Pigment compositions and methods for producing the same, paints and coated products

Abstract

The present invention aims to provide a pigment composition that can form a coating film with high viscosity stability, high color transparency, and vivid color tones (hereinafter referred to as vividness). [Solution] A pigment composition comprising an organic pigment (A), a compound (B), and an aliphatic amine (C), wherein compound (B) is a compound represented by the following general formula (1), The aliphatic amine (C) is an amine having a hydrocarbon chain and a molecular weight of 100 to 1000, which is used in the pigment composition. General formula (1) B(-X-COOM)n

Description

Technical Field

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

Background Art

[0002] In the field of industrial products such as automobile painting, a variety of colors and design properties according to the preferences of users and the like are required. Organic pigments such as perylene pigments, phthalocyanine pigments, and quinacridone pigments are used according to the required hue. For example, in Patent Document 1, a paint containing a metallic pigment and C.I. Pigment Red 179 is disclosed. Further, in Patent Document 2, a multilayer coating film in which a color clear coating film containing a coloring pigment is laminated on a coating film containing a brightening material and / or a coloring pigment is disclosed. Since the color and / or reflected light of the lower coating film can be visually recognized through the color clear coating film provided in the upper layer, this multilayer coating film has excellent color depth. For example, a coating film in which a color clear coating film containing a coloring pigment is laminated on a metallic base coating film containing a brightening material is called a so-called "candy color" coating film, and in the field of vehicle exterior parts and the like, it is known as a multilayer coating film with vivid colors, high brightness, and excellent color depth and high design properties.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] One of the recent color trends in the industrial product sector is the growing need for more transparent and vivid colors, which is difficult to meet with the above-mentioned coating technologies and coating components alone. Furthermore, when used on three-dimensional painted surfaces such as the exteriors of automobiles, a high degree of angle dependence of brightness (flip-flop property) is preferred. One method for obtaining highly transparent and sharp coatings is to refine the pigment. However, when pigments are refined, they tend to aggregate and thicken when dispersed in paints or other materials, leading to a problem of reduced viscosity stability in the dispersion. Furthermore, obtaining a paint with high flip-flop properties requires achieving both fine pigment particles and uniform dispersion at a high level. Therefore, there was a demand for pigments that are fine, do not easily re-aggregate when dispersed, and have high viscosity stability.

[0005] The present invention aims to provide a pigment composition that can form a coating film with high viscosity stability, high color transparency, and vivid color tones (hereinafter referred to as vividness). [Means for solving the problem]

[0006] The pigment composition of the present invention is a pigment composition comprising an organic pigment (A), a compound (B), and an aliphatic amine (C), Compound (B) is a compound represented by the following general formula (1): The aliphatic amine (C) is a pigment composition in which the amine has a molecular weight of 100 to 1000. General formula (1) B(-X-COOM)n (In general formula (1), X represents a direct bond or any linking group, M represents a hydrogen atom or a monovalent metal atom, n represents an integer from 1 to 4, and B represents an organic pigment residue or a compound residue having three or more five-membered or six-membered rings.) [Effects of the Invention]

[0007] According to the present invention described above, it is possible to provide a pigment composition that can form a coating film with high viscosity stability, high color transparency, and vivid color tones (hereinafter referred to as vividness). Furthermore, the present invention can provide paints and coated articles. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic diagram showing the measurement angles when measuring the color of a coated plate in a flip-flop test. [Modes for carrying out the invention]

[0009] The embodiments of the present invention will be described in more detail below. However, the present invention is not limited to the embodiments described below, and may be modified in various ways without changing the essence of the invention, and a variety of embodiments are included. First, let's explain the terminology used in this specification. "CI" stands for Color Index Number. "Painted material" has the same meaning as "printed material," "image-forming material," and "coated material."

[0010] <1> Pigment composition One embodiment of the present invention is a pigment composition comprising an organic pigment (A), a compound (B), and an aliphatic amine (C), Compound (B) is a compound represented by the following general formula (1): The aliphatic amine (C) is an amine having a hydrocarbon chain and a molecular weight of 100 to 1000, which is used in the pigment composition. General formula (1) B(-X-COOM)n (In general formula (1), X represents a direct bond or any linking group, M represents a hydrogen atom or a monovalent metal atom, n represents an integer from 1 to 4, and B represents an organic pigment residue or a compound residue having three or more five-membered or six-membered rings.)

[0011] The mechanism by which the pigment composition of the present invention can solve the problem is hypothesized to be as follows. Compound (B) is a compound having three or more organic pigment residues or five-membered or six-membered rings. Since organic pigments usually have a ring structure, compound (B) strongly interacts with the ring structure of organic pigment (A) and orients to the surface of organic pigment (A). The orientation of compound (B) on the surface of the organic pigment (A) promotes the refinement of the primary particles of the organic pigment (A) in the particle size control process, and suppresses the crystal growth of the primary particles. Since the primary particle size of the organic pigment (A) can be maintained in a fine state, the light scattering intensity by the organic pigment particles is reduced during coating film formation, improving transparency and clarity. In addition, the number of particles per unit weight increases, improving coloring power. Furthermore, the carboxyl group or carboxymetal salt of compound (B) interacts gently with the amino group of the aliphatic amine (C) through acid-base interactions, resulting in the presence of the aliphatic amine (C) on the outer periphery of the particulate organic pigment (A). The hydrocarbon chain of this aliphatic amine (C) generates steric repulsion in the dispersion medium, thereby suppressing aggregation between organic pigment particles. In addition, the flexible molecular structure of the aliphatic amine (C) mitigates the aggregation of organic pigment particles. This results in viscosity stability.

[0012] <Organic pigment (A)> In this specification, organic pigments are particles that absorb light in the wavelength range of 360 nm to 830 nm and are compounds that are substantially insoluble in water and oil (hereinafter, "pigment" has the same meaning as "organic pigment" in this specification). Examples of organic pigments (A) include phthalocyanine pigments, perylene pigments, quinacridone pigments, perinone pigments, diketopyrrolopyrrole pigments, azo pigments, dioxazine pigments, anthraquinone pigments, etc. Among these, phthalocyanine pigments, perylene pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, and diketopyrrolopyrrole pigments, etc., which have excellent weather resistance, are preferred.

[0013] Phthalocyanine pigments include, for example, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue 76, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, and the like. Perylene pigments include, for example, C.I. Pigment Red 144, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 179, C.I. Pigment Red 190, C.I. Pigment Red 224, C.I. Pigment Violet 29, C.I. Pigment Black 31, C.I. Pigment Black 32, and the like. Quinacridone pigments include, for example, C.I. Pigment Red 122, C.I. Pigment Red 202, C.I. Pigment Red 209, C.I. Pigment Violet 19, and the like. Examples of anthraquinone pigments include C.I. Pigment Blue 60, C.I. Pigment Red 177, and the like. Examples of dioxazine pigments include C.I. Pigment Violet 23, C.I. Pigment Violet 37, and the like. Examples of diketopyrrolopyrrole pigments include C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Orange 71, C.I. Pigment Orange 73, and the like.

[0014] The content of the organic pigment (A) is preferably 1.7% to 98% by mass, more preferably 6.5% to 85.5% by mass, in the non-volatile matter of the pigment composition.

[0015] <Compound (B)> Compound (B) has a carboxy group or a carboxy metal salt. Compound (B) is oriented on the surface of the organic pigment particles, and its carboxy group or carboxy metal salt forms an ionic bond with the aliphatic amine (C). Also, Compound (B) can refine the primary particle diameter of the organic pigment during the refinement treatment of the organic pigment (for example, the primary particle control step). Note that Compound (B) does not contain an amino group. Compound (B) is a compound represented by the following general formula (1). General formula (1): B(-X-COOM)n

[0016] In general formula (1), B is an organic pigment residue or a compound residue having three or more five-membered or six-membered rings. The organic pigment residue is a group derived from the pigments exemplified by organic pigment (A). The structures of organic pigment (A) and B may be the same or different. The five-membered and six-membered rings include, for example, ring structures in which the ring structures share their respective sides such as anthracene, phenanthrene, phenalene, and acenaphthylene, and ring structures in which a five-membered or six-membered ring is bonded directly or through a linking group such as triphenylmethane and terphenyl. The five-membered and six-membered rings are aromatic or alicyclic and may contain substituents. Examples of the substituents include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group, etc. B has three or more five-membered or six-membered rings. Among these rings, it is preferable that one or more of them are compound residues that are heterocyclic rings. Also, the number of five-membered or six-membered rings in B is preferably 3 or more and 12 or less, more preferably 3 or more and 7 or less. It is also preferable that B is an organic pigment residue. In general formula (1), X represents a direct bond or an arbitrary linking group. The linking group includes an alkylene group having 1 to 18 carbon atoms, an amide bond, an ester bond, and a phenylene group, and combinations thereof. Among these, a direct bond or -CH2-NHCO-C6H4- is preferable, and -CH2-NHCO-C6H4- is more preferable. In general formula (1), M represents a hydrogen atom or a monovalent metal atom. In general formula (1), n represents an integer of 1 to 4. n is preferably 1 or 2, more preferably 2. Also, -X-COOM may be further bonded to X which is a linking group. Compounds (B) in which B is an organic pigment residue include compounds in which the pigment exemplified in organic pigment (A) is directly substituted with a carboxyl group, and compounds of the following general formula (3) in which B is a pigment residue exemplified in organic pigment (A). Compounds (B) in which B is a compound residue having three or more 5-membered or 6-membered rings include modified rosins mainly composed of abietic acids (disproportionated rosin, hydrogenated rosin, polymerized rosin, maleated rosin, fumarated rosin, etc.). Preferred compounds of compound (B) include disproportionated rosin (main component: dehydroabietic acid and dihydroabietic acid, each having three 6-membered rings, with carboxyl groups directly substituted on the 6-membered rings), hydrogenated rosin (main component: dihydroabietic acid), polymerized rosin (a compound having 6 to 7 6-membered rings, with two carboxyl groups directly substituted on the 6-membered rings), and compounds represented by the following general formula (3). In this specification, the main component refers to the component that is present in the largest amount among multiple components.

[0017] General formula (3) [ka]

[0018] (In general formula (3), B represents a phthalocyanine residue, a quinacridone residue, or a perylene residue. R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, or a phthalimidomethyl group. n represents an integer from 1 to 4.) In particular, compounds of general formula (3) are preferred in terms of viscosity and viscosity stability during dispersion.

[0019] The content of compound (B) is preferably 0.002% to 15% by mass, and more preferably 0.1% to 9% by mass, in the nonvolatile content of the pigment composition.

[0020] <Aliphatic amines (C)> Aliphatic amine (C) is an amine having a hydrocarbon chain with a molecular weight of 100 to 1000, preferably between 200 and 900. Aliphatic amine (C) preferably has a secondary amino group or a primary amino group, and more preferably has a primary amino group. The valency of the amino group of the aliphatic amine (C) is preferably divalent or trivalent. The solubility of the aliphatic amine (C) in 1 L of water at 20°C is preferably 1 g or less. The aliphatic amine (C) coats the organic pigment (A) through an acid-base reaction with the carboxyl group of compound (B), and the hydrocarbon chain of the aliphatic amine (C) acts as a steric repulsion site, thereby suppressing aggregation of the pigment composition. Examples of monovalent aliphatic amines (C) include octylamine, laurylamine, stearylamine, and oleylamine. Similarly, examples of amines with a valency of 2 or higher include 1,10-diaminodecane, 1,12-diaminododecane, dimeramine, trimertriamine, and hydrogenated beef tallow propylenediamine. Among these, 1,2-diaminododecane, hydrogenated beef tallow propylenediamine, dimeramine, and trimertriamine are preferred, with dimeramine being even more preferred.

[0021] The content of aliphatic amine (C) is preferably 0.01% to 15% by mass, and more preferably 0.1% to 9.0% by mass, in the nonvolatile content of the pigment composition.

[0022] <Compound (D)> Compound (D) can be used in place of compound (B) during the primary particle control step described later. It contributes to the refinement of the primary particle size of the organic pigment and generates compound (B) through hydrolysis in the next step. Compound (D) is a compound represented by the following general formula (2).

[0023] General formula (2) [ka]

[0024] In general formula (2), B is an organic pigment residue or a compound residue having three or more 5-membered or 6-membered rings, as described in detail in general formula (1) above. In general formula (2), R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, and a phthalimidomethyl group. n represents an integer from 1 to 4. n is preferably 1 or 2, and more preferably 2.

[0025] The amount of compound (D) added is preferably 0.002% to 15% by mass, and more preferably 0.1% to 9% by mass, of the nonvolatile content of the pigment composition. The hydrolysate of compound (D) (compound B) only needs to be in the amount necessary for the acid-base reaction with the aliphatic amine (C). Therefore, this does not prevent the residue of unhydrolyzed compound (D) in the composition.

[0026] <Pigment composition> The pigment composition of the present invention preferably contains, in 100% by mass of the total of organic pigment (A), compound (B), and aliphatic amine (C), 70% by mass or more of organic pigment (A), 0.1% by mass or more and 20% by mass or less of compound (B), and 0.5% by mass or more and 20% by mass or less of aliphatic amine (C). The content of organic pigment (A) is preferably 80% by mass or more, and more preferably 90% by mass or more, from the viewpoint of coloring power. Furthermore, from the viewpoint of viscosity stability, it is preferably 98% by mass or less, and more preferably 95% by mass or less. The content of compound (B) is preferably 1% by mass or more, and more preferably 2.5% by mass or more, from the viewpoint of transparency and clarity. Furthermore, from the viewpoint of coloring power, it is preferably 15% by mass or less, and more preferably 10% by mass or less. The content of aliphatic amine (C) is preferably 1% by mass or more, and more preferably 2.5% by mass or more, from the viewpoint of viscosity stability. Furthermore, from the viewpoint of coloring power, it is preferably 15% by mass or less, and more preferably 10% by mass or less.

[0027] The average value of the major axis of the primary particles in the pigment composition (hereinafter also referred to as "average primary particle diameter") is preferably 200 nm or less from the viewpoint of transparency, and preferably 5 nm or more from the viewpoint of ease of pigment dispersion. A more preferable average primary particle diameter is 10 nm to 150 nm, and even more preferably 20 nm to 120 nm. Details of the method for measuring the major axis of the primary particles and the method for calculating the average value are shown in the examples.

[0028] Compound (B) may be added during the primary particle control step of the organic pigment (A), or after the primary particle control step. Of these, it is preferable to add it during the primary particle control step of the organic pigment (A). Alternatively, compound (D) may be added instead of compound (B), and then compound (B) may be produced by hydrolyzing compound (D). The aliphatic amine (C) may be added during the primary particle control step of the organic pigment (A), or after the primary particle control step. It is preferable to add the aliphatic amine (C) at the same time as or after the addition of compound (B) or compound (D).

[0029] <Particle size control agent (E)> In one embodiment, the pigment composition of the present invention may contain a particle size control agent (E). The particle size control agent (E) is a compound having three or more organic pigment residues or five-membered rings or six-membered rings, wherein at least one of the five-membered rings and six-membered rings is a heterocycle, and has an amino group. The particle size control agent (E) is preferably used when compound (B) is rosin or a rosin-modified product. This improves coloring power, clarity, and transparency.

[0030] The amount of particle size control agent (E) used is preferably 0.1 to 10 parts by mass per 100 parts by mass of the total of the organic pigment (A), compound (B), and aliphatic amine (C). The particle size control agent (E) is preferably added during the primary particle control step of the organic pigment (A) or after the primary particle control step, with the former being more preferable.

[0031] <Resin> In one embodiment, the pigment composition of the present invention may contain a resin. The resin referred to herein is a resin other than rosin, and has a weight-average molecular weight of 1000 or more. The resin is preferably one used in general paints. Examples of resins include acrylic resins, methacrylic resins, and polyester resins. The resin is preferably one having hydroxyl groups and / or carboxyl groups. Commercially available resins include the Dianaal series (manufactured by Mitsubishi Chemical Corporation), the JONCRYL series (manufactured by BASF), and the DEGALAN series (manufactured by Evonik Industries). Specifically, examples include 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, DEGALAN 64 / 12N (all manufactured by Evonik Industries), JONCRYL 67, JONCRYL 586, JONCRYL 611, JONCRYL 680, JONCRYL 682, JONCRYL 683 (all manufactured by BASF Corporation), etc.

[0032] Resins can be used individually or in combination of multiple types. Methods for adding resins include dissolving the resin in an aqueous solution of a metal hydroxide such as sodium hydroxide and then adding it to the aqueous slurry of the pigment composition; adding an emulsion of the resin, prepared using an organic solvent such as xylene, to the aqueous slurry of the pigment composition; and adding the resin when mechanically kneading the pigment composition together with a water-soluble inorganic salt and a water-soluble solvent. The amount of resin added is preferably 1 to 100 parts by mass, and more preferably 5 to 40 parts by mass, per 100 parts by mass of the total of the organic pigment (A), compound (B), and amine acid (C). After adding the resin to the pigment composition, the resin may be crosslinked using a curing agent or crosslinking agent. Examples of crosslinking agents include epoxy compounds, isocyanate compounds, blocked isocyanate compounds, polyamine compounds, and polyamide resins.

[0033] In one embodiment, the pigment composition of the present invention may contain a luminescent material. Examples of luminescent 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. The metal flakes may be surface-treated with fatty acids, resins, etc., from the viewpoint of oxidation prevention. 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 total of the organic pigment (A), compound (B), and amine acid (C). 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.

[0034] <2> Method for manufacturing pigment compositions In one embodiment, the pigment composition of the present invention preferably has a primary particle control step. The primary particle control step can be carried out using known methods, including, for example, a dissolution and deposition method in which an organic pigment (A) is dissolved in a good solvent such as sulfuric acid and released into a poor solvent such as water to reprecipitate it; a mechanical pulverization method in which hard media such as iron, zirconia, or glass are used to apply impact; a high-pressure pulverization method in which the pigment composition is sprayed and impacted under high pressure to pulverize it; and a wet kneading method in which the pigment composition is mixed with a water-soluble inorganic salt and 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, but among these, kneaders or trimixes are preferred. The primary particle control step preferably includes either step A or step B below.

[0035] Process A: Includes processes a and c, in which amine (C) is added in either process. Process B: Includes processes b1, b2, and c, in which amine (C) is added in any of the processes.

[0036] Step a: A process of kneading a mixture containing an organic pigment (A), a compound (B), a water-soluble salt, and a water-soluble organic solvent. Step a allows for the adjustment of the organic pigment (A) to a preferred primary particle size by mechanically kneading a mixture containing an organic pigment (A), a compound (B), a water-soluble salt, and a water-soluble organic solvent. Adding compound (B) and kneading it can make the primary particle size of the pigment finer. Furthermore, adding aliphatic amine (C) and kneading it allows for a uniform coating of the aliphatic amine (C) on the surface of the organic pigment. In particular, if compound (B) is not rosin or a rosin-modified product, it is preferable to add aliphatic amine (C) and knead it. During mixing, particle size control agents (E) or resins may be added as needed. Examples of water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, and sodium sulfate. Sodium chloride (table salt) is preferred from a cost standpoint. The amount of water-soluble inorganic salt used is preferably 50 to 3,000 parts by mass, and more preferably 300 to 1,500 parts by mass, per 100 parts by mass of the total of the organic pigment (A), compound (B), and aliphatic amine (C), considering both processing efficiency and production efficiency. 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 100 to 300 parts by mass, per 100 parts by mass of the total of the organic pigment (A), compound (B), and aliphatic amine (C). The temperature during mechanical mixing can be set according to the average particle size of the desired pigment composition, but 40 to 120°C is preferred, and 60 to 100°C is more preferred.

[0037] Step b1: A step of kneading a mixture containing an organic pigment (A), a compound (D) represented by the following general formula (2), a water-soluble salt, and a water-soluble organic solvent. Step b1 allows the organic pigment (A) to be adjusted to a preferred primary particle size by mechanically kneading a mixture containing the organic pigment (A), a compound (D) represented by the following general formula (2), a water-soluble salt, and a water-soluble organic solvent. Adding compound (D) and kneading it allows for finer primary particle size of the pigment. Furthermore, adding aliphatic amine (C) and kneading it is preferable because it allows for a uniform coating of the aliphatic amine (C) on the surface of the organic pigment. General formula (2) [ka]

[0038] (In general formula (2), n represents an integer from 1 to 4. R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, and a phthalimidomethyl group. B is an organic pigment residue, or a compound residue having three or more 5-membered or 6-membered rings.) During mixing, particle size control agents (E) or resins may be added as needed. The types and amounts of usable water-soluble salts and water-soluble organic solvents are the same as in step a1, except that the amount of compound (B) is replaced with the amount of compound (D). The preferred temperature for mechanical kneading is the same as in step a1.

[0039] Step b2: A step in which water and a base are added to the mixture to denature compound (D) into compound (B) by hydrolysis. Step b2 yields compound (B) by hydrolyzing compound (D). Known methods can be used to hydrolyze compound (D). For example, a pigment composition containing compound (D) is added to water to form a slurry, and a base is added and stirred. The base is not limited to any water-soluble base, but inorganic bases such as sodium hydroxide and potassium hydroxide are preferred from the standpoint of cost and post-processing. While there is no limit to the amount of base added once the hydrolysis of compound (D) has progressed, hydrolysis can be efficiently achieved by adding approximately 1.2 to 2 moles of base per mole of (substituted) phthalimidomethyl groups of compound (D). Hydrolysis will proceed at a pH of 10 or higher, but a pH of 11 or higher is preferred from the viewpoint of reaction rate. There are no particular restrictions on the temperature during hydrolysis, but 20°C to 80°C is preferred from the viewpoint of reaction rate. After hydrolysis, it is preferable to add an acid to lower the pH to 9 or lower. The acid is not limited as long as it dissolves in water and does not form an insoluble salt with the base, but sulfuric acid or hydrochloric acid are preferred from the standpoint of cost. Furthermore, an aliphatic amine (C) or resin may be added in this process. It is preferable to add the aliphatic amine (C) or resin after neutralization and dissolution or emulsion. The acid used to neutralize the aliphatic amine (C) is not limited, but hydrochloric acid, sulfuric acid, or acetic acid are preferred from the viewpoint of cost and washability. The base used to neutralize the resin is not limited, but sodium hydroxide or potassium hydroxide are preferred from the viewpoint of cost and washability. When emulsion formation is performed, the aliphatic amine (C) or resin is dissolved in a hydrophobic organic solvent such as xylene or toluene, and then water is added and stirred to obtain the emulsion. The above acids or bases can be added as needed. When an emulsion is added, the aliphatic amine (C) or resin can be efficiently adsorbed onto the surface of the pigment composition by heating the slurry to 60°C or higher to break down the emulsion. When adding aliphatic amine (C) or resin, the pH can be adjusted to 6-8 by adding an acid or base before filtration and washing with water, and then filtration can be performed. The aliphatic amine (C) or resin may be added before or after hydrolysis, or even during hydrolysis.

[0040] Step c: Step of removing water-soluble salts and water-soluble organic solvents from the mixture. Step c involves adding the mixture containing the pigment composition to water and stirring to obtain a suspension. The amount of water added is not particularly limited, as long as it is sufficient to obtain a suspension. Heating may be added as needed. 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 particularly limited, but a temperature of 25 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 may be rinsed again with water and washed. Furthermore, an aliphatic amine (C) or resin may be added in this process. It is preferable to add the aliphatic amine (C) or resin after neutralization and dissolution or emulsion formation. The acid used to neutralize the aliphatic amine (C) is not particularly limited, but hydrochloric acid, sulfuric acid, or acetic acid are preferred from the viewpoint of cost and washability. The base used to neutralize the resin is not particularly limited, but sodium hydroxide or potassium hydroxide are preferred from the viewpoint of cost and washability. When emulsion formation is performed, the aliphatic amine (C) or resin is dissolved in a hydrophobic organic solvent such as xylene or toluene, and then water is added and stirred to obtain the emulsion. The above acids or bases can be added as needed. When an emulsion is added, the aliphatic amine (C) or resin can be efficiently adsorbed onto the surface of the pigment composition by heating the slurry to 60°C or higher to break down the emulsion. When an aliphatic amine (C) or resin is added, it is preferable to add an acid or base to adjust the pH to 6-8 before filtration and washing with water.

[0041] Step b2 (hydrolysis) and step c (removal of water-soluble inorganic salts and water-soluble organic solvents) can be performed in any order. Performing steps b2 followed by c reduces the number of filtration and washing steps. The wet cake of the pigment composition obtained after filtration and washing can be used directly for dispersion, or it can be further dried in a dryer or the like and pulverized to obtain a powdered pigment composition.

[0042] <3> paint The paint of the present invention comprises the pigment composition of the present invention and a dispersion medium. The dispersion medium can be any medium capable of dispersing the pigment composition, such as a solvent.

[0043] The solvent is selected from organic solvents and water, depending on the type of paint. 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 paint industry are also included.

[0044] The paint of the present invention may further contain a resin. Examples of resins include those used in the pigment composition described above, as well as polyurethane resins, alkyd resins, amino resins, epoxy resins, and modified resins thereof. Furthermore, to accelerate the curing of the paint, it may contain a curing agent such as an isocyanate compound or a blocked isocyanate compound and / or a crosslinking agent.

[0045] The paint of the present invention may contain 1 to 70% by mass of the pigment composition of the present invention in terms of non-volatile content, based on 100% by mass of non-volatile content.

[0046] <4> Painted items The painted product of the present invention has a coating film formed by the paint of the present invention. The thickness of the coating film is approximately 15 to 150 μm. The coating can be formed on substrates such as metal, resin, wood, concrete, and stone. Among these, metal and resin are preferred. Examples of metals include iron, aluminum, stainless steel, silver, copper, gold, and alloys containing these. Examples of metal shapes include three-dimensional shapes such as plates, rods, cylinders, and spheres with flat or curved surfaces. Examples of resin shapes include sheets and molded three-dimensional objects. Examples of resins include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin. When the paint of the present invention is applied to a substrate to form a coating film, a coated product with excellent transparency, clarity, gloss, and weather resistance is obtained. Furthermore, because the coated product of the present invention has excellent transparency, clarity, gloss, and durability that can withstand outdoor use, it is preferably used for vehicle exterior parts.

[0047] [Example of an embodiment] Examples of embodiments of the present invention are given below. The present invention is not limited to the following.

[0048] <1> The present invention relates to a pigment composition comprising an organic pigment (A), a compound (B), and an aliphatic amine (C), Compound (B) is a compound represented by the following general formula (1): The aliphatic amine (C) is a pigment composition in which the aliphatic amine has a hydrocarbon chain and a molecular weight of 100 to 1000. General formula (1) B(-X-COOM)n (In general formula (1), X represents a direct bond or any linking group, M represents a hydrogen atom or a monovalent metal atom, n represents an integer from 1 to 4, and B represents an organic pigment residue or a compound residue having three or more five-membered or six-membered rings.) <2> Organic pigment (A) is an organic pigment selected from the group consisting of phthalocyanine pigments, perylene pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, and diketopyrrolopyrrole pigments. <1> A pigment composition. <3> Compound (B) is a compound represented by general formula (3). <2> or <2> A pigment composition. General formula (3) [ka]

[0049] (In general formula (3), B represents an organic pigment residue. R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, and a phthalimidomethyl group. n represents an integer from 1 to 4.) <4> Aliphatic amines (C) are divalent amines having a primary or secondary amino group. <1> ~ <3> Any of the pigment compositions. <5> The total of 100% by mass of organic pigment (A), compound (B), and aliphatic amine (C) contains 70% by mass or more of organic pigment (A), 0.1% by mass or more and 20% by mass or less of compound (B), and 0.5% by mass or more and 20% by mass or less of aliphatic amine (C). <1> ~ <4> Any of the pigment compositions. <6> Furthermore, including resin, <1> ~ <5> Any of the pigment compositions. <7> Furthermore, including a brightening material, <1> ~ <6> Any of the pigment compositions. <8> <1> ~ <7> A method for producing any pigment composition, comprising the following steps A or B. Process A: Includes processes a and c, and involves adding amine (C) in either process. Process B: Includes processes b1, b2, and c, and involves adding amine (C) in any of the processes. Step a: A process of kneading a mixture containing an organic pigment (A), a compound (B), a water-soluble salt, and a water-soluble organic solvent. Step b1: A step of kneading a mixture containing an organic pigment (A), a compound (D) represented by the following general formula (2), a water-soluble salt, and a water-soluble organic solvent. Step b2: A step in which water and a base are added to the mixture to denature compound (D) into compound (B) by hydrolysis. Step c: Step of removing water-soluble salts and water-soluble organic solvents from the mixture. General formula (2) [ka]

[0050] (In general formula (2), n represents an integer from 1 to 4. R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, and a phthalimidomethyl group. B is an organic pigment residue, or a compound residue having three or more 5-membered or 6-membered rings.) <9> <1> ~ <7> A paint comprising any of the pigment compositions and a dispersion medium. <10> <9> A painted object having a coating film formed from paint. <11> Vehicle exterior parts, <10> Painted items. [Examples]

[0051] 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".

[0052] The abbreviations and product names used in the following examples mean the following: <Organic pigment (A)> 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 7351, manufactured by Toyo Color Co., Ltd.) PB15:6:CI Pigment Blue 15:6 (LIONOL BLUE E manufactured by Toyo Color Co., Ltd.) PG7: CI Pigment Green 7 (Sun Chemical's HELIOGEN GREEN K8630) PR177: CI Pigment Red 177 (Cinilex Red SR4C manufactured by CINIC) PV23: CI Pigment Violet 23 (LIONOGENVIOLET 6150-20, manufactured by Toyo Color Co., Ltd.) PV19: CI Pigment Violet 19 (Heuback Hostaperm Red E5B 02) PR122: CI Pigment Red 122 (Sun Chemical's Cinquasia Pink K4410) PR202: CI Pigment Red 202 (Sun Chemical's Cinquasia Magenta K4535) PR179: CI Pigment Red 179 (EPSILON Perylene Red 2G) PV29: CI Pigment Violet 29 (EPSILON Perylene Violet B) PR254: CI Pigment Red 254 (Cinilex Red SR2P manufactured by CINIC)

[0053] <Compound (B)> Compound (B)-1: A compound represented by the following general formula (4), provided that it is a mixture of n=1 to 3.

[0054] General formula (4) [ka]

[0055] Compound (B)-2: A compound represented by the following general formula (5), provided that it is a mixture of n=1 to 3.

[0056] General formula (5) [ka]

[0057] Compound (B)-3: A compound represented by the following general formula (6), provided that it is a mixture of compounds n=1 to 3.

[0058] General formula (6) [ka]

[0059] Disproportionated rosin: Longis R-CH manufactured by Arakawa Chemical Industries, Ltd. (Main component: A compound represented by general formula (1) that has three 6-membered rings and one carboxyl group) Polymerized rosin: Arakawa Chemical Industries, Ltd., ARADAIGME R-95 (Main component: A compound represented by general formula (1), having 6-7 six-membered rings and 2 carboxyl groups)

[0060] <Aliphatic amines (C)> 1,10-Diaminodecane (manufactured by Tokyo Chemical Industry Co., Ltd.) Molecular weight 172 (Solubility in water at 20°C: 5.9 g / L) 1,12-Diaminododecane (manufactured by Tokyo Chemical Industry Co., Ltd.) Molecular weight 200 (Solubility in water at approximately 20°C: approximately 520 mg / L) Dimer amine (Cargill, Priamine 1075) Molecular weight approximately 533 (insoluble in water) Stearylamine (manufactured by Kao Corporation, Farmin 80S) Molecular weight approximately 269 (insoluble in water) Hydrogenated beef tallow propylenediamine (manufactured by Kao Corporation, diamine R-86), molecular weight approximately 310 (insoluble in water).

[0061] <Compound (D)> Compound (D)-1: A compound represented by the following general formula (7), provided that it is a mixture of n=1 to 3.

[0062] General formula (7) [ka]

[0063] Compound (D)-2: A compound represented by the following general formula (8), provided that n=1 to 3 is a mixture.

[0064] General formula (8) [ka]

[0065] Compound (D)-3: A compound represented by the following general formula (9), provided that it is a mixture of compounds n=1 to 3.

[0066] General formula (9) [ka]

[0067] Compound (D)-4: A compound represented by the following general formula (10), provided that it is a mixture of n=1 to 3.

[0068] General formula (10) [ka]

[0069] <Particle size control agent (E)> Particle size control agent (E)-1: A compound represented by the following general formula (11), where n=1 to 3 is a mixture.

[0070] General formula (11) [ka]

[0071] Particle size control agent (E)-2: A compound represented by the following general formula (12), where n=1 to 3 is a mixture.

[0072] General formula (12) [ka]

[0073] Particle size control agent (E)-3: A compound represented by the following chemical formula (13).

[0074] Chemical formula (13) [ka]

[0075] <Resin> Dianaal BR-605: Methacrylic resin manufactured by Mitsubishi Chemical Corporation JONCRYL 586: Styrene-acrylic resin manufactured by BASF.

[0076] [Measurement of average primary particle diameter] The average primary particle size of the obtained pigment composition was determined by transmission electron microscopy (TEM) observation as follows: For 50 primary particles of the pigment composition, arbitrarily selected from multiple photographs taken at a magnification of 10,000x with a transmission electron microscope, the image of the particle was enclosed by two parallel lines tangent to each other. The distance between the parallel lines when the distance was largest was defined as the major axis, and the average of the major axes was defined as the average primary particle size.

[0077] [Preparation of compound (D)] (Manufacturing Example D1) Manufacturing of Compound (D)-1 Compound (D)-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 filtered, washed with water, dried, and pulverized to obtain compound (D)-1 having copper phthalocyanine residues.

[0078] (Manufacturing Example D2) Manufacturing of Compound (D)-2 10 parts by mass of PV19 were 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.) were added little by little, and the mixture was stirred at 40°C for 2 hours. The reaction solution was dropped into 1000 parts of ice water, and the precipitate was filtered, washed with water, dried, and ground to obtain compound (D)-2, which has a PV19 residue and an average number of substituents of 1.5.

[0079] (Manufacturing Example D3) Manufacturing of Compound (D)-3 Compound (D)-3, which has a PR122 residue, was obtained in the same manner as in Production Example D2, except that 100 parts by mass of 98% sulfuric acid was replaced with 120 parts by mass and PV19 was replaced with 11 parts by mass of PR122.

[0080] (Manufacturing Example D4) Manufacturing of Compound (D)-4 Compound (D)-4 containing the PR179 residue was obtained in the same manner as in manufacturing example D1, except that 70 parts of PB15:3 were replaced with 51 parts of PR179.

[0081] [Preparation of compound (B)] (Manufacturing Example B1) Manufacturing of Compound (B)-1 Ten parts of compound (D)-1 were added to 40 parts of water and stirred. A 25% sodium hydroxide aqueous solution was then added to adjust the pH to 11. The mixture was stirred at 25°C for 2 hours, and 35% hydrochloric acid was added to lower the pH to 3 or less. The mixture was then filtered. The mixture was washed with 1% hydrochloric acid, dried, and ground to obtain compound (B)-1, which contains copper phthalocyanine residues.

[0082] (Manufacturing Example B2) Manufacturing of Compound (B)-2 Compound (B)-2, containing PV19 residues, was obtained in the same manner as in production example B1, except that compound (D)-1 was replaced with compound (D)-2.

[0083] (Manufacturing Example B3) Manufacturing of Compound (B)-3 Compound (B)-3 was prepared based on the examples described in Japanese Patent Publication No. 48-75627. A mixture of 1050 parts phthalic anhydride, 455 parts trimellitic anhydride, 330 parts cupric chloride anhydride, 14 parts sodium molybdate, 770 parts urea, and 3935 parts 1,2,4-trichlorobenzene was stirred at 150°C under reflux for 30 minutes. 1540 parts urea suspended in 4535 parts 1,2,4-trichlorobenzene was added to the reaction mixture, bringing the temperature to 110°C. The temperature was then raised to 170°C over 195 minutes and maintained at 170°C for 90 minutes. The temperature was further raised to 190°C over 45 minutes and maintained at 190°C for 90 minutes. The solvent was removed from the reaction mixture by heating and reducing the pressure, and the residue was added to 5000 parts water. The pH was adjusted to 11 or higher with a 25% sodium hydroxide aqueous solution. After stirring at 80°C for 2 hours, the pH was adjusted to 2 or lower with 98% sulfuric acid, and the mixture was filtered, washed with water, dried, and ground to obtain compound (B)-3 containing copper phthalocyanine residues.

[0084] [Preparation of particle size control agent (E)] (Manufacturing Example E1) Manufacturing of particle size control agent (E)-1 Particle size control agent (E)-1 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. Filter, wash with water, and dry to obtain particle size control agent (E)-1 containing copper phthalocyanine residues.

[0085] (Manufacturing Example E2) Manufacturing of particle size control agent (E)-2 The particle size control agent (E)-2 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 pigment violet 19 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 monosulfonate. 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. This water cake was then added to 300 parts by mass of 0.5% aqueous sodium carbonate solution, stirred for 1 hour, filtered, washed with water to neutral, and dried to obtain particle size control agent (E)-2 having PV19 residues.

[0086] (Manufacturing Example E3) Manufacturing of particle size control agent (E)-3 The particle size control agent (E)-3 was manufactured based on manufacturing example 3 of Japanese Patent Publication No. 60-88185. To a mixed solvent of 200 parts acetone and 100 parts water, 19 parts cyanuric chloride, 15 parts p-aminoacetanilide, and 11 parts sodium carbonate as a dehydrochlorinator were added and the mixture was stirred at 30-40°C for 1 hour. Then, at the same temperature, 30 parts N,N-diethylaminopropylamine was added dropwise and the mixture was stirred at 50-60°C for 3 hours. After the reaction was complete, the reaction solvent was removed by distillation under reduced pressure, and 300 parts 1% hydrochloric acid was added and the mixture was stirred at 90-100°C for 1 hour. The reaction mixture was cooled and sodium hydroxide was added to adjust the pH to 9-10 to obtain 40 parts of base. 22 parts of this base was added to 200 parts methanol, and under ice cooling, 30 parts hydrochloric acid was added. To this, 7.6 parts of 40% sodium nitrite aqueous solution were added to obtain a diazonium salt solution. A coupling component solution consisting of 12 parts of 5-acetoacetylamino-benzimidazolone, 520 parts of methanol, 1050 parts of water, and 22 parts of sodium carbonate was prepared separately, and the diazonium salt solution obtained above was added to carry out the coupling reaction. During the reaction, sodium carbonate was added as needed to maintain a pH of 9-10. By filtration, washing with water, drying at 80°C, and grinding, a particle size control agent (E)-3 having a total of four 5-membered rings and 6-membered rings including heterocycles was obtained.

[0087] <1> Manufacturing of pigment compositions (Example 1) Preparation of Pigment Composition 1 200 parts of PB15:1 as organic pigment (A), 14.2 parts of compound (B)-1 as compound (B), 1500 parts of sodium chloride as a water-soluble inorganic salt, and 250 parts of diethylene glycol as a water-soluble organic solvent were charged into a 3L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Further, 10.0 parts of dimeramine as aliphatic amine (C) were added and kneaded for another 30 minutes. After adding 9000 parts of 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 water to remove sodium chloride and diethylene glycol, obtaining a wet cake of the pigment composition. This was dried at 80°C for 24 hours and then pulverized in a hammer mill to obtain pigment composition 1.

[0088] (Example 2) Preparation of Pigment Composition 2 200 parts of PB15:1 as organic pigment (A), 14.0 parts of compound (D)-1 as compound (D), 10.0 parts of dimeramine as aliphatic amine (C), 1500 parts of sodium chloride as a water-soluble inorganic salt, and 250 parts of diethylene glycol as a water-soluble organic solvent were charged into a 3L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. After adding 9000 parts of water to this mixture, it was stirred in a high-speed mixer for 2 hours to form a slurry. Sodium chloride and diethylene glycol were removed by repeated filtration and washing with water to obtain an intermediate wet cake. This was added to 3000 parts of water and re-slurred, and a 25% sodium hydroxide aqueous solution was added until the pH reached 11. After stirring for 2 hours, 98% sulfuric acid was added until the pH was between 7 and 8. Sodium sulfate was removed by repeated filtration and washing with water to obtain a wet cake of the pigment composition. This was dried at 80°C for 24 hours, then ground in a hammer mill to obtain pigment composition 2.

[0089] (Example 3) Preparation of pigment composition 3 200 parts of PB15:1 as the organic pigment (A), 10.0 parts of polymerized rosin as the compound (B), 10 parts of particle size control agent (E)-1 as the particle size control agent (E), 1500 parts of sodium chloride as the water-soluble inorganic salt, and 250 parts of diethylene glycol as the water-soluble organic solvent were charged into a 3L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 75°C for 6 hours. Further, 10.0 parts of dimeramine as the aliphatic amine (C) were added and kneaded for another 30 minutes. After adding 9000 parts of water to this mixture, it was stirred in a high-speed mixer for 2 hours to form a slurry, and the slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, obtaining a wet cake of the pigment composition. This was dried at 80°C for 24 hours and then pulverized in a hammer mill to obtain pigment composition 3.

[0090] (Examples 4, 13, 14, 19, 24, 25, 27) Preparation of pigment compositions 4, 13, 14, 19, 24, 25, 27 Pigment compositions 4, 13, 14, 19, 24, 25, and 27 were obtained in the same manner as in Example 3, except that the types and amounts of the organic pigment (A), compound (B), particle size control agent (E), and aliphatic amine (C) were changed as shown in Table 1.

[0091] (Examples 5, 15, 21) Preparation of pigment compositions 5, 15, and 21 Pigment compositions 5, 15, and 21 were obtained in the same manner as in Example 1, except that the types and amounts of the organic pigment (A), compound (B), and aliphatic amine (C) were changed as shown in Tables 1-1 to 1-3.

[0092] (Examples 6-12, 16-18, 20, 22, 23, 26) Preparation of pigment compositions 6-12, 16-18, 20, 22, 23, 26 Pigment compositions 6-12, 16-18, 20, 22, 23, and 26 were obtained in the same manner as in Example 2, except that the types and amounts of the organic pigment (A), aliphatic amine (C), and compound (D) were changed as shown in Tables 1-1 to 1-3.

[0093] (Example 28) Preparation of pigment composition 28 200 parts of PB15:1 as organic pigment (A), 10.0 parts of compound (B)-1 as compound (B), 1500 parts of sodium chloride as a water-soluble inorganic salt, and 250 parts of diethylene glycol as a water-soluble organic solvent were charged into a 3L stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Further, 10.0 parts of dimeramine as aliphatic amine (C) were added and kneaded for another 30 minutes. Further, 10 parts of Dianal BR-605 as resin were added and kneaded for another 30 minutes. After adding 9000 parts of this mixture to water, it was stirred in a high-speed mixer for 2 hours to form a slurry, and the slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, obtaining a wet cake of the pigment composition. After drying this at 80°C for 24 hours, it was pulverized in a hammer mill to obtain pigment composition 28.

[0094] (Example 29) Preparation of pigment composition 29 Pigment composition 29 was obtained in the same manner as in Example 28, except that the types and amounts of organic pigment (A), compound (B), aliphatic amine (C), and resin were changed as shown in Table 1-3.

[0095] (Comparative Examples 1, 3-11, 13, 14, 16-19) Preparation of pigment compositions 101, 103-111, 113, 114, 116-119 Pigment compositions 101, 103-111, 113, 114, and 116-119 were obtained in the same manner as in Example 1, except that the types and amounts of the organic pigment (A), compound (B), and aliphatic amine (C) were changed as shown in Tables 1-4 to 1-5.

[0096] (Comparative Examples 2, 12, 15) Preparation of Pigment Compositions 102, 112, and 115 Pigment compositions 102, 112, and 115 were obtained in the same manner as in Example 2, except that the types and amounts of the organic pigment (A), aliphatic amine (C), and compound (D) were changed as shown in Tables 1-4 to 1-5.

[0097] The average primary particle size was determined for the pigment compositions obtained in Examples 1 to 29 and Comparative Examples 1 to 19 based on the method described above. The results are shown in Tables 1-1 to 1-5. In the tables, "composition ratio" refers to the content of organic pigment (A), compound (B), and aliphatic amine (C) in the total 100% by mass of organic pigment (A), compound (B), and aliphatic amine (C).

[0098] [Table 1-1]

[0099] [Table 1-2]

[0100] [Table 1-3]

[0101] [Table 1-4]

[0102] [Table 1-5]

[0103] <2> Paint manufacturing and evaluation The following are specific examples of paints containing pigment compositions. <Evaluation Grouping> Organic pigments (A) absorb and transmit different wavelengths of light depending on their structure, resulting in differences in coloring power, vividness, and transparency. Therefore, since it is not possible to compare the coloring power, vividness, and transparency of organic pigments (A) with different structures, we compared and evaluated the coloring power, vividness, and transparency of pigment compositions in which the main component is the same organic pigment (A). Similarly, luminosity and flip-flop properties were also evaluated by dividing the evaluation groups based on the main component of the organic pigment (A). The names of the organic pigments (A) and the reference comparative examples are as listed in each table.

[0104] Preparation and evaluation of dark-colored paints (A1) Preparation of dark-colored paints (Example A-1) Preparation of dark-colored paint a-1 Pigment composition 19 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 the mixture was 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. Afterward, the steel beads were removed to obtain dark-colored paint a-1 containing pigment composition 1.

[0105] (Examples A-2 to A-29, Comparative Examples A-1 to A-19) Preparation of dark-colored paints a-2 to a-29, a-101 to a-119 The procedure was carried out in the same manner as in Example A-1, except that the pigment composition 1 of Example A-1 was changed as shown in Table 2, to obtain dark-colored paints a-2 to a-29 and a-101 to a-119.

[0106] (A2) Evaluation of dark-colored paints <Initial viscosity and viscosity over time> The obtained dark-colored paint was placed in a glass bottle with a tight seal, sealed, and immersed in a 25°C constant temperature bath for 1 hour to maintain a constant temperature. The viscosity at 25°C and a rotation speed of 6 rpm (referred to as "initial viscosity") was measured using a Type B viscometer (Toki Sangyo Type BII viscometer). The viscosity was then measured again in the same manner after storage at 40°C for 1 week (referred to as "viscosity over time"). The results are shown in Table 2. A score of "4", "3", and "2" according to the evaluation criteria below indicates a level that is usable for practical purposes.

[0107] (Evaluation criteria for initial viscosity and viscosity over time) 4: Viscosity is less than 4000 mPa·s, extremely good. 3: Viscosity is 4000 mPa·s or higher and less than 10000 mPa·s; good. 2: If the viscosity is 10,000 mPa·s or higher and less than 13,000 mPa·s, it is usable. 1: If the viscosity is 13,000 mPa·s or higher, or if it has gelled, it is defective.

[0108] [Table 2]

[0109] Fabrication and evaluation of colored clear coatings and painted panels (B1) Preparation of top coat clear paint 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 in a high-speed stirrer to obtain a top coat clear paint.

[0110] (B2) Preparation of colored clear paint and painted boards (Example B-1) Fabrication of color clear coated board b-1 One part of the dark-colored paint a-1 prepared in Example A-1 was mixed with nine parts of the topcoat clear paint to prepare the color clear paint b'-1. This color clear paint was sprayed onto a mirror-finished stainless steel plate using a spray gun. To adjust the viscosity to one that was 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. The painting was done in nine separate coats, followed by six coats of topcoat clear paint. After drying at 25°C for 1 hour, the material was dried at 140°C for 30 minutes to obtain the color clear coated plate b-1. The film thickness after drying was approximately 35 μm.

[0111] (Examples B-2 to B-29, Comparative Examples B-1 to B-19) Preparation of color clear coated boards b-2 to b-29 and b-101 to b-119 The procedure was carried out in the same manner as in Example B-1, except that the dark-colored paint a-1 of Example B-1 was changed as shown in Table 3, to obtain color clear paints b'-2 to b'-29, b'-101 to b'-119, and color clear coated boards b'-2 to b'-29, b'-101 to b'-119.

[0112] (B3) Evaluation of color clear coated boards <Coloring power> The colored clear-coated boards were visually inspected and evaluated according to the following criteria. The results are shown in Table 3. A score of "4", "3", and "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.

[0113] <Sharpness> The colored clear-coated boards were visually inspected and evaluated according to the following criteria. The results are shown in Table 3. 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.

[0114] <Transparency> The colored clear-coated boards were visually inspected and evaluated according to the following criteria. The results are shown in Table 3. A score of "4", "3", and "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.

[0115] <Flip-flop properties> The following performance tests were performed on the fabricated color clear coated board. Since the color tone of the clear coating changes depending on the viewing angle or the angle of incident light, a multi-angle colorimeter (X-Rite, MA94) was used for color measurement. According to Figure 1, incident light 101 was shone onto the coated board 100 at a 45-degree angle, and the reflected light 15 degrees from the specularly reflected light 102 (reflected at 90 degrees) towards the incident light 101 was defined as the highlight 103. The highlight 103 represents the color tone of the bright areas where the amount of light reflection is high, as seen visually. Additionally, the reflected light 110 degrees from the specularly reflected light 102 towards the incident light 101 was defined as the shade 104. The shade 104 represents the color tone of the dark areas where the amount of light reflection is low, as seen visually. The brightness (L) of the obtained shade and highlight was then measured. * The absolute value of the difference between ) |ΔL * |=|L * (110°)-L * A larger (15°)| indicates a greater change in brightness with respect to angle changes, i.e., good flip-flop properties. The difference in flip-flop properties between the example and the standard was evaluated as ΔΔL* = |ΔL*| of the example - |ΔL*| of the standard. The results are shown in Table 3. A score of "4", "3", and "2" according to the following criteria indicates a practical level. (Evaluation criteria for flip-flops) 4: ΔΔL*>2 (The flip-flop properties are extremely high compared to the standard) 3:2≧ΔΔL*>1 (Higher flip-flop properties than the standard) 2:1 ≥ ΔΔL* > 0.5 (The flip-flop properties are slightly higher than the standard) 1:0.5≧ΔΔL*(Flip-flop properties are equivalent to or less than the standard)

[0116] [Table 3]

[0117] <c>Manufacturing and evaluation of metallic paints and painted panels (C1) Preparation of metallic base paint Aluminum flake paste (Toyo Aluminum Co., Ltd., Alpaste 1700NL) 10 units Aluminum flake paste (Toyo Aluminum Co., Ltd. Alpaste HS-2) 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 in a high-speed stirrer to obtain a metallic base paint.

[0118] (C2) Preparation of metallic paints and painted panels (Example C-1) Fabrication of metallic painted plate c-1 Twenty parts of the dark-colored paint a-1 prepared in Example A-1 and 18.5 parts of the metallic base paint were stirred and mixed in a high-speed stirrer to obtain metallic paint c'-1. This metallic paint was sprayed onto a steel plate using a spray gun. To adjust the viscosity to facilitate 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 appropriately mixed with the metallic paint in approximately equal mass. The painting was carried out in nine separate coats, followed by six separate sprays of topcoat clear paint. After drying at 25°C for one hour, the plate was dried at 140°C for 30 minutes to obtain metallic painted plate c-1. The film thickness after drying was approximately 40 μm.

[0119] (Examples C-2 to C-29, Comparative Examples C-1 to C-19) Preparation of metallic coated plates c-2 to c-29 and c-101 to c-119 Except for changing the dark-colored paint a-1 of Example C-1 as shown in Table 4, the procedure was carried out in the same manner as in Example C-1 to obtain metallic paints c'-2 to c'-29, c'-101 to c'-119, and color clear coated boards c'-2 to c-29, c-101 to c-119.

[0120] (C3) Evaluation of metallic painted panels <Sharpness> Metallic 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.

[0121] <Shining feeling> Metallic 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 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: Equivalent to or lower than the standard painted panel in terms of glossiness.

[0122] <Flip-flop properties> The following performance tests were conducted on the fabricated metallic painted panels. Since the color tone of metallic paints changes depending on the viewing angle or the angle of light incidence, a multi-angle colorimeter (X-Rite, MA94) was used for color measurement. According to FIG. 1, for the painted plate 100, incident light 101 is irradiated at an angle of 45 degrees, and the specularly reflected light 102 that is reflected at 90 degrees is used as highlight 103 in the direction of the incident light 101. The highlight 103 is the color tone of the part where the amount of light reflection is large and bright visually. Also, the reflected light at 110 degrees from the specularly reflected light 102 in the direction of the incident light 101 is used as shade 104. The shade 104 is the color tone of the part where the amount of light reflection is small and dark visually. The absolute value |ΔL * ) of the difference in lightness (L * ) between the obtained shade and highlight is such that the larger |ΔL * (110°)-L * (15°)| is, the greater the change in lightness with respect to the angle change, that is, the better the flip-flop property. The difference in flip-flop property of the example with respect to the reference was evaluated as ΔΔL* = |ΔL*| of the example - |ΔL*| of the reference. The results are shown in Table 4. If it is "4", "3", or "2" according to the following criteria, it is at a practical level. (Evaluation Criteria for Flip-Flop) 4: ΔΔL* > 3 (The flip-flop property is extremely high compared to the reference) 3: 3 ≥ ΔΔL* > 1 (The flip-flop property is high compared to the reference) 2: 1 ≥ ΔΔL* > 0.5 (The flip-flop property is slightly higher than the reference) 1: 0.5 ≥ ΔΔL* (The flip-flop property is equal to or lower than the reference)

[0123]

Table 4

[0124] The paint using the pigment composition of the present invention is excellent in viscosity stability, highly vivid, highly transparent, and excellent metallic luster, brilliance, and flip-flop property are obtained when coating a metal plate or when using a brightening material in combination, and it is suitable for coating vehicle exterior, electrical products, etc. On the other hand, the comparative pigment compositions and the paints and coated panels using them did not contain either or both of compound (B) and aliphatic amine (C). As a result, paints and coated panels with the desired transparency, clarity, gloss, and flip-flop properties could not be obtained, and the viscosity stability of the paints was also insufficient. [Explanation of symbols]

[0125] 100: Painted board 101: Light source 102: Specular reflection light 103: Highlights 104: Shade< / c>

Claims

1. A pigment composition comprising an organic pigment (A), a compound (B), and an aliphatic amine (C), Compound (B) is a compound represented by the following general formula (1): The aliphatic amine (C) is an amine having a hydrocarbon chain and a molecular weight of 100 to 1000, in this pigment composition. General formula (1) B(-X-COOM)n (In general formula (1), X represents a direct bond or any linking group, M represents a hydrogen atom or a monovalent metal atom, n represents an integer from 1 to 4, and B represents an organic pigment residue or a compound residue having three or more five-membered or six-membered rings.)

2. The pigment composition according to claim 1, wherein the organic pigment (A) is an organic pigment selected from the group consisting of phthalocyanine pigment, perylene pigment, quinacridone pigment, anthraquinone pigment, dioxazine pigment, and diketopyrrolopyrrole pigment.

3. The pigment composition according to claim 1, wherein compound (B) is a compound represented by general formula (3). General formula (3) 【Chemistry 1】 (In general formula (3), B represents an organic pigment residue. R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, and a phthalimidomethyl group. n represents an integer from 1 to 4.)

4. The pigment composition according to claim 1, wherein the aliphatic amine (C) is a divalent amine having a primary or secondary amino group.

5. The pigment composition according to claim 1, comprising 70% by mass or more of the organic pigment (A), compound (B), and aliphatic amine (C) in a total of 100% by mass, compound (B) in an amount of 0.1% by mass or more and 20% by mass or less, and aliphatic amine (C) in an amount of 0.5% by mass or more and 20% by mass or less.

6. Furthermore, the pigment composition according to claim 1, further comprising a resin.

7. Furthermore, the pigment composition according to claim 1, further comprising a luminescent material.

8. A method for producing a pigment composition according to claim 1, comprising the following steps A or B. Process A: Includes processes a and c, and involves adding amine (C) in either process. Process B: Includes processes b1, b2, and c, and involves adding amine (C) in any of the processes. Step a: A step of kneading a mixture containing an organic pigment (A), a compound (B), a water-soluble salt, and a water-soluble organic solvent. Step b1: A step of kneading a mixture containing an organic pigment (A), a compound (D) represented by the following general formula (2), a water-soluble salt, and a water-soluble organic solvent. Step b2: A step in which water and a base are added to the mixture to denature compound (D) into compound (B) by hydrolysis. Step c: Step of removing water-soluble salts and water-soluble organic solvents from the mixture. General formula (2) 【Chemistry 2】 (In general formula (2), n represents an integer from 1 to 4. R1, R2, R3, and R4 each independently represent a group selected from hydrogen, an alkyl group having 1 to 4 carbon atoms, a nitro group, a chlorine group, and a phthalimidomethyl group. B is an organic pigment residue, or a compound residue having three or more 5-membered or 6-membered rings.)

9. A paint comprising the pigment composition and dispersion medium according to any one of claims 1 to 7.

10. A painted article having a coating film formed from the paint described in claim 9.

11. A painted product according to claim 10, which is an exterior part of a vehicle.

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