Pigment composition and method for producing the same, coating and coated article

Abstract

To provide a pigment composition excellent in transparency that exhibits a red hue with a bluish hue, the pigment composition with viscosity stability, suppressing occurrence of color separation when made into a coating, and the pigment composition excellent in hue, clarity, brightening and weather resistance, reducing color separation and color shading when made into a coating film.SOLUTION: A pigment composition is a solid solution containing C.I. Pigment Red 179 and C.I. Pigment Violet 29, with an average value of major axis / minor axis, which is a ratio between major and minor axes of primary particles, of 1 or more and 3 or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a pigment composition and its production, a paint and a coated article. [Background technology]

[0002] In the field of industrial products such as automobile coatings, a variety of colors and designs according to the preferences of users and the like are required. For example, CI Pigment Red 179, which is a perylene pigment, is used as a pigment that exhibits a deep red hue. For example, Patent Document 1 discloses an example of a paint containing a metallic pigment and CI Pigment Red 179. In addition, Patent Document 2 discloses a multi-layer coating film in which a color clear coating film containing a color pigment is laminated on a coating film containing a glittering material and / or a color pigment. In this multi-layer coating film, the color and / or reflected light of the coating film in the lower layer can be visually recognized through the color clear coating film provided on the upper layer, resulting in a multi-layer coating film with excellent color depth. For example, a coating film in which a color clear coating film containing a color pigment is laminated on a metallic base coating film containing a glittering material is called a so-called "candy color" coating film, and is known in the field of vehicle exterior products and the like as a multi-layer coating film with high designability excellent in high saturation, high brightness, and color depth. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2012-067271 A [Patent Document 2] JP 2007-167720 A [Patent Document 3] Special Publication No. 45-033552 Summary of the Invention [Problem to be solved by the invention]

[0004] As one of the color trends in the field of industrial products in recent years, there is an increasing need for a red hue that is even bluish than CI Pigment Red 179. CI Pigment Violet 29 is known as a perylene pigment that is bluer than CI Pigment Red 179. As disclosed in Patent Document 3, these two pigments are known to form a solid solution under certain conditions. However, the solid solution of CI Pigment Red 179 and CI Pigment Violet 29 disclosed in Patent Document 3 has poor transparency in fields where transparency is required, such as when used in combination with paints that are applied in multiple layers or with glittering materials, and there is a problem that color unevenness occurs when used in combination with glittering materials. In addition, the solid solution produced by the method described in Patent Document 3 is more yellowish than CI Pigment Red 179 alone, and there is also a problem that it cannot meet the recent color trend demand of bluish high transparency. In addition, CI Pigment Violet 29 has a problem in that it has low viscosity stability when made into a dispersion such as a paint, and when CI Pigment Violet 29 is added to a dispersion containing CI Pigment Red 179 in order to enhance the blue color, there is a problem in that the viscosity stability of the dispersion is reduced.

[0005] The problem to be solved by the present invention is to provide a pigment composition which has excellent transparency and exhibits a bluish red hue, and which, when made into a paint, has excellent viscosity stability and inhibits the occurrence of color separation, and which, when made into a coating film, has excellent hue, clarity, brilliance, and weather resistance and exhibits little color separation or color unevenness. [Means for solving the problem]

[0006] In view of the above circumstances, the present inventors conducted extensive research and found that various properties can be improved by setting a specific combination of perylene pigments and particle shapes within specific ranges, and thus completed the present invention. That is, the present invention includes the following embodiments. The embodiments of the present invention are not limited to the following.

[0007] That is, one embodiment of the present invention is a pigment composition that is a solid solution containing CI Pigment Red 179 and CI Pigment Violet 29, and has an average major axis / minor axis ratio, which is the ratio of the major axis to the minor axis of the primary particles, of 1 or more and 3 or less.

[0008] Another embodiment of the present invention is the above pigment composition, in which the half-value width of a peak in the 2θ range of 24.5° or more and 26.0° or less in a powder X-ray diffraction spectrum represented by diffraction intensity versus diffraction angle 2θ measured using CuKα radiation is 0.1 or more and 0.6 or less.

[0009] Another embodiment of the present invention is the above pigment composition, in which the mass ratio of CI Pigment Red 179 to CI Pigment Violet 29 is 99.5:0.5 to 70:30.

[0010] Another embodiment of the present invention is the above pigment composition, which, after being completely dissolved in 98% sulfuric acid, exhibits a mass change rate of 2% by mass or less when precipitated with water.

[0011] Another embodiment of the present invention is the above pigment composition further comprising rosin.

[0012] Another embodiment of the present invention is the above pigment composition further comprising a resin.

[0013] Another embodiment of the present invention is the above pigment composition further comprising a luster material.

[0014] Another embodiment of the present invention is a method for producing the above pigment composition, comprising the step of kneading a mixture containing CI Pigment Red 179 and CI Pigment Violet 29.

[0015] Moreover, an embodiment of the present invention is a method for producing the above pigment composition, further comprising a step of dissolving a mixture containing CI Pigment Red 179 and CI Pigment Violet 29 in a solvent and then precipitating the mixture.

[0016] Another embodiment of the present invention is a paint comprising the above pigment composition and a dispersion medium.

[0017] Another embodiment of the present invention is a coated article having a coating film of the above-mentioned paint.

[0018] Another embodiment of the present invention is the above-mentioned coated article which is an exterior part of a vehicle. Effect of the Invention

[0019] According to the present invention, it is possible to provide a pigment composition having excellent transparency and exhibiting a bluish red hue, and a method for producing the same. In addition, by using the pigment composition, it is possible to provide a coating material having excellent viscosity stability and suppressed color separation, and a coated article having a coating film having excellent hue, clarity, brilliance, and weather resistance and having little color separation and color unevenness. [Brief description of the drawings]

[0020] [Figure 1] FIG. 2 is a schematic diagram for calculating the half-value width in the X-ray diffraction spectrum of a pigment composition. [Diagram 2] 1 is an X-ray diffraction spectrum of the pigment composition obtained in Example 2. [Diagram 3] 1 is an X-ray diffraction spectrum of the pigment composition obtained in Comparative Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Hereinafter, the embodiments of the present invention will be described in more detail. However, the present invention is not limited to the following embodiments, and may be modified in various ways without departing from the spirit and scope of the present invention, and various embodiments are included. The terms used in this specification are explained below. "CI" stands for Color Index number. "Colorant dispersion" is a liquid containing a pigment or pigment composition, a resin, and a dispersion medium, and may be simply described as "dispersion." "Coated material" is treated as synonymous with "printed material," "image-formed material," and "painted material."

[0022] <1> Pigment Composition One embodiment of the present invention relates to a pigment composition that is a solid solution containing CI Pigment Red 179 (hereinafter sometimes referred to as PR179) and CI Pigment Violet 29 (hereinafter sometimes referred to as PV29). PR179 is a compound represented by the following general formula (1) in which R1 and R2 are methyl groups, and PV29 is a compound represented by the following general formula (1) in which R1 and R2 are hydrogen.

[0023] [ka]

[0024] A solid solution is a homogeneous solid phase in which two or more components (molecules, elements, etc.) are contained in the same crystal lattice. A solid solution can be clearly distinguished from a physical mixture of the components by powder X-ray diffraction. In a physical mixture, the powder X-ray diffraction spectrum characteristic of each component is identified, and the diffraction spectrum of the mixture is observed as the sum of the diffraction spectra of each component. However, the powder X-ray diffraction spectrum of a solid solution is clearly different from the diffraction spectrum of the sum of the components, and some of the X-ray diffraction peaks in each component may disappear. In addition, if the crystal lattice of the solid solution is different from that of each component, new X-ray diffraction peaks will appear.

[0025] The powder X-ray diffraction peak of the pigment composition of the present invention has no peak derived from PV29. Specifically, the powder X-ray diffraction spectrum of the pigment composition of the present invention, which is shown by the diffraction intensity versus diffraction angle 2θ measured by CuKα radiation, shows a spectrum in which at least one of the peaks characteristic of PV29 at 2θ=15.9-16.5°, 21.1-21.7°, 26.7-27.3°, and 29.9-30.5° does not exist. Since the pigment composition does not show the peak derived from PV29, it is considered that the molecules of PV29 are incorporated into the crystals of PR179, and it is considered that the problem of poor viscosity stability when made into a dispersion caused by PV29 and the so-called "color separation" in which the pigment aggregates and separates according to structure in the paint can be solved.

[0026] The pigment composition of the present invention is characterized in that the average value of the long diameter / short diameter, which is the ratio of the long diameter to the short diameter of the primary particles (hereinafter sometimes referred to as the "aspect ratio"), is 1 to 3. The aspect ratio is preferably 1 to 2.5, more preferably 1 to 2. If the aspect ratio is 1 to 3, the particle shape of the pigment composition is close to a sphere and the distance between each particle is uniform, so that it is considered that aggregation between particles can be suppressed. By having the aspect ratio in the above range, it is possible to suppress thickening caused by aggregation between particles during long-term storage of the paint and color unevenness caused by the orientation of particles from coating to drying. It is not necessary for the aspect ratio of all particles to be in the above range, and it is sufficient that the average value of the ratio of the long diameter to the short diameter is within the above range.

[0027] The average value of the major axis 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 is preferably 5 nm or more from the viewpoint of ease of pigment dispersion. A more preferred average primary particle diameter is 10 nm or more and 150 nm or less, and even more preferably 20 nm or more and 120 nm or less. Details of the method for measuring the major axis and minor axis of the primary particles and the method for calculating the average value are shown in the Examples.

[0028] In one embodiment, the pigment composition of the present invention has a powder X-ray diffraction spectrum represented by a diffraction intensity versus diffraction angle 2θ measured using CuKα radiation, The peak showing the maximum diffraction intensity in the range of 2θ from 24.5° to 26.0° is designated as A, 2θ at A is Ax, The point B shows the minimum diffraction intensity when 2θ is within the range of Ax or less and Ax-1.5° or more. The point showing the minimum diffraction intensity within the range of 2θ from Ax to Ax+1.5° is designated as C. The line connecting B and C is the baseline. The intersection point of the perpendicular line drawn from A to the 2θ axis and the baseline is D. The intersection point of the line that passes through the midpoints of A and D and is parallel to the baseline, is E, F is the intersection point of the line that passes through the midpoints of A and D and is parallel to the baseline, and the curve AC. 2θ at E is Ex, 2θ at F is Fx, When Fx-Ex is the half width of A, The half width of A is preferably 0.1 or more and 0.6 or less, and more preferably 0.25 or more and 0.55 or less.

[0029] In addition, the smaller the half-width, the larger the crystallites in the particles of the pigment composition, indicating that the molecules constituting the pigment composition are regularly arranged, and it is expected that the light fastness, solvent resistance, and viscosity stability of the dispersion will be improved. The larger the half-width, the smaller the crystallites in the particles of the pigment composition, indicating that the molecules constituting the pigment composition are irregularly arranged. By having the half-width of the peak of the powder X-ray diffraction spectrum within the above range, it is possible to obtain a pigment composition that is bluish, highly vivid, and highly transparent, and has high viscosity stability when used as a paint and high color separation stability when used as a paint, and a coating film that is highly weather resistant when used as a coating material.

[0030] In one embodiment, the ratio of PR179 to PV29 in the pigment composition of the present invention is preferably in the range of 99.5:0.5 to 70:30 by mass, more preferably 99:1 to 80:20, from the viewpoint of blueness of the hue and dispersion stability of the pigment composition. By setting the ratio within the above range, it is possible to obtain a pigment composition having a bluish hue and having high dispersion stability when used as a paint.

[0031] The pigment composition of the present invention may contain pigments other than PR179 and PV29 (sometimes referred to as "heterogeneous pigments" in this specification) within the scope of not impairing the effects of the present invention. Examples of the heterogeneous pigments include pigments having a perylene skeleton, a diketopyrrolopyrrole skeleton, or a quinacridone skeleton. Suitable examples of pigments having a perylene skeleton include CI Pigment Red 123, 149, 178, 190, Pigment Violet 31, 33, etc. Examples of pigments having a diketopyrrolopyrrole skeleton include CI Pigment Red 254, 264, etc. Examples of pigments having a quinacridone skeleton include CI Pigment Red 122, 192, 202, 209, CI Pigment Violet 19, etc. These heterogeneous pigments are expected to improve transparency in addition to adjusting color tone.

[0032] In one embodiment, the pigment composition of the present invention is preferably completely dissolved in 98% sulfuric acid, and then precipitated with water, with a mass change rate (hereinafter sometimes referred to as "sulfuric acid elution component rate") of 2% by mass or less. In this specification, 98% sulfuric acid means 98% by mass sulfuric acid. By adjusting the sulfuric acid elution component rate to 2% by mass or less, it is possible to reduce unreacted organic impurities and the like eluted in the solvent dispersion, and it is possible to obtain a pigment composition with high dispersion stability. The method for adjusting the sulfuric acid elution component rate of the pigment composition to 2% by mass or less can be a known washing or purification method, and is not particularly limited. The sulfuric acid elution component rate can be adjusted to 2% by mass or less by dissolving the pigment composition in a good solvent such as sulfuric acid or polyphosphoric acid and releasing it into a poor solvent such as water to recrystallize it, washing with an organic solvent such as methanol, acetone, dimethyl sulfoxide, or N-methylpyrrolidone, or a basic solution such as an aqueous sodium hydroxide solution, or a combination of a plurality of these methods.

[0033] In one embodiment, the pigment composition of the present invention may contain rosin. As the rosin, generally used rosin and rosin derivatives can be suitably used. For example, disproportionated rosin, hydrogenated rosin, fumarated rosin, maleated rosin, ester gum, polymerized rosin, rosin ester, etc. can be mentioned. In particular, disproportionated rosin, hydrogenated rosin, and polymerized rosin are preferred. These may be used alone or in combination. As a method for adding rosin, a solution of rosin dissolved in an aqueous solution of a metal hydroxide salt such as sodium hydroxide may be added to the aqueous slurry of the pigment composition, an emulsion of rosin using an organic solvent such as xylene may be added to the aqueous slurry of the pigment composition, or rosin acid 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 rosin during mechanical kneading is preferred because it can be uniformly treated on the surface of the pigment composition. The rosin used during mechanical kneading preferably has a softening point of 100° C. or less. The amount of rosin added is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, relative to 100 parts by mass of the total of PR179 and PV29.

[0034] In one embodiment, the pigment composition of the present invention may contain a resin. In this specification, the term "resin" refers to a resin other than rosin. Any resin that is used in general paints can be used, and for example, acrylic resin, methacrylic resin, and polyester resin can be preferably used. The resin preferably has a hydroxyl group and / or a carboxyl group. Examples of resins that can be used include the Dianale series (manufactured by Mitsubishi Chemical), the JONCRYL series (manufactured by BASF), and the DEGALAN series (manufactured by Evonik Industries). Specifically, Dianal BR-605, Dianal MB-7922, Dianal 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), and the like can be used.

[0035] The resin may be used alone or in combination. The resin may be added by dissolving it in an aqueous solution of a metal hydroxide such as sodium hydroxide and adding it to the aqueous slurry of the pigment composition, or by forming an emulsion using an organic solvent such as xylene and adding it to the aqueous slurry of the pigment composition, or by adding the pigment composition together with a water-soluble inorganic salt and a water-soluble solvent when mechanically kneading. Adding it when mechanically kneading is preferred because it can be uniformly applied to the surface of the pigment composition. The glass transition temperature of the resin used when mechanically kneading is preferably lower than the kneading temperature. The amount of resin added is preferably 1 to 100 parts by mass, more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the total of PR179 and PV29. After the resin is treated, the resin may be crosslinked using a curing agent or a crosslinking agent. As the crosslinking agent, an epoxy resin, an isocyanate compound, a blocked isocyanate compound, a polyamine compound, a polyamide resin, or the like can be used.

[0036] In one embodiment, the pigment composition of the present invention may contain a luster material. Specific examples of the luster material include metal flakes, mica, and coated glass flakes. When used in applications requiring a particularly vivid hue, it is preferable to use metal flakes because the characteristics of the pigment composition of the present invention can be utilized. Examples of metal flakes include flakes of aluminum, zinc, copper, iron, nickel, titanium, stainless steel, and gold. Among them, aluminum flakes are preferable from the viewpoints of luster, cost, and specific gravity. The metal flakes may be particles with an average particle diameter of 1 to 100 μm. The average particle diameter is more preferably 5 to 50 μm. The metal flakes may be surface-treated with fatty acids, resins, and 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 coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide. The mica and glass flakes may be particles having an average particle size of 1 to 200 μm, and more preferably an average particle size of 10 to 150 μm. The content of the shining material may be 10 to 4000 parts by mass relative to 100 parts by mass of the pigment composition, and can be appropriately adjusted depending on the desired color tone. In particular, 10 to 1000 parts by mass is preferred. The average particle size of the shining material can be measured in the same manner as the average particle size of the pigment composition.

[0037] <2> Method for producing pigment composition The method for producing the pigment composition can be, for example, to obtain the pigment composition of the present invention by kneading a mixture containing at least PR179, PV29, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as 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 (hereinafter sometimes referred to as salt milling). Among these, a kneader or a trimix is ​​preferred. With these, it is possible to knead a mixture of PR179, PV29, a water-soluble inorganic salt, and a water-soluble organic solvent at a high viscosity, and it is possible to control the particle size and aspect ratio of the pigment composition and to form a solid solution between PR179 and PV29. The water-soluble inorganic salt has the function of grinding and polishing the pigment composition by utilizing its high hardness. On the other hand, the water-soluble organic solvent has the effect of slightly dissolving the pigment polished by the water-soluble inorganic salt, and orienting the molecules of PR179 and PV29 with each other to form a solid solution. By optimizing the conditions for the salt milling treatment, a pigment composition having an aspect ratio in the above range can be obtained. It is preferable to add rosin or resin during kneading. The temperature during mechanical kneading can be set according to the desired average particle size, the softening point of the rosin to be added, and the glass transition temperature of the resin, but is preferably 40 to 120°C, more preferably 60 to 100°C. By kneading at a temperature 0 to 30°C lower than the softening point of the rosin used and a temperature higher than the glass transition temperature of the resin, the pigment composition is firmly adsorbed on the surface of the pigment composition, which has the effect of further reducing the aspect ratio. In general, perylene pigments have high crystal growth in one direction, and the method described in Patent Document 3, in which the pigment is dissolved in a good solvent and precipitated in a poor solvent, produces needle-like crystals and cannot produce an aspect ratio in the above range.

[0038] The water-soluble inorganic salt may be any inorganic salt that exhibits water solubility, and is not limited within the scope of the present invention. Preferred examples include sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like. It is preferable to use sodium chloride (table salt) from the viewpoint of cost. From the viewpoints of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 30 to 3,000 parts by mass, more preferably 50 to 1,500 parts by mass, per 100 parts by mass of the total amount of PR179 and PV29. Any solvent that can be dissolved and mixed in water can be used as the water-soluble organic solvent. Specifically, glycerin, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, periethylene 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 are not limited thereto. In addition, these solvents can be used alone or in combination. The amount of the water-soluble organic solvent to be added is not particularly limited, but it is preferable to use 50 to 500 parts by mass, and more preferably 100 to 300 parts by mass, per 100 parts by mass of the total amount of PR179 and PV29.

[0039] The mixture containing the pigment composition is taken out of the kneader, water is added, and stirring is performed to obtain a suspension. The amount of water to be added is not particularly limited as long as it is sufficient to obtain a suspension. Heating may be performed as necessary. For example, water is added in a mass of 4 to 20 times the total mass of the water-soluble inorganic salt and the water-soluble organic solvent, and mixed and stirred. The mixing and stirring conditions at this time are not particularly limited, but it is preferable to perform the mixing and stirring at a temperature of 25 to 90°C. Then, the filtrate can be removed by filtering, washing with water, or other operations to remove the water-soluble organic solvent and the water-soluble inorganic salt. If necessary, the mixture may be reslurried in water and washed again. After reslurrying in water, the rosin or resin that has been neutralized, dissolved, or emulsified may be added. Any base can be used for neutralization as long as it can dissolve the rosin or resin, but sodium hydroxide and potassium hydroxide are preferred from the standpoint of cost and washability. When emulsifying, the rosin or resin can be added to a hydrophobic organic solvent such as xylene or toluene, dissolved, and then water is added and stirred to obtain the emulsion. The above-mentioned base may be added as necessary. When an emulsion is added, the slurry is heated to 60°C or higher to break the emulsion, so that the rosin or resin can be efficiently adsorbed onto the surface of the pigment composition. When rosin 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 before filtering and washing with water, and then filter. The obtained wet cake of the pigment composition may be used as it is for dispersion, or it may be further dried and pulverized in a dryer or the like to obtain a powdered pigment composition.

[0040] As an embodiment of the present invention, a step of dissolving the mixture containing PR179 and PV29 in a good solvent and precipitating the mixture in a poor solvent before carrying out salt milling treatment of the mixture containing PR179 and PV29 may be included. This step allows the sulfuric acid elution component rate to be adjusted to 2 mass% or less, and a pigment composition with high viscosity stability can be obtained. In addition, by forming the pigment composition into a solid solution in advance, it may be possible to shorten the salt milling treatment time. Any good solvent can be used as long as it dissolves the pigment composition and has no reactivity, and any poor solvent can be used as long as it is mixed with the good solvent at any ratio, does not dissolve the pigment composition, and has no reactivity. Suitable combinations of a good solvent and a poor solvent include sulfuric acid and water, polyphosphoric acid and water, etc., but a combination of sulfuric acid and water is preferred from the viewpoint of cost. As the good solvent, 98% sulfuric acid is preferably used from the viewpoints of treatment efficiency and solubility. It is preferable to use 300 to 2000 parts by mass of 98% sulfuric acid per 100 parts by mass of the total amount of PR179 and PV29, and more preferably 500 to 1500 parts by mass.

[0041] The dissolution conditions in sulfuric acid are not particularly limited as long as the pigment composition dissolves and the sulfuric acid elution component ratio can be adjusted to 2 mass% or less, but the temperature may be 5 to 70°C, the time may be 1 to 6 hours, and preferably 15 to 50°C, and the time may be 2 to 4 hours. The amount of water as a poor solvent is not limited as long as the pigment composition can be precipitated, but 3 to 10 times the mass of sulfuric acid can be used. The temperature during precipitation may be 25 to 105°C, and from the viewpoint of safety, 90°C or less is preferable. If necessary, the temperature may be adjusted by cooling or adding ice. Then, the filtrate is removed by operations such as filtration and washing with water, so that sulfuric acid and sulfuric acid-dissolved components can be removed. If necessary, the mixture may be reslurried in water and washed. In order to increase the efficiency of removing sulfuric acid, a small amount of a basic compound such as sodium hydroxide may be added during the reslurry. A solid solution of PR179 and PV29 can be obtained by further drying with a dryer or the like and pulverizing as necessary.

[0042] <3> paint The paint of the present invention refers to a paint containing the pigment composition of the present invention and a dispersion medium. In the paint, components other than the pigment composition can be appropriately selected depending on the application. The dispersion medium is not particularly limited as long as it can disperse the pigment composition, and a representative example is 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, glycol ethers such as methoxypropanol, methoxybutanol, butyl glycol and butyl diglycol, etc. Other solvents commonly used in the paint field are also included.

[0044] The coating material of the present invention may contain a resin, such as the resin used in the pigment composition described above, polyurethane resin, alkyd resin, amino resin, epoxy resin, modified resins thereof, etc. In order to promote curing of the coating material, the coating material may contain a curing agent and / or a crosslinking agent, such as an isocyanate compound or a blocked isocyanate compound.

[0045] <4> Painted items The coated object of the present invention refers to a substrate such as metal, resin, wood, concrete, or stone that is coated with the coating material of the present invention. In particular, a coated object having a metal or resin substrate that is suitable for industrial mass production is preferred. Metal substrates include iron, aluminum, stainless steel, silver, copper, gold, and alloys containing these processed into a plate, rod, cylinder, sphere, or the like having a flat or curved surface. Resin substrates include molded bodies formed by known methods. Examples of resin types 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 coating material of the present invention and forming a coating film, a coated object having excellent hue, clarity, brilliance, and weather resistance and little color separation or color unevenness can be obtained. Furthermore, the coated article of the present invention is excellent in hue, clarity and brilliance, and has durability sufficient to withstand outdoor use, and therefore can be suitably used as an exterior part for a vehicle. EXAMPLES

[0046] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples as long as it does not deviate from the gist of the invention. In addition, unless otherwise specified, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0047] [Measurement of particle size and major / minor diameter ratio] The average primary particle size and aspect ratio of the pigment compositions of the Examples and Comparative Examples were determined by observation with a transmission electron microscope (TEM) as follows. Fifty primary particles of the pigment composition were randomly selected from multiple photographs taken at a magnification of 10,000 times using a transmission electron microscope, and when the particle image was sandwiched between two parallel lines tangent to the particle image, the largest distance between the parallel lines was taken as the major axis, and the smallest distance was taken as the minor axis. The average of the major axes was taken as the average primary particle diameter, and the average ratio of the major axis to the minor axis was taken as the aspect ratio.

[0048] [Measurement of sulfuric acid elution rate] The sulfuric acid elution component ratio was determined by the following method. First, the mass of the pigment composition was measured and designated as A. Next, the weighed pigment composition was dissolved in 98% sulfuric acid in an amount 5 times by mass relative to A, and stirred at 25° C. for 2 hours. Thereafter, this sulfuric acid solution was poured into water in an amount 15 times by mass relative to A, and vigorously stirred, and then filtered through a Buchner-type glass filter whose empty mass had been measured in advance, and washed with water. The residue was dried together with the Buchner-type glass filter in a dryer at 80° C. for 24 hours, and then weighed; the difference between this and the empty mass of the Buchner-type glass filter was taken as B. The sulfuric acid elution component ratio was calculated based on the following formula. Sulfuric acid elution component rate (mass%) = (AB) / A×100 (mass%)

[0049] [Measurement of half-width] The X-ray diffraction spectrum was measured by the following method. Equipment: Rigaku X-ray diffraction equipment SmartLab (wide-angle X-ray diffraction measurement mode) X-ray source:CuKα Voltage: 45kV Current: 200mA Measurement range: 3.0° to 35.0° Step angle: 0.01° From the measurement results, the peak half-width was calculated by data processing under the following conditions. The half-width is a Bragg angle value defined as the peak width at an intensity position where the X-ray diffraction intensity is half the intensity of a certain 2θ peak. The half-width was calculated as follows: The peak showing the maximum diffraction intensity in the range of 2θ from 24.5° to 26.0° is designated as A, 2θ at A is Ax, The point B shows the minimum diffraction intensity when 2θ is within the range of Ax or less and Ax-1.5° or more. The point showing the minimum diffraction intensity within the range of 2θ from Ax to Ax+1.5° is designated as C. The line connecting B and C is the baseline. The intersection point of the perpendicular line drawn from A to the 2θ axis and the baseline is D. The intersection point of the line that passes through the midpoints of A and D and is parallel to the baseline, is E, F is the intersection point of the line that passes through the midpoints of A and D and is parallel to the baseline, and the curve AC. 2θ at E is Ex, 2θ at F is Fx, Fx-Ex was defined as the half-width of A. FIG. 1 is a schematic diagram for calculating the half-value width in the X-ray diffraction spectrum of a pigment composition, FIG. 2 is an X-ray diffraction spectrum of the pigment composition obtained in Example 2, and FIG. 3 is an X-ray diffraction spectrum of the pigment composition obtained in Comparative Example 4.

[0050] <1> Preparation of the pigment composition (Production Example 1) Production of PR179 (Pigment A) PR179 was prepared with reference to German Patent Publication DE2504481A1. 137 parts of perylene-3,4,9,10-tetracarboxylic dianhydride were added to 2800 parts of water at 0-5°C over 1 hour while stirring. Next, this mixture was added to a mixture consisting of 172 parts of 50.2% methylamine aqueous solution and 2 parts of 96% sulfuric acid at 0-5°C over 1 hour. After that, it was uniformly heated to 95°C over 90 minutes and heated for 3 hours. Next, the product was separated from the filtrate by filtration. The resulting residue was added to 2000 parts of 3% potassium hydroxide aqueous solution and stirred at 90-100°C for 1 hour. Then, it was filtered by suction, washed with hot water until the filtrate became colorless, and the residue was heated and dried at 80°C for 24 hours and pulverized with a hammer mill to obtain pigment A (PR179). The sulfuric acid elution component rate of this pigment A (PR179) was measured and found to be 2.9%.

[0051] (Production Example 2) Production of PV29 (Pigment B) PV29 was prepared with reference to JP-A-11-29499. 30.3 parts of potassium tert-butoxide, 44.71 parts of 1,5-diazabicyclo[4,3,0]-5-nonene (DBN) and 90 parts of diglyme were added to a round-bottom flask equipped with a stirrer and a reflux condenser, and the flask was immersed in an oil bath at 170°C and stirred for 1 hour under a nitrogen atmosphere, after which 17.75 parts of 1,8-naphthalimide was added and reacted at the same temperature for 8 hours. The reaction liquid was cooled to 25°C, 200 parts of water was added, and the mixture was stirred for 30 minutes, and then filtered. The residue was washed twice with 200 parts of water, twice with 200 parts of acetone, and twice with 200 parts of dichloromethane, and then dried at 80°C for 24 hours and ground with a hammer mill to obtain pigment B (PV29). The sulfuric acid elution rate of this pigment B (Pigment Violet 29) was measured and found to be 1.8%.

[0052] (Production Example 3) Production of a solid solution of PR179 and PV29 (Solid Solution C) 85 parts of PR179 and 15 parts of PV29 of Production Example 1 were added to 1500 parts of 98% sulfuric acid being stirred, and the mixture was stirred at 45 to 55°C for 3 hours. This sulfuric acid solution was added to 5000 parts of 50°C water being stirred over 1 hour to precipitate a pigment composition. The precipitate was then separated from the filtrate by filtration and washed with hot water at 50°C. This residue was reslurried in 3000 parts of 50°C water, and the pH was adjusted to 11 or more with a 25% aqueous sodium hydroxide solution. After stirring for 1 hour, the mixture was filtered and washed with hot water at 50°C until the pH of the filtrate became 7. The residue was dried by heating at 80°C for 24 hours, and pulverized with a hammer mill to obtain solid solution C. The sulfuric acid elution component rate of this solid solution C was measured and found to be 0.55%.

[0053] Example 1: Preparation of pigment composition 1 105 parts of pigment A (PR179), 45 parts of pigment B (PV29), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 3L kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 65°C. After adding this mixture to 9000 parts of water, it was stirred with a high-speed mixer for 2 hours to make a slurry, and the sodium chloride and diethylene glycol were removed by repeatedly filtering and washing with water to obtain 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.

[0054] (Examples 2 to 4) Preparation of Pigment Compositions 2 to 4 Pigment compositions 2 to 4 were obtained in the same manner as in Example 1, except that 105 parts of pigment A and 45 parts of pigment B in Example 1 were changed to the corresponding amounts in Table 1.

[0055] Example 5: Preparation of pigment composition 5 Pigment composition 5 was obtained in the same manner as in Example 1, except that 15 parts of Longis R-CH (disproportionated rosin, manufactured by Arakawa Chemical Industries, Ltd.) was added when pigment A and pigment B were added.

[0056] Example 6: Preparation of pigment composition 6 Pigment composition 6 was obtained in the same manner as in Example 2, except that 22.5 parts of Hyper CH-B (hydrogenated rosin: manufactured by Arakawa Chemical Industries, Ltd.) was added when Pigment A and Pigment B were added.

[0057] Example 7: Preparation of pigment composition 7 Pigment composition 7 was obtained in the same manner as in Example 3, except that when pigments A and B were charged, 7.5 parts of Arradime R-95 (polymerized rosin: manufactured by Arakawa Chemical Industries Co., Ltd.) was also charged and the kneading temperature was adjusted to 75°C.

[0058] Example 8: Preparation of pigment composition 8 2.4 parts of potassium hydroxide was dissolved in 75 parts of water and heated to 90°C, and 7.5 parts of Aradigm R-95 (polymerized rosin: manufactured by Arakawa Chemical Industries Co., Ltd.) was added and thoroughly mixed to dissolve. A wet cake of the pigment composition was obtained in the same manner as in Example 4. This wet cake was added to 1500 parts of water and reslurried using a high-speed mixer. While stirring this slurry, the above-mentioned alkaline solution of Aradigm R-95 was added and stirred for 30 minutes. Further, 35% hydrochloric acid was added to adjust the pH to 5 or less, and the mixture was filtered and washed with water to obtain a wet cake of the pigment composition. This was dried at 80°C for 24 hours and then pulverized using a hammer mill to obtain pigment composition 8.

[0059] Example 9: Preparation of pigment composition 9 Pigment composition 9 was obtained in the same manner as in Example 1, except that 105 parts of Pigment A and 45 parts of Pigment B in Example 1 were changed to 89.25 parts of Pigment A, 15.75 parts of Pigment B, and 45 parts of Solid Solution C.

[0060] Example 10: Preparation of pigment composition 10 Pigment composition 10 was obtained in the same manner as in Example 1, except that 105 parts of Pigment A and 45 parts of Pigment B in Example 1 were changed to 63.75 parts of Pigment A, 11.25 parts of Pigment B, and 75 parts of Solid Solution C.

[0061] Example 11: Preparation of pigment composition 11 Pigment composition 11 was obtained in the same manner as in Example 1, except that 105 parts of Pigment A and 45 parts of Pigment B in Example 1 were changed to 150 parts of Solid Solution C.

[0062] Example 12: Preparation of pigment composition 12 Pigment composition 12 was obtained in the same manner as in Example 11, except that 7.5 parts of Arradime R-95 (polymerized rosin: manufactured by Arakawa Chemical Industries Co., Ltd.) was added when solid solution C was added and the kneading temperature was adjusted to 75°C.

[0063] Example 13: Preparation of pigment composition 13 Pigment composition 13 was obtained in the same manner as in Example 7, except that 7.5 parts of Aradim R-95 in Example 7 was changed to 45 parts of Dianall BR-605 (methacrylic resin manufactured by Mitsubishi Chemical Corporation, glass transition point 56°C, acid value 8 mgKOH / g).

[0064] (Example 14) Preparation of pigment composition 14 Pigment composition 14 was obtained in the same manner as in Example 7, except that 7.5 parts of Arradime R-95 in Example 7 was changed to 22.5 parts of DEGALAN LP 64 / 11 (acrylic resin manufactured by Evonik Industries, glass transition point 60°C, acid value 228 mg KOH / g).

[0065] (Example 15) Preparation of pigment composition 15 Pigment composition 15 was obtained in the same manner as in Example 7, except that 7.5 parts of Arradime R-95 in Example 7 was changed to 7.5 parts of JONCRYL 586 (styrene acrylic resin manufactured by BASF, glass transition point 60°C, acid value 108 mgKOH / g).

[0066] Comparative Example 1: Preparation of Pigment 101 Pigment composition 101 was obtained in the same manner as in Example 1, except that 105 parts of pigment A and 45 parts of pigment B in Example 1 were changed to 150 parts of pigment A.

[0067] Comparative Example 2: Production of Pigment 102 A pigment composition 102 was obtained in the same manner as in Example 1, except that 105 parts of pigment A and 45 parts of pigment B in Example 1 were changed to 150 parts of pigment B.

[0068] Comparative Example 3: Preparation of Pigment Composition 103 Pigment composition 103 was obtained by mixing 127.5 parts of pigment composition 101 and 22.5 parts of pigment composition 102.

[0069] Comparative Example 4: Preparation of Pigment Composition 104 Solid solution C was designated as pigment composition 104.

[0070] The sulfuric acid elution component ratio, average primary particle size, aspect ratio, and half width were determined based on the above-mentioned methods for Examples 1 to 13 and Comparative Examples 1 to 4. The results are shown in Table 1. Of these, the pigment compositions obtained in Examples 1 to 13 and Comparative Example 4 were confirmed to contain a solid solution of PR179 and PV29 by X-ray diffraction spectrum, but the pigment composition of Comparative Example 3 was confirmed to not contain a solid solution of PR179 and PV29 by X-ray diffraction spectrum.

[0071] <2> Paint manufacturing and evaluation The following relates to specific examples of paints containing the pigment compositions prepared above. Preparation and evaluation of deep color paints

[0072] (A1) Preparation of dark paint (Example A-1) Preparation of dark color paint a-1 Pigment composition 1 9 parts Acrylic resin (DIC, Acrydic 47-712) 7.7 parts Dispersion solvent (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150FLUID manufactured by ENEOS in a mass ratio of 3:3:2:2) 40.7 parts 230 parts of steel beads were placed in a sealable glass container, sealed, and dispersed for 60 minutes using a paint shaker manufactured by Red Devil. Further, 75.4 parts of Acrydic 47-712 and 17.2 parts of melamine resin (Amidia L-117-60, manufactured by DIC Corporation) were added and dispersed for another 10 minutes. Thereafter, the steel beads were removed from the dispersion to obtain a deep color paint a-1 containing pigment composition 1.

[0073] (Examples A-2 to A-15, Comparative Examples A-1 to A-4) Preparation of dark color paints a-2 to a-15, a-101 to a-104 Dark color paints a-2 to a-15 and a-101 to a-104 were obtained in the same manner as in Example A-1, except that 9 parts of pigment composition 1 in Example A-1 was changed as shown in Table 2.

[0074] (A2) Evaluation of dark color paints <Initial viscosity and viscosity over time> The obtained dark color paint was placed in a glass bottle that could be sealed, and the bottle was then placed in a thermostatic chamber at 25°C for 1 hour to keep the temperature constant, and the viscosity was measured at 6 rpm using a B-type viscometer (a BII-type viscometer manufactured by Toki Sangyo Co., Ltd.). The same measurement was also carried out again after storing the paint at 40°C for 1 week. The results are shown in Table 2. A rating of "4", "3" or "2" on the following evaluation criteria is considered to be at a practical level.

[0075] (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 more and less than 10000 mPa·s, good 2: Viscosity is 10,000 mPa·s or more and less than 13,000 mPa·s, usable 1: If the viscosity is 13,000 mPa·s or more, or if gelation occurs, it is defective.

[0076] Preparation and evaluation of metallic paints (B1) Preparation of metallic base paint Aluminum flake paste (Toyo Aluminum Co., Ltd., Alpaste 1700NL) 10 parts Aluminum flake paste (Toyo Aluminum Co., Ltd., Alpaste HS-2) 10 parts Acrylic resin (DIC Corporation, Acrydic 47-712) 101.7 parts Melamine resin (DIC Corporation, Amidea L-117-60) 21.3 parts Dispersion solvent (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150FLUID manufactured by ENEOS in a mass ratio of 3:3:2:2) 20.9 parts The mixture was stirred with a high-speed stirrer to obtain a metallic base paint.

[0077] (B2) Preparation of metallic paint (Example B-1) Preparation of metallic paint b-1 20 parts of the dark paint a-1 prepared in Example A-1 Metallic base paint 18.5 parts The mixture was stirred and mixed using a high-speed stirrer to obtain metallic paint b-1.

[0078] (Examples B-2 to B-15, Comparative Examples B-1 to B-4) Preparation of metallic paints b-2 to b-15, b-101 to b-104 The same procedure as in Example B-1 was carried out except that the dark color paint a-1 in Example B-1 was changed as shown in Table 3, to obtain metallic paints b-2 to b-15 and b-101 to b-104.

[0079] (B3) Evaluation of metallic paints <Color separation test> The metallic paint obtained was placed in a glass bottle with a sealable cap, and after storing it at 25°C for 48 hours, the state of color separation was visually observed. The results are shown in Table 3. A score of "2" on the following scale is a practical level.

[0080] (Evaluation criteria for color separation) 2: Good, no color separation between red and purple 1: Red and purple color separation, defective

[0081] <Sedimentation test> The obtained metallic paint was placed in a glass bottle with a sealable cap, and after storing it at 25°C for 48 hours, the settling of aluminum flakes and pigment was visually observed. The results are shown in Table 3. The metallic paint used as the standard for the evaluation of settling was b-101. A rating of "3" or "2" on the following criteria is considered to be at a practical level.

[0082] (Subsidence evaluation criteria) 3: Compared to the standard metallic paint, there is little separation of the pigment and aluminum flakes, which is good. 2: Compared to the standard metallic paint, the separation of pigment and aluminum flakes is the same, so it can be used. 1: Compared to the standard metallic paint, there is a large separation of the pigment and aluminum flakes, poor quality

[0083] <c>Creation and evaluation of color clear coated panels (C1) Preparation of top coat clear paint Acrylic resin (DIC, Acrydic 44-179) 120 parts Melamine resin (DIC, Amidea L117-60) 30 parts Dilution solvent (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) 50 parts The mixture was stirred with a high-speed stirrer to obtain a top coat clear paint.

[0084] (C2) Creating color clear coated boards (Example C-1) Color clear coated plate c-1 One part of the dark color paint a-1 and 9 parts of the top coat clear paint were mixed to prepare color clear paint c'-1. This color clear paint was sprayed with a spray gun and applied to a stainless steel plate that had been given a mirror finish. In order to adjust the viscosity to make it easier to spray, a dilution solvent (a mixed solvent 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 into the color clear paint at a ratio of approximately 10 to 20% by mass. When painting, the stainless steel plate was placed on a table inclined at 15 degrees and sprayed vertically to the plate. At this time, the side that was in the higher position was above the plate to be painted, and the side that was in the lower position was below the plate to be painted. Painting was done in nine steps, and then the top coat clear paint was sprayed in six steps. After drying at 25° C. for 1 hour, it was dried at 140° C. for 30 minutes to obtain a color clear coated plate c-1.

[0085] (Examples C-2 to C-15, Comparative Examples C-1 to C-4) Preparation of color clear coated plates c-2 to c-15, c-101 to c-104 Except for changing the dark color paint a-1 of Example C-1 as shown in Table 4, the same procedure as in Example C-1 was performed to obtain color clear paints c'-2 to c'-15, c'-101 to c'-104 and color clear coated panels c-2 to c-15, c-101 to c-104.

[0086] (C3) Evaluation of color clear coated panels <Hue> The color clear coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 4. The standard coated panel was c-101. In the following criteria, "3" and "2" are preferred hues. (Evaluation criteria for hue) 4: The hue is much bluer than the standard painted board. 3: The hue is bluer than the standard painted board. 2: The hue is slightly bluer than the standard painted board. 1: Same hue as the standard painted board

[0087] <Clarity> The color clear coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 4. The standard coated panel was c-101. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Equivalent clarity to the standard painted board 1: Less clear than the standard painted board

[0088] <Transparency> The color clear coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 4. The standard coated panel was c-101. (Transparency Evaluation Criteria) 4: Extremely high transparency compared to the standard painted plate, with extremely strong metallic luster of the base 3: Higher transparency than the standard painted board, with a stronger metallic luster of the base 2: The transparency is the same as the standard painted board, and the metallic luster of the base is also the same. 1: Less transparent than the standard painted board, and the metallic luster of the base is weaker

[0089] <Color separation> The color clear coated panels were visually observed and rated according to the following criteria. The results are shown in Table 4. (Evaluation criteria for color separation) 2: The color tone is the same on the top and bottom of the painted plate, good 1: The color tone is different between the top and bottom of the painted plate. Defective.

[0090] <Color unevenness> The color clear coated panels were visually observed and rated according to the following criteria. The results are shown in Table 4. The standard coated panel was C-101. A rating of "3" or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for color unevenness) 3: The color difference when observed from an angle of 45° from the vertical to the top and bottom and from an angle of 45° from the vertical to the left and right is small compared to the standard painted board. Good. 2: The color difference when observed at an angle of 45° from the vertical to the top and bottom and at an angle of 45° from the vertical to the left and right is the same as that of the standard painted board, and it can be used. 1: The color difference when observed from an angle of 45° from the vertical to the top and bottom and from an angle of 45° from the vertical to the left and right is large compared to the standard painted board. Poor.

[0091] <d>Preparation and evaluation of metallic painted panels (D1) Creating metallic painted panels (Example D-1) Metallic painted plate d-1 Metallic paint b-1 was sprayed onto a steel plate using a spray gun. To adjust the viscosity to make it easier to spray, the same amount of dilution solvent (toluene, xylene, ENEOS T-SOL150FLUID, 3-ethoxypropionate ethyl, and ethyl acetate mixed in a mass ratio of 3:2:2:1:2) was mixed with the metallic paint. When painting, the steel plate was placed on a table inclined at 15 degrees and sprayed vertically to the plate. Painting was done in nine steps, and then the top coat clear paint was sprayed in six steps. The side that was in the higher position was above the plate and the side that was in the lower position was below the plate. After drying at 25° C. for 1 hour, it was dried at 140° C. for 30 minutes to obtain a metallic coated plate d-1.

[0092] (Examples D-2 to D-15, Comparative Examples D-1 to D-4) Preparation of metallic coated plates d-2 to d-15 and d-101 to d-104 The same procedure as in Example D-1 was carried out except that the metallic paint b-1 in Example D-1 was changed as shown in Table 5, to obtain metallic-coated panels d-2 to d-15 and d-101 to d-104.

[0093] (D2) Evaluation of metallic painted panels <Hue> The metallic coated panels were visually observed and rated according to the following criteria. The results are shown in Table 5. The standard coated panel was d-101. (Evaluation criteria for hue) 4: The hue is much bluer than the standard painted board. 3: The hue is bluer than the standard painted board. 2: The hue is slightly bluer than the standard painted board. 1: Same hue as the standard painted board

[0094] <Clarity> The metallic coated panels were visually observed and rated according to the following criteria. The results are shown in Table 5. The standard coated panel was d-101. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Equivalent clarity to the standard painted board 1: Less clear than the standard painted board <Shining feeling> The metallic coated panels were visually observed and rated according to the following criteria. The results are shown in Table 5. The standard coated panel was d-101. (Evaluation Criteria for Brilliance) 4: Significantly more lustrous than the standard painted plate 3: Higher shine than the standard painted board 2: The gloss is the same as the standard painted board. 1: Less shiny than the standard painted plate

[0095] <Color separation> The metallic-coated panels were visually observed and rated according to the following criteria, and the results are shown in Table 5. (Evaluation criteria for color separation) 2: The color tone is the same on the top and bottom of the painted plate, good 1: The color tone is different between the top and bottom of the painted plate. Defective.

[0096] <Color unevenness> The metallic coated panels were visually observed and rated according to the following criteria. The results are shown in Table 5. The standard coated panel was d-101. A rating of "3" or "2" on the following criteria is considered to be at a practical level. (Evaluation criteria for color unevenness) 3: The color difference when observed from an angle of 45° from the vertical to the top and bottom and from an angle of 45° from the vertical to the left and right is small compared to the standard painted board. Good. 2: The color difference when observed at an angle of 45° from the vertical to the top and bottom and at an angle of 45° from the vertical to the left and right is the same as that of the standard painted board, and it can be used. 1: The color difference when observed at an angle of 45° from the vertical to the top and bottom and when observed at an angle of 45° from the vertical to the left and right is large compared to the standard painted board. Poor

[0097] <Weather resistance> For the weather resistance test, an ultra-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151) was used, and the light intensity was 90 mW / cm 2 The test was carried out for 96 hours (four cycles of 12 hours day and night), and the color difference before and after the weather resistance test was visually evaluated. The results are shown in Table 5. The standard painted plate was d-101. A rating of "3" or "2" on the following scale is considered to be at a practical level. (Evaluation criteria for light resistance) 3: The color change before and after the test is smaller than that of the standard painted plate, good 2: The color change before and after the test is the same as that of the standard painted board, and it can be used. 1: The color change before and after the test is greater than that of the standard painted plate, defective

[0098] <e>Creating multi-layer metallic painted panels (Example E-1) Multi-layer metallic coated plate e-1 The metallic paint b-1 was sprayed onto a steel plate using a spray gun. The viscosity was adjusted in the same manner as in Example D. The painting was done in nine separate steps, followed by four separate steps of spraying the color clear paint c'-1, and then four separate steps of spraying the top coat clear paint. After drying at 25° C. for 1 hour, it was dried at 140° C. for 30 minutes to obtain a multi-layer metallic coated plate e-1.

[0099] (Examples E-2 to E-15, Comparative Examples E-1 to E-4) Preparation of multilayer metallic coated plates e-2 to e-15, e-101 to e-104 Except for changing the metallic paint b-1 and color clear paint c'-1 of Example E-1 as shown in Table 6, the same procedure as in Example E-1 was performed to obtain multilayer metallic coated panels e-2 to e-15 and e-101 to e-104.

[0100] (E2) Evaluation of multi-layer metallic painted panels <Hue> The multi-layer metallic coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 6. The standard coated panel was e-101. (Evaluation criteria for hue) 4: The hue is much bluer than the standard painted board. 3: The hue is bluer than the standard painted board. 2: The hue is slightly bluer than the standard painted board. 1: Same hue as the standard painted board

[0101] <Clarity> The multi-layer metallic coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 6. The standard coated panel was e-101. (Evaluation criteria for clarity) 4: Extremely clearer than the standard painted board 3: Higher clarity than the standard painted board 2: Equivalent clarity to the standard painted board 1: Less clear than the standard painted board

[0102] <Shining feeling> The multi-layer metallic coated panels were visually observed and evaluated according to the following criteria. The results are shown in Table 6. The standard coated panel was e-101. (Evaluation Criteria for Brilliance) 4: Significantly more lustrous than the standard painted plate 3: Higher shine than the standard painted board 2: The gloss is the same as the standard painted board. 1: Less shiny than the standard painted plate

[0103] Comparative Example 1 and the paint and coated plate using it did not contain PV29, so the desired bluish red hue was not obtained. Also, the transparency (brilliance in the case of metallic paints) specific to a solid solution of PR179 and PV29 was not obtained. Comparative Example 2 and the paint using it had poor viscosity stability, and the hue of the coated plate was purple, failing to obtain the desired bluish red hue. Comparative Example 3 and the paint and coated plate using it were merely a physical mixture of PR179 and PV29, and the viscosity stability was insufficient due to the low viscosity stability of PV29. Also, color separation occurred during the period from coating to drying. In Comparative Example 4 and the paint and coated plate using it, the aspect ratio of the pigment composition was large, so that the pigment composition particles were oriented in the metallic paint, causing color unevenness.In addition, the half-width of the powder X-ray diffraction was large and the crystallinity was low, so the weather resistance was insufficient. A paint using the pigment composition of the present invention has high viscosity stability, exhibits a bluish red color, is highly vivid and highly transparent, and when applied to metal plates or when used in combination with a luster material, gives off an excellent metallic luster and a sense of brilliance. It also shows little fading even when used outdoors for a long period of time, making it suitable for painting the exterior of vehicles and outdoor structures.

[0104] [Table 1]

[0105] [Table 2]

[0106] [Table 3]

[0107] [Table 4]

[0108] [Table 5]

[0109] [Table 6] [Explanation of symbols]

[0110] A Peak showing maximum diffraction intensity within the range of 2θ between 24.5° and 26.0° 2θ at Ax A B: The point showing the minimum diffraction intensity when 2θ is within the range of Ax or less and Ax-1.5° or more C. The point showing the minimum diffraction intensity within the range of 2θ from Ax to Ax+1.5° The intersection point between the perpendicular line drawn from DA to the 2θ axis and the baseline, which is the line connecting B and C The intersection point of the line that passes through the midpoint between EA and D and is parallel to the baseline and the curve AB The intersection point of a line that passes through the midpoint of FA and D and is parallel to the baseline and the curve AC 2θ in Ex E 2θ at Fx F Fx-Ex A half-width< / e> < / d> < / c>

Claims

1. A pigment composition which is a solid solution containing C. I. Pigment Red 179 and C. I. Pigment Violet 29, and has an average major axis / minor axis ratio of the major axis to the minor axis of primary particles of 1 or more and 3 or less.

2. 2. The pigment composition according to claim 1, wherein in a powder X-ray diffraction spectrum shown by diffraction intensity versus diffraction angle 2θ measured using CuKα radiation, the half-value width of a peak within the 2θ range of 24.5° to 26.0° is 0.1 to 0.

6.

3. The pigment composition according to claim 1, wherein the mass ratio of C. I. Pigment Red 179 to C. I. Pigment Violet 29 is 99.5:0.5 to 70:

30.

4. 2. The pigment composition according to claim 1, which, when completely dissolved in 98% sulfuric acid and then precipitated with water, has a mass change rate of 2% by mass or less.

5. The pigment composition of claim 1 , further comprising rosin.

6. The pigment composition according to claim 1 , further comprising a resin other than rosin.

7. The pigment composition according to claim 1 , further comprising a metallic luster material.

8. The method for producing the pigment composition according to any one of claims 1 to 6, comprising a step of kneading a mixture containing C. I. Pigment Red 179 and C. I. Pigment Violet 29.

9. The method for producing a pigment composition according to claim 8, further comprising a step of dissolving a mixture containing C. I. Pigment Red 179 and C. I. Pigment Violet 29 in a solvent and then precipitating the mixture.

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

11. A coated article having a coating film of the paint according to claim 10.

12. The coated article according to claim 11, which is an exterior vehicle part.

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