colorant or colored composition. The average particle size of the luminescent 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 paint of the present invention may contain other known additives, such as viscosity modifiers, preservatives, surfactants, UV absorbers, and light stabilizers.

[0040] The paint of the present invention can be manufactured by mixing a colorant dispersion, a binder resin, and a curing agent. Alternatively, it can be manufactured by dispersing a colorant or colorant composition with a dispersion medium and a binder resin, and then mixing in a curing agent. Dispersion or mixing can be carried out using the dispersers and mixers exemplified in the description of the colorant dispersion.

[0041] <5> coating film The coating film of the present invention is obtained by applying a paint containing the coloring agent of the present invention or the coloring agent composition of the present invention onto a substrate to form a coating film.

[0042] Examples of substrates for forming a coating film include metals, resins, wood, concrete, and stone. 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 flat or curved plates, rods, cylinders, and spherical shapes. Examples of resin shapes include sheets and molded three-dimensional objects. Examples of resins 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.

[0043] Coating methods include roll coating, brush painting, and spray painting. Among these, spray painting is preferred. The coating thickness is preferably between 15 μm and 150 μm. A thickness of 15 μm or more improves the protective function and flip-flop properties of the coated object. A coating with higher transparency can be obtained at a thickness of 150 μm or less.

[0044] The aforementioned coating film is preferably a cured coating film that hardens upon exposure to light, heat, or oxidation.

[0045] The coating film of the present invention may 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). Specifically, examples of phthalocyanine pigments include CIPigmentBlue15, PigmentBlue15:1, PigmentBlue15:2, PigmentBlue15:3, PigmentBlue15:4, and PigmentBlue15:6. An example of a dioxazine pigment is PigmentViolet23. Examples of carbon black include thermal black, acetylene black, lamp black, and furnace black, depending on the manufacturing method and raw materials. These pigments have high color flop properties on their own, but when used in combination with the coloring agent of the present invention, color flop is suppressed, and a coating film that exhibits the pigment's original hue regardless of the viewing angle can be obtained. Methods for using high color flop pigments in combination include mixing them during primary particle control, mixing them during the production of colorant dispersions, preparing and mixing colorant dispersions separately, or preparing and mixing paints separately; any of these methods is acceptable.

[0046] The multilayer coating of the present invention preferably comprises a first coating that does not contain a colorant represented by chemical formula (1), and a second coating as the coating of claim 5 on the first coating. One embodiment of the present invention is a single-layer coating containing a high color-flop pigment and a coloring agent represented by chemical formula (1). However, in another embodiment, when a multilayer coating is formed in which the first coating contains a high color-flop pigment and the coating of the present invention is used as the second coating, diffuse reflection of light is less likely to occur, and hues with high dark-flop properties and suppressed color-flop properties can be 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 sum of the thickness of the first coating and the thickness of the second coating is preferably 30 μm or more and 150 μm or less.

[0048] The multilayer coating of the present invention yields a highly aesthetic coating with unique color tones as follows. For example, when a phthalocyanine pigment is used in the first coating, the multilayer coating yields a reddish-blue color; similarly, when a dioxazine pigment is used, the multilayer coating yields a bluish-purple color; similarly, when carbon black is used, the multilayer coating yields a bluish-black color.

[0049] The vehicle exterior coating of the present invention has a coating film of the present invention. The coating film may be a multilayer coating film of the present invention. The vehicle exterior coating of the present invention has excellent transparency, clarity, and luster, and has the durability to withstand outdoor use, so it is preferable to use it on automobiles, motorcycles, etc.

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

[0051] <1> The coloring agent of the present invention is a coloring agent represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3. Condition 1: The average primary particle diameter captured by a transmission microscope is between 20 nm and 300 nm. Condition 2: The average ratio of the major axis to the minor axis of primary particles, as captured by a transmission microscope, is between 1 and 2.5. Condition 3: The powder X-ray diffraction spectrum, expressed as the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays, has a peak in the range where 2θ is between 25.55° and 25.95°. Chemical formula (1) [ka] <2> The aforementioned coloring agent has a coefficient of variation of the primary particle size of the particles in the image captured by a transmission microscope that is between 0 and 0.29. <1> A coloring agent. <3> <1> or <2> A colorant composition comprising a colorant and at least one additive selected from a pigment derivative (A) and a resin (B). <4> <1> or <2> colorants, or <3> A colorant dispersion comprising a colorant composition and a dispersion medium. <5> <4> A paint comprising a colorant dispersion, a binder resin, and a curing agent. <6> <1> or <2> colorants, or <3> A coating film comprising a coloring agent composition. <7> Furthermore, it includes pigments other than the compound of chemical formula (1), <6> The coating film. <8> A first coating film that does not contain a colorant represented by chemical formula (1), and a second coating film applied on the first coating film as <6> A multilayer coating having a coating film. <9> <6> A vehicle exterior coating having a coating film. <10> <3> A method for producing a colorant composition, A method for producing a colorant composition, comprising the step of kneading a mixture containing at least one additive selected from a pigment derivative (A) and a resin (B), a colorant represented by chemical formula (1), a water-soluble inorganic salt, and a water-soluble organic solvent. [Examples]

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

[0053] The abbreviations and product names used in the following examples mean the following: <Colorants, Pigments> PB60: Indanthrene compound with a peak at 25.75±0.2° (Preparation Example 9) PB15:1:CI Pigment Blue 15:1 (LIONOL BLUE 7189-PM, manufactured by Toyo Color Co., Ltd.) PB15:3:CI Pigment Blue 15:3 (LIONOL BLUE FG-7330 manufactured by Toyo Color Co., Ltd.) PB15:6:CI Pigment Blue 15:6 (LIONOL BLUE ESP-S manufactured by Toyo Color Co., Ltd.) PV23: CI Pigment Violet 23 (LIONOGEN VIOLET FG-6150 manufactured by Toyo Color Co., Ltd.) PBk7: CI Pigment Black 7 (Birla Carbon Raven 5000 Ultra 3)

[0054] <Dye derivative (A)> Dye derivative (A)-1: A compound represented by the following general formula (2), provided that it is a mixture of n=1 to 3. General formula (2) [ka]

[0055] Dye derivative (A)-2: A compound represented by the following general formula (3), provided that it is a mixture of n=1 to 3. General formula (3) [ka]

[0056] Dye derivative (A)-3: A compound represented by the following general formula (4), provided that n=1 to 3 is a mixture. General formula (4) [ka]

[0057] Dye derivative (A)-4: A compound represented by the following general formula (5), provided that n=1 to 3 is a mixture. 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 compound represented by the following general formula (8), provided that n=1 to 3 is a mixture. General formula (8) [ka]

[0061] <Resin (B)> SOLSPERSE 36000 (manufactured by Lubrizol, resin-type dispersant, comb-type polymer, acid value 45 mg KOH / g, amine value 13 mg KOH / g) SOLSPERSE J200 (manufactured by Lubrizol, resin-type dispersant, comb-type polymer, acid value 10.5 mg KOH / g, amine value 33 mg KOH / g) SOLSPERSE 35000 (manufactured by Lubrizol, resin-type dispersant, comb-type 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 (manufactured by Bic Chemie, resin-type dispersant, acid value 30 mg KOH / g, amine value 20 mg KOH / g) DISPERBYK-2013 (manufactured by Bic Chemie, resin-type dispersant, acid value 8 mg KOH / g, amine value 18 mg KOH / g) DISPERBYK-2055 (manufactured by Bic Chemie, resin-type dispersant, amine value 40 mg KOH / g) Hyros X-210 (manufactured by Seikoh PMC, resin-type dispersant, acid value 220 mg KOH / g) DispexUltraPX4585 (BASF Corporation, 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 diameter and aspect ratio] The average primary particle size of the obtained colorant composition was determined by transmission electron microscopy (TEM) observation as follows: For approximately 50 primary particles of the colorant composition, arbitrarily selected from photographs taken with a transmission electron microscope at a magnification of 10,000x, the length of the long side of the rectangle with the smallest area circumscribing the particle image was defined as the major axis, and the length of the short side as the minor axis. The average values ​​of each were calculated. The average of the major axes was defined as the average primary particle size, and the ratio of major axis to minor axis was defined as the aspect ratio. The standard deviation of the major axis divided by the average primary particle size was defined as the coefficient of variation.

[0063] [Measurement of X-ray diffraction spectrum] The X-ray diffraction spectrum was measured using the following method. Equipment: Rigaku SmartLab X-ray diffractometer (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 at 2θ = 25.75 ± 0.2° was confirmed.

[0064] [Evaluation of darkflop and colorflop properties] The following performance tests were conducted on the dark flop and color flop properties of the prepared coated panels. Since the color tone of clear and metallic paints changes depending on the viewing angle or the angle of incidence of light, a multi-angle colorimeter (X-Rite, MA94) was used for color measurement. As shown in Figure 1, which shows the color measurement test from the side, incident light 101 was shone onto the painted panel 100 at an angle of 45 degrees, and the reflected light at a position 15 degrees from the specular reflected light 102, which is reflected at 90 degrees from the incident light, towards the direction of the incident light 101, was defined as the highlight 103. The highlight 103 is the color tone of the bright area where the amount of light reflection is high as seen by the eye. In addition, the reflected light at a position 110 degrees from the specular reflected light 102 towards the direction of the incident light 101 was defined as the shade 104. The shade 104 is the color tone of the dark area where the amount of light reflection is low as seen by the eye. The resulting shade and highlight brightness (L * The absolute value of the difference between ) |ΔL * |=|L * (110°)-L * A larger (15°)| value indicates a greater change in brightness with respect to angle changes, meaning a higher darkflop property. Furthermore, painted panels that appear to have high darkflop property visually have a low shade brightness (L*(110°)). The following DF value, combining these factors, was used as an indicator of darkflop property. A larger DF value indicates higher and better darkflop property. DF value=|L*(110°)-L*(15°)| / L*(110°) Also, the hue (H) of the obtained shade and highlight * The absolute value of the difference between the two angles is defined as the CF value below. A smaller CF value indicates less change in hue with respect to angle changes, i.e., better color flop properties. CF value = |H * (110°)-H * (15°)

[0065] [Preparation of dye derivative (A)] (Manufacturing Example 1) Manufacturing of dye derivative (A)-1 Dye derivative (A)-1 was prepared based on Comparative Production Example 1 of Japanese Patent Publication No. 2023-159499. 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 obtained reaction solution was poured into 8,000 parts of ice water, and the resulting precipitate was sequentially filtered, washed with water, dried, and ground to obtain dye derivative (A)-1 represented by general formula (2).

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

[0067] (Manufacturing Example 3) Manufacturing of dye derivative (A)-3 Dye derivative (A)-3 was manufactured based on Example 1 of Japanese Patent Publication No. 52-132031. Dissolve 100 parts chlorosulfonic acid in 10 parts PB15:3, then add 7 parts thionyl chloride and raise the temperature, stirring at 112-113°C for 4 hours. After cooling, filter the mixture in ice and wash with ice water. Re-slurry this paste with 100 parts water, add 8 parts N,N-diethylaminopropylamine and stir at 25°C for 12 hours, then raise the temperature to 60°C and stir for 1 hour. This slurry was filtered, washed with water, dried, and ground sequentially to obtain the pigment derivative (A)-3 represented by general formula (4).

[0068] (Manufacturing Example 4) Manufacturing of dye derivative (A)-4 Dye derivative (A)-4 was prepared based on Production Example 1 of Japanese Patent Publication No. 56-118462. 100 parts by mass of chlorosulfonic acid was mixed with 10 parts by mass of Hostaperm Red E5B 02 at 10-20°C, stirred at 40-50°C for 3 hours, and then poured into 1,000 parts of ice water. The mixture was filtered and washed with water to obtain a water cake of quinacridone chlorosulfonate. This water cake of chlorosulfonate was added to 300 parts by mass of ice water and stirred as a slurry. 28 parts by mass of N,N-dibutylaminopropylamine was added and stirred at 10°C or below for 4 hours, then filtered and washed with water. Next, this water cake was added to 300 parts by mass of 0.5% aqueous sodium carbonate solution and stirred for 1 hour. The mixture was filtered, washed with water to neutral, dried, and then ground to obtain the dye derivative (A)-4 represented by general formula (5).

[0069] (Manufacturing Example 5) Manufacturing of dye derivative (A)-5 Dye derivative (A)-5 was manufactured based on manufacturing example 5 of Japanese Patent Publication No. 2016-132693. 800 parts of dimethylacetamide were mixed with 44 parts of Cinilex Red SR4C (CI Pigment Red 177, manufactured by CINIC) and 37 parts of cyanuryl chloride, and the mixture was stirred at 100-110°C for 5 hours. After cooling, 104 parts of 3-diethylaminopropylamine were 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. It was dried at 60°C and further ground to obtain the pigment derivative (A)-5 represented by chemical formula (6).

[0070] (Manufacturing Example 6) Manufacturing of dye derivative (A)-6 Dye derivative (A)-6 was manufactured based on manufacturing example 1 of Japanese Patent Publication No. 4-209660. 150 parts of 12% fuming sulfuric acid and 10 parts of crude indanthrene blue were added at a temperature below 30°C and stirred to dissolve. Subsequently, 9 parts of paraformaldehyde and 20 parts of monochloroacetate amide were added at a temperature below 30°C, stirred at 25°C for 50 hours, then placed in ice water, filtered, and washed with water to obtain a blue wet cake. This wet cake was re-slurred with 200 parts of water, 10.6 parts of dibutylamine were added, and the mixture was heated under reflux for 2 hours, followed by filtration, washing with water, drying, and grinding to obtain the dye derivative (A)-6 represented by general formula (7).

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

[0072] (Manufacturing Example 8) Manufacturing of Comparative Resin (B)-1 Resin (B)-1 was manufactured in accordance with resin A-12 of Japanese Patent Publication No. 2023-091898. [First Reaction] In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, dropping funnel, and stirrer, 61.3 parts (60 mol%) of maleic anhydride, 62.4 parts (3 mol%) of Unilube PKA-5013 (manufactured by NOF Corporation, polyethylene glycol-polypropylene glycol-allyl ether: number average molecular weight 2,000) as a monomer mixture, 7.4 parts (37 mol%) of 1-hexadecene as α-olefin, 100 parts of MEK, and 0.5 parts of octyl thioglycolate as a chain transfer agent were charged. After purging with nitrogen, the mixture was heated to 105°C with stirring. A mixture of 2.0 parts of Asobis dimethyl isobutyrate (manufactured by Fujifilm Wako Pure Chemical Industries, trade name: V-601) and 5 parts of MEK was added dropwise over 1 hour as a radical polymerization initiator. Subsequently, while stirring at a temperature of 85°C, a mixture of 5 parts V-601 and 12 parts MEK was added dropwise over 6 hours, and the mixture was allowed to react for 1 hour while maintaining the temperature at 85°C to obtain a polymer having maleic anhydride as an acid anhydride group. [Second reaction] Next, 81.3 parts of isopropyl alcohol (82% in equivalence to the acid anhydride groups in the maleic anhydride monomer) and 0.1 parts of diazabicycloundecene as a catalyst were added, and the reaction was carried out by stirring for 6 hours while maintaining the temperature at 85°C, which opened the ring of maleic anhydride and half-esterified it. The solvent of the obtained product was concentrated under reduced pressure to completely remove it, and comparative resin (B)-1 (number average molecular weight (Mn): 13,200, acid value 125 mgKOH / g) was prepared.

[0073] (Production Example 9) Preparation of indanthrene compound PB60 having a peak at 25.75±0.2° 120 parts of Vat Blue RSN (an indanthrene compound manufactured by Hanghzou Emperor Chemical) were gradually added to 1000 parts of 98% sulfuric acid and dissolved. The mixture was stirred at 25°C for 1 hour to obtain a sulfuric acid solution. Next, the sulfuric acid solution was added to 7000 parts of ice water while stirring, stirred for 10 minutes, and then filtered and washed 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 a 25% sodium hydroxide aqueous solution. Further, 100 parts of isobutanol were added and the mixture was refluxed and stirred at 90-95°C for 4 hours, and then stirred at over 95°C for 1 hour to remove the isobutanol by distillation. After adding water until the temperature was below 70°C, the mixture was filtered and washed to obtain a PB60 wet cake. This wet cake was dried at 80°C for 24 hours and then pulverized to obtain the indanthrene compound PB60, which has a peak at 2θ = 25.75 ± 0.2° in the powder X-ray diffraction spectrum.

[0074] <1> Manufacturing of colorants and colorant compositions (Example A-1) Preparation of colorant composition a-1 100 parts of PB60 as a coloring agent, 10 parts of dye derivative (A)-1 as dye derivative (A), 10 parts of Joncryl 690 as 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 placed in a 3L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. After adding 5000 parts of deionized water to this mixture, it was stirred in a high-speed mixer for 2 hours to form a slurry. The slurry was then filtered and washed with deionized water to remove sodium chloride and diethylene glycol, obtaining a wet cake of coloring agent 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) Manufacturing of colorant a-101 100 parts of PB60 as a coloring agent, 500 parts of sodium chloride as a water-soluble inorganic salt, and 85 parts of diethylene glycol as a water-soluble organic solvent were placed in a 3L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours. This mixture was then added to 9,000 parts of deionized water and stirred in a high-speed mixer for 2 hours to form a slurry. The slurry was then filtered and washed with deionized water to remove sodium chloride and diethylene glycol, obtaining a wet cake of coloring agent a-101.

[0077] (Comparative Example A-2) Manufacture of colorant composition a-102 A wet cake of colorant composition a-102 was obtained in the same manner as Comparative Example A-1, except that 28 parts of comparative resin (B)-1 prepared in production example 8 was added as non-volatile content as resin (B), and the mixing temperature was changed to 75°C.

[0078] (Comparative Example A-3) Manufacturing of colorant a-103 In manufacturing example 9, the PB60 wet cake was colored with coloring agent a-103.

[0079] (Comparative Example A-4) Manufacturing of colorant a-104 Colorant a-104 was manufactured in accordance with International Publication No. 96 / 05255. 600 parts of water were placed in a reaction vessel and heated to 60°C while stirring. Next, 54.4 parts of 48% sodium hydroxide aqueous solution and 18.8 parts of hydrosulfite were added to the reaction vessel, and then 12.0 parts of indanthrene blue crude was added. The reduction reaction was carried out at 60°C for 15 minutes while stirring to obtain a reduced indanthrene blue solution. The reduction potential at this time was -1060mV. Separately, 400 parts of water and 25.0 parts of 30% hydrogen peroxide solution were placed in another reaction vessel and kept warm at 20°C while stirring to prepare an oxidizing solution. Next, the reduced indanthrene blue solution was injected into the stirring oxidizing solution at a rate of 500 ml per minute using a pump to carry out the oxidation reaction. After the oxidation reaction was completed, stirring was continued for another hour, then the mixture was filtered and washed with water until the filtrate was neutral to obtain a wet cake of coloring agent a-104.

[0080] (Examples B-1 to B-26) Manufacture 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 ground with a hammer mill to obtain the colorants or colorant compositions b-1 to b-26.

[0081] (Comparative Examples B-1 to B-4) Manufacture 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 ground 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 of the X-ray diffraction spectra, average primary particle size, aspect ratio, and CV values ​​were determined based on the method described above. The results are shown in Tables 1-1 to 1-3 and Table 2. In Tables 1-1 to 1-3 and Table 2, "composition ratio" refers to the content of the colorant, dye derivative (A), and resin (B) in the total 100% by mass of the colorant, dye derivative (A), and resin (B).

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

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

[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 1.25 mm diameter zirconia beads were placed in a 70 ml glass bottle and dispersed for 180 minutes using Candex SK450 manufactured by Fast & Fluid Management to obtain a dispersion with a pigment content of 20% and a non-volatile content of 30.5%. • Wet cake of coloring agent composition a-1: 6.3 parts in terms of non-volatile content • Pigment dispersant (BASF acrylic block copolymer, DispexUltraPX4585, 50% non-volatile content): 6.3 parts • Defoaming agent (BASF FoamStar ST 2400, 100% non-volatile content): 0.16 parts • Ion-exchanged water: Remaining portion (31.5 parts total) Next, the zirconia beads were removed from the above 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) Except for changing the wet cake of colorant composition a-1 in Example C-1 as shown in Table 3, the procedure was carried out in the same manner as in Example C-1 to obtain colorant dispersions c-2 to c-14, c-23 to c-26, and c-101 to c-108. Comparative Examples C-5 to C-8 used the pigments listed in Table 3 instead of wet cake.

[0087] [Table 3]

[0088] <d>Water-based clear color paint (D1) Preparation of water-based clear paint Using a stirrer, the following raw materials were stirred to obtain a water-based clear paint with a non-volatile content of 31.1%. Alkaline swelling acrylic dispersion (Setaqua 6802, Allnex, 24% non-volatile content): 15 parts Thermosetting aqueous acrylic emulsion (Allnex Setaqua 6169, 45% non-volatile content): 9 parts Aliphatic polyester polyurethane emulsion (Allnex Daotan TW6466 / 36WA, non-volatile content 36%): 52 parts Methylated monomer melamine crosslinking agent (Allnex Cymel303LF, non-volatile content 98% or more): 4.8 parts Base (dimethylethanolamine): Adjust the pH to be within the range of 8.0 to 8.5. Ion-exchanged water and ethylene glycol monobutyl ether: remainder (100 parts total) The amounts of deionized water and ethylene glycol monobutyl ether were adjusted as appropriate to achieve a viscosity suitable for spray painting (stormer viscosity 58-60 KU).

[0089] (D2) Preparation of water-based color clear paint and painted boards (Example D-1) Preparation of water-based color clear paint d-1 and fabrication of painted board Using a stirrer, the following raw materials were stirred to obtain 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 Furthermore, dimethylethanolamine, deionized water, and ethylene glycol monobutyl ether were added as needed to achieve a pH in the range of 8.0 to 8.5 and a stormer viscosity in the range of 58 to 60 KU. This water-based color clear paint was sprayed onto a mirror-finished stainless steel plate using a spray gun. The painting was done in nine separate coats, followed by standing at 25°C for at least two hours, and then drying at 80°C for 15 minutes. The water-based clear paint was then applied again using a spray gun in the same manner. The painting was done in six separate coats, followed by standing at 25°C for at least two hours, and then baking 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 thickness of the color clear coating film was approximately 35 μm, and the thickness of the clear coating film 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 paints d-2 to d-14, d-23 to d-26, d-101 to d-108 and fabrication of painted boards) Except for changing the colorant dispersion c-1 of Example D-1 as shown in Table 4, the procedure was carried out in the same manner as in Example D-1 to obtain water-based color clear paints d-2 to d-14, d-23 to d-26, d-101 to d-108 and their coated boards.

[0091] (D3) Evaluation of painted boards The obtained painted panels were evaluated against the following criteria, using the painted panel of Comparative Example D-1 as a baseline. Note that Comparative Examples D-5 to D-8 used colorants other than indanthrene, resulting in different color characteristics; therefore, their coloring strength, clarity, and gloss were not evaluated. <Coloring power> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 4. A score of "4", "3", or "2" according to the criteria below indicates a usable level. (Evaluation criteria for coloring power) 4: Has significantly higher coloring power than standard painted boards. 3: Higher coloring power than standard painted boards 2: Slightly higher coloring power than the standard painted board. 1: Equivalent coloring power to the standard painted board.

[0092] <Sharpness> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 4. A score of "4", "3", or "2" according to the criteria below indicates a usable level. (Criteria for evaluating clarity) 4: The clarity is significantly higher than that of the standard painted panel. 3: Higher clarity than the standard painted panel. 2: Slightly higher clarity than the standard painted panel. 1: The clarity is equivalent to or lower than that of the standard painted panel.

[0093] <Transparency> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 4. A score of "4", "3", or "2" according to the criteria below indicates a usable level. (Transparency evaluation criteria) 4: It has significantly higher transparency than the standard painted board and exhibits an extremely strong metallic sheen on the underlying surface. 3: It has higher transparency and a stronger metallic sheen than the standard painted board. 2: Slightly higher transparency and slightly stronger metallic sheen than the standard painted board. 1: Compared to the standard painted board, the transparency is equivalent to or lower, and the metallic sheen of the underlying surface is equivalent to or weaker.

[0094] <Darkflop properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 4. A score of "4", "3", or "2" according to the following criteria indicates a usable level. 4: The DF value is 7 or more higher compared to the standard painted board (the darkflop properties are significantly higher than the standard). 3: The DF value is 4 to less than 7 higher compared to the standard painted board (higher darkflop properties than the standard). 2: The DF value is 1 to 4 greater than the standard painted board (slightly higher darkflop properties than the standard). 1: The DF value is less than 1 greater than or equal to the standard painted board (darkflop properties are equal to or less than the standard).

[0095] <ColorFlop Properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 4. A score of "4", "3", or "2" according to the following criteria indicates a usable level. 4:4 > CF value (extremely low color flop properties, extremely good) 3:6 > CF value ≥ 4 (low color flop properties, good) 2:8 > CF value ≥ 6 (slightly low color flop properties, usable) 1: CF value ≥ 8 (high color flop characteristics, defective)

[0096] [Table 4]

[0097] <e>Water-based metallic paint (E1) Preparation of aqueous metallic base Using a stirrer, the following raw materials were stirred 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, 60% aluminum content, 65% non-volatile content): 10 parts Pigment wetting agent (Additol XL250, Allnex, 55% non-volatile content): 2 parts Water-based clear paint (non-volatile content 31.1%) produced with D1: 50 parts Ion-exchanged water: 27 parts Ethylene glycol monobutyl ether: 11 parts

[0098] (E2) Preparation of water-based metallic paint and painted board (Example E-1) Preparation of water-based metallic paint e-1 and painted board Using a stirrer, the following raw materials were stirred to obtain water-based metallic paint e-1 with a pigment content of 2.1%, aluminum content of 2.2%, and 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 Furthermore, dimethylethanolamine, deionized water, and ethylene glycol monobutyl ether were added as needed to achieve a pH in the range of 8.0 to 8.5 and a Stormer viscosity in the range of 55 to 58 KU. This water-based metallic paint was sprayed onto steel plates using a spray gun. The painting was carried out in nine separate coats, followed by standing at 25°C for at least two hours, and then drying at 80°C for 15 minutes. Next, a water-based clear paint was applied in the same manner using a spray gun. The painting was carried out in six separate coats, followed by standing at 25°C for at least two hours, and then baking at 140°C for 20 minutes to obtain a water-based metallic painted plate. The PWC of the metallic coating was 7.4%, the thickness of the metallic coating was approximately 40 μm, and the thickness of the clear coating 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 fabrication of painted panels) Except for changing the colorant dispersion c-1 of Example E-1 as shown in Table 5, the procedure was carried out in the same manner as in Example E-1 to obtain water-based metallic paints e-2 to e-14, e-23 to e-26, e-101 to e-108 and their coated plates.

[0100] (E3) Preparation of water-based mixed paints and painted boards (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 fabrication of painted boards Using a stirrer, the paints were mixed according to the combinations and mixing ratios listed in Table 6 to obtain mixed paints e-27 to e-28 and e-109 to e-110. Using these mixed paints, spray coating was performed in the same manner as in Example E-1 to obtain metallic painted boards.

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

[0102] (E5) Evaluation of painted boards The obtained painted panels 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 painted panel of Comparative Example E-1 was used as the standard, and for Examples E-27 to E-32, the painted panels of the corresponding comparative examples listed in Tables 6 and 7 were used as the standard. Note that Comparative Examples E-5 to E-8 used colorants other than indanthrene and therefore have different color characteristics, so vividness and gloss were not evaluated.

[0103] <Sharpness> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Tables 5 to 7. A score of "4", "3", and "2" according to the following criteria indicates a usable level. (Criteria for evaluating clarity) 4: The clarity is significantly higher than that of the standard painted panel. 3: Higher clarity than the standard painted panel. 2: Slightly higher clarity than the standard painted panel. 1: The clarity is equivalent to or lower than that of the standard painted panel.

[0104] <Shining feeling> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Tables 5 to 7. A score of "4", "3", and "2" according to the following criteria indicates a usable level. (Evaluation criteria for luster) 4: It has a significantly higher gloss than the standard painted board. 3: Higher gloss than standard painted boards 2: Slightly higher gloss than the standard painted board. 1: The gloss level is equivalent to or lower than that of the standard painted board.

[0105] <Darkflop properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 5 to 7. A score of "4", "3", or "2" according to the following criteria indicates a usable level. 4: The DF value is 7 or more higher compared to the standard painted board (the darkflop properties are significantly higher than the standard). 3: The DF value is more than 4 and less than 7 greater compared to the reference painted board (higher dark flop property than the reference). 2: The DF value is more than 1 and less than 4 greater compared to the reference painted board (slightly higher dark flop property than the reference). 1: The DF value is less than 1 greater, or equal to or less than, compared to the reference painted board (dark flop property is equal to or less than the reference).

[0106] <Color flop property> The painted board was measured with a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 5 to 7. If it is "4", "3", or "2" according to the following criteria, it is a practical level. 4: 4 > CF value (extremely low color flop property, extremely good) 3: 6 > CF value ≥ 4 (low color flop property, good) 2: 8 > CF value ≥ 6 (slightly low color flop property, usable) 1: CF value ≥ 8 (high color flop property, defective)

[0107] <Weather resistance> Regarding the weather resistance test, the above painted board was used in an accelerated weather resistance test machine (manufactured by Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151), and the test was carried out under the conditions of 90 mW / cm 2 , 96 hours (12 hours of day and night, 4 cycles), and the color difference (ΔE * ) before and after the weather resistance test was evaluated with a Konica Minolta color difference meter CM-700d. The results are shown in Tables 5 to 7. If it is "3" and "2" according to the following criteria, it is a practical level. (Evaluation criteria for weather resistance) 3: The change in color before and after the test (ΔE * ) is less than 2.5, good 2: The change in color before and after the test (ΔE * ) is 2.5 or more and less than 3, practically usable 1: The change in color before and after the test (ΔE * ) is 3 or more, defective

[0108]

Table 5

[0109] Table 6

[0110] Table 7

[0111] <f>Preparation and evaluation of solvent-based paints (F1) Preparation of solvent-based paints (Example F-6) Preparation of solvent-based paint f-6 Colorant composition b-6, 9 parts Acrylic resin (DIC Corporation, Acrydic 47-712) 7.7 parts Dispersion medium (a mixed solvent of toluene, xylene, butyl acetate, and ENEOS T-SOL150FLUID 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 glass container that could be sealed tightly, and dispersed for 60 minutes using a Red Devil paint shaker. Then, 75.4 parts of Acrydic 47-712 and 17.2 parts of melamine resin (DIC Amidia L-117-60) were added and dispersed for another 10 minutes. After that, the steel beads were removed to obtain dark color 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, f-101 to f-109 The procedure was carried out in the same manner as in Example F-6, 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 coatings and painted panels (G1) Preparation of solvent-based clear coating Acrylic resin (DIC Corporation, Acrydic 44-179) 120 units Melamine resin (DIC Corporation, Amidia L117-60) 30 units Dilution solvent (a mixed solvent consisting of toluene, xylene, ENEOS T-SOL150FLUID, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2) 50 parts The above materials were stirred and mixed using a high-speed stirrer to obtain a solvent-based clear coating.

[0115] (G2) Preparation of solvent-based color clear paint and painted boards (Example G-6) Preparation of solvent-based color clear paint g-6 and painted board One part of the solvent-based paint f-6 prepared in Example F-6 and nine parts of the solvent-based clear paint prepared in G1 were mixed to prepare the solvent-based color clear paint g-6. This solvent-based color clear paint was sprayed onto a mirror-finished stainless steel plate using a spray gun. To adjust the viscosity to one that is easy to spray, a diluent (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 10-20% by mass to adjust the viscosity to one suitable for spray painting (stormer viscosity 58-60 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 material was dried at 140°C for 30 minutes to obtain a solvent-based color clear coated board. The PWC of the color clear coating was 1.5%, the thickness of the color clear coating was approximately 35 μm, and the thickness of the clear coating was approximately 20 μm.

[0116] (Examples G-7 to G-26, Comparative Examples G-1 to G-8) Preparation of solvent-based color clear paints g-7 to g-26, g-101 to g-108 and painted boards. Except for changing the solvent-based paint f-6 of Example G-6 as shown in Table 9, the procedure was carried out in the same manner as in Example G-6 to obtain solvent-based color clear paints g-7 to g-26, g-101 to g-108 and their coated plates.

[0117] (G3) Evaluation of solvent-based color clear coated boards The obtained painted panels were evaluated for the following items. The painted panel of Comparative Example G-1 was used as the baseline. Note that Comparative Examples G-5 to G-8 used colorants other than indanthrene and therefore have different color characteristics, so their coloring strength, vividness, and gloss were not evaluated. <Coloring power> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 9. A score of "4", "3", or "2" according to the following criteria indicates a usable level. (Evaluation criteria for coloring power) 4: Has significantly higher coloring power than standard painted boards. 3: Higher coloring power than standard painted boards 2: Slightly higher coloring power than the standard painted board. 1: Equivalent coloring power to the standard painted board.

[0118] <Sharpness> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 9. A score of "4", "3", or "2" according to the following criteria indicates a usable level. (Criteria for evaluating clarity) 4: The clarity is significantly higher than that of the standard painted panel. 3: Higher clarity than the standard painted panel. 2: Slightly higher clarity than the standard painted panel. 1: The clarity is equivalent to or lower than that of the standard painted panel.

[0119] <Transparency> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Table 9. A score of "4", "3", or "2" according to the following criteria indicates a usable level. (Transparency evaluation criteria) 4: It has significantly higher transparency than the standard painted board and exhibits an extremely strong metallic sheen on the underlying surface. 3: It has higher transparency and a stronger metallic sheen than the standard painted board. 2: Slightly higher transparency and slightly stronger metallic sheen than the standard painted board. 1: Compared to the standard painted board, the transparency is equivalent to or lower, and the metallic sheen of the underlying surface is equivalent to or weaker.

[0120] <Darkflop properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 9. A score of "4", "3", or "2" according to the following criteria indicates a usable level. 4: The DF value is 7 or more higher compared to the standard painted board (the darkflop properties are significantly higher than the standard). 3: The DF value is 4 to less than 7 higher compared to the standard painted board (higher darkflop properties than the standard). 2: The DF value is 1 to 4 greater than the standard painted board (slightly higher darkflop properties than the standard). 1: The DF value is less than 1 greater than or equal to the standard painted board (darkflop properties are equal to or less than the standard).

[0121] <ColorFlop Properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Table 9. A score of "4", "3", or "2" according to the following criteria indicates a usable level. 4:4 > CF value (extremely low color flop properties, extremely good) 3:6 > CF value ≥ 4 (low color flop properties, good) 2:8 > CF value ≥ 6 (slightly low color flop properties, usable) 1: CF value ≥ 8 (high color flop characteristics, poor performance)

[0122] [Table 9]

[0123] <h>Preparation and evaluation of solvent-based metallic paints and painted panels. (H1) Preparation of solvent-based metallic base paint Aluminum flake paste (Toyo Aluminum Co., Ltd. Aluminum Paste 5620NS) 10 units 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 ENEOS T-SOL150FLUID in a mass ratio of 3:3:2:2) 20.9 parts The above materials were stirred and mixed using 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 fabrication of coated plate Twenty parts of the solvent-based paint f-6 prepared in Example F-6 and 18.5 parts of solvent-based metallic base paint were stirred and mixed in a high-speed stirrer 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 to a level suitable for spraying, a diluent (a mixed solvent of toluene, xylene, ENEOS T-SOL150FLUID, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2) was added to the metallic paint in an appropriate amount by mass to achieve a viscosity suitable for spray painting (Stormer viscosity 58-60 KU). The painting was carried out in nine separate coats, followed by six separate spray coats of solvent-based clear paint. After drying at 25°C for one hour, the plate was dried at 140°C for 30 minutes to obtain a solvent-based metallic painted plate. The PWC (Periodic Water Contamination) 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) Solvent-based metallic paints h-7 to h-26, h-101 to h-109 and preparation of painted panels thereof. Except for changing the solvent-based paint f-6 in Example H-6 as shown in Table 10, the procedure was the same as in Example H-6 to obtain solvent-based metallic paints h-7 to h-26, h-101 to h-109 and their coated panels. However, in Comparative Example H-9, only the solvent-based metallic paint h-109 had its mixing ratio of solvent-based paint to solvent-based metallic base paint changed from 20:18.5 to 3:1.

[0126] (H3) Preparation of solvent-based mixed paints and painted boards (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 fabrication of painted boards Using a stirrer, the paints were mixed according to the combinations and mixing ratios listed 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 painted boards.

[0127] (H4) Fabrication of solvent-based multi-layer coated boards (Examples H-31 to H-33, Comparative Examples H-14 to H-16) Preparation of multi-layer coated panels h-31 to h-33, h-114 to h-116 Paint (1) listed in Table 12 was sprayed onto the steel plate using a spray gun. The painting was done in nine separate coats. Paint (2) listed in Table 12 was then sprayed onto the steel plate in seven separate coats using a spray gun. In addition, a solvent-based clear paint was similarly sprayed onto the steel plate using a spray gun. The painting was done in six separate coats, and after being left to stand at 25°C for more than one hour, the plates were baked at 140°C for 30 minutes to obtain metallic multi-layer painted plates h-31 to h-33 and h-114 to h-116.

[0128] (H5) Evaluation of solvent-based metallic painted panels The obtained coated panels were evaluated for the following items. For Examples H-6 to H-26 and Comparative Examples H-2 to H-9, the coated panel of Comparative Example H-1 was used as the reference, and for Examples H-27 to H-33, the coated panels of the corresponding comparative examples listed in Tables 11 and 12 were used as the reference. Note that Comparative Examples H-5 to H-9 used a coloring agent with a structure other than indanthrene and therefore have different color characteristics, and for Examples H-33 and Comparative Example H-16, since they are black, the clarity and glossiness were not evaluated. <Sharpness> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Tables 10 to 12. A score of "4", "3", and "2" according to the following criteria indicates a level that is usable. (Criteria for evaluating clarity) 4: The clarity is significantly higher than that of the standard painted panel. 3: Higher clarity than the standard painted panel. 2: Slightly higher clarity than the standard painted panel. 1: The clarity is equivalent to or lower than that of the standard painted panel.

[0129] <Shining feeling> The painted panels were visually inspected and evaluated according to the following criteria. The results are shown in Tables 10 to 12. A score of "4", "3", and "2" according to the following criteria indicates a level that is usable. (Evaluation criteria for luster) 4: It has a significantly higher gloss than the standard painted board. 3: Higher gloss than standard painted boards 2: Slightly higher gloss than the standard painted board. 1: The gloss level is equivalent to or lower than that of the standard painted board.

[0130] <Darkflop properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 10 to 12. A score of "4", "3", and "2" according to the following criteria indicates a usable level. 4: The DF value is 7 or more higher compared to the standard painted board (the darkflop properties are significantly higher than the standard). 3: The DF value is 4 to less than 7 higher compared to the standard painted board (higher darkflop properties than the standard). 2: The DF value is 1 to 4 greater than the standard painted board (slightly higher darkflop properties than the standard). 1: The DF value is less than 1 greater than or equal to the standard painted board (darkflop properties are equal to or less than the standard).

[0131] <ColorFlop Properties> Painted panels were measured using a multi-angle colorimeter and evaluated according to the following criteria. The results are shown in Tables 10 to 12. A score of "4", "3", and "2" according to the following criteria indicates a usable level. 4:4 > CF value (extremely low color flop properties, extremely good) 3:6 > CF value ≥ 4 (low color flop properties, good) 2:8 > CF value ≥ 6 (slightly low color flop properties, usable) 1: CF value ≥ 8 (high color flop characteristics, poor performance)

[0132] <Weather resistance> For the weather resistance test, the above-mentioned painted board was subjected to an accelerated weathering tester (Iwasaki Electric Co., Ltd., iSuper Xenon Tester SUV-W151) at 90 mW / cm². 2 The test was conducted under conditions of 96 hours (4 cycles of 12 hours day and night), and the color difference (ΔE) before and after the weather resistance test was measured. * The color was evaluated using a Konica Minolta CM-700d colorimeter. The results are shown in Tables 10 to 12. A score of "3" or "2" according to the following criteria indicates a usable level. (Criteria for evaluating weather resistance) 3: Change in color before and after the test (ΔE * ) less than 2.5, good 2: Change in color before and after the test (ΔE * ) is 2.5 or higher and less than 3, usable. 1: Change in color before and after the test (ΔE * ) 3 or more, defective

[0133] [Table 10]

[0134] [Table 11]

[0135] [Table 12]

[0136] The paints using the colorant or colorant composition of the present invention exhibit high clarity and transparency, and when applied to metal plates or used in combination with a brightening agent, they provide excellent metallic luster, brilliance, dark flop properties, and color flop properties, making them suitable for painting vehicle exteriors, electrical products, and the like. Furthermore, by mixing the paint of the present invention with a high color flop paint, or by forming a multi-layer coating film of the paint film of the present invention with a high color flop coating film, a low color flop coating film can be obtained while controlling the hue, making it suitable for painting vehicle exteriors, electrical products, and the like. On the other hand, colorants with a primary particle diameter aspect ratio of 2.5 or higher, or colorants that do not have a peak at a predetermined angle (meaning they are from a different crystal system than the crystal system of the present invention), and paints and coated panels using them, did not yield the desired transparency, clarity, brilliance, and flip-flop properties. [Explanation of symbols]

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

Claims

1. A coloring agent represented by chemical formula (1) that satisfies the following conditions 1, 2, and 3. Condition 1: The average primary particle diameter captured by a transmission microscope is between 20 nm and 300 nm. Condition 2: The average ratio of the major axis to the minor axis of the primary particles photographed with a transmission microscope is between 1 and 2.

5. Condition 3: The powder X-ray diffraction spectrum, expressed as the diffraction intensity with respect to the diffraction angle 2θ measured by CuKα rays, has a peak in the range where 2θ is between 25.55° and 25.95°. Chemical formula (1) 【Chemistry 11】

2. The coloring agent according to claim 1, wherein the coefficient of variation of the primary particle size of the particles in an image taken with a transmission microscope is 0 or more and 0.29 or less.

3. A colorant composition comprising the colorant described in claim 1, and at least one additive selected from a pigment 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 a colorant dispersion according to claim 4, a binder resin, and a curing agent.

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

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

8. A multilayer coating comprising a first coating film that does not contain a colorant represented by chemical formula (1), and a second coating film according to claim 6 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, A method for producing a colorant composition, comprising the step of kneading a mixture containing at least one additive selected from a pigment derivative (A) and a resin (B), a colorant represented by chemical formula (1), a water-soluble inorganic salt, and a water-soluble organic solvent.

Images