Pigment composition and method for manufacturing the same, coating material, and coated product

Abstract

To provide a pigment composition having excellent transparency, clarity, and weather resistance.SOLUTION: A pigment composition contains perylene pigment (A), particle size control agent (B) and carboxylic acid (C), where the perylene pigment (A) is perylene pigment having a specific structural formula, the particle size control agent (B) is a compound which has three or more of 5-membered ring or 6-membered ring, and at least one of the 5-membered ring and 6-membered ring is heterocycle, the carboxylic acid (C) is carboxylic acid having the molecular weight of 100 or more and 1000 or less, and the pigment composition contains the perylene pigment (A) by 70 mass% or more, the particle size control agent (B) by 0.1 mass% or more and 20 mass% or less, and the carboxylic acid (C) by 0.5 mass% or more and 20 mass% or less in the total 100 mass% of the perylene pigment (A), the particle size control agent (B) and the carboxylic acid (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a pigment composition, its production, paints, and coated articles.

Background Art

[0002] In the field of industrial products such as automotive painting, a variety of colors and designs according to the preferences of users and the like are required. For example, as pigments exhibiting hues of deep red to purple, C.I. Pigment Red 179 and C.I. Pigment Violet 29, which are perylene pigments, are used. For example, Patent Document 1 discloses an example of a paint containing a metallic pigment and C.I. Pigment Red 179. Further, Patent Document 2 mentions 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. In this multilayer coating film, 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, resulting in a multilayer coating film with 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 is known as a multilayer coating film with high color saturation, high brightness, and excellent color depth and high design in the field of vehicle exterior parts and the like.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] As one of the color trends in the field of industrial products in recent years, there has been an increasing need for higher transparency and higher chroma color tones, and it has become difficult to meet the requirements with only the above coating technology and coating film components. One of the measures to obtain high-transparency and high-chroma paints and coatings is the refinement of pigments. However, depending on the additives used for the refinement of pigments, there has been a problem that the weather resistance is insufficient in long-term outdoor exposure, and there has been an issue that it is impossible to achieve both high transparency, high chroma and weather resistance. In addition, there has been a problem that when made into a dispersion such as a paint, it easily aggregates and thickens, and the viscosity stability of the dispersion decreases.

[0005] Therefore, the problem to be solved by the present invention is to provide a pigment composition excellent in transparency, clarity, and weather resistance, and when made into a paint, to provide a pigment composition excellent in viscosity stability and, when made into a coating film, excellent in transparency, clarity, gloss, and weather resistance.

Means for Solving the Problems

[0006] In view of the above situation, the present inventor has studied a method for improving the dispersion stability of perylene pigments. As a result, it has been found that various properties can be improved by combining a specific particle size control agent and a carboxylic acid, and the present invention has been completed.

[0007] That is, the present invention is a pigment composition comprising a perylene pigment (A), a particle size control agent (B), and a carboxylic acid (C), The perylene pigment (A) is a perylene pigment having a structure of the following general formula (1), The particle size control agent (B) is a compound having three or more 5-membered rings or 6-membered rings, and at least one of the 5-membered rings and 6-membered rings is a heterocyclic ring, The carboxylic acid (C) is a carboxylic acid having a molecular weight of 100 or more and 1000 or less, The present invention relates to a pigment composition containing 70% by mass or more of the perylene pigment (A), 0.1% by mass or more and 20% by mass or less of the particle size control agent (B), and 0.5% by mass or more and 20% by mass or less of the carboxylic acid (C) in a total of 100% by mass of the perylene pigment (A), the particle size control agent (B), and the carboxylic acid (C). However, the particle size control agent (B) excludes perylene compounds having a sulfo group or an amino group and the perylene pigment (A).

[0008] [Chemical formula]

[0009] [In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group.]

[0010] The present invention also relates to the above pigment composition wherein the particle size control agent (B) is a compound having a structure of the following general formula (2), general formula (3) or general formula (4).

[0011] [Chemical formula]

[0012] [In general formula (2), R3 and R4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent. However, R3 and R4 do not form a combination of groups selected from the group consisting of a hydrogen atom and an alkyl group.]

[0013] [Chemical formula]

[0014] [In general formula (3), X represents an oxygen atom or NR5. R5 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent.]

[0015] [Chemical formula]

[0016] In general formula (4), R6 represents a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, a carboxy group, an amino group which may have a substituent, an amide group which may have a substituent, or a sulfo group.

[0017] The present invention also relates to the above pigment composition wherein the carboxylic acid (C) is an aliphatic carboxylic acid having 8 to 54 carbon atoms and having 1 to 3 carboxy groups.

[0018] The present invention also relates to the above pigment composition further comprising a resin.

[0019] The present invention also relates to the above pigment composition further comprising a brightening agent.

[0020] The present invention also relates to a method for producing the above pigment composition, which includes a step of kneading a mixture containing a perylene pigment (A), a particle size control agent (B), and a carboxylic acid (C).

[0021] The present invention also relates to a paint comprising the above pigment composition and a dispersion medium.

[0022] The present invention also relates to a coated article having a coating film of the above paint.

[0023] The present invention also relates to the above coated article which is an exterior part of a vehicle.

Advantages of the Invention

[0024] According to the present invention, it has become possible to provide a pigment composition excellent in transparency, clarity, and weather resistance, and a method for producing the same. Further, by using the pigment composition, it has become possible to provide a paint excellent in viscosity stability, and a coated article having a coating film excellent in transparency, clarity, weather resistance, and brilliance when used as a metallic paint.

Embodiments for Carrying Out the Invention

[0025] Hereinafter, embodiments of the present invention will be described more specifically. However, the present invention is not limited to the following embodiments, and various modifications may be made without changing the gist, and various embodiments are included. First, the terms used in this specification will be explained. "C.I." represents a Color Index number. "Coated object" shall be treated as synonymous with "printed matter", "image-formed matter", and "coated matter".

[0026] <1> Pigment composition One embodiment of the present invention relates to a pigment composition comprising a perylene pigment (A), a particle size control agent (B), and a carboxylic acid (C). <Perylene pigment (A)> The perylene pigment (A) is a pigment represented by the following general formula (1).

[0027]

Chemical formula

[0028] [In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group.]

[0029] The alkyl groups in R1 and R2 preferably have 1 to 8 carbon atoms, and may be any of a linear structure, a branched structure, and a cyclic structure. In one embodiment, the alkyl groups more preferably have 1 to 5 carbon atoms, still more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom. Also, it is preferable that R1 and R2 are hydrogen. In one embodiment, the perylene pigment (A) may be a known perylene pigment and can also be obtained as a commercial product. Examples of commercially available perylene pigments (A) include C.I. Pigment Red 179 (hereinafter sometimes abbreviated as PR179), C.I. Pigment Violet 29 (hereinafter sometimes abbreviated as PV29), etc. One or a combination of two or more of these can be used as the perylene pigment (A).

[0030] <Particle size control agent (B)> The particle size control agent (B) is a compound having three or more five-membered or six-membered rings, and at least one of the five-membered and six-membered rings is a heterocyclic ring. However, perylene compounds and perylene pigments (A) having a sulfo group or an amino group are excluded from the particle size control agent (B).

[0031] Among the particle size control agents (B), compounds having the structure of general formula (2), general formula (3) or general formula (4) can be preferably used.

[0032] [Chemical formula]

[0033] [In general formula (2), R3 and R4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent or a heterocyclic group which may have a substituent. However, R3 and R4 do not form a combination of groups selected from the group consisting of a hydrogen atom and an alkyl group.]

[0034] The carbon number of the alkyl group which may have a substituent in R3 and R4 is preferably 1 to 14. Further, the alkyl group is preferably a bulky group, and more preferably a branched alkyl group rather than a linear alkyl group. In the case of an alkyl group having a substituent, the substituent on the alkyl group is preferably an aryl group. Preferred specific examples of the alkyl group having a substituent include a benzyl group, a phenethyl group, and a methoxybenzyl group.

[0035] The carbon number of the aryl group which may have a substituent in R3 and R4 is preferably 6 to 14. Further, as the substituent on the aryl group, an alkyl group and an alkoxy group are preferable. Preferred specific examples of the aryl group which may have a substituent include a phenyl group, a tolyl group, a xylyl group, and a methoxyphenyl group.

[0036] The carbon number of the heterocyclic group which may have substituents at R3 and R4 is preferably 2 to 14. Further, as the substituent on the heterocyclic group, an alkyl group and an alkoxy group are preferable. Preferable specific examples of the heterocyclic group which may have substituents include a pyridyl group and the like.

[0037] R3 and R4 do not form a combination of groups selected from the group consisting of a hydrogen atom and an alkyl group, but at least one of R3 and R4 is preferably a substituted alkyl group, an aryl group which may have substituents or a heterocyclic group which may have substituents. Further, R3 and R4 in the general formula (2) preferably do not have a sulfo group or an amino group. When R3 and R4 have a sulfo group or an amino group, the crystallinity of the pigment composition is significantly reduced, resulting in a decrease in weather resistance, which is not preferable.

[0038] The particle size control agent (B) may be a known compound and can also be obtained as a commercial product. Examples of the particle size control agent (B) available as a commercial product include C.I. Pigment Red 123, 149, 190, C.I. Pigment Black 31, 32, etc. (hereinafter, C.I. Pigment Red may be abbreviated as PR and C.I. Pigment Black may be abbreviated as PBk).

[0039] [In the general formula (3), X represents an oxygen atom or NR5. R5 represents a hydrogen atom, an alkyl group which may have substituents, an aryl group which may have substituents or a heterocyclic group which may have substituents.]

[0040] [In the general formula (3), X represents an oxygen atom or NR5. R5 represents a hydrogen atom, an alkyl group which may have substituents, an aryl group which may have substituents or a heterocyclic group which may have substituents.]

[0041] Among the alkyl group which may have a substituent at R5, the aryl group which may have a substituent, or the heterocyclic group which may have a substituent, preferred embodiments include the same groups as the preferred embodiments of the alkyl group which may have a substituent, the aryl group which may have a substituent, or the heterocyclic group which may have a substituent at R3 and R4 described above. Therefore, preferably, X is an oxygen atom or NR5 which is the above-described preferred R5.

[0042]

Chemical formula

[0043] [In General Formula (4), R6 represents a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, a carboxy group, an amino group which may have a substituent, an amide group which may have a substituent, or a sulfo group.]

[0044] Among the alkyl groups which may have a substituent at R6, preferred embodiments include the same groups as the preferred embodiments of the alkyl groups which may have a substituent at R3 and R4 described above.

[0045] The number of carbon atoms of the amino group which may have a substituent at R6 is preferably 1 to 27. Further, as the substituent on the amino group, an aryl group or a heterocyclic group is preferred. Preferred specific examples of the amino group which may have a substituent include a phenylamino group and a group having the structure of the following General Formula (5).

[0046] The number of carbon atoms of the amide group which may have a substituent at R6 is preferably 1 to 33. Further, as the substituent on the amide group, an aryl group or a heterocyclic group is preferred. Preferred specific examples of the amide group which may have a substituent include a phenylcarbamoyl group and a group having the structure of the following General Formula (6). Note that the "amide group" as used in this specification is synonymous with the "carbamoyl group".

[0047]

Chemical formula

[0048] [Chemical formula]

[0049] [In General Formula (5) and General Formula (6), Y each independently represents a linking group having 1 to 4 carbon atoms, and R7 each independently represents an alkyl group having 1 to 4 carbon atoms.]

[0050] It is preferable that Y has 2 to 3 carbon atoms. Also, Y is preferably an alkylene group. Therefore, preferable specific examples of Y include an ethylene group, a propylene group, etc. Also, it is preferable that R7 has 1 to 3 carbon atoms. Therefore, preferable specific examples of R7 include a methyl group, ethyl, propyl group, and isopropyl group.

[0051] Preferable specific examples of the compound having the structure of General Formula (4) include compounds represented by the following Structural Formula (7) and the following Structural Formula (8).

[0052] [Chemical formula]

[0053] [Chemical formula]

[0054] The particle size control agent (B) has the effect of suppressing the particle growth (increase in particle size) of the perylene pigment (A) caused by the influence of an organic solvent or heat. Further, it has the effect of shifting the balance of the primary particle size to the smaller side in the primary particle control step of the perylene pigment (A). The particle size control agent (B) can be used alone or in combination of two or more. As the addition method of the particle size control agent (B), it may be added during the primary particle control step of the perylene pigment (A), or may be added after the primary particle control step, but it is preferably added during the primary particle control step of the perylene pigment (A). The effect of suppressing particle growth can also be obtained by mixing with the micronized perylene pigment (A). Part of it may be added during the primary particle control step, and the remainder may be added after the primary particle control step.

[0055] <Carboxylic acid (C)> The carboxylic acid (C) is a carboxylic acid having a molecular weight of 100 or more and 1000 or less. The carboxylic acid (C) may have any of a linear structure, a branched structure or a cyclic structure, and may have an unsaturated bond. The number of carbon atoms of the carboxylic acid (C) is preferably 8 to 54. The number of carboxy groups in the carboxylic acid (C) is preferably 1 to 3, more preferably 2 or 3.

[0056] Examples of the carboxylic acid (C) include saturated fatty acids, unsaturated fatty acids, polymers of unsaturated carboxylic acids, rosin, rosin derivatives, and the like. In one embodiment, monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and oleic acid, dicarboxylic acids such as sebacic acid, dodecanedioic acid, and C36 dimer acid, and tricarboxylic acids such as C54 trimer acid are preferred. In addition, rosin acids such as disproportionated rosin, hydrogenated rosin, and polymerized rosin are preferred. In particular, aliphatic carboxylic acids are preferred in terms of initial viscosity. These can be used alone or in combination of two or more as the carboxylic acid (C). As a method for adding the carboxylic acid (C), it may be added during the primary particle control step of the perylene pigment (A), or may be added after the primary particle control step. As a method for adding the carboxylic acid (C), it may be added to the aqueous slurry of the pigment composition by dissolving it in an aqueous solution of a metal hydroxide salt such as sodium hydroxide, or an emulsion prepared using an organic solvent such as xylene may be added to the aqueous slurry of the pigment composition, or the carboxylic acid (C) may be added as it is when the pigment composition is mechanically kneaded together with a water-soluble inorganic salt and a water-soluble solvent. Adding it during mechanical kneading is preferred because the surface of the pigment composition can be uniformly treated.

[0057] In the pigment composition of the present invention, in a total of 100% by mass of the perylene pigment (A), the particle size control agent (B), and the carboxylic acid (C), the perylene pigment (A) is 70% by mass or more, the particle size control agent (B) is 0.1% by mass or more and 20% by mass or less, and the carboxylic acid (C) is 0.5% by mass or more and 20% by mass or less. The content of the perylene pigment (A) is preferably 80% by mass or more, more preferably 90% by mass or more, from the viewpoint of coloring power, and preferably 98.8% by mass or less, more preferably 98.5% by mass or less, from the viewpoint of transparency. The content of the particle size control agent (B) is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of transparency, and preferably 15% by mass or less, more preferably 10% by mass or less, from the viewpoint of coloring power. The content of the carboxylic acid (C) is preferably 1% by mass or more, from the viewpoint of viscosity stability, and preferably 15% by mass or less, from the viewpoint of coloring power.

[0058] The average value of the major axis length of the primary particles of the pigment composition of the present invention (hereinafter sometimes 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 or more and 150 nm or less, and still more preferably 20 nm or more and 120 nm or less. Details of the method for measuring the major axis length of the primary particles and the method for calculating the average value are shown in the examples.

[0059] In one embodiment, the pigment composition of the present invention may contain a resin. The resin referred to in this specification means a resin excluding rosin and refers to those having a weight average molecular weight of 1000 or more. Any resin generally used in paints can be used. For example, acrylic resins, methacrylic resins, and polyester resins can be preferably used. The resin preferably has a hydroxyl group and / or a carboxyl group. Examples of usable resins include the Dianal series (manufactured by Mitsubishi Chemical Corporation), the Joncryl series (manufactured by BASF), the Degalan series (manufactured by Evonik Industries), etc. Specifically, Dianal BR-605, Dianal MB-7922, Dianal BR-116 (all of the above manufactured by Mitsubishi Chemical Corporation), Degalan LP64 / 11, Degalan LP64 / 12, Degalan LP63 / 11, Degalan LP67 / 11, Degalan PM381N, Degalan 64 / 12N (all of the above manufactured by Evonik Industries), Joncryl 67, Joncryl 586, Joncryl 611, Joncryl 680, Joncryl 682, Joncryl 683 (all of the above manufactured by BASF), etc. can be used.

[0060] The resin may be used alone or in combination of multiple types. As a method of adding the resin, after dissolving the resin in an aqueous solution of a metal hydroxide such as sodium hydroxide, it may be added to an aqueous slurry of a pigment composition (hereinafter referred to as pigment composition (D)) consisting only of perylene pigment (A), particle size control agent (B), and carboxylic acid (C). Alternatively, an emulsion in which the resin is emulsified using an organic solvent such as xylene may be added to the aqueous slurry of pigment composition (D). It may also be added when mechanically kneading pigment composition (D) together with a water-soluble inorganic salt and a water-soluble solvent. Adding it during mechanical kneading is preferable because the surface of perylene pigment (A) is uniformly coated with the resin. The glass transition temperature of the resin used during mechanical kneading is preferably lower than the kneading temperature. The addition amount of the resin is preferably 1 to 100 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass in total of perylene pigment (A), particle size control agent (B), and carboxylic acid (C). After treating the resin, the resin may be crosslinked using a curing agent or a crosslinking agent. As the crosslinking agent, an epoxy compound, an isocyanate compound, a blocked isocyanate compound, a polyamine compound, a polyamide resin, etc. can be used.

[0061] In one embodiment, the pigment composition of the present invention may contain a brightening material. Specific examples of the brightening material include metal flakes, mica, coated glass flakes, and the like. When used in applications where a particularly vivid hue is required, using metal flakes is preferable because it can bring out the characteristics of the pigment composition of the present invention. Examples of the metal flakes include flakes of aluminum, zinc, copper, iron, nickel, titanium, stainless steel, gold, and the like. Among them, aluminum flakes are preferable from the viewpoints of brightness, cost, and specific gravity. The average particle diameter 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 a fatty acid, a resin, or the like from the viewpoint of oxidation prevention. Examples of mica include ordinary mica and coated mica coated with a metal oxide such as titanium oxide. Examples of the coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide. The average particle diameter of the mica and the glass flakes is preferably 1 to 200 μm, and more preferably 10 to 150 μm. The content of the brightening material can be appropriately adjusted according to the desired color tone, but it is preferably 10 to 4000 parts by mass, and more preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the pigment composition (D). The average particle diameter of the brightening material can be measured in the same manner as the average particle diameter of the pigment composition.

[0062] <2> Method for Producing Pigment Composition The method for producing the pigment composition of the present invention is not particularly limited as long as it is a method for controlling the primary particle diameter of the pigment composition, and known methods can be adopted. Examples include a solution precipitation method including a step of dissolving a perylene pigment (A) and a particle size control agent (B) in a good solvent such as sulfuric acid and releasing it into a poor solvent such as water for precipitation, a mechanical kneading method including a step of kneading a mixture containing a perylene pigment (A), a particle size control agent (B), and a carboxylic acid (C), and combinations of these methods. However, it is preferably produced by a mechanical kneading method. When kneading, it is preferable to knead the above mixture with a mixture further containing a water-soluble inorganic salt and a water-soluble organic solvent (hereinafter sometimes referred to as salt milling). Examples of the kneader include a kneader, a trimix, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, a vertical sand mill, and / or an annular bead mill. Among these, a kneader or a trimix is preferable. When kneading, it is preferable to add a carboxylic acid (C) or a resin in advance. The temperature during mechanical kneading can be set according to the average particle diameter of the desired pigment composition, but it is preferably 40 to 120°C, more preferably 60 to 100°C.

[0063] The water-soluble inorganic salt may be any water-soluble inorganic salt and is not limited as long as it does not deviate from the gist of the present invention. Preferred examples include sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. From the viewpoint of price, it is preferable to use sodium chloride (table salt). The water-soluble inorganic salt is preferably used in an amount of 50 to 3,000 parts by mass, more preferably 300 to 1,500 parts by mass, based on 100 parts by mass in total of the perylene pigment (A) and the particle size control agent (B) from both the treatment efficiency and the production efficiency aspects. As the water-soluble organic solvent, any water-soluble organic solvent can be used as long as it is soluble or miscible in water. Specifically, glycerin, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, monoacetin, diacetin, triacetin, tripropionin, tributyrin, and 2-butyl-2-ethyl-1,3-propanediol can be mentioned, but it is not limited thereto. These solvents can be used alone or in combination of two or more. The amount of the water-soluble organic solvent used is not particularly limited, but it is preferably used in an amount of 50 to 500 parts by mass, more preferably 100 to 300 parts by mass, based on 100 parts by mass in total of the perylene pigment (A) and the particle size control agent (B).

[0064] A mixture containing a pigment composition is taken out from a kneader, water is added and stirred to obtain a suspension. The amount of water to be added may be an amount sufficient to obtain a suspension and is not particularly limited. Heating may be performed as necessary. For example, water having a mass 4 to 20 times the total mass of the water-soluble inorganic salt and the water-soluble organic solvent is added and mixed and stirred. The mixing and stirring conditions at this time are not particularly limited, but it is preferably performed at a temperature of 25 to 90°C. Then, by removing the filtrate by operations such as filtration and washing with water, the water-soluble organic solvent and the water-soluble inorganic salt can be removed. If necessary, it may be reslurried in water and washed again. After reslurrying in water, a neutralized and dissolved or emulsified carboxylic acid compound (C) or resin may be added. Any base that can dissolve the carboxylic acid (C) or resin can be used for neutralization, but sodium hydroxide and potassium hydroxide are preferred from the viewpoints of cost and detergency. When emulsifying, it can be obtained by adding the carboxylic acid (C) or resin to a hydrophobic organic solvent such as xylene or toluene, dissolving it, and adding water and stirring. The above base may be added as necessary. When the emulsion is added, the slurry is heated to 60°C or higher to break the emulsion, so that the carboxylic acid (C) or resin can be efficiently adsorbed on the surface of the pigment composition. When the carboxylic acid (C) or resin is added, it is preferable to add an acid such as hydrochloric acid or acetic acid to adjust the pH to 7 or less and then perform filtration before performing filtration and washing with water. The wet cake of the obtained pigment composition may be used as it is for dispersion, or a powdery pigment composition can be obtained by further drying and pulverizing it with a dryer or the like.

[0065] <3>Paint The paint of the present invention refers to a composition comprising the pigment composition of the present invention and a dispersion medium. In the paint, components other than the pigment composition can be appropriately selected according to the use. The dispersion medium is not particularly limited as long as it can disperse the pigment composition, and typically includes a solvent.

[0066] The solvent is selected from organic solvents and water according to 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, glycol ether solvents such as methoxypropanol, methoxybutanol, butyl glycol, and butyl diglycol, and other solvents commonly used in the paint field.

[0067] Also, the paint of the present invention may contain a resin, and in addition to the resins used in the pigment composition described above, polyurethane resins, alkyd resins, amino resins, epoxy resins, and modified resins thereof may be mentioned. Further, in order to accelerate the curing of the paint, a curing agent and / or a crosslinking agent such as an isocyanate compound or a blocked isocyanate compound may be included.

[0068] <4>Painted object The coated article of the present invention refers to an article having a coating film obtained by coating a substrate (coated article) such as metal, resin, wood, concrete, or stone with the paint of the present invention. In particular, coated articles having a metal or resin substrate, which are suitable for industrial mass production, are preferred. Examples of the metal substrate include those obtained by processing iron, aluminum, stainless steel, silver, copper, gold, and alloys containing these into plate-like, rod-like, tubular, spherical, etc. shapes having a flat or curved surface. Examples of the resin substrate include molded articles formed by known methods. Examples of the resin type include known resins such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin. By coating the surface of a substrate made of metal or resin with the paint of the present invention to form a coating film, a coated article excellent in transparency, clarity, gloss, and weather resistance can be obtained. Further, since the coated article of the present invention is excellent in transparency, clarity, and gloss and has resistance to withstand outdoor use, it can be suitably used as a vehicle exterior part.

Examples

[0069] The present invention will be described more specifically with reference to the following examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, "parts" represents "parts by mass" and "%" represents "% by mass".

[0070] The abbreviations and product names described in the following examples have the following meanings. <Perylene pigment (A)> PR179: C.I. Pigment Red 179 (a pigment in which R1 and R2 are methyl groups in the general formula (1)) PV29: C.I. Pigment Violet 29 (a pigment in which R1 and R2 are hydrogen atoms in the general formula (1)) Perylene pigment 1: A pigment in which R1 and R2 are n-propyl groups in the general formula (1) Perylene pigment 2: A pigment in which R1 and R2 are n-pentyl groups in the general formula (1)

[0071] <Particle Size Controller (B)> Particle Size Controller 1: C.I. Pigment Red 123 (a compound in which R3 and R4 are 4-ethoxyphenyl groups in General Formula (2)) Particle Size Controller 2: C.I. Pigment Red 149 (a compound in which R3 and R4 are 3,5-dimethylphenyl groups in General Formula (2)) Particle Size Controller 3: C.I. Pigment Red 190 (a compound in which R3 and R4 are 4-methoxyphenyl groups in General Formula (2)) Particle Size Controller 4: C.I. Pigment Black 31 (a compound in which R3 and R4 are phenethyl groups in General Formula (2)) Particle Size Controller 5: C.I. Pigment Black 32 (a compound in which R3 and R4 are 4-methoxybenzyl groups in General Formula (2)) Particle Size Controller 6: N-methyl-1,8-naphthalimide (a compound in which X is an N-methylimino group in General Formula (3)) Particle Size Controller 7: 1,8-naphthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.) (a compound in which X is an imino group in General Formula (3)) Particle Size Controller 8: 1,8-naphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (a compound in which X is an oxygen atom in General Formula (3)) Particle Size Controller 9: A compound represented by the following Structural Formula (7) (a compound belonging to the above General Formula (4))

[0072]

Chemical Structure

[0073] Particle Size Controller 10: A compound represented by the following Structural Formula (8) (a compound belonging to the above General Formula (4))

[0074]

Chemical Structure

[0075] <Particle Size Controller (not Particle Size Controller (B)) (for comparison)> Particle size control agent 11: A compound represented by the following structural formula (9) (a compound corresponding to general formula (33) disclosed in International Publication No. 2019 / 065359)

[0076] [Chemical formula]

[0077] [Carboxylic acid (C)] Lauric acid: A saturated fatty acid with 12 carbon atoms and a molecular weight of 200 Oleic acid: An unsaturated fatty acid with 18 carbon atoms and a molecular weight of 282 Dodecanedioic acid: 1,10 - Decanedicarboxylic acid, with a molecular weight of 230 Dimer acid 1: Tsuno Dimer 216 manufactured by Tsuno Oleochemicals Co., Ltd. (C18 monomer acid: C36 dimer acid: C54 trimer acid = 4% or less: 76% or more: 20% or less), a mixture of compounds with molecular weights of approximately 282, approximately 560, and approximately 839 Dimer acid 2: Tsuno Dimer 228 manufactured by Tsuno Oleochemicals Co., Ltd. (C18 monomer acid: C36 dimer acid: C54 trimer acid = 3% or less: 77% or more: 20% or less), a mixture of compounds with molecular weights of approximately 282, approximately 560, and approximately 839 Disproportionated rosin: Longis R-CH manufactured by Arakawa Chemical Industries, with a molecular weight of approximately 300 Polymerized rosin: Aradime R-95 manufactured by Arakawa Chemical Industries, with a molecular weight of approximately 600

[0078] [Resin] Dianal BR-605: A methacrylic resin manufactured by Mitsubishi Chemical Corporation JONCRYL 586: A styrene acrylic resin manufactured by BASF

[0079] [Measurement of average primary particle size] The average primary particle size of the pigment compositions in the examples and comparative examples was determined as follows by observation with a transmission electron microscope (TEM). For 50 primary particles of the pigment composition arbitrarily selected from a plurality of photographs taken at a magnification of 10,000 times with a transmission electron microscope, when the particles were sandwiched between two parallel straight lines in contact with the image of the particles, the interval when the distance between the parallel lines was the largest was taken as the major axis, and the average value of the major axes was taken as the average primary particle size.

[0080] [Preparation of perylene pigment (A)] (Production Example 1) Production of perylene pigment 1 Perylene pigment 1 was produced with reference to Synthesis Example 1 of U.S. Patent No. 5,853,933. 3.92 parts of 3,4,9,10 - perylenetetracarboxylic dianhydride were added to 200 parts of 1 - methyl - 2 - pyrrolidone, and 5.9 parts of 1 - aminopropane were added. Then, while stirring the mixture, it was heated to 202 °C and refluxed for 40 minutes. Thereafter, it was cooled to 150 °C, filtered, and washed 4 times with 50 parts of dimethylformamide heated to 100 °C. Further, it was washed with 25 parts of dimethylformamide at 25 °C and washed 3 times with 20 parts of methanol, and the residue was dried at 60 °C for 6 hours to obtain 4.1 parts of perylene pigment 1.

[0081] (Production Example 2) Production of perylene pigment 2 Perylene pigment 2 was obtained in the same manner as in Production Example 1, except that 5.9 parts of 1 - aminopropane was changed to 8.7 parts of 1 - aminopentane.

[0082] [Preparation of particle size control agent (B)] (Production Example 3) Production of particle size control agent 6 5 parts of 1,8 - naphthalic anhydride were added to 50 parts of ethanol, and 3 parts of methylamine (40% methanol solution) were added 3 times at 1 - hour intervals while stirring at 25 °C. Then, the solution was heated until refluxing, and stirred at that temperature for 1 hour. After cooling to 25 °C, it was filtered, washed with ethanol, and the residue was dried at 80 °C for 4 hours to obtain 4.9 parts of particle size control agent 6.

[0083] (Production Example 4) Production of particle size control agent 9 Particle size control agent 9 was produced with reference to Production Example 3 of JP - A - 60 - 88185. 19 parts of cyanuric chloride, 15 parts of p-aminoacetanilide, and 11 parts of sodium carbonate as a hydrogen chloride scavenger were added to a mixed solvent of 200 parts of acetone and 100 parts of water, and the mixture was stirred at 30 to 40 °C for 1 hour. Then, 30 parts of N,N-diethylaminopropylamine was added dropwise at the same temperature, and the mixture was stirred at 50 to 60 °C for 3 hours. After completion of the reaction, the reaction solvent was distilled off under reduced pressure, 300 parts of 1% hydrochloric acid was added, and the mixture was stirred at 90 to 100 °C for 1 hour. The reaction solution was cooled, sodium hydroxide was added, and the pH was adjusted to 9 to 10 to obtain 40 parts of a base. 22 parts of this base was added to 200 parts of methanol, and 30 parts of hydrochloric acid was added under ice cooling. 7.6 parts of a 40% aqueous sodium nitrite solution was added thereto to obtain a diazonium salt solution. Separately, a coupling component solution consisting of 12 parts of 5-acetylamino-benzimidazolone, 520 parts of methanol, 1050 parts of water, and 22 parts of sodium carbonate was prepared, and the diazonium salt solution obtained above was added thereto to cause a coupling reaction. During the reaction, sodium carbonate was appropriately added so that the pH became 9 to 10. By performing filtration, washing with water, drying at 80 °C, and pulverization, a particle size control agent 9 was obtained.

[0084] (Production Example 5) Production of Particle Size Control Agent 10 The particle size control agent 10 was produced with reference to Synthesis Example 2 of JP-A-2000-239554. (1) 50 parts of dimethyl 5-nitroisophthalate and 130 parts of N,N-diethyl-1,3-propanediamine were reacted at 80 to 100 °C for about 4 hours while weakly reducing the pressure. After confirming the disappearance of the starting dimethyl 5-nitroisophthalate and the monoamide compound, the excess N,N-diethyl-1,3-propanediamine was removed under reduced pressure to obtain 92 parts of 5-nitroisophthalic acid bis-3-diethylaminopropylamide. (2) 18.5 parts of the obtained 5-nitroisophthalic acid bis-3-diethylaminopropylamide and 5.1 parts of triethylamine were dissolved in 60 parts of dimethylformamide and cooled with ice. To this, a solution of 9.3 parts of 4-nitrobenzoyl chloride in 60 parts of acetone was added to cause an amidation reaction. After the reaction, 800 parts of water was added, the crystals were collected by filtration, and recrystallized from ethyl acetate to obtain 14 parts of 4-nitrobenzoyl-4-[3,5-bis(3-diethylaminopropylcarbamoyl)]phenylamide. (3) The 14 parts of the obtained amide were refluxed and reduced together with 18 parts of reduced iron and 2 parts of ammonium chloride in 31 parts of 2-propanol and 6 parts of water to obtain 13.2 parts of an aniline derivative. (4) 13.2 parts of the obtained aniline derivative was added to 120 parts of methanol, and 18 parts of hydrochloric acid was added under ice cooling. The mixture was further cooled to -15°C. An aqueous solution (20 parts of water) of 1.8 parts of sodium nitrite was added dropwise thereto for diazotization (preparation of a diazonium salt solution). Separately, a coupling component solution consisting of 5.9 parts of 5-acetylacetylaminobenzimidazolone, 260 parts of methanol, 530 parts of water, and 10.8 parts of sodium carbonate was prepared and cooled to 10°C or lower. The diazonium salt solution obtained above was added dropwise thereto while maintaining the temperature at 10°C or lower for reaction. Potassium carbonate was added to make the entire reaction system basic, and the precipitated product was collected by filtration and recrystallized with dimethylformamide and acetonitrile to obtain 19 parts of the particle size controller 10.

[0085] [Preparation of Particle Size Controller (Comparison)] (Production Example 6) Production of Particle Size Controller 11 The particle size controller 11 was produced with reference to International Publication No. 2019 / 065359. Perylene-3,4-dicarboximide was dissolved in 105% sulfuric acid prepared by mixing fuming sulfuric acid and 98% sulfuric acid, and stirred at 70°C for 3 hours. Thereafter, the obtained red solid precipitated by pouring the sulfuric acid solution into 100 mass times of ice water with respect to perylene-3,4-dicarboximide was washed with water and filtered, further washed with acetone, and then dried, and a dry grinding treatment was performed to obtain the particle size controller 11.

[0086] <1> Production of Pigment Composition (Example 1) Production of Pigment Composition 1 As the perylene pigment (A), 138.0 parts of PR179 and 4.5 parts of PV29, as the particle size control agent (B), 7.5 parts of particle size control agent 1, as the carboxylic acid (C), 3.6 parts of lauric acid, 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. After this mixture was poured into 9000 parts of water, it was stirred with a high-speed mixer for 2 hours to form a slurry, and filtration and washing with water were repeated 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 with a hammer mill to obtain Pigment Composition 1.

[0087] (Examples 2 to 15) Production of Pigment Compositions 2 to 15 and (Comparative Examples 1 to 8) Production of Pigment Compositions 101 to 108 Except that the types and blending amounts of the perylene pigment (A), particle size control agent (B), and carboxylic acid (C) used in Example 1 were changed as shown in Table 1, Pigment Compositions 2 to 15 and 101 to 108 were obtained in the same manner as in Example 1.

[0088] (Example 16) Production of Pigment Composition 16 Except that the types and blending amounts of the perylene pigment (A), particle size control agent (B), and carboxylic acid (C) used in Example 1 were changed as shown in Table 1, and further, 15 parts of Dianal BR-605 (methacrylic resin manufactured by Mitsubishi Chemical Corporation) as the resin was added 5 hours after the start of kneading, Pigment Composition 16 was obtained in the same manner as in Example 1.

[0089] (Example 17) Production of Pigment Composition 17 Except that 15 parts of Dianal BR-605 used in Example 16 was changed to 15 parts of JONCRYL 586 (styrene acrylic resin manufactured by BASF), Pigment Composition 17 was obtained in the same manner as in Example 16.

[0090] For the pigment compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 8, the average primary particle diameter was determined based on the above method. The results are shown in Table 1. In Table 1, the "composition ratio" means the content of perylene pigment (A), particle size control agent (B), and carboxylic acid (C) in a total of 100% by mass of perylene pigment (A), particle size control agent (B), and carboxylic acid (C).

[0091]

Table 1

[0092]

Table 1

[0093]

Table 1

[0094] <2>Manufacture and Evaluation of Paint The following relates to specific examples of paints containing pigment compositions. <Grouping of Evaluations> Depending on its structure, the perylene pigment (A) has different wavelengths of light absorbed and transmitted, and differences in coloring power, clarity, and transparency are also observed. Therefore, since it is not possible to compare the coloring power, clarity, and transparency between perylene pigments (A) with different structures, the pigment compositions in which the main component in the pigment composition is the same perylene pigment (A) were grouped and evaluated so as to compare the coloring power, clarity, and transparency. Also, regarding the brilliance and weather resistance, evaluations were similarly made by grouping based on the main component of the perylene pigment (A). Specifically, the four pigment compositions whose main components are PR179, PV29, perylene pigment 1, and perylene pigment 2 were grouped, and the evaluation serving as a reference in each evaluation item was set to "1" and evaluated according to relative superiority and inferiority. The evaluation groups and the numbers of the comparative examples serving as references are as described in each table.

[0095] Preparation and Evaluation of Dark-colored Paints (A1) Preparation of Dark-colored Paints (Example A-1) Preparation of Dark-colored Paint a-1 9 parts of Pigment Composition 1, 7.7 parts of acrylic resin (manufactured by DIC Corporation, Acrylic 47-712) 40.7 parts of dispersion medium (mixed solvent of toluene:xylene:butyl acetate:ENEOS Corporation's T-SOL150FLUID with a mass ratio of 3:3:2:2) The above materials and 230 parts of steel beads were charged into a glass container that could be sealed, sealed, and dispersed for 60 minutes using a paint shaker manufactured by Red Devil. Furthermore, 75.4 parts of Acrylic 47-712 and 17.2 parts of melamine resin (Amidia L-117-60 manufactured by DIC Corporation) were added and dispersed for an additional 10 minutes. Then, the steel beads were removed to obtain dark-colored paint a-1 containing Pigment Composition 1.

[0096] (Examples A-2 to A-17, Comparative Examples A-1 to A-8) Preparation of Dark-colored Paints a-2 to a-17, a-101 to a-108 Except that the Pigment Composition 1 of Example A-1 was changed as shown in Table 2, the same procedure as in Example A-1 was carried out to obtain dark-colored paints a-2 to a-17, a-101 to a-108.

[0097] (A2) Evaluation of Dark-colored Paints <Initial Viscosity and Viscosity over Time The obtained dark-colored paint was put into a glass bottle that could be sealed, sealed, immersed in a constant-temperature bath at 25°C for 1 hour to make the temperature constant, and the viscosity (referred to as "initial viscosity") at a rotational speed of 6 rpm at 25°C was measured using a B-type viscometer (BII-type viscometer manufactured by Toki Sangyo Co., Ltd.). Also, after storage at 40°C for 1 week, the viscosity measurement was carried out again in the same manner (referred to as "viscosity over time"). The results are shown in Table 2. If it is "4", "3", or "2" according to the following evaluation criteria, it is at a practical level.

[0098] (Evaluation Criteria for Initial Viscosity and Viscosity over Time) 4: The viscosity is less than 4000 mPa·s, extremely good. 3: The viscosity is 4000 mPa·s or more and less than 10000 mPa·s, good. 2: It can be used when the viscosity is 10,000 mPa·s or more and less than 13,000 mPa·s. 1: It is defective when the viscosity is 13,000 mPa·s or more or it has gelled.

[0099]

Table 2

[0100] Preparation and Evaluation of Color Clear Coated Boards (B1) Preparation of Top Coat Clear Paint 120 parts of acrylic resin (manufactured by DIC Corporation, Acrylic 44 - 179) 30 parts of melamine resin (manufactured by DIC Corporation, Amidia L117 - 60) 50 parts of diluting solvent (mixed solvent consisting of toluene:xylene:ENEOS Corporation's T - SOL150FLUID:ethyl 3 - ethoxypropionate:ethyl acetate with a mass ratio of 3:2:2:1:2) The above materials were stirred and mixed with a high - speed stirrer to obtain a top coat clear paint.

[0101] (B2) Preparation of Color Clear Coated Boards (Example B - 1) Preparation of Color Clear Coated Board b - 1 1 part of the dark paint a - 1 prepared in Example A - 1 and 9 parts of the top coat clear paint were mixed to prepare a color clear paint b´ - 1. This color clear paint was sprayed onto a stainless steel plate with a mirror finish using a spray gun. To adjust the viscosity for easy spraying, a diluting solvent (mixed solvent consisting of toluene:xylene:ENEOS Corporation's T - SOL150FLUID:ethyl 3 - ethoxypropionate:ethyl acetate with a mass ratio of 3:2:2:1:2) was appropriately mixed at a rate of 10 - 20% by mass based on the color clear paint. The coating was carried out in 9 steps, and then the top coat clear paint was sprayed in 6 steps. After drying at 25°C for 1 hour, it was dried at 140°C for 30 minutes to obtain a color clear coated board b - 1 as the coated object.

[0102] (Examples B - 2 to B - 17, Comparative Examples B - 1 to B - 8) Preparation of Color Clear Coated Boards b - 2 to b - 17, b - 101 to b - 108 The same procedure as in Example B - 1 was carried out except that the dark paint a - 1 in Example B - 1 was changed as shown in Table 3 to obtain color clear paints b´ - 2 to b´ - 17, b´ - 101 to b´ - 108, and color clear coated boards b - 2 to b - 17, b - 101 to b - 108.

[0103] (B3) Evaluation of Color Clear Coated Panels <Color Strength> The color clear coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 3. If the evaluation results are "4", "3", or "2" according to the following criteria, it is a practical level. (Evaluation Criteria for Color Strength) 4: The color strength is extremely higher than that of the reference coated panel 3: The color strength is higher than that of the reference coated panel 2: The color strength is slightly higher than that of the reference coated panel 1: The color strength is equivalent to that of the reference coated panel

[0104] <Clarity> The color clear coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 3. If the evaluation results are "4", "3", or "2" according to the following criteria, it is a practical level. (Evaluation Criteria for Clarity) 4: The clarity is extremely higher than that of the reference coated panel 3: The clarity is higher than that of the reference coated panel 2: The clarity is slightly higher than that of the reference coated panel 1: The clarity is equivalent to or lower than that of the reference coated panel

[0105] <Transparency> The color clear coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 3. If the evaluation results are "4", "3", or "2" according to the following criteria, it is a practical level. (Evaluation Criteria for Transparency) 4: The transparency is extremely higher than that of the reference coated panel, and the metallic luster of the substrate is extremely strong 3: The transparency is higher than that of the reference coated panel, and the metallic luster of the substrate is strong 2: The transparency is slightly higher than that of the reference coated panel, and the metallic luster of the substrate is slightly strong 1: The transparency is equivalent to or lower than that of the reference coated panel, and the metallic luster of the substrate is also equivalent to or weak

[0106]

Table 3

[0107] <c>Fabrication and Evaluation of Metallic Coated Sheets (C1) Preparation of Metallic Base Paint 10 parts of aluminum flake paste (Alpaste 1700NL manufactured by Toyo Aluminum Co., Ltd.) 10 parts of aluminum flake paste (Alpaste HS-2 manufactured by Toyo Aluminum Co., Ltd.) 101.7 parts of acrylic resin (Acrylic 47-712 manufactured by DIC Corporation) 21.3 parts of melamine resin (Amidia L-117-60 manufactured by DIC Corporation) 20.9 parts of dispersion solvent (mixed solvent of toluene:xylene:butyl acetate:T-SOL150FLUID manufactured by ENEOS Corporation with a mass ratio of 3:3:2:2) The above materials were stirred and mixed with a high-speed stirrer to obtain a metallic base paint.

[0108] (C2) Fabrication of Metallic Coated Sheet c-1 20 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 with a high-speed stirrer to obtain a metallic paint c'-1. This metallic paint was sprayed onto a steel sheet using a spray gun. To adjust the viscosity for easy spraying, a dilution solvent (mixed solvent of toluene, xylene, T-SOL150FLUID manufactured by ENEOS Corporation, ethyl 3-ethoxypropionate, and ethyl acetate with a mass ratio of 3:2:2:1:2) was appropriately mixed with the metallic paint based on the same mass. The coating was performed in 9 steps, and then the topcoat clear paint was sprayed in 6 steps. After drying at 25°C for 1 hour, it was dried at 140°C for 30 minutes to obtain a metallic coated sheet c-1.

[0109] (Examples C-2 to C-17, Comparative Examples C-1 to C-8) Preparation of Metallic Coated Sheets c-2 to c-17, c-101 to c-108 Except that the dark-colored paint a-1 of Example C-1 was changed as shown in Table 4, the same procedure as in Example C-1 was carried out to obtain metallic paints c'-2 to c'-17, c'-101 to c'-108, and color clear coated sheets c-2 to c-17, c-101 to c-108.

[0110] (C3) Evaluation of Metallic Coated Boards <Clarity The metallic coated boards were visually observed and evaluated according to the following criteria. The results are shown in Table 4. If the evaluation result is "4", "3" or "2" according to the following criteria, it is at a practical level. (Evaluation Criteria for Clarity) 4: The clarity is extremely higher than that of the reference coated board 3: The clarity is higher than that of the reference coated board 2: The clarity is slightly higher than that of the reference coated board 1: The clarity is equal to or lower than that of the reference coated board

[0111] <Gloss The metallic coated boards were visually observed and evaluated according to the following criteria. The results are shown in Table 4. If the evaluation result is "4", "3" or "2" according to the following criteria, it is at a practical level. (Evaluation Criteria for Gloss) 4: The gloss is extremely higher than that of the reference coated board 3: The gloss is higher than that of the reference coated board 2: The gloss is slightly higher than that of the reference coated board 1: The gloss is equal to or lower than that of the reference coated board

[0112] <Weather Resistance For the weather resistance test, an ultra-accelerated weather resistance tester (manufactured by Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151) was used, and the test was conducted under the conditions of 90 mW / cm 2 , 96 hours (12 hours of day and night, 4 cycles), and the color difference before and after the weather resistance test was visually evaluated. The results are shown in Table 4. If the evaluation result is "3" or "2" according to the following criteria, it is at a practical level. (Evaluation Criteria for Light Resistance) 3: The change in color before and after the test is extremely small and extremely good compared to the reference coated board 2: The change in color before and after the test is small and good compared to the reference coated board 1: The change in color before and after the test is equal to or larger than that of the reference coated board, poor

[0113]

Table 4

[0114] In Comparative Example 1 and the paint and coated board using the same, since the particle size control agent (B) was not included, a paint and a coated board having desired sharpness, transparency, and glossiness could not be obtained. In Comparative Examples 2, 4, 6, and 8 and the paints and coated boards using the same, the sharpness decreased due to the inclusion of the particle size control agent 11 which is a red pigment derivative, and a paint having the desired sharpness could not be obtained. Further, the weather resistance decreased due to the inclusion of the particle size control agent 11, and a coated board having excellent weather resistance could not be obtained. In Comparative Examples 3, 5, 7 and the paints and coated boards using the same, since the particle size control agent (B) and the carboxylic acid (C) were not included, a paint and a coated board having desired sharpness, transparency, and glossiness could not be obtained, and the viscosity stability of the paint was also insufficient. The paint using the pigment composition of the present invention is excellent in viscosity stability, highly sharp and highly transparent, and excellent metallic luster and glossiness can be obtained when coating a metal plate or when using a brightening material in combination. There is little discoloration even during long-term use outdoors, and it is suitable for coating vehicle exteriors and outdoor buildings.< / c>

Claims

1. A pigment composition comprising a perylene pigment (A), a particle size control agent (B), and a carboxylic acid (C), wherein the perylene pigment (A) is a perylene pigment having a structure represented by the following general formula (1); the particle size control agent (B) is a compound having three or more 5-membered or 6-membered rings, at least one of which is a heterocyclic ring among the 5-membered and 6-membered rings; the carboxylic acid (C) is a carboxylic acid having a molecular weight of 100 or more and 1000 or less; in 100% by mass of the total of the perylene pigment (A), the particle size control agent (B), and the carboxylic acid (C), the perylene pigment (A) is 70% by mass or more, the particle size control agent (B) is 0.1% by mass or more and 20% by mass or less, and the carboxylic acid (C) is 0.5% by mass or more and 20% by mass or less. A pigment composition. However, the particle size control agent (B) excludes perylene compounds having a sulfo group or an amino group and the perylene pigment (A). 【Chemical 1】 [In the general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group.]

2. The pigment composition according to claim 1, wherein the particle size control agent (B) is a compound having a structure represented by the following general formula (2), general formula (3), or general formula (4). 【Chemical 2】 [In the general formula (2), R3 and R4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. However, R3 and R4 do not form a combination of groups selected from the group consisting of a hydrogen atom and an alkyl group.] 【Chemical Formula 3】 [In the general formula (3), X represents an oxygen atom or NR5. R5 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.] 【Chemical Formula 4】 [In the general formula (4), R6 represents a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, a carboxy group, an amino group which may have a substituent, an amide group which may have a substituent, or a sulfo group.]

3. The pigment composition according to claim 1, wherein the carboxylic acid (C) is an aliphatic carboxylic acid having 8 to 54 carbon atoms and having 1 to 3 carboxy groups.

4. The pigment composition according to claim 1, further comprising a resin.

5. The pigment composition according to claim 1, further comprising a brightening material.

6. A method for producing a pigment composition according to any one of claims 1 to 4, comprising a step of kneading a mixture containing a perylene pigment (A), a particle size control agent (B), and a carboxylic acid (C).

7. A paint comprising the pigment composition according to any one of claims 1 to 5 and a dispersion medium.

8. A coated article having a coating film of the paint according to claim 7.

9. The coated article according to claim 8, which is an exterior vehicle part.

Images