Pigment composition, coloring composition, ink, ink set, printed matter, and packaging material

Abstract

To provide a C.I. Pigment Yellow 180-containing pigment composition that is excellent in dispersibility and storage stability, and has high transparency.SOLUTION: Provided is a pigment composition that contains C.I. Pigment Yellow 180 and an azo compound represented by the following formula. Here, the contained amount of an azo compound represented by the following formula preferably is 0.1 to 30 pts.mass for 100 pts.mass of C.I. Pigment Yellow 180. [In the formula, R1 represents -NR2R3 or -OR4, and R2 to R4 each independently represent H, an alkyl group, an aryl group, or an acyl group.].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a pigment composition containing a specific azo compound. [Background technology]

[0002] In recent years, from the viewpoints of reducing environmental impact and ensuring safety and hygiene, there has been an increasing demand for organic pigments and colorants that do not contain specific aromatic amines, halogens, heavy metals, etc. In this environment, azo pigments are mainly used as organic pigments with yellow to red hues among the pigments used to color plastic products, toners, paints, printing inks, etc. Azo pigments may contain specific aromatic amines derived from raw materials or from pigment decomposition due to light or heat. For example, CI Pigment Yellow 74, a typical monoazo yellow pigment, easily decomposes under heat or light to produce the specific aromatic amine o-anisidine. CI Pigment Yellow 14, a typical disazo yellow pigment, uses the specific aromatic amine dichlorobenzidine as a raw material, which may leave unreacted residues. CI Pigment Yellow 14 may also decompose under heat or light to produce dichlorobenzidine or o-toluidine.

[0003] On the other hand, CI Pigment Yellow 180 does not contain any specific aromatic amines, halogens, or heavy metals in its structure, and because it has a benzimidazolone structure, it is a disazo pigment that has high heat and light resistance.It is known as a useful yellow pigment and is used in a variety of applications.

[0004] However, it is difficult to control the particle size of pigment compositions containing CI Pigment Yellow 180, which makes dispersion difficult. Furthermore, this results in poor storage stability and a lack of transparency, making them difficult to use.

[0005] For example, Patent Document 1 discloses a crude pigment of CI Pigment Yellow 180 in which the coupling process has been improved, and Patent Document 2 discloses a pigment composition containing CI Pigment Yellow 180 and a benzimidazolone monoazo pigment. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-201379 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-057509 Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional pigment compositions lack dispersibility and transparency.

[0008] An object of the present invention is to provide a pigment composition having good dispersibility and transparency. [Means for solving the problem]

[0009] The present invention is a pigment composition containing CI Pigment Yellow 180 and an azo compound represented by the following formula (1): Formula (1) [ka]

[0010] [In the formula, R1 represents -NR2R3 or -OR4, and R2 to R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.] [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a pigment composition having good dispersibility and transparency, and also to provide an ink set, printed matter, packaging material, and the like, which contain a yellow ink having excellent dispersibility and storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0012] First, the terms used in this specification are defined. Unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" mean "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Additionally, "CI" refers to the Color Index (CI).

[0013] <Pigment composition> The pigment composition of the present invention contains CI Pigment Yellow 180 and an azo compound represented by formula (1).

[0014] Formula (1) [ka]

[0015] [In the formula, R1 represents -NR2R3 or -OR4, and R2 to R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.]

[0016] By containing the azo compound represented by formula (1) as described above, the pigment composition of the present invention improves dispersibility, storage stability, and transparency, which have traditionally been weaknesses of CI Pigment Yellow 180. The pigment composition of the present invention can be used in a wide range of applications requiring coloration, such as molded products, toners, paints, printing inks, and inkjet inks.

[0017] [Azo compound (1)] The azo compound represented by the above formula (1) is called azo compound (1).

[0018] In formula (1), R1 represents -NR2R3 or -OR4, and R2 to R4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

[0019] The pigment composition of the present invention contains CI Pigment Yellow 180 and azo compound (1), and thus can produce a dispersion having excellent dispersibility and stability over time, and can form images with high saturation and transparency. The reason for this is that one benzimidazolone moiety of the azo group of azo compound (1) easily adsorbs to CI Pigment Yellow 180, while the other has a different structure, preventing it from adsorbing to CI Pigment Yellow 180 and preventing pigment crystal growth. This prevents pigment particle enlargement and aggregation during the preparation of the pigment composition and the subsequent dispersion process. It is therefore believed that inks, paints, etc. that use the pigment composition have high stability over time. It is also believed that the presence of azo compound (1) during the preparation of the pigment composition allows for the pigment particle size to be adjusted appropriately, improving dispersibility and transparency.

[0020] In the pigment composition of the present invention, the content of the azo compound (1) relative to 100 parts by mass of CI Pigment Yellow 180 is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 0.1 to 5 parts by mass, and particularly preferably 1 to 5 parts by mass.

[0021] In the above formula (1), the alkyl group (-R) in R2 to R4 preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 4, still more preferably 1 to 3, and is still more preferably an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, an isopentyl group, a 2-ethylhexyl group, a 2-hexyldodecyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and a 4-decylcyclohexyl group.

[0022] In the alkyl group, at least one hydrogen atom may be substituted with another substituent such as a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, an ester group, a sulfo group, a sulfanyl group, a sulfamoyl group, an amino group, an alkylamino group, or an amide group. The alkyl group may have a plurality of substituents. The substituents are not limited to those listed above.

[0023] The alkyl group may have a structure in which two or more alkyl groups (one of which is an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (-COO-), an ether bond (-O-), and a sulfide bond (-S-). That is, in this specification, the alkyl group may be, for example, a group represented by "-R'-OR" (R' represents an atomic group obtained by removing one hydrogen atom from the alkyl group). A specific example is -C2H4-O-C2H5.

[0024] In the above formula (1), the aryl group (-Ar) in R2 to R4 is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, and preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a biphenylyl group, a terphenylyl group, a quaterphenylyl group, a pentalenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a ternaphthalenyl group, a quaternaphthalenyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group, an indacenyl group, a fluoranthenyl group, an acephenanthrylenyl group, an aceanthryllenyl group, a phenalenyl group, a fluorenyl group, an anthryl group, a bianthracenyl group, a thiazolin ... Examples of the alkyl group include anthracenyl, quaternary anthracenyl, anthraquinolyl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, pleiadenyl, picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl, hexaphenyl, hexacenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, heptacenyl, pyrantrenyl, and ovalenyl. Of these, phenyl and tolyl groups are preferred.

[0025] The aryl group may have at least one hydrogen atom substituted with another substituent such as a halogen atom, a hydroxy group, an alkoxy group, a carboxy group, an ester group, a sulfo group, a sulfanyl group, a sulfamoyl group, an amino group, an alkylamino group, or an amide group. The aryl group may have a plurality of substituents. The substituents are not limited to those listed above.

[0026] In the above formula (1), examples of the acyl group in R2 to R4 include an acetyl group, a propioyl group, a benzoyl group, an acrylyl group, a trifluoroacetyl group, etc. Among these, an acetyl group is preferred from the viewpoint of ease of synthesis.

[0027] In the above formula (1), R1 is preferably an amino group or a hydroxyl group.

[0028] The azo compound (1) can be used alone or in combination of two or more kinds.

[0029] Azo compound (1) can be represented by the following formula (1A), (1B), or (1C), which will be referred to as azo compound (1A), azo compound (1B), and azo compound (1C), respectively, hereinafter.

[0030] [ka] (1A) (1B) (1C)

[0031] In the above formula (1A), R5 represents -NR6R7 or -OR8, and R6 to R7 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, where either R6 or R7 is other than a hydrogen atom, and R8 represents an alkyl group, an aryl group, or an acyl group.

[0032] Preferred specific examples of the azo compound (1) represented by formula (1) include azo compounds (1)-1 to (1)-11 represented by the following formulas (1)-1 to (1)-11, but the present invention is not limited thereto.

[0033] [ka] [ka]

[0034] [Method for producing azo compound (1)] Azo compound (1) can be obtained, for example, as shown in Scheme 1 below, by adding an aqueous solution of sodium nitrite to a compound represented by formula (3) (hereinafter referred to as compound (3)) in the presence of a strong acid under ice-cooling conditions to carry out a diazotization reaction, and then coupling the resulting diazonium salt solution with 5-acetoacetylamino-benzimidazolone represented by formula (4) (hereinafter referred to as compound (4)). Furthermore, excess nitrous acid after the diazotization reaction can be removed by adding an aqueous solution of sulfamic acid.

[0035] (Scheme 1) [ka]

[0036] R9 in the above formula (3) is -NR 10 R 11 -OR 12 represents R 10 ~R 11 each independently represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group; R 10 Or R 11 is other than a hydrogen atom, and R 12 represents an alkyl group, an aryl group, or an acyl group.

[0037] Furthermore, azo compound (1) can be obtained by using a compound represented by formula (6) (hereinafter referred to as compound (6)) instead of compound (3) in scheme (1), as shown in scheme 2 below.

[0038] (Scheme 2) [ka]

[0039] Furthermore, azo compound (1) can be obtained by coupling reaction of compound (4) with a diazonium salt solution obtained by adding an aqueous solution of sodium nitrite to 1,2-bis(2-aminophenoxy)-ethane (hereinafter referred to as compound (7)) represented by formula (7) under ice-cooling in the presence of a strong acid, as shown in Scheme 3 below. In this case, azo compound (1C) can be obtained by reacting sodium nitrite with compound (7) in equimolar amounts.

[0040] (Scheme 3) [ka]

[0041] Furthermore, as shown in the following scheme 4, a diazonium salt solution obtained by diazotizing compound (7) is coupled with an equimolar amount of compound (4) to compound (7), and excess diazonium salt is hydrolyzed, thereby obtaining azo compound (1B).

[0042] (Scheme 4) [ka]

[0043] Furthermore, the azo compound (1B) or the azo compound (1C) can be alkylated, arylated or acylated to obtain the azo compound (1A).

[0044] [Method of producing pigment composition] A method for producing a pigment composition containing CI Pigment Yellow 180 and azo compound (1) will be exemplified below. (I) a method of synthesizing two or more types at once (co-synthesis method), (II) a method of mixing CI Pigment Yellow 180 and azo compound (1) when preparing a dispersion, (III) a method of converting CI Pigment Yellow 180 and azo compound (1) together into a pigment using an acid pasting method, an acid slurry method, a dry milling method, a salt milling method, a solvent salt milling method, a solvent method (heat treatment in a high-boiling point solvent such as alcohol or an aromatic solvent), or the like, and (IV) a method of combining the above methods. Among these, (I) the co-synthesis method, (III) a method of converting CI Pigment Yellow 180 and azo compound (1) together into a pigment by acid pasting, solvent salt milling, or solvent method, and (IV) a method of combining (I) and (III) are preferred.

[0045] In the (I) co-synthesis method, for example, compound (7) and compound (3) are mixed in a desired ratio, diazotized, and then subjected to a coupling reaction with compound (4), thereby obtaining a co-synthetic product of CI Pigment Yellow 180 and azo compound (1A).Furthermore, by using compound (6) instead of compound (3), a co-synthetic product of CI Pigment Yellow 180 and azo compound (1B) can be obtained.

[0046] In addition, compound (7) can be diazotized to a desired ratio and subjected to a coupling reaction with compound (4) to obtain a co-synthetic product of CI Pigment Yellow 180 and azo compound (1C).

[0047] Furthermore, a co-composite of CI Pigment Yellow 180 and azo compound (1B) can be obtained by coupling compound (4) to a diazonium salt solution obtained by diazotizing compound (7) in a desired ratio and hydrolyzing the excess diazonium salt.

[0048] The particle size of the pigment composition of the present invention is preferably adjusted by heating a slurry obtained by dispersing the pigment composition in a liquid medium that does not dissolve the pigment composition. Adjusting the particle size is expected to result in more vivid color development and improved dispersibility and storage stability when the pigment composition of the present invention is used in inks and the like. The slurry may be obtained by synthesizing the pigment, or by redispersing a wet cake obtained by filtering and washing, or by redispersing a dried and pulverized product. It is preferable to use a wet cake for the pigment composition, as this avoids the increased effort required for pigmentation due to drying and agglomeration, and can eliminate the effects of excess salt.

[0049] In this case, the liquid medium may be water or an organic solvent, such as an alcohol solvent (e.g., methanol, ethanol, isopropanol, isobutanol, etc.), a ketone solvent (e.g., methyl ethyl ketone, acetone, etc.), an ester solvent (e.g., ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc.), or a polar aprotic solvent (e.g., tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, hexamethylphosphoramide, sulfolane, etc.).

[0050] The liquid medium is preferably used in an amount of 300 to 8000 parts by mass, more preferably 500 to 5000 parts by mass, and even more preferably 600 to 3000 parts by mass, per 100 parts by mass of the pigment composition.

[0051] The temperature for the heat treatment is preferably 50 to 200°C, more preferably 80 to 150°C. The heating and stirring time is preferably 0.5 to 15 hours. If necessary, the heat treatment may be carried out under pressure. A base may also be used in combination with the liquid medium.

[0052] The pigment composition of the present invention is preferably subjected to particle size regulation by solvent salt milling. By narrowing the particle size distribution of primary particle diameters by solvent salt milling, it is expected that when the pigment composition of the present invention is used in inks and the like, it will exhibit more vivid color development and improved dispersibility and storage stability. Particle size regulation by solvent salt milling involves vigorously kneading a clay-like mixture consisting of at least three components: pigment, water-soluble inorganic salt, and water-soluble solvent, using a kneader or the like. The kneaded mixture is then poured into water and stirred with various stirrers to form a slurry. The resulting slurry is filtered to remove the water-soluble inorganic salt and water-soluble solvent. Repeating the above slurrying, filtration, and water washing processes can yield a particle-regulated pigment.

[0053] Examples of water-soluble inorganic salts that can be used include sodium chloride, sodium sulfate, and potassium chloride. These inorganic salts are used in an amount of at least 1 time by mass, preferably at most 20 times by mass, relative to the pigment. When the amount of inorganic salt is at least 1 time by mass, the pigment can be sufficiently refined. When the amount of inorganic salt is at most 20 times by mass, the great effort required to remove the water-soluble inorganic salt and water-soluble solvent after kneading is eliminated, and the amount of pigment that can be processed at one time is not reduced, which is preferable from the viewpoint of productivity.

[0054] Pigment particle size regulation often generates heat during kneading. Therefore, from a safety standpoint, it is preferable to use a water-soluble solvent with a boiling point of approximately 120 to 250°C. Specific examples of water-soluble solvents include 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and low-molecular-weight polypropylene glycol.

[0055] [Dye derivatives] The pigment composition can contain a dye derivative. The dye derivative is a known compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a sulfonamide group or a basic substituent such as a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0056] The dye derivatives can be used alone or in combination of two or more.

[0057] <Coloring composition> The coloring composition of the present invention preferably contains the above-mentioned pigment composition and a dispersion medium.

[0058] [Dispersion medium] Examples of the dispersion medium include resins and solvents. Examples of the resin include resin-type dispersants and binder resins. Examples of the solvent include water and organic solvents. If necessary, a low-molecular-weight dispersant such as a surfactant can be used.

[0059] Resin-type dispersants have pigment-affinity moieties that adsorb to pigments and relaxation moieties that have high affinity with components other than pigments and cause steric repulsion between dispersed particles. Resin-type dispersants have acidic or basic groups. Examples of acidic groups include carboxyl groups, sulfo groups, and phosphate groups. Examples of basic groups include primary to tertiary amino groups and quaternary ammonium salt groups. Examples of acidic resin-type dispersants include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters. Examples of basic resin-type dispersants for resin types such as acrylic resin, polyester resin, and urethane resin include nitrogen-atom-containing graft copolymers, nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups in the side chains including tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles.

[0060] Examples of resin-type dispersants include JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL62J, JONCRYL63J, JONCRYLHPD-96J, JONCRYL501J, and JONCRYLPDX-6102B manufactured by BASF Japan Ltd.; DISPERBYK180, DISPERBYK187, and DISPERBYK188 manufactured by BYK-Chemie Co., Ltd. 90, DISPERBYK191, DISPERBYK194, DISPERBYK2010, DISPERBYK2015, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2155, SOLSPERSE24000, SOLSPERSE32000, SOLSPERSE41000 manufactured by The Lubrizol Japan Corporation, and SMA1000H, SMA1440H, SMA2000H, SMA3000H, SMA17352H manufactured by Sartomer Corporation.

[0061] The binder resin may be any resin that can be coated or molded by printing or molding, and may be, for example, a polyolefin resin, a polyester resin, a styrene copolymer, an acrylic resin, or a modified resin thereof. Specific examples include polyethylenes such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), and polypropylene; polyester resins such as polyethylene terephthalate; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-butadiene copolymer. polymers, styrene copolymers such as styrene-isoprene copolymers and styrene-acrylonitrile-indene copolymers; acrylic resins such as acrylic resins and methacrylic resins; polyvinyl chloride, phenolic resins, naturally modified phenolic resins, natural resin-modified maleic acid resins, silicone resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, nitrocellulose resins, polyamide resins, epoxy resins, xylene resins, polyvinyl butyral resins, polyvinyl acetal resins, cellulose ester resins, alkyd resins, rosin resins, ketone resins, cyclized rubbers, chlorinated polyolefin resins, terpene resins, coumarone-indene resins, amino resins, petroleum resins, and modified resins thereof.

[0062] Organic solvents can be classified into water-soluble solvents and water-insoluble solvents. Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Examples of water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.

[0063] Each material constituting the coloring composition can be used alone or in combination of two or more kinds.

[0064] The coloring composition of the present specification may be exemplified by the following embodiments: Aspect 1 (for example, a molding composition or a toner) containing a pigment composition and a resin; Aspect 2 (for example, a solvent-based coloring composition) containing a pigment composition and an organic solvent; and Aspect 3 (for example, a water-based coloring composition) containing a pigment composition, a resin, and water.

[0065] To explain the uses of each embodiment, the first embodiment is, for example, a molding composition, a toner, a dyed fiber, and a solventless printing ink (such as a UV-curable offset ink or a UV-curable inkjet ink). The second embodiment is a solvent-based coloring composition, for example, a paint or a printing ink (such as a gravure ink or a solvent-based inkjet ink). The third embodiment is a water-based coloring composition, for example, a water-based paint or a water-based printing ink (such as a water-based flexo ink or a water-based inkjet ink). In this specification, when the solvent contains water, it is referred to as "aqueous," but when the solvent is an "organic solvent," it is not particularly referred to as "solvent-based." The water is preferably ion-exchanged water or distilled water from which metal ions and the like have been removed.

[0066] <Molding composition> The molding composition of the present invention contains a coloring composition (pigment composition, resin). The molding composition preferably contains a thermoplastic resin as the resin. The molding composition containing a thermoplastic resin is preferably melted and kneaded, and molded into a desired shape to produce a molded product. The resin is not limited to a thermoplastic resin.

[0067] Examples of thermoplastic resins include homopolymers or copolymers using ethylene, propylene, butylene, styrene, or the like as monomer components. More specifically, examples include polyethylenes such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), as well as polyolefin resins such as polypropylene and polybutylene. Specific examples of other useful resins include polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polystyrene resins, and thermoplastic ionomer resins. Among these, polyolefin resins and polyester resins are preferred. The number-average molecular weight of the thermoplastic resin is preferably greater than 30,000 and not greater than 200,000.

[0068] The content of the thermoplastic resin is preferably 10,000 to 10,000,000 parts by mass, and more preferably 10,000 to 2,000,000 parts by mass, relative to 100 parts by mass of the pigment composition containing CI Pigment Yellow 180 and the azo compound (1).

[0069] The molding composition may contain wax. Waxes are made of low-molecular-weight polyolefins. These are polymers of olefin monomers such as ethylene, propylene, and butylene, and may be block or random copolymers or terpolymers. Specifically, they are polymers of α-olefins such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP).

[0070] The number average molecular weight of the wax is preferably 1,000 to 30,000, more preferably 2,000 to 25,000. Within this range, the wax migrates appropriately to the surface of the molded article, resulting in an excellent balance between sliding properties and bleed-out suppression.

[0071] The melting point of the wax is preferably 60 to 150° C., more preferably 70 to 140° C. Within this range, the processability when melt-kneading the thermoplastic resin and wax is improved. The melt flow rate (MFR) of the wax determined in accordance with JIS K-7210 is preferably greater than 100 g / 10 min.

[0072] The amount of wax to be added is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

[0073] The molding composition may contain other additives, which are materials commonly used in the technical field of molded articles, such as antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and colorants other than the pigment composition containing CI Pigment Yellow 180 and azo compound (1).

[0074] The molding composition can be prepared, for example, in the composition ratio of the molded article. Alternatively, it can be prepared as a masterbatch containing a pigment composition containing CI Pigment Yellow 180 and azo compound (1) at a high concentration. In this specification, a masterbatch is preferred because it makes it easier to uniformly disperse the pigment composition containing CI Pigment Yellow 180 and azo compound (1) in the molded article. The masterbatch is preferably prepared by, for example, melt-kneading a thermoplastic resin and a pigment composition, and then molding the mixture into any desired shape for easy use in the next step. The masterbatch is then melt-kneaded with a diluting resin (e.g., the thermoplastic resin used in the masterbatch) to form a molded product of the desired shape. Examples of the masterbatch shape include pellets, powder, and plates. To prevent aggregation of the pigment composition, it is preferable to first melt-knead the pigment composition and wax to produce a dispersion, and then melt-knead this dispersion with the thermoplastic resin to produce the masterbatch. The device used for the dispersion is preferably, for example, a blend mixer or a three-roll mill.

[0075] When the molding resin composition is produced as a masterbatch, a total of 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass, of the pigment composition containing CI Pigment Yellow 180 and the azo compound (1) is blended with 100 parts by mass of the thermoplastic resin. The mass ratio of the masterbatch (X) to the diluent resin (Y) that serves as the base resin of the molded article is preferably X / Y=1 / 1 to 1 / 100, and more preferably 1 / 3 to 2 / 100. Within this range, the pigment composition containing CI Pigment Yellow 180 and the azo compound (1) is easily dispersed uniformly in the molded article, making it easier to achieve good coloring.

[0076] The diluent resin (Y) is preferably a thermoplastic resin used in the masterbatch, but other thermoplastic resins may also be used as long as there is no problem with compatibility.

[0077] The melt kneading may be carried out using, for example, a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, etc. The melt kneading temperature varies depending on the type of thermoplastic resin, but is usually about 150 to 300°C.

[0078] The molding composition can be used for, for example, plastic molded articles, sheets, films, and the like.

[0079] <Toner> The toner of this specification contains a coloring composition (pigment composition, resin). The resin in the toner is called a binder resin, and is preferably a thermoplastic resin. The toner may be a dry toner or a wet toner, with a dry toner being preferred. For example, a dry toner can be produced by melt-kneading the pigment composition and binder resin, cooling, and then performing a pulverization and classification process. This is followed by a post-processing process in which additives are blended and mixed.

[0080] Examples of binder resins include styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-(meth)acrylate copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, polyvinyl chloride, phenolic resins, naturally modified phenolic resins, naturally resin-modified maleic acid resins, (meth)acrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins.

[0081] Among these, polyester resins and styrene copolymers are preferred, and polyester resins are more preferred. The pigment composition of the present specification has particularly excellent compatibility with polyester resins, so that the pigment composition containing CI Pigment Yellow 180 and azo compound (1) can be uniformly and finely dispersed in the toner, thereby producing a high-quality toner.

[0082] The weight average molecular weight (Mw) of the polyester resin is preferably 5,000 or more, more preferably 10,000 to 1,000,000, and even more preferably 20,000 to 100,000. When a polyester resin with an appropriate Mw is used, a toner having good offset resistance and low-temperature fixability can be obtained.

[0083] The acid value of the polyester resin is preferably 10 to 60 mgKOH / g, more preferably 15 to 55 mgKOH / g. When a polyester resin with an appropriate acid value is used, it is easy to suppress the release of the release agent, and a decrease in image density in a high-humidity environment is unlikely to occur.

[0084] The hydroxyl value of the polyester resin is preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less. When a polyester resin with an appropriate hydroxyl value is used, a decrease in image density is unlikely to occur in a high-humidity environment. The lower limit of the hydroxyl value is 0.1 mgKOH / g.

[0085] The glass transition temperature (Tg) of the polyester resin is preferably 50 to 70° C., more preferably 50 to 65° C. A suitable Tg can suppress toner aggregation. Tg can be measured using a differential scanning calorimeter (device: DSC-6, manufactured by Shimadzu Corporation).

[0086] The toner may further contain a charge control agent. The use of a charge control agent makes it easier to obtain a toner with a stable charge amount. The charge control agent may be selected appropriately from positive and negative charge control agents.

[0087] When the toner is a positively charged toner, examples of the positive charge control agent include nigrosine dyes, triphenylmethane dyes, organic tin oxides, quaternary ammonium salt compounds, and styrene-acrylic polymers in which quaternary ammonium salts are copolymerized with styrene-acrylic resins as functional groups. Among these, quaternary ammonium salt compounds are preferred. Examples of quaternary ammonium salt compounds include salt-forming compounds of quaternary ammonium salts with organic sulfonic acids or molybdic acid. Examples of the organic sulfonic acids include naphthalenesulfonic acid.

[0088] When the toner is a negatively charged toner, examples of the negative charge control agent include metal complexes of monoazo dyes, styrene-acrylic polymers in which sulfonic acid functional groups are copolymerized with styrene-acrylic resins, metal salt compounds of aromatic hydroxycarboxylic acids, metal complexes of aromatic hydroxycarboxylic acids, phenolic condensates, and phosphonium compounds. Preferred aromatic hydroxycarboxylic acids include salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, and 3-phenylsalicylic acid. Metals used in the metal salt compounds include zinc, calcium, magnesium, chromium, and aluminum.

[0089] The toner may contain a release agent, such as hydrocarbon waxes such as polypropylene wax, polyethylene wax, and Fischer-Tropsch wax, synthetic ester waxes, and natural ester waxes such as carnauba wax and rice wax.

[0090] If necessary, lubricants, fluidizing agents, abrasives, conductivity-imparting agents, image peeling prevention agents, etc. may be added to the toner.

[0091] Examples of lubricants include polyvinylidene fluoride and zinc stearate. Examples of fluidizing agents include silica, aluminum oxide, titanium oxide, silicon-aluminum co-oxide, and silicon-titanium co-oxide produced by a dry or wet process, as well as hydrophobic products thereof. Among these, hydrophobically treated silica, silicon-aluminum co-oxide, and silicon-titanium co-oxide fine powders are preferred. Methods for hydrophobizing these fine powders include treatment with silicone oil or a silane coupling agent such as tetramethyldisilazane, dimethyldichlorosilane, or dimethyldimethoxysilane. Examples of abrasives include silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, and hydrophobically treated versions of these. Examples of conductivity-imparting agents include tin oxide.

[0092] The toner herein can be used as a one-component developer or a two-component developer. The two-component developer can further contain a carrier.

[0093] Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, as well as those whose surfaces are coated with resin or the like. Examples of the resin that coats the carrier surface include styrene-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester copolymers, fluorine-containing resins, silicone-containing resins, polyamide resins, ionomer resins, and polyphenylene sulfide resins. Among these, silicone-containing resins, which cause less spent toner formation, are preferred. The weight-average particle size of the carrier is preferably 30 to 100 μm.

[0094] The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner:carrier=1:100 to 30:100.

[0095] <Paint> The paint of this specification contains a coloring composition (pigment composition, resin, solvent). The resin may be a thermosetting resin or a thermoplastic resin. The thermosetting resin preferably has a glass transition temperature of 10°C or higher. Examples of the thermosetting resin include acrylic resin, polyester, and polyurethane. The thermosetting resin preferably has a functional group that can react with a curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Examples of the curing agent include an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, and an amine curing agent. The thermoplastic resin is preferably a resin having a glass transition temperature of 30° C. or higher. Examples of the thermoplastic resin include nitrocellulose, polyester, etc. Note that the thermosetting resin and the thermoplastic resin can be used in combination.

[0096] Among the solvents, examples of the water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons. Among the above solvents, examples of water-soluble solvents include water, monohydric alcohols, dihydric alcohols, and glycols. Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Other examples include water-dilutable monoethers derived from polyhydric alcohols. Specific examples include methoxypropanol and methoxybutanol. Other examples include water-dilutable glycol ethers such as butyl glycol and butyl diglycol. As already explained, paints containing water as a solvent are called water-based paints.

[0097] The coating material may further contain known additives.

[0098] Examples of uses of the paint include metal paint, plastic paint, and wood paint.

[0099] <Printing ink> The printing ink of this specification contains a coloring composition (pigment composition, resin, solvent). Examples of printing inks include offset printing ink, flexographic printing ink, gravure printing ink, inkjet printing ink, silkscreen printing ink, and color filter ink. As mentioned above, when the solvent contains water, it is called an aqueous printing ink.

[0100] The ink production method (mixing means) is not particularly limited, but the ink can be preferably produced by mixing using, for example, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, or the like.

[0101] The substrate on which the printing ink is printed is not particularly limited, and known substrates can be used. Specific examples include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid; polystyrene-based resins such as polystyrene, AS resin, and ABS resin; nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane; coated paper such as art paper, coated paper, and cast paper; uncoated paper such as fine paper, medium-quality paper, and newsprint; synthetic paper such as Yupo paper; aluminum; and film-like substrates made of composite materials thereof. Other examples include vapor-deposited substrates in which inorganic compounds such as silica, alumina, and aluminum are vapor-deposited onto polyethylene terephthalate or nylon film. The substrate may further have a coating treatment of polyvinyl alcohol or the like on the vapor-deposited surface of the inorganic compound, or may further have a surface treatment such as corona treatment.

[0102] The method for applying the printing ink is not particularly limited, and any known method can be used, including, for example, a roll coater, a rod coater, a blade, a wire bar, a doctor knife, a spin coater, a screen coater, a gravure coater, an offset gravure coater, and a flexo coater. If necessary, heating may be performed during printing.

[0103] The printing ink may further contain known binder resins, solvents, luster materials, additives, etc., depending on the intended use.

[0104] Examples of the binder resin include rosin resin, rosin-modified phenolic resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, and petroleum resin.

[0105] Examples of the water-insoluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.

[0106] Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Other examples include water-dilutable monoethers derived from polyhydric alcohols, such as methoxypropanol and methoxybutanol. Other examples include water-dilutable glycol ethers such as butyl glycol and butyl diglycol.

[0107] The lustrous material is a particle having an average thickness of 0.5 to 10 μm and an average particle diameter of 5 to 50 μm, and examples thereof include metal flakes, mica, and coated glass flakes. Examples of metal flakes include aluminum flakes and gold powder. Examples of mica include normal mica and coated mica. Examples of coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide.

[0108] The content of the lustrous material is preferably 0.1 to 10% by mass relative to 100% by mass of the printing ink. In addition, other color pigments and various additives commonly used in the art may be blended as needed.

[0109] The printing ink may further contain known additives, such as pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, hydrocarbon waxes, isocyanate-based curing agents, and silane coupling agents.

[0110] <Gravure ink> The gravure ink of the present invention contains a pigment composition and a binder resin, and preferably further contains a solvent.

[0111] [Polyurethane resin] The binder resin used in the gravure ink of the present invention is preferably a polyurethane resin, which includes a polyurethane urea resin. Polyurethane resins can be synthesized, for example, by a two-step method in which a polyol and a diisocyanate compound are reacted in such a ratio that the isocyanate groups are in excess to synthesize a urethane prepolymer having isocyanate groups at its terminals, followed by reaction of the urethane prepolymer having isocyanate groups with a chain extender and / or end-capping agent having amino groups in a solvent; or by a one-step method in which polypropylene glycol, a polyol, a diisocyanate compound, and a chain extender and / or end-capping agent having amino groups are reacted all at once in a suitable solvent.

[0112] The weight-average molecular weight of the polyurethane resin is preferably in the range of 15,000 to 100,000. When the weight-average molecular weight of the polyurethane resin is 15,000 or more, the ink will have excellent blocking resistance, and the printed film will have excellent strength and oil resistance, and when it is 100,000 or less, the viscosity of the resulting ink will be in an appropriate range, and the printed film will have excellent gloss.

[0113] In addition, the polyurethane resin preferably has an amine value from the viewpoint of printability and laminate strength. The amine value is preferably 0.5 to 20 mgKOH / g, more preferably 1 to 15 mgKOH / g.

[0114] The content of the binder resin in the ink is preferably 4 to 25% by mass, and more preferably in the range of 6 to 20% by mass.

[0115] [Organic solvents] Examples of organic solvents used in the gravure ink of the present invention include aromatic organic solvents such as toluene and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester-based organic solvents such as ethyl acetate, n-propyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol; and glycol ether-based solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether. It is preferable to use a mixture of two or more of these organic solvents. For gravure ink, it is preferable to use a mixed solvent of an ester-based organic solvent and an alcohol-based organic solvent. The mass ratio of the ester-based organic solvent to the alcohol-based organic solvent (mass of the ester-based organic solvent:mass of the alcohol-based organic solvent) is preferably 95:5 to 40:60, more preferably 90:10 to 50:50. The content of the organic solvent in the ink is preferably 60 to 90 mass %, more preferably 70 to 85 mass %, based on the mass of the ink.

[0116] The viscosity of the gravure ink is preferably 10 mPa·s or more to prevent pigment sedimentation and ensure adequate dispersion, and is preferably 1,000 mPa·s or less to ensure efficient ink production and printing. The above viscosity values ​​are measured at 25°C using a Tokimec B-type viscometer.

[0117] [water] The gravure ink of the present invention may further contain water. By containing a predetermined amount of water, the pigment dispersibility by the polyurethane resin is improved, and printing suitability such as highlight transferability, plate fogging resistance, and trapping properties is improved. The water content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 4% by mass, based on the mass of the gravure ink.

[0118] [Silica particles] The gravure ink of the present invention can further contain silica particles, which promotes wetting and spreading of the ink during overprinting, improves trapping properties, and maintains highlight transfer properties. Examples of silica particles include natural products, synthetic products, crystalline, amorphous, hydrophobic, and hydrophilic silica particles.Silica particles can be synthesized by dry or wet methods, and known dry methods include combustion and arc methods, while known wet methods include precipitation and gel methods.Silica particles synthesized by either method may be used.In addition, the silica particles may be hydrophilic silica having hydrophilic functional groups on the surface, or hydrophobic silica in which the hydrophilic functional groups have been modified with alkylsilane or the like to be hydrophobic.Hydrophilic silica is preferred. Examples of such silica particles include the Nipgel series and Nipsil series manufactured by Tosoh Silica Corporation, and the Mizukasil series manufactured by Mizusawa Chemical Industries, Ltd.

[0119] The silica particles create irregularities on the surface of the ink layer, so the average particle size is preferably 1 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1 to 6 μm. The average particle size of the silica particles means the particle size at 50% cumulative value (D50) in the particle size distribution, and can be determined by the Coulter counter method. The specific surface area of ​​silica particles is 50 to 600 m by the BET method. 2 / g, more preferably 100 to 450 m 2 The silica particles used in the gravure ink of the present invention may be a combination of two or more types having different average particle sizes or BET specific surface areas.

[0120] The content of silica particles is preferably 0.1 to 3 mass %, more preferably 0.2 to 2.5 mass %, even more preferably 0.2 to 2 mass %, and particularly preferably 0.2 to 1.5 mass %, based on the mass of the gravure ink.

[0121] [Other additives] The gravure ink of the present invention may contain other additives, such as extender pigments, pigment dispersants, leveling agents, antifoaming agents, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, and flame retardants, as required.

[0122] <Inkjet ink> The inkjet ink of the present invention contains a pigment composition and a resin, and preferably further contains a solvent. Inkjet inks can be broadly classified into (solvent-based) inkjet inks, aqueous inkjet inks, and solvent-free inkjet inks depending on the presence or absence of a solvent and the type of solvent. The following description will focus on aqueous inkjet inks.

[0123] It is preferable to prepare the aqueous inkjet ink of the present invention by first preparing an aqueous coloring composition, and then adding a solvent, additives, etc. to adjust the composition.

[0124] (Aqueous coloring composition) The aqueous coloring composition preferably contains a pigment composition, a resin as a dispersion medium, water, and a water-soluble solvent. The resin used as the dispersion medium is preferably resin type dispersant.The kind of resin can be, for example, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymer, styrene-(meth)acrylic acid-(meth)acrylic acid alkyl ester copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylic acid alkyl ester copolymer, poly(meth)acrylic acid, vinylnaphthalene-(meth)acrylic acid copolymer, styrene-maleic acid copolymer, maleic acid-maleic anhydride copolymer, α-olefin-(anhydride)maleic acid copolymer, α-olefin-(anhydride)maleic acid-polyalkylene glycol allyl ether copolymer vinylnaphthalene-maleic acid copolymer, polyester modified (meth)acrylic acid polymer and their salts etc.

[0125] The resin may be in the form of a water-soluble resin, an emulsion (water-insoluble resin), or the like.

[0126] The water is preferably ion-exchanged water or distilled water.

[0127] Examples of water-soluble solvents include 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol.

[0128] The aqueous coloring composition may contain a surfactant, such as an anionic surfactant or a nonionic surfactant.

[0129] Examples of the anionic surfactant include fatty acid salts, alkyl sulfate ester salts, alkylaryl sulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyldiaryletherdisulfonates, alkylphosphates, polyoxyethylene alkylether sulfates, polyoxyethylene alkylarylether sulfates, naphthalenesulfonate-formalin condensates, and polyoxyethylene alkylphosphate ester salts.

[0130] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters polyoxyethylene alkylamines, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.

[0131] The content of the surfactant is preferably from 0.3 to 20 mass %, more preferably from 1 to 10 mass %, in 100 parts by mass of the aqueous coloring composition.

[0132] The content of the surfactant is preferably from 5 to 200 parts by mass, more preferably from 25 to 100 parts by mass, per 100 parts by mass of the pigment.

[0133] The aqueous coloring composition may contain other additives, such as preservatives, pH adjusters, antifoaming agents, and wetting agents.

[0134] Examples of preservatives include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, and amine salts of 1-benzisothiazolin-3-one. The content of the preservative is preferably 0.1 to 2% by mass in 100 parts by mass of the aqueous coloring composition.

[0135] Examples of pH adjusters include various amines, inorganic salts, ammonia, various buffer solutions, and the like.

[0136] The antifoaming agent is used to prevent the generation of foam when producing the water-based coloring composition. Commercially available antifoaming agents include, for example, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, and Surfynol PSA-336 (all manufactured by Nissin Chemical Industry Co., Ltd.), ADDITOL VXW6211, ADDITOL VXW4973, ADDITOL VXW6235, ADDITOL XW375, ADDITOL XW376, ADDITOL VXW6381, ADDITOL VXW6386, ADDITOL VXW6392, ADDITOL VXW6393, ADDITOL VXW6399, and ADDITOL VXW6391. XW6544, etc. (all manufactured by Allnex).

[0137] Wetting agents are used to obtain a smooth coating during printing or coating. Commercially available wetting agents include ADDITOL VXL6237N, ADDITOL XL260N, ADDITOL VXL6212, ADDITOL UVX7301 / 65, ADDITOL XW330, ADDITOL VXW6200, ADDITOL VXW6205, ADDITOL VXW6394, ADDITOL VXW6208, ADDITOL VXW6208 / 60, and ADDITOL VXW6374 (all manufactured by Allnex).

[0138] Each material used in the preparation of the water-based coloring composition can be used alone or in combination of two or more kinds.

[0139] The water-based coloring composition can be prepared by dispersing materials such as a pigment composition, a resin, water, and, if necessary, other additives.

[0140] Examples of dispersing machines used in the dispersion treatment include horizontal sand mills, vertical sand mills, annular bead mills, attritors, microfluidizers, high-speed mixers, homomixers, homogenizers, high-pressure homogenizers, ball mills, paint shakers, roll mills, stone mills, ultrasonic dispersers, counter-impingement type high-pressure dispersers, and oblique collision type high-pressure dispersers.

[0141] More specifically, when a resin-type dispersant that is a water-soluble resin is used as the resin, the aqueous colored composition of the present invention can be obtained by the method described in the examples described later, that is, by mixing a pigment composition, a resin-type dispersant, water, etc., and then performing a dispersion treatment using the disperser.

[0142] In addition, when a resin-type dispersant that is a water-insoluble resin is used as the resin, for example, the resin-type dispersant is dissolved in an organic solvent that can dissolve the water-insoluble resin, and then mixed with a pigment composition, and a dispersion treatment is performed using the disperser. Thereafter, phase inversion emulsification is performed using water, and then the organic solvent is distilled off to obtain an aqueous coloring composition.

[0143] On the other hand, it is preferable to crosslink the resin-type dispersant on the surface of the pigment composition, since this can significantly improve the dispersibility and dispersion stability of the pigment composition in the aqueous coloring composition. Aqueous inkjet inks using such pigment compositions in which the resin-type dispersant present on the surface is crosslinked (hereinafter also referred to as "pigment composition-containing crosslinked resin particles") also have excellent redispersibility (the pigment composition in the aqueous inkjet ink can be redispersed by adding water after the aqueous inkjet ink has dried and aggregated / thickened), which can suppress nozzle clogging and "fading" during continuous printing, for example. Furthermore, coating the pigment composition with a crosslinked resin-type dispersant can also achieve improved weather resistance and pH resistance.

[0144] Examples of methods for producing the water-based colored composition containing the pigment composition-containing crosslinked resin particles include the following four methods.

[0145] [[Method (i)]] This method involves the following four steps to produce crosslinked resin particles containing a pigment composition. Step (i-1): A step of carrying out a dispersion treatment using a pigment composition; a resin-type dispersant having a crosslinkable functional group and a carboxy group, the carboxy group of which has been neutralized with a basic compound to be hydrophilic; and water. Step (i-2): A step of adding an acidic compound to the dispersion of the pigment composition prepared in the above step (i-1) to neutralize or acidify the pH of the dispersion, thereby precipitating and fixing the resin-type dispersant on the surface of the pigment composition. Step (i-3): After step (i-2), the carboxyl groups in the resin-type dispersant are neutralized with a basic compound (which may be the same as or different from the basic compound used in step (i-1)), and the pigment composition to which the resin-type dispersant has been fixed is re-dispersed in water. Step (i-4): a step following step (i-3) in which the crosslinkable functional groups in the resin-type dispersant are reacted with a crosslinking agent to crosslink the functional groups, thereby obtaining a waterborne coloring composition containing crosslinked resin particles containing a pigment composition. The crosslinking agent may be added at the start of step (i-4) or at any stage of steps (i-1) to (i-3).

[0146] [[Method (ii)]] The pigment composition to which the resinous dispersant has adhered is redispersed in water in the same manner as in steps (i-1) to (i-3) described above, except that the resinous dispersant used is a resinous dispersant having a self-crosslinkable functional group and a carboxyl group, the carboxyl group of which has been neutralized with a basic compound to make it hydrophilic. The resinous dispersant is then self-crosslinked to obtain a waterborne colored composition containing crosslinked resin particles containing the pigment composition.

[0147] [[Method (iii)]] This method involves producing crosslinked resin particles containing a pigment composition through the following two steps. Step (iii-1): A step of mixing a pigment, a resin having a carboxy group, a basic compound, and water. Step (iii-2): After the step (iii-1), a crosslinking agent is added to carry out a crosslinking treatment, thereby obtaining a water-based coloring composition containing crosslinked resin particles containing a pigment composition.

[0148] [[Method (iv)]] This method involves producing crosslinked resin particles containing a pigment composition through the following two steps. Step (iv-1): A step of mixing a pigment, a resin having a carboxy group, and an organic solvent. Step (iv-2): After the step (iv-1), water is added and the organic solvent is removed by vacuum distillation or the like. Step (iv-3): After the step (iv-2), a crosslinking agent is added to carry out a crosslinking treatment, thereby obtaining a water-based coloring composition containing crosslinked resin particles containing a pigment composition.

[0149] When the aqueous coloring composition obtained by the above-mentioned method is subjected to a heat treatment or post-treatment, the dispersion stability of the pigment composition containing CI Pigment Yellow 180 and azo compound (1) is improved. The heat treatment is a treatment in which the aqueous coloring composition is heated to 30 to 80°C and maintained for several hours to about one week. The post-treatment is a treatment in which the aqueous coloring composition is dispersed using an ultrasonic disperser or a collision-type beadless disperser.

[0150] Before the dispersion treatment, a pre-dispersion treatment can be carried out without using water or a water-soluble solvent. Examples of the apparatus used for the pre-dispersion treatment include a kneader, a three-roll mill or other grinding mixer, a two-roll mill or other non-volatile disperser, and an MK mixer or other media-less disperser.

[0151] (Water-based inkjet ink) The content of the pigment composition is preferably from 0.5 to 30% by mass, and more preferably from 1 to 15% by mass, based on 100% by mass of the aqueous inkjet ink.

[0152] The resin used in aqueous inkjet ink is important for ensuring the ink adheres well to the substrate. Examples of resin types include acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, and polyurethane resins. Resin forms include water-soluble resins and emulsion particles. Among these, emulsion particles are preferred. Emulsion particles include single-component particles and core-shell particles, and any type can be selected and used. The use of emulsion particles facilitates the reduction of the viscosity of aqueous inkjet inks, making it easy to obtain recorded materials with excellent water resistance. The acidic functional groups of the resin can be neutralized, if necessary, with a pH adjuster such as ammonia, various amines, or various inorganic alkalis.

[0153] The resin content is preferably 2 to 30% by mass, and more preferably 3 to 20% by mass, based on 100% by mass of the non-volatile content of the inkjet ink. A moderate content improves the ejection stability and fixability.

[0154] Examples of solvents include water-insoluble solvents, water, and water-soluble solvents. Examples of water-soluble solvents include glycol ethers and diols. These solvents penetrate substrates very quickly, even into low-absorbency or non-absorbent substrates such as coated paper, art paper, vinyl chloride sheets, films, and fabrics. This allows for fast drying during printing, resulting in accurate printing. Furthermore, due to their high boiling points, they also function as wetting agents.

[0155] The water-soluble solvent is important for preventing drying and solidification at the nozzle portion of the printer head of the aqueous inkjet ink and for achieving ink ejection stability. Examples of the water-soluble solvent include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone.

[0156] The content of the water-soluble solvent including water is preferably 15 to 50% by mass in 100% by mass of the inkjet ink.

[0157] The inkjet ink may further contain additives such as a drying accelerator, a penetrating agent, a chelating agent, a preservative, and a pH adjuster.

[0158] Drying accelerators are used to accelerate the drying of aqueous inkjet inks after printing. Examples of drying accelerators include alcohols such as methanol, ethanol, and isopropyl alcohol. The content of the drying accelerator is preferably 1 to 50% by mass relative to 100% by mass of the aqueous inkjet ink.

[0159] When the substrate is a permeable material such as paper, a penetrant is used to promote the penetration of the ink into the substrate and speed up the apparent drying time. Examples of penetrants include water-soluble solvents as well as surfactants such as polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, and dioctyl sodium sulfosuccinate. The amount of penetrant used is preferably 0.1 to 5% by mass based on 100% by mass of the aqueous inkjet ink. When used in an appropriate amount, problems such as bleeding of the print and ink smearing on the paper are less likely to occur.

[0160] The chelating agent is used to capture metal ions contained in the aqueous inkjet ink and prevent the precipitation of insoluble matter in the nozzle or in the ink. Examples of the chelating agent include ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, and tetraammonium salt of ethylenediaminetetraacetic acid. The amount of the chelating agent used is preferably 0.005 to 0.5% by mass relative to 100% by mass of the aqueous inkjet ink.

[0161] Inkjet ink is prepared by blending and mixing the various materials. Mixing can be performed using a blade stirrer, various dispersers, emulsifiers, etc. The order in which the materials are added and the mixing method are optional.

[0162] After mixing, the inkjet ink is preferably filtered or centrifuged to remove coarse particles, which improves the ejection properties from the inkjet printer. Filtration and centrifugation can be performed by known methods.

[0163] The inkjet ink of the present specification can be used in various inkjet systems, including, for example, charge control systems, continuous jet systems such as spray systems, piezo systems, thermal systems, and electrostatic suction systems.

[0164] <Water-based flexographic ink> The aqueous flexographic ink of this specification contains at least a coloring composition (pigment composition, resin) and water. A variety of substrates can be selected, and the ink is suitable for printing on non-permeable substrates other than general printing paper, such as coated paper and plastic films (including plastic sheets).

[0165] The content of the pigment composition in the water-based flexographic ink is not particularly limited, but is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass.

[0166] Below, each component contained in the water-based flexographic ink and, if necessary, the method for synthesizing the component will be described.

[0167] (binder resin) The aqueous flexographic ink preferably contains a binder resin. Examples of binder resins include aqueous resins such as aqueous urethane resins, polyester resins, acrylic resins, styrene-acrylic resins, styrene-maleic anhydride resins, rosin-modified maleic acid resins, cellulose-based resins, and chlorinated polyolefins. Among these, it is preferable to contain at least an aqueous urethane resin. The binder resins can be used alone or in combination of two or more.

[0168] (water-based urethane resin) A urethane resin is generally a resin obtained by reacting a polyisocyanate having two or more isocyanate groups per molecule with a hydroxyl group-containing compound having two or more hydroxyl groups per molecule. The aqueous urethane resin of this embodiment has the following configuration. This configuration can be preferably introduced by appropriately selecting the structure and type of the hydroxyl group-containing compound, as described below.

[0169] The number of urethane bonds (mmol / g) of the aqueous urethane resin is not particularly limited, but is preferably 2.2 to 3.0 mmol / g, more preferably 2.3 to 2.9 mmol / g, from the viewpoint of adjusting the molecular weight of the resin and the hardness of the coating film, etc. This number of urethane bonds can be adjusted to a desired range by appropriately adjusting the amounts of the hydroxyl group-containing compound and polyisocyanate, as well as the reaction conditions.

[0170] The glass transition temperature (Tg) of the aqueous urethane resin is not particularly limited, but is preferably −70° C. or lower, and more preferably −70° C. to −90° C. When the Tg of the aqueous urethane resin is −70° C. or lower, the film-forming properties of the ink are improved, and the adhesion of the coating film is also improved.

[0171] The weight average molecular weight (measured by GPC, converted into standard polystyrene) of the aqueous urethane resin is not particularly limited, but is preferably 10,000 to 100,000, and more preferably 30,000 to 70,000.

[0172] The hydroxyl value (mgKOH / g) of the aqueous urethane resin is not particularly limited, but from the viewpoint of water resistance etc., it is preferably 0.0 to 3.0 mgKOH / g, and more preferably 0.0 to 2.0 mgKOH / g.

[0173] The aqueous urethane resin is preferably contained in an amount of 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more, based on the total amount of the aqueous flexographic ink, while the content of the aqueous urethane resin is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less, based on the total amount of the rotary printing ink.

[0174] The content of the hydrocarbon wax in the water-based flexographic ink is preferably 0.5 to 7 mass %, more preferably 1 to 4 mass %.

[0175] Aqueous flexographic inks contain an aqueous solvent, such as water or alcohol, including n-propanol and isopropyl alcohol.

[0176] The content of the aqueous solvent in the aqueous flexographic ink is preferably 40 to 60% by mass.

[0177] (Other ingredients) The aqueous flexographic ink may contain other known additives such as antifoaming agents, thickeners, leveling agents, pigment dispersants, and UV absorbers as needed. Furthermore, as long as the problem can be solved, non-aqueous solvents other than alcohol (e.g., ketone solvents and ester solvents) may also be contained. The content of non-aqueous solvents in the ink is preferably 20% by mass or less, and more preferably 10% by mass or less. is more preferred.

[0178] <Active energy ray curable ink> The active energy ray-curable ink of this specification contains a coloring composition (pigment composition, resin), a polymerizable compound, and a photopolymerization initiator.

[0179] In addition to the pigment composition of the present invention, known colorants may be used in any combination in the actinic ray-curable ink, as needed, within the scope of the effects of the present invention. The pigment composition of the present invention preferably accounts for 5 to 30% by mass, more preferably 10 to 25% by mass, based on the total mass of the active energy ray-curable ink.

[0180] Components that are or can be contained in the active energy ray-curable ink of this embodiment will be described below.

[0181] (polymerizable compound) The polymerizable compound is a compound having one or more ethylenically unsaturated bonds in the molecule, and examples of the polymerizable compound include a monomer and an oligomer.

[0182] (monomer) The monomer is more preferably a (meth)acrylate monomer of a compound having a (meth)acryloyl group. Specifically, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxyethyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the molecule, such as acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and acryloylmorpholine; 1,3-Butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, polyethylene glycol (300) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, neopentyl glycol di(meth)acrylate hydroxypivalate , dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified (2) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth)acrylate, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and other bifunctional (meth)acrylate monomers having two (meth)acryloyl groups in the molecule; Trimethylolpropane tri(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, EO-modified (6) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate, ethoxylated isocyanuric acid tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, etc. a trifunctional (meth)acrylate monomer having three (meth)acryloyl groups in the molecule; tetrafunctional (meth)acrylate monomers having four acryloyl groups in the molecule, such as pentaerythritol tetra(meth)acrylate, EO-modified (4) pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate; Pentafunctional (meth)acrylate monomers having five (meth)acryloyl groups in the molecule, such as dipentaerythritol penta(meth)acrylate; Examples include hexafunctional (meth)acrylate monomers having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate, etc. In addition, vinyl group-containing monomers having no (meth)acryloyl groups can also be used.

[0183] (oligomer) Examples of the oligomer include urethane acrylate oligomers such as aliphatic urethane acrylate oligomers and aromatic urethane acrylate oligomers, acrylic ester oligomers, polyester acrylate oligomers, and epoxy acrylate oligomers. The oligomer preferably contains about 2 to 10 ethylenically unsaturated bonds.

[0184] The weight average molecular weight of the oligomer is preferably 400 to 10,000, more preferably 500 to 5,000. Here, the "weight average molecular weight" can be determined as a polystyrene-equivalent molecular weight by general gel permeation chromatography (hereinafter, referred to as GPC).

[0185] The polymerizable compounds can be used alone or in combination of two or more kinds.

[0186] The content of the polymerizable compound in the active energy ray-curable ink is preferably from 40 to 80% by mass, and more preferably from 45 to 70% by mass.

[0187] (Photopolymerization initiator) Examples of the photopolymerization initiator include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, and thioxanthone compounds.

[0188] Examples of the benzophenone-based compounds include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, and [4-(methylphenylthio)phenyl]-phenylmethanone.

[0189] Examples of the dialkoxyacetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

[0190] Examples of the α-hydroxyalkylphenone compounds include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one.

[0191] Examples of the α-aminoalkylphenone compounds include 2-methyl-1-[4-(methoxythio)-phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0192] Examples of the acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0193] Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

[0194] The photopolymerization initiators can be used alone or in combination of two or more.

[0195] The content of the photopolymerization initiator in the active energy ray-curable ink is preferably from 1 to 20% by mass, and more preferably from 5 to 15% by mass.

[0196] The actinic energy ray-curable ink of the present invention may contain a hydrocarbon wax. From the viewpoint of the balance between abrasion resistance, gloss, and piling, the content of the hydrocarbon wax is preferably 0.5 to 5 mass %, and more preferably 0.5 to 4 mass %, relative to the total mass of the actinic energy ray-curable ink.

[0197] The active energy ray-curable ink of the present invention may contain a binder resin. The inclusion of a binder resin alleviates cure shrinkage of the coating film that occurs during curing, suppresses curling of the substrate, and further improves adhesion to the substrate.

[0198] The weight average molecular weight of the binder resin is preferably 10,000 to 100,000, and more preferably 10,000 to 70,000.

[0199] The binder resins can be used alone or in combination of two or more kinds. The content of the binder resin is preferably 5 to 15% by mass relative to the total mass of the ink.

[0200] (sensitizer) The actinic ray-curable ink may contain a sensitizer. By including a sensitizer, curability can be further improved. Examples of sensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and dibutylethanolamine.

[0201] (polymerization inhibitor) The active energy ray-curable ink of the present invention may contain a polymerization inhibitor, such as 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, and aluminum salt of N-nitrosophenylhydroxylamine.

[0202] The content of the polymerization inhibitor in the actinic energy ray-curable ink is preferably 0.01 to 2% by mass, from the viewpoint of improving the storage stability of the actinic energy ray-curable ink while maintaining the curability.

[0203] It is preferable that the active energy ray-curable ink contains substantially no water, which means that the amount of water contained is 3% by mass or less relative to the total mass of the active energy ray-curable ink.

[0204] (extender pigment) The active energy ray-curable ink may contain an extender pigment, such as clay, talc, barium sulfate, calcium carbonate, ground calcium carbonate, barium carbonate, magnesium carbonate, silica, or bentonite.

[0205] <Printed matter using active energy ray curable ink> The printed matter of the present invention can be obtained by printing an actinic ray-curable ink on a substrate and curing it with actinic ray.

[0206] The active energy ray-curable ink can be cured by, for example, irradiation with α-rays, γ-rays, electron beams, X-rays, ultraviolet light, visible light, infrared light, or the like. Of these, ultraviolet light and electron beams are preferred, and ultraviolet light is more preferred. The peak wavelength of the active energy ray is preferably 200 to 600 nm, and more preferably 350 to 420 nm.

[0207] Examples of sources of active energy rays include mercury lamps, xenon lamps, metal hydride lamps, LEDs (light-emitting diodes) such as ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs), and gas / solid-state lasers.

[0208] <Ink set> The ink set of the present invention is an ink set containing at least a yellow ink, a cyan ink, and a magenta ink, and the yellow ink is an ink containing the pigment composition of the present invention.

[0209] The ink set of the present invention may further contain other inks such as black ink, white ink, and special color ink.

[0210] The ink set of the present invention can be used as a printing ink set such as an offset printing ink, a flexographic printing ink, a gravure printing ink, a screen printing ink, etc., and as an ink set for an ink jet ink. Among these, a gravure printing ink set and an ink jet ink set used for packaging materials are preferred, and a gravure printing ink set is more preferred.

[0211] <Yellow ink> The yellow ink of the present invention contains the above pigment composition and a binder resin. By containing the azo compound (1) as described above, the yellow ink improves dispersibility and storage stability, which have been weaknesses of CI Pigment Yellow 180 in the past.

[0212] <Binder resin> Examples of binder resins include polyurethane resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, nitrocellulose resins, polyamide resins, polyvinyl acetal resins, cellulose ester resins, polystyrene resins, acrylic resins, polyester resins, alkyd resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubber, butyral, petroleum resins, and chlorinated polyolefin resins.

[0213] The content of the binder resin in the yellow ink is preferably from 4 to 25% by mass, and more preferably from 6 to 20% by mass.

[0214] The yellow ink may further contain other pigments, resins, organic solvents, and, if necessary, additives such as pigment dispersants, leveling agents, antifoaming agents, waxes, plasticizers, infrared absorbers, and ultraviolet absorbers.

[0215] <Cyan ink> The cyan ink in the present invention is an ink that can produce a cyan color and contains a pigment and a binder resin. The binder resin can be any of the resins already described above.

[0216] <Magenta ink> The magenta ink of the present invention is an ink that can produce a magenta color and contains a pigment and a binder resin. The binder resin can be any of the resins already described above.

[0217] <Pigments> Examples of the pigment include organic pigments and inorganic pigments. In this specification, for example, the following pigments can be used.

[0218] [Organic pigments] The pigment is preferably an organic pigment, and examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, azomethine azo pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, isoindoline pigments, and indanthrone pigments.

[0219] Examples of pigments are listed by CI pigment number.

[0220] Examples of indigo pigments include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, and CI Pigment Blue 60. Other examples include phthalocyanine pigments such as aluminum phthalocyanine (compound (11)) and titanyl phthalocyanine (compound (12)). The cyan ink preferably contains the above-mentioned indigo pigments, of which CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 16 are more preferred.

[0221] [ka]

[0222] Red pigments include, for example, CI Pigment Red 2, CI Pigment Red 32, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 63:1, CI Pigment Red 81, CI Pigment Red 122, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 166, CI Pigment Red 170, CI Pigment Red 174, CI Pigment Red 178, CI Pigment Red 179, and CI Pigment Red 18. 4, CI Pigment Red 185, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 238, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 260, CI Pigment Red 264, CI Pigment Red 269, CI Pigment Red 272, CI Pigment Violet 19, etc. The magenta ink preferably contains the above-mentioned red pigments, of which CI Pigment Red 48:3, CI Pigment Red 57:1, CI Pigment Red 122, CI Pigment Red 146, CI Pigment Red 185, and CI Pigment Violet 19 are more preferred.

[0223] Examples of yellow pigments include CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 120, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 151, CI Pigment Yellow 155, CI Pigment Yellow 174, CI Pigment Yellow 180, CI Pigment Yellow 185, and CI Pigment Yellow 234. When used in the yellow ink constituting the ink set of the present invention, the above yellow pigment may be contained.

[0224] Examples of purple pigments include CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, and CI Pigment Violet 37.

[0225] Examples of green pigments include CI Pigment Green 7.

[0226] Examples of orange pigments include CI Pigment Orange 13, CI Pigment Orange 34, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 64, CI Pigment Orange 71, and CI Pigment Orange 73.

[0227] The special color inks include inks of colors other than cyan, magenta, and yellow, such as purple, green, and vermilion, and preferably contain the above-mentioned purple pigment, green pigment, orange pigment, and the like.

[0228] In the ink set of the present invention, for example, the cyan ink preferably contains CI Pigment Blue 16, and the magenta ink preferably contains one or more of CI Pigment Violet 19 and CI Pigment Red 122. By including the above pigments, the environmental compatibility and safety and hygiene of the ink can be improved.

[0229] [Inorganic pigments] Examples of inorganic pigments include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithopone, antimony white, and gypsum; black inorganic pigments such as carbon black, iron black, and copper-chromium complex oxide; aluminum particles, mica, bronze powder, chrome vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, Prussian blue, red iron oxide, yellow iron oxide, and zircon.

[0230] For black ink, it is preferable to use carbon black, such as CI Pigment Black 7, because it provides excellent coloring power, hiding power, chemical resistance, and weather resistance. For white ink, it is preferable to use titanium oxide, because it provides excellent coloring power, hiding power, chemical resistance, and weather resistance. For printing performance, it is preferable that the titanium oxide is surface-treated with silica and / or alumina.

[0231] Each ink can use a single pigment or two or more pigments in combination to obtain the desired color tone.

[0232] The average primary particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably in the range of 50 to 150 nm. In order to ensure the density and coloring strength of the ink, the pigment content in the ink is preferably in the range of 1 to 60 mass% based on the mass of the ink, and preferably in the range of 10 to 90 mass% based on the mass of the non-volatile matter in the ink.

[0233] <Gravure printing ink set> The gravure printing ink set of the present invention preferably comprises the above-mentioned ink set. The gravure inks of each color constituting the gravure printing ink set of the present invention are as described above.

[0234] <Clear ink> The gravure printing ink set of the present invention can further contain a clear ink. The release layer formed from the clear ink has the function of peeling from the substrate by being neutralized with an alkaline aqueous solution and dissolving or swelling. This promotes the release of the printed layer from the substrate and facilitates the recycling of printed matter and packaging materials. Examples of basic compounds used in the alkaline aqueous solution include sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), ammonia, barium hydroxide (Ba(OH)2), and sodium carbonate (Na2CO3). More preferred is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide. In this specification, the process of neutralizing with an alkaline aqueous solution and dissolving or swelling may be referred to as "alkali treatment." Furthermore, the layer that has releasability due to the alkaline treatment may be referred to as "detachment layer." In other words, the printed layer formed by the clear ink corresponds to the layer that has releasability (detachment layer).

[0235] [Carboxy group-containing resin] The clear ink preferably contains a carboxyl group-containing resin, which functions, for example, as a primer composition that is printed on a substrate before the color inks are applied. Examples of the carboxyl group-containing resin include acrylic resin, polyurethane resin, polyester resin, amino resin, phenol resin, epoxy resin, and cellulose. Among these, polyurethane resin is preferred because of its good suitability for lamination.

[0236] The hydroxyl value of the carboxyl group-containing polyurethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. A hydroxyl value of 1 mgKOH / g or more is preferred because it improves the releasability with an alkaline aqueous solution, while a hydroxyl value of 35 mgKOH / g or less is preferred because it improves the adhesion to substrates. The acid value of the carboxyl group-containing polyurethane resin is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. An acid value of 15 mgKOH / g or more is preferable because it improves releasability with an alkaline aqueous solution, while an acid value of 70 mgKOH / g or less improves adhesion to substrates and improves retort resistance when used as a packaging material. The hydroxyl value and acid value are both values ​​measured in accordance with JIS K0070.

[0237] The weight average molecular weight of the carboxy group-containing polyurethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and even more preferably 15,000 to 50,000.

[0238] The molecular weight distribution (Mw / Mn) of the carboxy group-containing polyurethane resin is preferably not more than 6. When the molecular weight distribution is not more than 6, the effects caused by excess high molecular weight components and unreacted components, side reaction components, and other low molecular weight components can be avoided, resulting in good releasability, drying properties of the primer composition, and retort resistance. Furthermore, the smaller the molecular weight distribution, i.e., the sharper the molecular weight distribution, the more uniform the dissolution and peeling action by the alkaline aqueous solution occurs, improving the releasability, which is preferable. The molecular weight distribution is more preferably 5 or less, and even more preferably 4 or less. The molecular weight distribution is also preferably 1.2 or more, and more preferably 1.5 or more.

[0239] The carboxyl group-containing polyurethane resin may have an amine value. When the carboxyl group-containing polyurethane resin has an amine value, the amine value is preferably 0.1 to 20 mgKOH / g, and more preferably 1 to 10 mgKOH / g.

[0240] The carboxyl group-containing polyurethane resin is not particularly limited and can be synthesized, for example, by reacting a polyol, a hydroxy acid, and a polyisocyanate. The use of a hydroxy acid can impart an acid value to the polyurethane resin. The polyurethane resin is preferably further modified into a polyurethane urea resin by reacting with a polyamine.

[0241] The clear ink may further contain a polyisocyanate as a curing component. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, such as aliphatic polyisocyanates and aralkyl polyisocyanates. The clear ink may also contain other components in addition to the carboxyl group-containing resin and polyisocyanate, and may contain additives such as organic solvents and anti-blocking agents, as in the case of the cyan, yellow, and magenta inks described above.

[0242] <Inkjet ink set> The inkjet ink set of the present invention preferably includes the ink set described above. The inkjet inks of each color constituting the inkjet ink set of the present invention are as described above.

[0243] <Printed material> The printed matter of the present invention includes a substrate and a print layer formed from a gravure printing ink set, the print layer being formed by printing cyan ink, yellow ink, and magenta ink onto the substrate. The gravure printing method is not particularly limited and can be appropriately selected from known methods. Gravure printing methods are roughly divided into front printing and back printing. For example, in front printing, when the substrate is white paper or white film, a printed matter can be obtained by printing on the substrate in the order of yellow ink, magenta ink, cyan ink, and black ink. Furthermore, for example, when reverse printing is performed and the substrate is a transparent film, it is preferable to produce a printed matter by printing black ink, cyan ink, magenta ink, yellow ink, and white ink on the substrate in this order. When the ink set of the present invention includes a clear ink, the clear ink is preferably printed on the substrate before the color inks. The thickness of the printed layer can be appropriately selected depending on the application, the type and number of inks used, and the number of overprints, but is usually in the range of 0.5 to 10 μm.

[0244] [Base material] Examples of substrates include polyolefin substrates such as polyethylene and polypropylene; polycarbonate substrates; polyester substrates such as polyethylene terephthalate and polylactic acid; polystyrene substrates; polystyrene-based resins such as AS and ABS; polyamide substrates such as nylon; polyvinyl chloride substrates; polyvinylidene chloride substrates; cellophane substrates; paper substrates; aluminum foil substrates; and composite substrates made of these composite materials. The substrate may be in the form of a film or a sheet. Among these, polyester substrates and polyamide substrates with high glass transition points are preferably used.

[0245] The surface of the substrate may be vapor-deposited with a metal oxide or the like, or may be coated with polyvinyl alcohol or the like. Examples of such surface-treated substrates include GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., both of which have aluminum oxide vapor-deposited on their surfaces. The substrate may be treated with additives such as an antistatic agent or an ultraviolet inhibitor, as needed, or may be corona-treated or low-temperature plasma-treated.

[0246] The thickness of the substrate is not particularly limited, and is usually in the range of 5 to 100 μm.

[0247] [Detachment layer] The printed matter of the present invention can contain a detachment layer. Here, the term "detachment layer" refers to a material that has the property of being peeled off from a substrate by being neutralized with an alkaline aqueous solution and dissolving or swelling. The layer having detachment properties is preferably a layer formed from the above-mentioned clear ink, but the detachment layer may also be any other layer.

[0248] The thickness of the release layer is not particularly limited, and is usually in the range of 0.5 to 5 μm.

[0249] <Packaging materials> The packaging material of the present invention includes a printed matter at least in part. For example, the packaging material may be configured by sequentially laminating a printed matter, an adhesive layer, and a sealant substrate. The packaging material can be suitably used for packaging of various shapes, such as four-sided sealed packages, three-sided sealed packages, pillow packages, stick bags, gusset bags, square-bottom bags, standing pouches, deep-draw containers, vacuum packages, skin packs, zipper bags, spout pouches, twist packages, wrap packages, shrink packages, labels, liquid paper cartons, and paper trays.

[0250] Examples of items packaged in packaging materials include food products (e.g., rice, confectionery, seasonings, edible oils and fats, cooked foods, etc.), beverages (e.g., alcoholic beverages, soft drinks, mineral water, etc.), daily necessities (e.g., pharmaceuticals, cosmetics, stationery, etc.), electronic components, etc.

[0251] [Adhesive layer] Adhesive components that can be used to form the adhesive layer include laminating adhesives, hot melt adhesives, and thermoplastic resins. Among the adhesive components, laminating adhesives and hot melt adhesives include, for example, polyether adhesives, polyurethane adhesives, epoxy adhesives, polyvinyl acetate adhesives, cellulose adhesives, and (meth)acrylic adhesives. Among these adhesive components, polyurethane adhesives are preferably used.

[0252] The adhesive component can be used alone or in combination of two or more kinds. The thickness of the adhesive layer is usually in the range of 1 to 6 μm.

[0253] The polyurethane adhesive may be a reactive adhesive containing a polyol and a polyisocyanate, and may have releasability. Examples of the polyurethane adhesive having releasability include the laminating adhesive described in JP 2020-084130 A. The polyurethane adhesive having such releasability preferably has an acid value of 5 to 45 mgKOH / g. Furthermore, it is preferable that the polyol constituting the polyurethane adhesive includes a polyester polyol, and the polyisocyanate includes one selected from the group consisting of an aliphatic polyisocyanate and an araliphatic polyisocyanate.

[0254] [Sealant base material] The sealant substrate is the substrate that constitutes the innermost layer of the laminate film and is made of a resin material that can be fused to each other by heat (has heat-sealing properties). Examples of the sealant substrate include solid polypropylene (CPP), vapor-deposited solid polypropylene film (VQCPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ethylene-vinyl acetate copolymer (EVA). The thickness of the sealant substrate is not particularly limited, but is preferably in the range of 10 to 200 μm, more preferably 15 to 150 μm, taking into consideration processability into packaging materials, heat sealing properties, etc. Furthermore, by providing the sealant substrate with unevenness with a height difference of 5 to 20 μm, it is possible to impart slip properties to the sealant substrate and tearability of packaging materials. The method for laminating the sealant substrate is not particularly limited, and examples thereof include a method of thermally laminating an adhesive layer and a sealant substrate film (thermal lamination, dry lamination), and a method of melting a sealant substrate resin, extruding it onto the adhesive layer, and cooling and solidifying it to form a laminate (extrusion lamination). [Example]

[0255] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" means "parts by mass" and "%" means "% by mass".

[0256] (Method for identifying azo compound (1)) Azo compound (1) in the pigment composition of the present invention was identified using MALDI TOF-MS spectroscopy. A Bruker Daltonics Autoflex III MALDI mass spectrometer was used for MALDI TOF-MS spectroscopy. The resulting compound was identified by matching the molecular ion peak in the mass spectrum with the calculated mass number (theoretical molecular weight). Note that in negative ion measurements, the measured value is the mass number of the compound minus 1 (theoretical molecular weight), since the H (proton) is removed from the compound. Therefore, the compound matches the theoretical molecular weight. The composition ratio was calculated from the peak area ratio.

[0257] (Measurement of hydroxyl value) It was determined in accordance with JIS K0070.

[0258] (Acid value measurement) It was determined in accordance with JIS K0070.

[0259] (Amine value measurement) The amine value was determined by the following method in accordance with JIS K0070, in terms of the equivalent amount of hydrochloric acid required to neutralize the amino groups contained in 1 g of resin and the equivalent amount of potassium hydroxide in mg. 0.5 to 2 g of sample was precisely weighed out (sample nonvolatile content: Sg). 50 mL of a 60 / 40 (mass ratio) mixed solution of methanol and methyl ethyl ketone was added to dissolve the precisely weighed sample. Bromophenol blue was added to the resulting solution as an indicator, and the resulting solution was titrated with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the color of the solution changed from green to yellow was set as the endpoint, and the titer (A mL) at this point was used to calculate the amine value using the following formula. Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

[0260] (Measurement of average molecular weight) The number average molecular weight and weight average molecular weight were determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (HLC-8220 manufactured by Tosoh Corporation) and calculating the molecular weight converted using polystyrene as a standard substance. The measurement conditions are shown below. Columns: The following columns were used in series. Tosoh guard column HXL-H Tosoh TSKgelG5000HXL Tosoh TSKgel G4000HXL Tosoh TSKgel G3000HXL Tosoh TSKgel G2000HXL Detector: RI (differential refractometer) Measurement conditions: Column temperature 40°C Eluent: tetrahydrofuran Flow rate: 1.0mL / min

[0261] (Measurement of glass transition temperature) The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC) using a Rigaku DSC8231 measuring instrument, with a measurement temperature range of -70 to 250°C, a heating rate of 10°C / min, and the midpoint between the endothermic start and end temperatures due to the glass transition in the DSC curve.

[0262] <Production of Pigment Composition> (Example A-1) While stirring 1,300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after one hour, 223.9 parts of 35% hydrochloric acid was added. After stirring for another hour, ice was added to adjust the temperature to 0-5°C, and 119.6 parts of 38% aqueous sodium nitrite solution was added to carry out the diazotization reaction. Sulfamic acid was added to remove excess nitrite, and the mixture was stirred for 30 minutes or more to obtain a diazo component. On the other hand, 153.6 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 1,500 parts of methanol, and then 316.1 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion. 4.4 parts of sodium dialkyl sulfosuccinate (Pelex OT-P, manufactured by Kao Corporation) was then added to obtain a coupler component. Separately, 500 ml of ice was added to 654.3 parts of 80% aqueous acetic acid, and 223.9 parts of 25% aqueous sodium hydroxide was added while stirring to prepare an acetic acid-sodium acetate buffer solution. The diazo component and coupler component were simultaneously added dropwise to the stirred buffer solution maintained at 20°C to carry out a coupling reaction. The dropwise addition rate was adjusted so that the dropwise addition of the diazo component and coupler component was completed within 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was present in the reaction solution, and the solution was heated to 90°C and maintained for 30 minutes. The solution was then filtered and washed with water to obtain a hydrous wet cake. The entire amount of the above-mentioned wet cake in a pressurizable reaction vessel equipped with a stirrer was placed in the reactor. Water was added to bring the mass of the vessel to 3,500 parts, and the mixture was stirred. 2,100 parts of isobutanol was then added, followed by heating at 120°C for 2 hours under autogenous pressure in an autoclave. After removing the isobutanol by steam distillation, the mixture was filtered, washed with water, dried at 80°C, and pulverized to obtain 257.9 parts of pigment composition (A-1). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0263] (Example A-2) The same procedure as in Example A-1 was repeated to obtain 282.0 parts of pigment composition (A-2). The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0264] (Example A-3) The same procedure as in Example A-1 was repeated to obtain 289.6 parts of pigment composition (A-3). The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0265] (Example A-4) The same procedure as in Example A-1 was repeated to obtain 291.6 parts of pigment composition (A-4). The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0266] (Example A-5) The same procedure as in Example A-1 was repeated to obtain 296.6 parts of pigment composition (A-5). The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0267] (Example A-6) The same procedure as in Example A-1 was repeated to obtain 285.7 parts of pigment composition (A-6). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0268] (Example A-7) The same procedure as in Example A-1 was repeated to obtain 287.2 parts of pigment composition (A-7). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0269] (Example A-8) The same procedure as in Example A-1 was repeated to obtain 287.9 ​​parts of pigment composition (A-8). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0270] (Example A-9) The same procedure as in Example A-1 was repeated, except that the diazo component preparation was changed from 100 parts to 93.0 parts of 1,2-bis(2-aminophenoxy)ethane and 7.8 parts of 2-(2-(2-aminophenoxy)ethoxy)-N,N-dimethylaniline, 119.6 parts to 143.5 parts of 38% aqueous sodium nitrite solution, 153.6 parts to 184.3 parts of 5-acetoacetylaminobenzimidazolone, 316.1 parts to 379.2 parts of 25% aqueous sodium hydroxide solution, and 654.3 parts to 785.0 parts of 80% aqueous acetic acid solution for buffer preparation. 286.2 parts of pigment composition (A-9) was obtained. The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0271] (Example A-10) The same procedure as in Example A-1 was repeated, except that 100 parts of 1,2-bis(2-aminophenoxy)-ethane used to prepare the diazo component was replaced with 60.9 parts of 1,2-bis(2-aminophenoxy)-ethane and 39.3 parts of 2-(2-(2-aminophenoxy)ethoxy)phenol, to obtain 254.2 parts of pigment composition (A-10). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0272] (Example A-11) The same procedure as in Example A-1 was repeated to obtain 278.3 parts of pigment composition (A-11). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0273] (Example A-12) The same procedure as in Example A-1 was repeated to obtain 285.1 parts of pigment composition (A-12). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0274] (Example A-13) The same procedure as in Example A-1 was repeated to obtain 290.7 parts of pigment composition (A-13). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0275] (Example A-14) The same procedure as in Example A-1 was repeated to obtain 292.0 parts of pigment composition (A-14). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0276] (Example A-15) The same procedure as in Example A-1 was repeated to obtain 285.7 parts of pigment composition (A-15). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0277] (Example A-16) The same procedure as in Example A-1 was repeated to obtain 287.3 parts of pigment composition (A-16). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0278] (Example A-17) The same procedure as in Example A-1 was repeated to obtain 287.9 ​​parts of pigment composition (A-17). The composition ratios calculated from the MALDI TOF-MS spectrum were shown in Table 1.

[0279] Example B-1 While stirring 1,300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after one hour, 223.9 parts of 35% hydrochloric acid was added. After stirring for another hour, ice was added to adjust the temperature to 0-5°C, and 143.4 parts of a 38% aqueous solution of sodium nitrite was added to carry out a diazotization reaction. Sulfamic acid was added to remove excess nitrite, and the mixture was stirred for 30 minutes or more to obtain a diazo component. On the other hand, 184.1 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 1,500 parts of methanol, and then 379.0 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion. 4.4 parts of sodium dialkyl sulfosuccinate (Pelex OT-P, manufactured by Kao Corporation) was then added to obtain a coupler component. Separately, 500 parts of ice was added to 784.5 parts of 80% aqueous acetic acid, and 223.9 parts of 25% aqueous sodium hydroxide was added while stirring to prepare an acetic acid-sodium acetate buffer solution. The diazo component and coupler component were simultaneously added dropwise to the stirred buffer solution maintained at 20°C to carry out a coupling reaction. The dropwise addition rate was adjusted so that the dropwise addition of the diazo component and coupler component was completed within 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was present in the reaction solution, and the solution was heated to 90°C and maintained for 30 minutes. The solution was then filtered and washed with water, followed by a sprinkling of N,N-dimethylformamide (DMF) to obtain a DMF-containing wet cake. The entire amount of the obtained DMF-containing wet cake was poured into 1,500 parts of DMF and stirred for 1 hour. Further, 4.14 parts of iodomethane and 12.1 parts of potassium carbonate were added, and the mixture was stirred at 30° C. for 6 hours. The reaction liquid was poured into 15,000 parts of water and stirred for 1 hour, then filtered and washed with water to obtain a water-containing wet cake. The entire amount of the above-mentioned wet cake in a pressurizable reaction vessel equipped with a stirrer was placed in the reactor. Water was added to bring the mass of the vessel to 3,500 parts, and the mixture was stirred. 2,100 parts of isobutanol was then added, followed by heating at 120°C for 2 hours under autogenous pressure in an autoclave. After removing the isobutanol by steam distillation, the mixture was filtered, washed with water, dried at 80°C, and pulverized to obtain 286.1 parts of pigment composition (B-1). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0280] (Example B-2) While stirring 1,300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after one hour, 223.9 parts of 35% hydrochloric acid was added. After stirring for another hour, ice was added to adjust the temperature to 0-5°C, and 143.7 parts of 38% aqueous sodium nitrite solution was added to carry out the diazotization reaction. Sulfamic acid was added to remove excess nitrite, and the mixture was stirred for 30 minutes or more to obtain a diazo component. On the other hand, 184.6 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 1,500 parts of methanol, and then 380.0 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion. 4.4 parts of sodium dialkyl sulfosuccinate (Pelex OT-P, manufactured by Kao Corporation) was then added to obtain a coupler component. Separately, 500 ml of ice was added to 786.6 parts of 80% aqueous acetic acid, and 223.9 parts of 25% aqueous sodium hydroxide was added while stirring to prepare an acetic acid-sodium acetate buffer solution. The diazo component and coupler component were simultaneously added dropwise to the stirred buffer solution maintained at 20°C to carry out a coupling reaction. The dropwise addition rate was adjusted so that the diazo component and coupler component were each completed within 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was present in the reaction solution, and the solution was heated to 90°C and maintained for 30 minutes. The solution was then filtered and washed with water, followed by a sprinkling of N,N-dimethylformamide (DMF) to obtain a DMF-containing wet cake. The entire amount of the obtained DMF-containing wet cake was poured into 1,500 parts of DMF and stirred for 1 hour. Further, 4.98 parts of 1-iodobutane and 11.2 parts of potassium carbonate were added, and the mixture was stirred at 60°C for 6 hours. The reaction liquid was poured into 15,000 parts of water and stirred for 1 hour, then filtered and washed with water to obtain a water-containing wet cake. The entire amount of the above-mentioned wet cake in a pressurizable reaction vessel equipped with a stirrer was placed in the reactor. Water was added to bring the mass of the vessel to 3,500 parts, and the mixture was stirred. 2,100 parts of isobutanol was then added, followed by heating at 120°C for 2 hours under autogenous pressure in an autoclave. After removing the isobutanol by steam distillation, the mixture was filtered, washed with water, dried at 80°C, and pulverized to obtain 286.6 parts of pigment composition (B-2). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0281] (Example B-3) While stirring 1,300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after one hour, 223.9 parts of 35% hydrochloric acid was added. After stirring for another hour, ice was added to adjust the temperature to 0-5°C, and 143.5 parts of a 38% aqueous solution of sodium nitrite was added to carry out a diazotization reaction. Sulfamic acid was added to remove excess nitrite, and the mixture was stirred for 30 minutes or more to obtain a diazo component. On the other hand, 184.3 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 1,500 parts of methanol, and then 379.3 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion. 4.4 parts of sodium dialkyl sulfosuccinate (Pelex OT-P, manufactured by Kao Corporation) was then added to obtain a coupler component. Separately, 500 ml of ice was added to 785.2 parts of 80% aqueous acetic acid, and 223.9 parts of 25% aqueous sodium hydroxide was added while stirring to prepare an acetic acid-sodium acetate buffer solution. The diazo component and coupler component were simultaneously added dropwise to the stirred buffer solution maintained at 20°C to carry out a coupling reaction. The dropwise addition rate was adjusted so that the dropwise addition of the diazo component and coupler component was completed within 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was present in the reaction solution, and the solution was heated to 90°C and maintained for 30 minutes. The solution was then filtered and washed with water, followed by a sprinkling of N,N-dimethylformamide (DMF) to obtain a DMF-containing wet cake. The entire amount of the obtained DMF-containing wet cake was poured into 1,500 parts of DMF and stirred for 1 hour. Further, 8.08 parts of iodomethane and 39.3 parts of potassium carbonate were added, and the mixture was stirred at 30° C. for 6 hours. The reaction liquid was poured into 15,000 parts of water and stirred for 1 hour, then filtered and washed with water to obtain a water-containing wet cake. The entire amount of the above-mentioned wet cake in a pressurizable reaction vessel equipped with a stirrer was placed in the reactor. Water was added to bring the mass of the vessel to 3,500 parts, and the mixture was stirred. 2,100 parts of isobutanol was then added, followed by heating at 120°C for 2 hours under autogenous pressure in an autoclave. After removing the isobutanol by steam distillation, the mixture was filtered, washed with water, dried at 80°C, and pulverized to obtain 286.2 parts of pigment composition (B-3). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0282] (Example B-4) While stirring 1,300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after one hour, 223.9 parts of 35% hydrochloric acid was added. After stirring for another hour, ice was added to adjust the temperature to 0-5°C, and 143.6 parts of 38% aqueous sodium nitrite solution was added to carry out a diazotization reaction. Sulfamic acid was added to remove excess nitrite, and the mixture was stirred for 30 minutes or more to obtain a diazo component. On the other hand, 184.5 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 1,500 parts of methanol, and then 379.7 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion. 4.4 parts of sodium dialkyl sulfosuccinate (Pelex OT-P, manufactured by Kao Corporation) was then added to obtain a coupler component. Separately, 500 ml of ice was added to 785.9 parts of 80% aqueous acetic acid, and 223.9 parts of 25% aqueous sodium hydroxide was added while stirring to prepare an acetic acid-sodium acetate buffer solution. The diazo component and coupler component were simultaneously added dropwise to the stirred buffer solution maintained at 20°C to carry out a coupling reaction. The dropwise addition rate was adjusted so that the dropwise addition of the diazo component and coupler component was completed within 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was present in the reaction solution, and the solution was heated to 90°C and maintained for 30 minutes. The solution was then filtered and washed with water, followed by a sprinkling of tetrahydrofuran (THF) to obtain a THF-containing wet cake. The entire amount of the obtained THF-containing wet cake was poured into 1,500 parts of THF and stirred for 1 hour. Further, 14.1 parts of triethylamine and 10.9 parts of acetyl chloride were added, and the mixture was stirred at 10° C. for 3 hours. The reaction liquid was poured into 15,000 parts of water and stirred for 1 hour, then filtered and washed with water to obtain a water-containing wet cake. The entire amount of the above-mentioned wet cake in a pressurizable reaction vessel equipped with a stirrer was placed in the reactor. Water was added to bring the mass of the vessel to 3,500 parts, and the mixture was stirred. 2,100 parts of isobutanol was then added, followed by heating at 120°C for 2 hours under autogenous pressure in an autoclave. After removing the isobutanol by steam distillation, the mixture was filtered, washed with water, dried at 80°C, and pulverized to obtain 286.4 parts of pigment composition (B-4). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0283] (Example B-5) While stirring 1,300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after one hour, 223.9 parts of 35% hydrochloric acid was added. After stirring for another hour, ice was added to adjust the temperature to 0-5°C, and 148.7 parts of 38% aqueous sodium nitrite solution was added to carry out a diazotization reaction. Sulfamic acid was added to remove excess nitrite, and the mixture was stirred for 30 minutes or more to obtain a diazo component. On the other hand, 184.0 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 1,500 parts of methanol, and then 378.6 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion. 4.4 parts of sodium dialkyl sulfosuccinate (Pelex OT-P, manufactured by Kao Corporation) was then added to obtain a coupler component. Separately, 500 parts of ice was added to 783.8 parts of 80% aqueous acetic acid, and 223.9 parts of 25% aqueous sodium hydroxide was added while stirring to prepare an acetic acid-sodium acetate buffer solution. The diazo component and coupler component were simultaneously added dropwise to the stirred buffer solution maintained at 20°C to carry out a coupling reaction. The dropwise addition rate was adjusted so that the dropwise addition of the diazo component and coupler component was completed within 2 hours. After completion of the coupling reaction, 47.8 parts of 25% aqueous sodium hydroxide was added, and after confirming that no unreacted diazo component was present in the reaction solution, the solution was heated to 90°C and maintained for 30 minutes. The solution was then filtered and washed with water to obtain a hydrous wet cake. The entire amount of the above-mentioned wet cake in a pressurizable reaction vessel equipped with a stirrer was placed in the reactor. Water was added to bring the mass of the vessel to 3,500 parts, and the mixture was stirred. 2,100 parts of isobutanol was then added, followed by heating at 120°C for 2 hours under autogenous pressure in an autoclave. After removing the isobutanol by steam distillation, the mixture was filtered, washed with water, dried at 80°C, and pulverized to obtain 289.6 parts of pigment composition (B-5). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 1.

[0284] (Example B-6) The same procedure as in Example B-4 was carried out, except that 100 parts of 1,2-bis(2-aminophenoxy)-ethane used to prepare the diazo component was replaced with 93.2 parts of 1,2-bis(2-aminophenoxy)-ethane and 6.8 parts of 2-(2-(2-aminophenoxy)ethoxy)phenol, to obtain 285.6 parts of pigment composition (B-6). The composition ratio calculated from the results of MALDI TOF-MS spectrum measurement is shown in Table 1.

[0285] (Manufacturing example C-1) The same procedure as in Example A-1 was repeated to obtain 296.6 parts of pigment composition (C-1). The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0286] (Manufacturing example C-2) The same procedure as in Example A-1 was repeated to obtain 197.8 parts of pigment composition (C-2). The composition ratios calculated from the MALDI TOF-MS spectrum are shown in Table 1.

[0287] (Manufacturing example C-3) The same procedure as in Production Example C-2 was repeated, except that 100 parts of 1,2-bis(2-aminophenoxy)-ethane used to prepare the diazo component was replaced with 100.4 parts of 2-(2-(2-phenoxyphenoxy)ethoxy)aniline, to obtain 195.2 parts of pigment composition (C-3). The composition ratio calculated from the results of MALDI TOF-MS spectrum measurement is shown in Table 1.

[0288] [Table 1]

[0289] Example D-1 135.0 parts of pigment composition (C-1), 15.0 parts of pigment composition (C-2), 1,050 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 60° C. Next, the kneaded mixture was poured into warm water at approximately 70° C. and stirred for 1 hour to form a slurry. After repeated filtration and washing with water to remove the salt and diethylene glycol, the mixture was dried overnight at 80° C. and pulverized to obtain 145 parts of pigment composition (D-1).

[0290] (Examples D-2 to D-6) Pigment compositions (D-2) to (D-6) were obtained by the same procedure as in Example D-1, except that 135.0 parts of pigment composition (C-1) was changed to the amount shown in Table 2, and 15.0 parts of pigment composition (C-2) was changed to the amount shown in Table 2.

[0291] [Table 2]

[0292] Example E-1 271.9 parts of 1,2-bis(2-aminophenoxy)-ethane were dispersed in 2700 parts of water with stirring, while 645.9 parts of 35% hydrochloric acid was added. After stirring for 1 hour, ice was added to adjust the temperature to 0-5°C, and 404.2 g of 40% aqueous sodium nitrite solution was added to carry out the diazotization reaction. After stirring for more than 1 hour, 118.1 parts of 10% aqueous sulfamic acid solution was added to remove excess nitrite and stirred for more than 30 minutes, and then 27 parts of activated carbon was added and stirred for more than 30 minutes to prepare a bisdiazonium salt solution. Separately, 539.2 parts of 5-acetoacetylamino-benzimidazolone was dispersed in 4000 parts of water, and then 712.9 parts of a 25% aqueous sodium hydroxide solution was added to dissolve the dispersion, yielding a coupler component. The liquid volumes of the diazo component and coupler component were adjusted to 8100 parts and 5400 parts, respectively, by adding water and ice. 218.7 parts of the hydrous wet cake (80.8 parts nonvolatiles) prepared in Production Example C-3 were placed in a reaction vessel. Water was added to adjust the mass of the vessel to 8,100 parts, and the mixture was dispersed. 35.8 parts of 90% acetic acid was then added, and the solution temperature was adjusted to 40°C and the pH to 5.0. For coupling, the pH was adjusted to 8.0 by adding a coupler component, while simultaneously adding the diazo component at a constant rate. Coupling was completed in approximately 3 hours, with ice or 5% aqueous sodium hydroxide added as needed to maintain a temperature of 40°C and a pH of 8.0. After confirming that no unreacted diazo component was present in the reaction solution, the mixture was heated to 90°C and maintained for 1 hour. The mixture was then filtered and washed with water to obtain a hydrous wet cake. A pressurizable reaction vessel equipped with a stirrer was charged with 101.3 parts of the above-mentioned hydrous wet cake (20 parts in terms of nonvolatile content). After adding water to adjust the mass of the vessel to 600 parts, the vessel was heated from room temperature to 140°C over approximately 2 hours with stirring, maintained for 5 hours, cooled to room temperature, and the contents were removed. The contents were filtered, washed with water, dried at 80°C, and pulverized to obtain 19.5 parts of pigment composition (E-1). The composition ratio calculated from the MALDI TOF-MS spectrum measurement results is shown in Table 3.

[0293] (Comparative Example E-1) A pigment composition (E-2) was obtained according to the same production method as in Example 1 described in JP-A No. 2009-057509. The composition ratio calculated from the results of MALDI TOF-MS spectrum measurement is shown in Table 3.

[0294] (Comparative Example E-2) A pigment composition (E-3) was obtained according to the same production method as in Example 2 described in JP-A-2009-057509. The composition ratio calculated from the results of MALDI TOF-MS spectrum measurement is shown in Table 3.

[0295] [Table 3]

[0296] In Table 3, PY151 represents CI Pigment Yellow 151 (formula (13) below), and PY154 represents CI Pigment Yellow 154 (formula (14) below).

[0297] [ka]

[0298] <Coloring composition and its property evaluation> Using the obtained pigment composition, coloring compositions for various uses were prepared and their physical properties were evaluated.

[0299] <1> Production and evaluation of molded body (film)

[0300] [Production of molding composition (masterbatch)] (Example FM-1) (Manufacturing of masterbatch (FM-1)) A pre-dispersion of masterbatch (F-1) was obtained by mixing 100 parts of pigment composition (A-2) and 100 parts of Mitsui Chemicals' Hiwax (NL-100: decomposable LDPE-WAX) and dispersing using a three-roll mill. Then, 10 parts of the pre-dispersion and 90 parts of Mitsubishi Chemical's Novatec LD (LF342M1: film-grade low-density polyethylene pellets) were added to a tumbler mixer (Kawata Co., Ltd.) and stirred at 25°C for 3 minutes. The mixture was then added to a twin-screw extruder (Nippon Placon Co., Ltd.) and melt-kneaded at 180°C to obtain masterbatch (FM-1).

[0301] (Examples FM-2 to FM-13, Comparative Examples FM-1 to FM-3) (Manufacturing of masterbatches (FM-2) to (FM-16)) Thereafter, masterbatches (FM-2) to (FM-16) were produced in the same manner as in Example FM-1, except that the pigment composition (A-2) was changed to the pigment compositions shown in Table 4.

[0302] [Table 4]

[0303] [Production of Molded Body (Film)] (Example FF-1) (Production of resin molded body (FF-1) made from masterbatch (FM-1)) Four parts of the masterbatch (FM-1) and 100 parts of the same Novatec LD (LF342M1: film-grade low-density polyethylene pellets) as above were placed in a tumbler mixer (Kawata Corporation) and stirred at 25°C for 3 minutes, after which the mixture was melt-kneaded and film-molded at 180°C using a T-die extruder to obtain a resin molded product (FF-1) (film) made from the masterbatch (FM-1). The molding temperature was 180°C, and the film was produced to a thickness of 50 μm.

[0304] (Examples FF-2 to FF-13, Comparative Examples FF-1 to FF-3) (Production of resin molded bodies (FF-2) to (FF-16) from masterbatches (FM-2) to (FM-16)) Resin molded products (FF-2) to (FF-16) (films) were obtained in the same manner as for resin molded product (FF-1) (film), except that masterbatch (FM-1) was changed to masterbatches (FM-2) to (FM-16).

[0305] [Evaluation of resin molded body (film) made from masterbatch] The resin molded products (FF-1) to (FF-16) were evaluated for dispersibility by the following method. The results are shown in Table 5.

[0306] [Dispersibility] The surface of the film made of the obtained masterbatch was observed with an optical microscope to evaluate the dispersibility of the pigment in the film. The evaluation criteria were as follows:

[0307] (Evaluation criteria) 4: No pigment agglomerates are present and the pigment is dispersed very uniformly. Good 3: Pigment aggregates are almost absent and the pigment is uniformly dispersed. Suitable for practical use. 2: Pigment aggregates are present and the pigment is not uniformly dispersed. Not suitable for practical use. 1: There are many pigment aggregates and the pigment is not uniformly dispersed. Not suitable for practical use.

[0308] [Table 5]

[0309] The resin molded products (FF-1) to (FF-13) (films) made from the masterbatch of the present invention exhibited better dispersibility than the resin molded products (FF-14) to (FF-16) (films) made from the masterbatch not of the present invention.

[0310] <2> Evaluation of molding compositions

[0311] (Examples FS-1 to FS-13, Comparative Examples FS-1 to FS-3) [Hue evaluation] The resulting pigment composition and high-density polyethylene resin (product name: Hizex 2208J, manufactured by Prime Polymer Co., Ltd.) were melt-kneaded in a twin-screw extruder at 200°C and injection-molded under conditions where the temperature inside the barrel was 200°C. The color strength was adjusted to a concentration of SD 1 / 3, and 11 3mm-thick colored plates were produced. The injection molding was performed under conditions that minimized the residence time of the composition inside the barrel. The resulting pigment compositions used are shown in Table 6. To determine the average color difference, six colored plates (6th to 11th) were each measured using a colorimeter capable of measuring total luminous flux (Konica Minolta CM-700d). The average of the obtained colorimetric values ​​was used as the control (reference value). Each of the measured colorimetric values ​​was compared with a colored plate using pigment composition (C-1) to determine the color difference (ΔE*). Evaluation was performed according to the following criteria.

[0312] (Evaluation criteria) 4. ΔE* is less than 1.0. Very good. 3. ΔE* is 1.0 or more and less than 2.0. Good. 2. ΔE* is 2.0 or more and less than 3.0. Suitable for practical use. 1. ΔE* is 3.0 or more. Poor.

[0313] [Heat resistance test] The heat resistance test was conducted in accordance with German Industrial Standard DIN 12877-1. After adjusting the molding conditions so that the residence time in the barrel was 5 minutes, 11 colored plates were molded at 300°C. Six of the obtained colored plates, from the sixth to the eleventh, were measured for each color, and the average of the colorimetric values ​​was calculated. The color difference (ΔE*) between the control and the measured value of the plate molded at 300°C was determined and evaluated according to the following criteria. The results are shown in Table 6. The smaller the color difference, the better the heat resistance.

[0314] (Evaluation criteria) 5. ΔE* is less than 2.0. Very good. 4. ΔE* is 2.0 or more and less than 4.0. Good. 3. ΔE* is 4.0 or more and less than 6.0. Suitable for practical use. 2. ΔE* is 6.0 or more and less than 8.0. Suitable for practical use. 1. ΔE* is 8.0 or more. Not suitable for practical use.

[0315] [Table 6]

[0316] The molding composition comprising the pigment composition of the present invention exhibited good heat resistance without impairing the hue of CI Pigment Yellow 180. That is, from the results of Table 6, it can be seen that CI Pigment Yellow 180 containing the azo compound (1) of the present invention has improved dispersibility compared to CI Pigment Yellow 180 not containing the azo compound (1), and can be used for molding compositions having good hue and heat resistance.

[0317] <3> Manufacturing of molded bodies (plates) (Example FP-1) Preparation of molded body One part of the pigment composition (A-3) and 1,000 parts of polypropylene resin (product name: Prime Polypro J105, manufactured by Prime Polymer Co., Ltd.) were melt-kneaded at 220 ° C. in a twin-screw extruder, and then cut with a pelletizer to obtain a pelletized molding composition. Next, the obtained molding composition was melt-kneaded at a temperature of 220 ° C., and injection-molded using an injection molding machine set at a molding temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a molded product FP-1 (plate) with a thickness of 1 mm. Visual observation of the molded product revealed no coarse particles or the like, even in the watermark, and a yellow plate with good coloring was obtained.

[0318] (Example FP-2) Preparation of molded body The same procedure as in Example FP-1 was carried out, except that 1 part of the pigment composition (A-3) used in Example FP-1 was replaced with 1 part of the pigment composition (A-12), to obtain a 1 mm thick molded product FP-2 (plate). Visual observation of the molded product revealed no coarse particles or the like, even in the watermark, and a yellow plate with good coloring was obtained.

[0319] (Example FP-3) Preparation of molded body 0.5 parts of pigment composition (A-3) and 1000 parts of pre-dried polyethylene terephthalate resin (product name: Vylopet EQC-307, manufactured by Toyobo Co., Ltd.) were melt-kneaded at 275 ° C. in a twin-screw extruder, and then cut with a pelletizer to obtain a pelletized molding composition. Next, while melt-kneading the obtained molding composition, it was injection-molded using an injection molding machine set at a molding temperature of 275 ° C. and a mold temperature of 85 ° C. to obtain a 3 mm thick molded product FP-3 (plate). Visual observation of the molded product revealed no coarse particles or the like, even in the watermark, and a yellow plate with good coloring was obtained.

[0320] (Example FP-4) Preparation of molded body The same procedure as in Example FP-3 was carried out, except that 0.5 parts of the pigment composition (A-3) used in Example FP-3 was replaced with 0.5 parts of the pigment composition (A-12), to obtain a 3 mm thick molded product FP-4 (plate). Visual observation of the molded product revealed no coarse particles or the like, even in the watermark, and a yellow plate with good coloring was obtained.

[0321] <4> Toner evaluation A negatively charged toner was prepared and evaluated.

[0322] (Example FT-1) 2500 parts of pigment composition (A-3) and 2500 parts of polyester resin (product name: M-325, manufactured by Sanyo Chemical Industries, Ltd.) were kneaded using a pressure kneader at 120°C for 15 minutes. The resulting kneaded mixture was then removed from the pressure kneader and further kneaded using a three-roll mill at a roll temperature of 95°C. The resulting kneaded mixture was cooled and then coarsely pulverized to 10 mm or less to obtain a colored composition. 500 parts of the obtained coloring composition, 4375 parts of polyester resin, 50 parts of a calcium salt compound of 3,5-di-tert-butylsalicylic acid (charge control agent), and 75 parts of an ethylene homopolymer (release agent, molecular weight 850, Mw / Mn=1.08, melting point 107°C) were mixed using a 20 L Henschel mixer (3000 rpm, 3 minutes), and then melt-kneaded using a twin-screw kneading extruder at a discharge temperature of 120°C. The kneaded mixture was then cooled and solidified, and then coarsely pulverized using a hammer mill. The coarsely pulverized mixture was then finely pulverized using an I-type jet mill (IDS-2 model) and classified to obtain toner base particles. Next, 2500 parts of the toner base particles obtained above and 12.5 parts of hydrophobic titanium oxide (STT-30A, manufactured by Titan Kogyo Co., Ltd.) were mixed in a 10 L Henschel mixer to obtain negatively charged toner FT-1.

[0323] (Example FT-2) Negatively charged toner FT-2 was obtained by the same procedure as in Example FT-1, except that 2,500 parts of pigment composition (A-3) used in Example FT-1 was changed to 2,500 parts of pigment composition (A-12).

[0324] (Comparative Example FT-1) Negatively charged toner FT-3 was obtained by the same procedure as in Example FT-1, except that 2,500 parts of pigment composition (A-3) used in Example FT-1 was changed to 2,500 parts of pigment composition (C-1).

[0325] [Dispersibility evaluation] The resulting negatively charged toners FT-1 to FT-3 were each sliced ​​to a thickness of 0.9 μm using a microtome to form samples. The pigment dispersion state of each sample was then observed using a transmission electron microscope. As a result, it was confirmed that the pigment was more uniformly distributed and had better dispersibility in the negatively charged toner FT-1 using pigment composition (A-3) and the negatively charged toner FT-2 using pigment composition (A-12) than in the negatively charged toner FT-3 using pigment composition (C-1).

[0326] <5> Evaluation of active energy ray curable ink [Preparation of inactive resin varnish] Resin varnish A was prepared by dissolving 30 parts of a diallyl phthalate resin (Daiso DAP A, manufactured by Daiso Co., Ltd.) having a weight average molecular weight of 50,000 in 70 parts of ditrimethylolpropane tetraacrylate and mixing the mixture at elevated temperature (80°C).

[0327] [Preparation of active energy ray-curable ink] (Example H-1) (Production of active energy ray curable ink (H-1)) 15 parts of pigment composition (A-1), 9.7 parts of EO (3)-modified trimetrolpropane triacrylate, 9.2 parts of dimethylolpropane tetraacrylate, 23 parts of dipentaerythritol hexaacrylate, 2 parts of Omnirad 369, 2 parts of Omnirad 907, 2 parts of Omnirad DETX, 2 parts of Omnirad EMK, 0.5 parts of solid wax (polytetrafluoroethylene wax), 1 part of talc, 0.3 parts of polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum), and 33.3 parts of resin varnish A were mixed and stirred using a butterfly mixer. The mixture was then dispersed using a three-roll mill to produce an active energy ray-curable ink (H-1).

[0328] Details of the materials used are as follows:

[0329] [Polymerization initiator] Omnirad369: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, manufactured by iGM Resins Omnirad907: 2-methyl-4'-methylthio-2-morpholinopropiophenone, manufactured by iGM RESINS OmniradDETX: 2,4-diethylthioxanthone, manufactured by iGM RESINS OmniradEMK: 4,4'-bis(diethylamino)benzophenone manufactured by iGM RESINS

[0330] [Anti-friction agent] (solid wax) Teflon (registered trademark) modified polyethylene wax (polytetrafluoroethylene wax, Shamrock "Fluoroslip 511", melting point: 126°C)

[0331] [Other ingredients] (extender pigment) Talc: Hi-Filler 5000PJ (Matsumura Sangyo Co., Ltd.)

[0332] (Examples H-2 to H-30, Comparative Examples H-1 to H-3) (Production of active energy ray curable inks (H-2) to (H-30), (H-33) to (H-35)) Actinic ray-curable inks H-2) to (H-30) and (H-33) to (H-35) were prepared in the same manner as in Example H-1, except that the pigment compositions shown in Table 7 were used instead of the pigment composition (A-1) used in Example H-1.

[0333] (Example H-31) (Production of active energy ray curable ink (H-31)) An active energy ray-curable ink (H-31) was obtained by the same procedure as in Example H-1, except that the 15 parts of pigment composition (A-1) used in Example H-1 was changed to 14.25 parts of pigment composition (C-1) and 0.75 parts of pigment composition (C-2).

[0334] (Example H-32) (Production of active energy ray curable ink (H-32)) An active energy ray-curable ink (H-32) was obtained in the same manner as in Example H-1, except that the 15 parts of pigment composition (A-1) used in Example H-1 was changed to 14.25 parts of pigment composition (C-1) and 0.75 parts of pigment composition (C-3).

[0335] The performance of the obtained active energy ray-curable ink was evaluated by the following methods, and the results are shown in Table 7.

[0336] [Test sample preparation method] Using an RI tester (manufactured by Tester Sangyo Co., Ltd.), a solid image was printed on the substrate, Tokubishi art paper, using 0.25 ml of the obtained active energy ray-curable ink. The ink composition was then cured at a conveyor speed of 60 m / min using an LED lamp ("XP-9" manufactured by Air Motion Systems Co., Ltd., irradiation distance 10 mm, output 70%) to prepare a test sample. The RI tester is a testing machine that prints ink on paper or film, and can adjust the amount of ink transfer and printing pressure.

[0337] [Dispersibility] The shorter the preparation time of the active energy ray-curable ink, the higher the dispersibility. When the dispersion time of Comparative Example H-1 was taken as 100%, the dispersibility of each pigment composition was evaluated according to the following criteria.

[0338] (Evaluation criteria) 5. Dispersion time is less than 40% (very good) 4. Dispersion time is 40% or more but less than 60% (good) 3. Dispersion time is 60% or more but less than 80% (fairly good) 2. Dispersion time is 80% or more but less than 100% (practical). 1. Dispersion time is over 100% (bad)

[0339] Gloss Using the test sample prepared by the above method, the gloss value (in accordance with JIS Z 8741) of the surface on which the ink composition was spread was measured at a reflection angle of 60° using a gloss meter GM62D manufactured by Murakami Color Research Institute Co., Ltd. Evaluation was performed according to the following criteria, with the gloss value of the test sample obtained in Comparative Example H-1 as the standard. The gloss improves as the pigment is more dispersed.

[0340] (Evaluation criteria) 5: Gloss value is 115% or more (very good) 4: Gloss value is 110% or more but less than 115% (good) 3: Gloss value is 105% or more but less than 110% (fairly good) 2: Gloss value is 95% or more but less than 105% (practical) 1: Gloss value is less than 95% (poor)

[0341] [Hue evaluation] The test samples prepared by the above method were measured using a colorimeter capable of measuring total luminous flux (CM-700d, manufactured by Konica Minolta, Inc.), and the color difference (ΔE*) was determined based on the test sample obtained in Comparative Example H-1, and evaluated according to the following criteria.

[0342] (Evaluation criteria) 5. ΔE* is less than 0.5. Very good 4. ΔE* is 0.5 or more and less than 1.0. Very good 3. ΔE* is 1.0 or more and less than 1.5. Good 2. ΔE* is 1.5 or more and less than 3.0. 1. ΔE* is 3.0 or more. Not suitable for practical use.

[0343] [Table 7]

[0344] The results in Table 7 show that, compared with Comparative Example H-1, which is CI Pigment Yellow 180 not containing azo compound (1), Examples H-1 to H-32, which are CI Pigment Yellow 180 containing azo compound (1) of the present invention, had improved dispersibility and gloss. Furthermore, Comparative Examples H-2 to H-3 had a large effect on hue, while Examples H-1 to H-32 had improved dispersibility and gloss without adversely affecting hue.

[0345] <6> Evaluation of water-based coloring compositions 1. Preparation of water-based coloring composition (Example J-1) (Preparation of Water-Based Coloring Composition (J-1)) The following raw materials and 70 parts of zirconia beads with a diameter of 1.25 mm were placed in a 70 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil Co., Ltd. to obtain a dispersion liquid. Pigment composition (A-2): 3.15 parts Polyester-modified acrylic acid polymer (Allnex, ADDITOL XW 6528): 5.25 parts Wetting agent (Allnex, ADDITOL XW 6374): 0.95 parts Antifoaming agent (Allnex, ADDITOL XW 6211): 0.63 parts Ion-exchanged water: 21.52 parts Next, the zirconia beads were removed from the dispersion to obtain a water-based colored composition (J-1).

[0346] (Examples J-2 to J-13, Comparative Examples J-1 to J-3) (Preparation of Water-Based Colored Compositions (J-2) to (J-13), (J-16) to (J-18)) The same procedure as in Example J-1 was carried out except that the pigment composition (A-2) used in Example J-1 was changed to the pigment composition shown in Table 8, and water-based colored compositions (J-2) to (J-13) and (J-16) to (J-18) were obtained.

[0347] (Example J-14) (Preparation of Water-Based Coloring Composition (J-14)) The same procedure as in Example J-1 was carried out, except that the 3.15 parts of pigment composition (A-2) used in Example J-1 was replaced with 2.99 parts of pigment composition (C-1) and 0.16 parts of pigment composition (C-2), to obtain a water-based coloring composition (J-14).

[0348] (Example J-15) (Preparation of Water-Based Coloring Composition (J-15)) The same procedure as in Example J-1 was carried out, except that the 3.15 parts of pigment composition (A-2) used in Example J-1 was replaced with 2.99 parts of pigment composition (C-1) and 0.16 parts of pigment composition (C-3), to obtain a water-based coloring composition (J-15).

[0349] 2. Evaluation of dispersion stability (Evaluation of initial viscosity and viscosity stability) The initial viscosity of the obtained aqueous colored composition at 25°C was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). In the same manner, the viscosity was measured after aging at 25°C for one week and after accelerated aging at 50°C for one week. The viscosity increase rate relative to the initial viscosity was calculated based on the obtained measurements, and used as an index of viscosity stability, which was evaluated according to the following evaluation criteria. The results are shown in Table 8. The lower the initial viscosity, the better the dispersibility. Furthermore, the smaller the viscosity increase rate, the better the dispersion stability. A rating of "4", "3", or "2" on the following evaluation criteria is considered to be at a practical level.

[0350] (Evaluation criteria for initial viscosity) 4. Initial viscosity is less than 5.0 mPa·s. Excellent 3. The initial viscosity is 5.0 mPa·s or more and less than 7.5 mPa·s. Good 2. The initial viscosity is 7.5 mPa·s or more and less than 10.0 mPa·s. 1. The initial viscosity is 10.0 mPa·s or more. Not suitable for practical use.

[0351] (Evaluation criteria for viscosity stability) 4. Viscosity increase rate is less than 20%. Excellent 3. Viscosity increase rate is 20% or more and less than 30%. Good 2. Viscosity increase rate is 30% or more and less than 40%. 1. Viscosity increase rate is 40% or more. Not practical.

[0352] [Table 8]

[0353] The results in Table 8 show that the pigment composition containing the azo compound (1) of the present invention and CI Pigment Yellow 180 exhibited good results.

[0354] <7> Water-based paint evaluation The water-based coloring compositions prepared above were used to prepare water-based paints and evaluated.

[0355] <7-1> Preparation of water-based paint (Example JB-1) (1) Preparation of water-based paint (JB-1-1) The ingredients were mixed to obtain the following composition in terms of nonvolatile content, and then stirred using a high-speed stirrer to obtain a water-based paint (JB-1-1) (stored at 25°C for 1 week). Water-based coloring composition (J-1) (stored at 25°C for 1 week): 4.8 parts Watersol S-751 (acrylic resin for baking paint, manufactured by DIC): 60.0 parts Cymel 303 (Mitsui Cytec, melamine resin): 45.0 parts

[0356] (2) Preparation of water-based paint (JB-1-2) The ingredients were mixed to obtain the following composition in terms of nonvolatile content, and then stirred using a high-speed stirrer to obtain a water-based paint (JB-1-2) (stored at 50°C for 1 week). Water-based coloring composition (J-1) (stored at 50°C for 1 week): 4.8 parts Watersol S-751 (acrylic resin for baking paint, manufactured by DIC): 60.0 parts Cymel 303 (Mitsui Cytec, melamine resin): 45.0 parts

[0357] (Examples JB-2 to JB-15, Comparative Examples JB-1 to JB-3) The water-based coloring composition (J-1) (stored at 25 ° C for 1 week) used in Example JB-1 was replaced with water-based coloring compositions (J-2) to (J-18) (stored at 25 ° C for 1 week, respectively), and the same operation as in Example JB-1 was carried out to obtain water-based paints (JB-2-1) to (JB-18-1). In addition, the water-based coloring composition (J-1) (stored at 50 ° C for 1 week) used in Example JB-1 was sequentially replaced with water-based coloring compositions (J-2) to (J-18) (stored at 50 ° C for 1 week, respectively), and the same operation as in Example JB-1 was carried out to obtain water-based paints (JB-2-2) to (JB-18-2).

[0358] [Table 9]

[0359] <7-2> Preparation of PET film coating (Example JP-1) (Preparation of PET film coating (JP-1)) Water-based paint (JB-1-1) and water-based paint (JB-1-2) were applied to Lumirror 100T60 (Toray Industries, Inc., polyester terephthalate (PET) film, 100 μm thick) using a 6-mil applicator. The coated PET film was dried at room temperature for 18 hours. It was then dried at 60°C for 5 minutes and at 140°C for 20 minutes to obtain a PET film coating (JP-1) with a film thickness of 70 μm.

[0360] (Examples JP-2 to JP-15, Comparative Examples JP-1 to JP-3) (Production of PET film coatings (JP-2) to (JP-18)) The same operations as in Example JP-1 were carried out except that the water-based paint (JB-1-1) used in Example JP-1 was successively changed to water-based paints (JB-2-1) to (JB-18-1), and the water-based paint (JB-1-2) was successively changed to water-based paints (JB-2-2) to (JB-18-2), to obtain PET film coatings (JP-2) to (JP-18).

[0361] <7-3> Evaluation of PET film coating The PET film coatings obtained in Examples JP-1 to JP-15 and Comparative Examples JP-1 to JP-3 were evaluated for color stability according to the following method.

[0362] (Evaluation method for color stability) Using a colorimeter (Konica Minolta, CM-700d), the paints of the water-based coloring compositions applied to each of the PET film coatings (JP-1) to (JP-18) and stored at 25°C for one week, and the paints of the water-based coloring compositions stored at 50°C for one week, were each measured for color, and the color difference (ΔE*) was determined and evaluated according to the following criteria. The results are shown in Table 10. The smaller the color difference, the more excellent the dispersion stability of the coloring material is considered to be, and in the following evaluation criteria, "4" and "3" are practical. (Evaluation criteria) 4. ΔE* is less than 1.0. 3. ΔE* is 1.0 or more and less than 2.0. 2. ΔE* is 2.0 or more and less than 3.0. 1. ΔE* is 3.0 or more.

[0363] [Table 10]

[0364] The results in Table 10 show that the pigment composition containing the azo compound (1) of the present invention and CI Pigment Yellow 180 exhibited good results.

[0365] <8> Evaluation of water-based flexographic inks

[0366] (Synthesis Example 1) (Synthesis of Water-Based Urethane Resin B) A four-necked 2000 ml flask equipped with a reflux condenser, dropping funnel, gas inlet tube, stirrer, and thermometer was charged with 82.3 parts of polytetramethylene glycol having a number average molecular weight of 2,000, 3 parts of polyethylene glycol having a number average molecular weight of 2,000, 13 parts of dimethylolbutanoic acid, and 1.7 parts of 1,4-cyclohexanedimethanol. The mixture was purged with dry nitrogen and heated to 100°C. With stirring, 33.3 parts of isophorone diisocyanate were added dropwise over 20 minutes, and the temperature was gradually raised to 140°C (NCO / OH = 0.98). The reaction was continued for an additional 30 minutes to obtain a urethane resin. Next, while cooling, 399.8 parts of distilled water containing 5.3 parts of 28% aqueous ammonia was added to obtain aqueous urethane resin B (weight average molecular weight approximately 40,000, nonvolatile content 25%, acid value 36.9 (mgKOH / g), hydroxyl value 11.1 (mgKOH / g)).

[0367] [Production of water-based flexographic ink] (Example K-1) (Manufacturing of water-based flexographic ink (K-1)) Aqueous flexographic ink (K-1) was produced by dispersing 45 parts of aqueous urethane resin B, 15 parts of pigment composition (A-1), 2 parts of polyethylene wax (W310 manufactured by Mitsui Chemicals, Inc., particle size 9.5 μm, softening point 132°C, penetrometer hardness 0.8), 0.2 parts of adipic acid dihydrazide, 0.2 parts of aqueous ammonia (28%), 18.8 parts of water, and 18.8 parts of isopropanol in an Eiger mill until the particle size measured with a grind gauge reached 10 μm or less.

[0368] (Examples K-2 to K-30, Comparative Examples K-1 to K-3) (Production of Water-Based Flexographic Inks (K-2) to (K-30), (K-33) to (K-35)) In the method for producing the water-based flexographic ink (K-1) described in Example K-1, water-based flexographic inks (K-2) to (K-30) and (K-33) to (K-35) were obtained in the same manner as in Example K-1, except that the pigment composition (A-1) was changed as shown in Table 11.

[0369] (Example K-31) (Manufacturing of water-based flexographic ink (K-31)) A water-based flexo ink (K-31) was obtained in the same manner as in Example K-1, except that in the method for producing the water-based flexo ink (K-1) described in Example K-1, 15 parts of the pigment composition (A-1) was changed to 14.25 parts of the pigment composition (C-1) and 0.75 parts of the pigment composition (C-2).

[0370] (Example K-32) (Manufacturing of water-based flexographic ink (K-32)) A water-based flexographic ink (K-32) was obtained in the same manner as in Example K-1, except that in the method for producing the water-based flexographic ink (K-1) described in Example K-1, 15 parts of the pigment composition (A-1) was changed to 14.25 parts of the pigment composition (C-1) and 0.75 parts of the pigment composition (C-3).

[0371] [Evaluation method and criteria] Printing in the examples and comparative examples was carried out as follows. Flexographic rotary printing: Using a center drum type 6-color flexographic printing press "SOLOFLEX" manufactured by Windmuller & Hoelscher, printing was performed on plastic film at a speed of 100 m / min and dried at 60-70°C to obtain a printed product. An anilox roll of 350 lines / cm was used, and a solid plate made from DuPont's "Cyrel DPU" (thickness 1.14 mm) was used as the plate cylinder, attached with double-sided tape (Toyochem's "DF7382T" thickness 0.50 mm).

[0372] (1) Dispersibility The shorter the preparation time of the water-based flexographic ink, the higher the dispersibility. When the dispersion time of Comparative Example K-1 was taken as 100%, the dispersibility of each pigment composition was evaluated according to the following criteria.

[0373] (Evaluation criteria) 5. Dispersion time is less than 40% (very good) 4. Dispersion time is 40% or more but less than 60% (good) 3. Dispersion time is 60% or more but less than 80% (fairly good) 2. Dispersion time is 80% or more but less than 100% (practical). 1. Dispersion time is over 100% (bad)

[0374] (2) Stability over time After storing the ink at a constant temperature of 40°C for 3 months, the viscosity over time was measured using a Zahn Cup No. 4 (25°C) and the difference from the finished (initial) viscosity was evaluated. The evaluation criteria are shown below. A practical level is 3 or higher.

[0375] (Evaluation criteria) 5. The difference between the finished viscosity and the viscosity over time is less than 2 seconds 4. The difference between the finished viscosity and the viscosity over time is 2 seconds or more but less than 4 seconds 3. The difference between the finished viscosity and the viscosity over time is 4 seconds or more but less than 6 seconds 2. The difference between the finished viscosity and the viscosity over time is 6 seconds or more but less than 8 seconds 1. The difference between the finished viscosity and the viscosity over time is 8 seconds or more

[0376] (3) Hue The ink was applied to a PET film (polyethylene terephthalate film, Toyobo E-5102, 12 μm) using a Meyer bar, which was then placed over a white application paper (BYK Byko-chart uncoated N2C), and the color was measured using a colorimeter capable of measuring total luminous flux (Konica Minolta CM-700d). The color difference (ΔE*) was determined using Comparative Example K-1 as the standard, and evaluated according to the following criteria.

[0377] (Evaluation criteria) 5. ΔE* is less than 0.5. Very good 4. ΔE* is 0.5 or more and less than 1.0. Very good 3. ΔE* is 1.0 or more and less than 1.5. Good 2. ΔE* is 1.5 or more and less than 3.0. 1. ΔE* is 3.0 or more. Not suitable for practical use.

[0378] [Table 11]

[0379] The results in Table 11 show that, compared with Comparative Example K-1, which is CI Pigment Yellow 180 not containing azo compound (1), Examples K-1 to K-32, which are CI Pigment Yellow 180 containing azo compound (1) of the present invention, had improved dispersibility and stability over time. Furthermore, Comparative Examples K-2 to K-3 had a large effect on hue, while Examples K-1 to K-32 had improved dispersibility and stability over time without adversely affecting hue.

[0380] <9> Evaluation of water-based inkjet inks <9-1> Preparation of aqueous inkjet coloring composition (hereinafter referred to as "IJ aqueous coloring composition") (Example L-1) (Preparation of aqueous coloring composition for inkjet printing (L-1)) Pigment composition (A-1): 19.0 parts Styrene-acrylic acid copolymer (BASF Japan, JONCRYL 61J): 16.4 parts Surfactant (Kao Corporation, Emulgen 420): 5.0 parts Ion-exchanged water: 59.6 parts and 200 parts of zirconia beads with a diameter of 1.25 mm were placed in a 200 ml glass bottle and dispersed for 6 hours using a paint shaker manufactured by Red Devil Co. The resulting liquid was diluted with ion-exchanged water, the zirconia beads for dispersion were separated by filtration, and the resulting solution was diluted with ion-exchanged water so that the colorant content was 15%, thereby obtaining an aqueous inkjet coloring composition (L-1) of pigment composition (A-1).

[0381] (Examples L-2 to L-30, Comparative Examples L-1 to L-3) (Preparation of aqueous inkjet coloring compositions (L-2) to (L-30), (L-36) to (L-38)) The same procedure as in Example L-1 was carried out except that the pigment composition (A-1) used in Example L-1 was changed to the pigment composition shown in Table 12, and aqueous inkjet coloring compositions (L-2) to (L-30), (L-36) to (L-38) were obtained.

[0382] (Example L-31) (Preparation of aqueous coloring composition for inkjet printing (L-31)) The same procedure as in Example L-1 was carried out except that the 19.0 parts of pigment composition (A-1) used in Example L-1 was replaced with 18.05 parts of pigment composition (C-1) and 0.95 parts of pigment composition (C-2), to obtain an aqueous inkjet coloring composition (L-31).

[0383] (Example L-32) (Preparation of aqueous coloring composition for inkjet printing (L-32)) The same procedure as in Example L-1 was carried out, except that the 19.0 parts of pigment composition (A-1) used in Example L-1 was replaced with 18.05 parts of pigment composition (C-1) and 0.95 parts of pigment composition (C-3), to obtain an aqueous inkjet coloring composition (L-32).

[0384] (Synthesis Example 2) Styrene-acrylate-methacrylate copolymer having carboxyl and hydroxyl groups [PA1] A 3-liter, four-neck flask equipped with a dropping funnel, thermometer, nitrogen gas inlet tube, stirrer, and reflux condenser was charged with 1,000 parts of methyl ethyl ketone and heated to 78°C. A mixture of 100 parts of styrene, 538 parts of n-butyl methacrylate, 104 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 108 parts of methacrylic acid, and 80 parts of tert-butyl peroxy-2-ethylhexanoate was added dropwise over 4 hours, and the mixture was allowed to react at the same temperature for 8 hours. After the reaction was completed, additional methyl ethyl ketone was added to adjust the nonvolatile content to 50%, yielding a styrene-acrylate-methacrylate copolymer [PA1] solution with an acid value of 70 mgKOH / g and a number-average molecular weight of 6,000.

[0385] (Example L-33) (Preparation of aqueous coloring composition for inkjet printing (L-33)) 12.8 parts of a styrene-acrylate-methacrylate copolymer [PA1] solution (50% nonvolatile content) was neutralized with 0.71 parts dimethylethanolamine and then mixed with 2.29 parts (1.6 parts as resin) of methyl etherified melamine resin (Nicalac MX-041, manufactured by Sanwa Chemical Industry Co., Ltd.). 50 parts of a previously prepared aqueous slurry of pigment composition (A-2) (16% nonvolatile content) was added to this mixed solution with stirring. Next, the mixture was placed in a 250 ml glass bottle together with 130 parts of 1.5 mm diameter glass beads and dispersed for 4 hours using a Red Devil paint shaker. After obtaining a dispersion, an equal amount of ion-exchanged water was added to the mixture. Then, 1 N aqueous hydrochloric acid solution was added with stirring to precipitate and fix the copolymer [PA1] on the surface of the pigment composition (A-2). The pH of the mixed solution after fixation was 3 to 5. Thereafter, the mixed solution was suction filtered and washed with ion-exchanged water until the pH of the washings exceeded 6, to obtain a pigment composition (A-2) to which the copolymer [PA1] was fixed. Next, water was added until the pigment composition (A-2) with the copolymer [PA1] fixed thereto became fluid, and then 0.8 parts of dimethylethanolamine was added while stirring with a stirrer. Stirring was then continued for 1 hour, yielding a redispersion of the pigment composition (A-2) with the copolymer [PA1] fixed thereto. Water was added to this redispersion to adjust the non-volatile content to 19%, and then an acid crosslinking catalyst (Nacure 2500X, manufactured by Kusumoto Chemicals Co., Ltd.) was added in an amount of 0.5% relative to the amount of copolymer [PA1] contained in the redispersion, and a crosslinking reaction was carried out at 95°C for 1 hour to obtain an aqueous coloring composition containing crosslinked resin particles containing a pigment composition (aqueous coloring composition for inkjet printer (L-33)).

[0386] (Synthesis Example 3) Styrene-acrylate-methacrylate copolymer having carboxyl groups and epoxy groups [PA2] A 3-liter, four-necked flask equipped with a dropping funnel, thermometer, nitrogen gas inlet tube, stirrer, and reflux condenser was charged with 1,000 parts of methyl ethyl ketone and heated to 78 ° C. A mixture of 100 parts of styrene, 476 parts of n-butyl methacrylate, 116 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 50 parts of glycidyl methacrylate, 108 parts of methacrylic acid, and 80 parts of tert-butyl peroxy-2-ethylhexanoate was added dropwise over 4 hours and allowed to react at the same temperature for 8 hours. After completion of the reaction, additional methyl ethyl ketone was added to adjust the nonvolatile content to 50%, yielding a styrene-acrylate-methacrylate copolymer [PA2] solution with an acid value of 70 mg KOH / g and a number average molecular weight of 10,500.

[0387] (Example L-34) (Preparation of aqueous coloring composition for inkjet printing (L-34)) 16 parts of the resulting styrene-acrylate-methacrylate copolymer [PA2] solution (50% nonvolatile content), 8 parts of pigment composition (A-2), and 40 parts of methyl ethyl ketone were placed in a 250 ml glass bottle along with 130 parts of 1.5 mm diameter glass beads and dispersed for 4 hours using a Red Devil paint shaker to obtain a dispersion. Next, 0.8 parts of hydrophilic epoxy resin (DIC Corporation, CR-5L) and 24 parts of methyl ethyl ketone were added to this dispersion and stirred, after which the glass beads were separated by filtration. 87.2 parts of the resulting dispersion were poured into a mixture of 1.2 parts of dimethylethanolamine and 100 parts of water with stirring, followed by the addition of an equal volume of ion-exchanged water to the mixture. Then, 1 N aqueous phosphoric acid solution was added with stirring to precipitate and fix the copolymer [PA2] to the surface of the pigment composition (A-2). After fixation, the pH of the mixed solution was 5. Thereafter, the mixed solution was subjected to suction filtration and washed with ion-exchanged water until the pH of the washings exceeded 6, thereby obtaining a pigment composition (A-2) to which the copolymer [PA2] was fixed. Next, water was added until the pigment composition (A-2) with the copolymer [PA2] fixed thereto became fluid, and then 0.8 parts of dimethylethanolamine was added while stirring with a stirrer. Stirring was then continued for 1 hour, yielding a redispersion of the pigment composition (A-2) with the copolymer [PA2] fixed thereto. Water was added to this redispersion to adjust the non-volatile content to 19%, and then the redispersion was heated to 95°C and a crosslinking reaction was carried out for 1 hour to obtain an aqueous coloring composition (aqueous coloring composition for inkjet printer (L-34)) containing crosslinked resin particles containing a pigment composition.

[0388] (Synthesis Example 4) Styrene-acrylic acid ester copolymer [PA3] A monomer mixture was prepared by mixing 62 parts of acrylic acid, 129 parts of styrene, and 9 parts of α-methylstyrene. A reaction vessel was charged with 20 parts of methyl ethyl ketone, 0.3 parts of 2-mercaptoethanol (a polymerization chain transfer agent), and 10% of the monomer mixture, and the mixture was thoroughly purged with nitrogen gas. Separately, a dropping funnel was charged with a mixture of the remaining 90% of the monomer mixture, 0.27 parts of the polymerization chain transfer agent, 60 parts of methyl ethyl ketone, and 2.2 parts of an azo radical polymerization initiator (V-65, 2,2'-azobis(2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.). Under a nitrogen atmosphere, the mixture in the reaction vessel was heated to 65°C while stirring, and then the mixture in the dropping funnel was added dropwise over 3 hours. After the dropwise addition, the mixture was allowed to react at 65°C for 1 hour, and then a solution of 0.3 parts of the polymerization initiator dissolved in 5 parts of methyl ethyl ketone was added, and the reaction was continued at 65°C for 1 hour. After adding the polymerization initiator solution and continuing the reaction two more times, the mixture was heated to 70°C and allowed to react for another 1 hour, and then 200 parts of methyl ethyl ketone was added to obtain a styrene-acrylate copolymer [PA3] solution (non-volatile content 40.9%) with an acid value of 240 mgKOH / g, a number average molecular weight of 5,700, and a weight average molecular weight of 12,500. This styrene-acrylate copolymer [PA3] solution was dried under reduced pressure to completely remove the solvent, yielding 32 parts of resin, which was then mixed with 204 parts of ion-exchanged water, and 11.1 parts of triethanolamine was added to neutralize approximately 55 mol% of the carboxy groups in the copolymer [PA3]. This mixed solution was heated to 90°C and stirred for 1 hour to obtain an aqueous dispersion of the copolymer [PA3] in water.

[0389] (Example L-35) (Preparation of aqueous coloring composition for inkjet printing (L-35)) After the aqueous dispersion of copolymer [PA3] was cooled to room temperature, 100 parts of pigment composition (A-2) was added and the mixture was stirred at 20°C for 3 hours using a stirrer. 124 parts of ion-exchanged water was added to the mixed solution, and the mixture was dispersed using a Microfluidizer (manufactured by Powrex Corporation) at a pressure of 150 MPa for 15 passes. The resulting dispersion was then centrifuged at 20°C and 3660 rpm for 20 minutes using a high-speed refrigerated centrifuge (Hitachi Koki Co., Ltd., Himac CR22G). The liquid layer was then recovered and filtered through a membrane filter with a pore size of 5 μm to obtain an aqueous dispersion of pigment composition (A-2) (non-volatile content: 25%). To 100 parts of the aqueous dispersion of this pigment composition (A-2), 32 parts of ion-exchanged water was added, and then 1.8 parts of trimethylolpropane polyglycidyl ether (Denacol EX-321, manufactured by Nagase ChemteX Corporation) was added as a crosslinking agent, and the mixture was heated with stirring at 70°C for 5 hours. The mixture was then cooled to room temperature and filtered through a membrane filter with a pore size of 5µm. Further, ion-exchanged water was added to adjust the nonvolatile content to 19%, thereby obtaining an aqueous colored composition containing crosslinked resin particles containing the pigment composition (aqueous colored composition for inkjet printers (L-35)).

[0390] [Table 12]

[0391] <9-2> Preparation of water-based inkjet ink (hereinafter referred to as "water-based IJ ink") The components listed in Tables 13-1 to 13-3 were mixed by stirring and then filtered through a 3 μm membrane filter to obtain aqueous IJ inks for evaluation tests (Examples LB-1 to LB-35 and Comparative Examples LB-1 to LB-3). In Tables 13-1 to 13-3, the numerical values ​​indicating the amount of each component are all in parts, and "-" indicates that the component is not included. Ion-exchanged water was used for "water." Other abbreviations in the tables have the following meanings. PG: Propylene glycol AMP: 2-amino-2-methyl-1-propanol TEA: Triethanolamine

[0392] (Evaluation method for color stability) The color stability was evaluated according to the following method.

[0393] (Hue stability 1) The aqueous inkjet inks prepared in each example and comparative example were filled into mayonnaise bottles and stored in a 50°C oven for two weeks. Each ink was applied to an OK topcoat using a Matsuo Sangyo K Control Coater at a wet film thickness of 6 μm, and the resulting coating was dried in a 70°C oven for one minute to produce a coated product. The L*, a*, and b* values ​​of the ink coating were measured using an X-rite eXact manufactured by X-Rite before and after long-term storage. The color difference (ΔE*) before and after storage was calculated and evaluated from these values. A rating of "5," "4," "3," or "2" based on the following evaluation criteria indicates practical quality.

[0394] (Hue stability 2) The water-based inkjet inks prepared in each example and comparative example were filled into mayonnaise bottles and stored in an oven at 50°C for 4 weeks, and evaluated in the same manner as in hue stability 1. A rating of "5," "4," "3," or "2" on the following evaluation criteria indicates that the inks are of a practical quality.

[0395] (Evaluation criteria) 5: Color difference (ΔE*) is less than 1 4: Color difference (ΔE*) is 1 or more and less than 2 3: Color difference (ΔE*) is 2 or more and less than 3 2: Color difference (ΔE*) is 3 or more and less than 5 1: Color difference (ΔE*) is 5 or more

[0396] [Table 13-1]

[0397] [Table 13-2]

[0398] [Table 13-3]

[0399] The results in Tables 13-1 to 13-3 demonstrate that inkjet inks capable of suppressing color change in ink coating films during long-term storage were obtained by using a pigment composition containing the azo compound (1) of the present invention and CI Pigment Yellow 180. In particular, it was confirmed that the use of the pigment composition as crosslinked resin particles enables further improvement in long-term storage stability.

[0400] <10> Paint evaluation <10-1> Preparation of solvent-based paint 1. Preparation of base paint (Example M-1) (Preparation of base paint (M-1)) First, the following raw materials and 230 parts of steel beads were charged into a 225 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil Co., Ltd. to obtain a mixture. Pigment composition (A-2): 19 parts Acrylic resin (DIC Corporation, Acrydic 47-712): 7.7 parts Dispersion solvent (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150 FLUID manufactured by ENEOS Corporation in a mass ratio of 3:3:2:2): 40.7 parts Next, 75.4 parts of Acrydic 47-712 and 17.2 parts of melamine resin (Amidia L-117-60 manufactured by DIC Corporation) were added to the mixture, and the mixture was dispersed for another 10 minutes to obtain a dispersion. Next, the steel beads were removed from the dispersion to obtain a base paint (M-1) of the pigment composition (A-2).

[0401] (Examples M-2 to M-15, Comparative Examples M-1 to M-3) (Preparation of base paints (M-2) to (M-13), (M-16) to (M-18)) The same procedure as in Example M-1 was carried out except that the pigment composition (A-2) used in Example M-1 was changed to the pigment composition shown in Table 14, and base paints (M-2) to (M-13) and (M-16) to (M-18) were obtained.

[0402] (Example M-14) (Preparation of base paint (M-14)) The same procedure as in Example M-1 was carried out except that the 19 parts of pigment composition (A-2) used in Example M-1 was replaced with 18.05 parts of pigment composition (C-1) and 0.95 parts of pigment composition (C-2), to obtain a base paint (M-14).

[0403] (Example M-15) (Preparation of base paint (M-15)) The same procedure as in Example M-1 was carried out except that the 19 parts of pigment composition (A-2) used in Example M-1 was replaced with 18.05 parts of pigment composition (C-1) and 0.95 parts of pigment composition (C-3), to obtain a base paint (M-15).

[0404] [Table 14]

[0405] 2. Preparation of White Paint The following is an example of the preparation of a white paint for use in a solid base paint. First, the following raw materials and 900 parts of steel beads were charged into a 900 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil Co., Ltd. to obtain a dispersion liquid. Titanium oxide (Tipake CR90 titanium oxide manufactured by Ishihara Sangyo Kaisha): 66.6 parts Acrylic resin (DIC Corporation, Acrydic 47-712): 101.7 parts Melamine resin (DIC Corporation, Amidia L-117-60): 21.3 parts Dispersion solvent (a mixed solvent of toluene, xylene, butyl acetate, and T-SOL150 FLUID manufactured by ENEOS Corporation in a mass ratio of 3:3:2:2): 20.9 parts Then, the steel beads were removed from the dispersion to obtain a white paint.

[0406] 3. Preparation of Solid Base Paint Example MS-1 (Preparation of solid base paint (MS-1)) The following components were mixed using a high-speed mixer to obtain a solid base paint (MS-1). Base paint (M-1) prepared in Example J-1: 10 parts Obtained white paint: 31.9 parts

[0407] (Examples MS-2 to MS-15, Comparative Examples MS-1 to MS-3) (Preparation of solid base paints (MS-2) to (MS-18)) Solid base paints (MS-2) to (MS-18) were obtained by the same procedure as in Example MS-1, except that the base paint (M-1) used in Example MS-1 was replaced with base paints (M-2) to (M-18), respectively. The pigment compositions of the base paints used in the solid base paints prepared in each Example and Comparative Example are as shown in Table 15.

[0408] [Table 15]

[0409] 4. Preparation of Topcoat Clear Paint The following raw materials were mixed using a high-speed mixer to obtain a top coat clear paint. Acrylic resin (DIC Corporation, Acrydic 44-179): 120 parts Melamine resin (DIC Corporation, Amidia L117-60): 30 parts Dilution solvent (toluene, xylene, ENEOS T-SOL150 FLUID, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2): 50 parts

[0410] 5. Preparation of solid base coated panels and evaluation of weather resistance (Example MP-1) (Production of solid base painted board (MP-1)) The solid base paint (MS-1) was sprayed with a spray gun onto a steel plate whose surface had been prepared with #1000 sandpaper. To adjust the viscosity to make it easier to spray, an equal amount of dilution solvent (toluene, xylene, ENEOS T-SOL150FLUID, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2) was mixed with the solid base paint. The coating was performed in nine steps, followed by spraying a top coat clear paint in six steps. The plate was then dried at 25°C for 8 hours and then at 140°C for 30 minutes to obtain a solid base coated plate (MP-1).

[0411] (Examples MP-2 to MP-15, Comparative Examples MP-1 to MP-3) (Production of solid base painted boards (MP-2) to (MP-18)) Solid base paints (MP-2) to (MP-18) were obtained by carrying out the same operations as in Example MP-1, except that the solid base paint (MS-1) used in Example MP-1 was changed to solid base paints (MS-2) to (MS-18), respectively.

[0412] (1) Hue The resulting solid base coated plates (MP-1) to (MP-18) were each measured for color using a colorimeter (CM-700d, manufactured by Konica Minolta, Inc.), and the color difference (ΔE*) was determined based on Comparative Example MP-1 and evaluated according to the following criteria. The results are shown in Table 16. A rating of "5," "4," "3," or "2" on the following criteria indicates a practically acceptable level.

[0413] (Evaluation criteria) 5. ΔE* is less than 0.5. 4. ΔE* is 0.5 or more and less than 1.0. 3. ΔE* is 1.0 or more and less than 1.5. 2. ΔE* is 1.5 or more and less than 3.0. 1. ΔE* is 3.0 or more.

[0414] (2) Color stability over time The resulting solid base paints (MS-1) to (MS-18) were stored at a constant temperature of 40°C for two months, and then painted in the same manner as in Examples MP-1 to MP-15 and Comparative Examples MP-1 to MP-3, to obtain solid base painted panels (MP-1b) to (MP-18b). Each was measured using a colorimeter (Konica Minolta, CM-700d) to determine the color difference (ΔE*) before and after storage and evaluated according to the following criteria. The results are shown in Table 16. A rating of "5," "4," "3," or "2" on the following rating scale indicates a practically acceptable level.

[0415] (Evaluation criteria) 5. ΔE* is less than 0.5. 4. ΔE* is 0.5 or more and less than 1.0. 3. ΔE* is 1.0 or more and less than 1.5. 2. ΔE* is 1.5 or more and less than 3.0. 1. ΔE* is 3.0 or more.

[0416] (3) Weather resistance The obtained solid base coated plates (MP-1) to (MP-18) were subjected to a weather resistance test as follows. The weather resistance test was carried out using an ultra-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151) at an illuminance of 90 mW / cm 2 The weathering test was conducted under the following conditions: 12 hours of daytime irradiation, 63°C temperature, 70% humidity; 12 hours of rest (nighttime) irradiation, 70°C temperature, 99% humidity; and 48 hours (two 12-hour day and night cycles). The color of the coated panels before and after the weathering test was measured using a colorimeter (Konica Minolta, CM-700d). The color difference (ΔE*) was calculated and evaluated according to the following criteria. The results are shown in Table 16. A rating of "5," "4," "3," or "2" on the following criteria indicates a practical level.

[0417] (Evaluation criteria) 5. ΔE* is less than 3.0. 4. ΔE* is 3.0 or more and less than 4.0. 3. ΔE* is 4.0 or more and less than 5.0. 2. ΔE* is 5.0 or more and less than 6.0. 1. ΔE* is 6.0 or more.

[0418] [Table 16]

[0419] The results in Table 16 show that the pigment composition containing the azo compound (1) of the present invention and CI Pigment Yellow 180 exhibited good stability over time without impairing the hue and weather resistance.

[0420] <11> Gravure printing ink evaluation

[0421] (Synthesis Example 5) Polyurethane resin [PU1] 200 parts of polypropylene glycol (PPG700) with a number-average molecular weight of 700, 127 parts of isophorone diisocyanate (IPDI), and 81.8 parts of ethyl acetate were reacted at 80°C for 4 hours under a nitrogen stream to obtain a resin solution of isocyanate-terminated urethane prepolymer. The resulting resin solution of isocyanate-terminated urethane prepolymer was then gradually added at 40°C to a mixture of 49.5 parts of isophorone diamine (IPDA), 3 parts of 2-ethanolamine, and 803.9 parts of a 50 / 50 ethyl acetate / isopropanol (IPA) mixed solvent at a mass ratio of 50:50. The resulting mixture was then reacted at 80°C for 1 hour to obtain a polyurethane resin solution [PU1] with a nonvolatile content of 30%, an amine value of 3.5 mg KOH / g, a hydroxyl value of 7.3 mg KOH / g, and a weight-average molecular weight of 40,000. The glass transition temperature was -32°C.

[0422] <11-1> Preparation of gravure printing ink (Example N-1) (Preparation of gravure printing ink (N-1)) 30 parts of polyurethane resin solution [PU1] (30% non-volatile content) as a binder resin, 0.8 parts of polyethylene wax (Honeywell A-C400A) as a hydrocarbon wax (based on non-volatile content), 0.5 parts of chlorinated polypropylene resin (Nippon Paper Industries Co., Ltd., product name: 370M, chlorine content 30%, non-volatile content 50%) (based on non-volatile content), 10 parts of pigment composition (A-1), and 58.7 parts of a solution of methyl ethyl ketone (hereinafter referred to as "MEK") / n-propyl acetate (hereinafter referred to as "NPAC") / IPA = 40 / 40 / 20 (mass ratio) were mixed and dispersed for 15 minutes using an Eiger mill to obtain gravure printing ink (N-1).

[0423] (Examples N-2 to N-30, Comparative Examples N-1 to N-3) (Preparation of gravure printing inks (N-2) to (N-30), (N-33) to (N-35)) In the method for preparing the gravure printing ink (N-1) described in Example N-1, gravure printing inks (N-2) to (N-30) and gravure printing inks (N-33) to (N-35) were obtained in the same manner as in Example N-1, except that the pigment composition (A-1) was changed as shown in Table 17.

[0424] (Example N-31) (Preparation of gravure printing ink (N-31)) A gravure printing ink (N-31) was obtained in the same manner as in Example N-1, except that in the method for preparing the gravure printing ink (N-1) described in Example N-1, 10 parts of the pigment composition (A-1) was changed to 9.5 parts of the pigment composition (C-1) and 0.5 parts of the pigment composition (C-2).

[0425] (Example N-32) (Preparation of gravure printing ink (N-32)) A gravure printing ink (N-32) was obtained in the same manner as in Example N-1, except that in the method for preparing the gravure printing ink (N-1) described in Example N-1, 10 parts of the pigment composition (A-1) was changed to 9.5 parts of the pigment composition (C-1) and 0.5 parts of the pigment composition (C-3).

[0426] <11-2> Gravure printing ink (Example NP-1) The gravure printing ink (N-1) obtained above was diluted with a mixed solvent consisting of MEK / NPAC / IPA = 40 / 40 / 20 (mass ratio) to a viscosity of 16 seconds (25°C, Zahn cup No. 3), and printed on the following substrates (corona discharge treated surface in the case of OPP) at a printing speed of 80 m / min using a gravure printing press equipped with a Helio 175 line gradation plate (plate type compressed gradation 100% to 3%) to obtain printed matter NP1-1 (OPP) and NP1-2 (CPP).

[0427] (base material) OPP: Biaxially oriented polypropylene (OPP) film with one side corona discharge treatment (Futamura Chemical Co., Ltd., thickness 25 μm) CPP: Non-corona treated unstretched polypropylene (CPP) film (Mitsui Chemicals Tocello CP-S, thickness 30 μm)

[0428] (Examples NP-2 to NP-32, Comparative Examples NP-1 to NP-3) Printed materials NP2-1 to NP35-1 (OPP) and NP2-2 to NP35-2 (CPP) were obtained in the same manner as in Example NP-1, except that the gravure printing ink (N-1) used in Example NP-1 was changed to the gravure printing ink listed in Table 18.

[0429] <11-3> Evaluation of gravure printing ink The gravure printing inks (N-1) to (N-35), and printed matters NP1-1 to NP35-1 (OPP) and printed matters NP1-2 to NP35-2 (CPP) were used to carry out the following evaluations.

[0430] (Ink stability over time) Gravure printing inks (N-1) to (N-35) were each placed in a sealed container and stored at 40°C for 10 days or at 70°C for 10 days. After that, the viscosity was measured and the change in viscosity from before storage was evaluated. The viscosity was measured at 25°C using a Zahn cup No. 4 in seconds. The viscosity of all inks measured with a Brookfield viscometer before storage was within the range of 40 to 500 cps (25°C). According to the following evaluation criteria, a rating of "5," "4," "3," or "2" is considered to be at a practical level.

[0431] (Evaluation criteria) 5. Viscosity change in less than 2 seconds 4. Viscosity change is between 2 seconds and 3 seconds 3. Viscosity change is between 3 seconds and 4 seconds 2. Viscosity change is between 4 and 5 seconds 1. Viscosity change lasts for 5 seconds or more

[0432] (Transparency Assessment) The gravure printing inks (N-1) to (N-35) were applied to a drawing paper with a black band, and the degree of transparency on the black band was compared with that of Comparative Example N-1 to make a judgment.

[0433] (Evaluation criteria) 5. Extremely transparent 4.Transparent 3. Equivalent 2. Opaque 1. Extremely opaque

[0434] [Table 17]

[0435] (Scratch resistance) Using the printed materials NP1-1 to NP35-1 (OPP) and the printed materials NP1-2 to NP35-2 (CPP), the surface of the printed layer was rubbed with a fingernail in three places, and the degree of damage to the printed layer was evaluated. A rating of "5" or "4" on the following evaluation criteria was considered to be at a practical level.

[0436] (Evaluation criteria) 5. No damage to the printing layer 4. The print layer is not scratched, but slight fingernail marks remain. 3. The printing layer is scratched and the surface of the printing layer is slightly gouged 2. The print layer is scratched and the substrate is slightly visible 1. Scratches on the printing layer and the substrate are clearly visible

[0437] (Adhesiveness) For the prints NP1-1 to NP35-1 (OPP) and prints NP1-2 to NP35-2 (CPP), 3 hours after printing, a 12 mm wide adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) was applied to the printed surface, and the appearance of the printed surface was visually evaluated when the tape was quickly peeled off. The evaluation criteria were as follows: "5", "4", and "3" on the following evaluation criteria were considered to be at a practical level.

[0438] (Evaluation criteria) 5. The ink coating on the printed surface does not peel off at all. 4. The area of ​​the ink film that has peeled off is 1% or more but less than 3% 3. The area of ​​the ink film peeling is 3% or more but less than 5% 2. The area of ​​the ink film peeling is 5% or more but less than 20% 1. Ink film peeling off by 20% or more

[0439] [Table 18]

[0440] The results in Tables 17 and 18 show that the pigment composition containing the azo compound (1) of the present invention and CI Pigment Yellow 180 exhibited good results in terms of stability over time, transparency, scratch resistance, and adhesion.

[0441] <12> Ink setting and its characteristics evaluation An ink set was prepared using the resulting pigment composition, and its properties were evaluated.

[0442] (Synthesis Example 6) Polyurethane resin solution [PU2] 54.719 parts of a polyester diol with a number average molecular weight of 2,000 obtained from adipic acid and 3-methyl-1,5-pentanediol, 3.989 parts of isophorone diisocyanate, and 10.0 parts of n-propyl acetate were reacted under a nitrogen stream at 85°C for 3 hours, followed by the addition of 10.0 parts of n-propyl acetate and cooling to obtain 78.718 parts of a solvent solution of a terminal isocyanate prepolymer. 78.718 parts of the solvent solution of the terminal isocyanate prepolymer was then gradually added at room temperature to a mixture of 1.031 parts of isophorone diamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate, and 19.6 parts of isopropyl alcohol, and the mixture was then reacted at 50°C for 1 hour to obtain a polyurethane resin solution [PU2] with a nonvolatile content of 30%, a weight average molecular weight of 60,000, and an amine value of 3.0 mgKOH / g.

[0443] (Synthesis Example 7) Polyurethane resin solution [PU3] In a reactor equipped with a reflux condenser, a dropping funnel, a gas inlet, a stirrer, and a thermometer, 161.9 parts of PPA (poly(propylene glycol) adipate diol) with a number average molecular weight of 2,000), 27.7 parts of 2,2-dimethylolbutanoic acid (DMBA), 96.4 parts of isophorone diisocyanate (IPDI), and 200 parts of methyl ethyl ketone (MEK) were charged and reacted at 90 ° C for 5 hours to obtain a resin solution of a urethane prepolymer having terminal isocyanate groups. A mixture of 13.6 parts of 2-(2-aminoethylamino)ethanol (AEA), 0.5 parts of ethanolamine (MEA), and 350 parts of isopropyl alcohol (IPA) was added dropwise to the resulting urethane prepolymer resin solution containing terminal isocyanate groups at room temperature over 60 minutes, and then reacted at 70 ° C for 3 hours. Further, 150 parts of MEK was used to adjust the nonvolatile content, yielding a polyurethane resin solution [PU3] with a nonvolatile content of 30%, a weight average molecular weight of 35,000, Mw / Mn=3.0, an acid value of 35.0 mgKOH / g, and a hydroxyl value of 25.7 mgKOH / g.

[0444] (Synthesis Example 8) Aluminum phthalocyanine A reaction vessel was charged with 1,250 parts of n-amyl alcohol, 225 parts of phthalodinitrile, and 78 parts of anhydrous aluminum chloride, and the mixture was stirred. To this mixture, 266 parts of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) was added, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent of 5,000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine represented by the following chemical formula (15).

[0445] Chemical formula (15) [ka]

[0446] Next, 1500 parts of concentrated sulfuric acid was added to a reaction vessel, and then 100 parts of the above chloroaluminum phthalocyanine was added in an ice bath, followed by stirring for 4 hours at 25° C. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3° C. The resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water again, and then dried to obtain 98 parts of aluminum phthalocyanine represented by the following chemical formula (11).

[0447] Chemical formula (11) [ka]

[0448] (Synthesis Example 9) Titanyl phthalocyanine A reaction vessel was charged with 1,280 parts of 1-hexanol, 320 parts of quinoline, 320 parts of 1,3-diiminoisoindoline, and 206.3 parts of tetrabutyl orthotitanate, and the mixture was stirred. The temperature was raised to 155°C and refluxed for 8 hours. The n-butanol generated within the system was collected without returning to the system. The reaction solution was cooled to 60°C while stirring, and 1,000 parts of methanol was added. The slurry was filtered, washed with 1,000 parts of methanol, 500 parts of N-methylpyrrolidone, and 1,000 parts of methanol, and then dried to obtain 250 parts of a titanyl phthalocyanine crude represented by the following chemical formula (12).

[0449] Chemical formula (12) [ka]

[0450] Next, 1500 parts of concentrated sulfuric acid was added to a reaction vessel, followed by 100 parts of the titanyl phthalocyanine crude in an ice bath, and the mixture was stirred at 25°C for 4 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3°C, and the resulting precipitate was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and then washed with water to obtain a cake. Next, 1000 parts of diethylene glycol and the resulting cake were added to the reaction vessel and stirred to form a slurry, which was then stirred at 120°C for 3 hours. The slurry was cooled to 60°C, filtered, washed with 5000 parts of water, and dried to obtain 87 parts of titanyl phthalocyanine.

[0451] <12-1> Gravure printing ink manufacturing (Example PY-1) 7.0 parts of pigment composition (A-1), 34.5 parts of polyurethane resin solution [PU2], 20 parts of N-propyl acetate, and 5 parts of isopropyl alcohol were mixed with stirring and ground in a sand mill. Then, 20 parts of polyurethane resin solution [PU2], 11 parts of N-propyl acetate, and 3 parts of isopropyl alcohol were added to obtain yellow ink [PY-1].

[0452] (Examples PY-2 to PY-32, Production Examples PY-1 to PY-3, PC-1 to PC-5, PM-1 to PM-10) Inks shown in Tables 19-1 and 19-2 were obtained in the same manner as in Example PY-1, except that 7.0 parts of pigment composition (A-1) was changed to the pigments and amounts shown in Tables 19-1 and 19-2.

[0453] [Table 19-1]

[0454] [Table 19-2]

[0455] The pigments used in preparing the inks are listed in Table 20.

[0456] [Table 20]

[0457] The ink set is shown in Table 21-1 below.

[0458] [Table 21-1]

[0459] <12-2> Evaluation of gravure ink and ink set (1) Evaluation of ink viscosity stability over time Yellow inks [PY-1] to [PY-35], cyan inks [PC-1] to [PC-5], and magenta inks [PM-1] to [PM-10] were each placed in a sealed container and stored at 40°C for 14 days. The viscosity was then measured and evaluated by comparing the viscosity change before and after storage. Viscosity measurements were performed at 25°C using a Zahn cup No. 4 in seconds. The viscosity of each ink measured using a Brookfield viscometer before storage was within the range of 40 to 500 cps (25°C). The results are shown in Tables 21-2 and 21-3.

[0460] (Evaluation criteria) ○: Viscosity change is less than 2 seconds (good) △: Viscosity change is between 2 seconds and 5 seconds (practical) ×: Viscosity change is 5 seconds or more (bad)

[0461] (2) Ink set evaluation (Examples PS-1 to PS-81, Comparative Examples PS-1 to PS-16) The resulting inks were combined as shown in Table 21-1 to form ink sets 1 to 97. The resulting ink sets were evaluated for trapping ability and gamut using the following methods. The results are shown in Tables 21-2 and 21-3.

[0462] [Trapping] (cyan ink / yellow ink) The cyan ink and yellow ink were each diluted with mixed solvent 1 (methyl ethyl ketone:N-propyl acetate:isopropanol=40:40:20) to a viscosity of 16 seconds (25° C., Zahn cup No. 3). Cyan and yellow were printed in this order on the corona discharge treated surface of a 12 μm thick corona discharge treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.) to obtain a print (initial evaluation of trapping properties). The printing conditions were a temperature of 25°C, humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. The cyan ink was printed using a Helio 175 line gradation plate (compressed printing type, 75% solid pattern and 100% to 3% gradation pattern), and the yellow ink was printed using a Helio 175 line gradation plate (elongated printing type, 75% solid pattern and 100% to 3% gradation pattern). Furthermore, the cyan ink and the yellow ink were each placed in a sealed container and stored at 40° C. for 14 days, and then diluted and printed in the same manner as above to obtain printed matter (trapping property evaluation over time).

[0463] (Yellow ink / Magenta ink) The yellow ink and magenta ink were each diluted with the above mixed solvent 1 so that the viscosity became 16 seconds (25° C., Zahn cup No. 3). Yellow and magenta were printed in this order on the corona-discharge-treated surface of a 12 μm-thick corona-discharge-treated polyester film (E-5100, manufactured by Toyobo Co., Ltd.) to obtain a print (initial evaluation of trapping properties). The printing conditions were a temperature of 25°C, humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. The yellow ink used a Helio 175 line gradation plate (elongated plate type, 75% solid pattern and 100% to 3% gradation pattern), and the magenta ink used a Helio 175 line gradation plate (elongated plate type, 75% solid pattern and 100% to 3% gradation pattern). The yellow ink and magenta ink were each placed in a sealed container and stored at 40° C. for 14 days, after which they were diluted and printed in the same manner as above to obtain printed matter (trapping property evaluation over time).

[0464] The gradation overlapping printed portion of the obtained print was observed for trapping ability using a microscope (VHX-5000) manufactured by Keyence Corporation, and evaluated according to the following criteria.

[0465] (Evaluation criteria) ○: Print unevenness occurs at less than 70% plate depth (good) △: Print unevenness occurs at a plate depth of 70% or more but less than 80% (usable) ×: Printing unevenness occurs at a depth of 80% or more, or the overlapping inks all become halftone dots and do not spread (unusable)

[0466] [Gamut evaluation] (Initial evaluation) The cyan ink, magenta ink, and yellow ink were diluted with the above mixed solvent 1 to a viscosity of 16 seconds (25°C, Zahn cup No. 3). Using each diluted ink, printing was carried out in the order of cyan, magenta, and yellow, resulting in printed matter with single-color solid areas (cyan, magenta, yellow) and single-color solid overprint areas (cyan x magenta, cyan x yellow, yellow x magenta). The printing conditions are shown below.

[0467] (Printing conditions) Printing machine: Fuji Machine 5 color machine Cyan version: Helio 175L / inch, stylus angle 120°, elongated Magenta version: Helio 175L / inch, stylus angle 120°, compressed Yellow version: Helio 175L / inch, stylus angle 120°, compressed Printing speed: 150m / min Substrate: Corona-treated biaxially oriented polypropylene (OPP) film (Toyobo Pylen P-2161, 20 μm) Drying temperature: 50℃

[0468] The density values ​​of the solid color areas (yellow, magenta, cyan) of the obtained prints were measured using a Gretagmacbeth D196. In addition, the color of the solid color areas and the overprinted areas was measured using a Gretagmacbeth SpectroEye as a measuring instrument under the conditions of a D50 light source, a 2-degree observation field, a white background (a standard white board), and no filters. In a two-dimensional space with a* on the horizontal axis and b* on the vertical axis, the a* vs. b* values ​​for the six solid color areas (yellow, magenta, cyan) and the solid color overlapping areas (cyan x magenta, cyan x yellow, yellow x magenta) were plotted to create a hexagon and calculate the area. The area ratio was calculated based on the area of ​​the comparative example PS-1 as 100%, and the evaluation was based on the area ratio and the following criteria. Note that - indicates that the evaluation was not performed.

[0469] (Evaluation criteria) ○: Area ratio is 90% or more (good) △: Area ratio is 85% or more and less than 90% (usable) ×: Area ratio is less than 85% (unusable)

[0470] (Evaluation over time) The cyan ink, magenta ink, and yellow ink were each placed in a sealed container and stored at 40° C. for 14 days, after which they were diluted and printed in the same manner as in the initial evaluation to obtain printed matter.

[0471] The resulting prints were subjected to color measurement in the same manner as in the initial evaluation described above. In a two-dimensional space with a* on the horizontal axis and b* on the vertical axis, a hexagon was created by plotting the a* vs. b* values ​​for six colors: solid single-color areas (yellow, magenta, cyan) and overlapping solid single-color areas (cyan x magenta, cyan x yellow, yellow x magenta). The area of ​​each example and comparative example after aging was divided by the area of ​​the initial evaluation to determine the area ratio, and the results were evaluated based on the following criteria. "-" indicates that the results were not evaluated.

[0472] (Evaluation criteria) ○: Area ratio is 98% or more (good) △: Area ratio is 95% or more and less than 98% (practical) ×: Area ratio is less than 95% (bad)

[0473] [Table 21-2]

[0474] [Table 21-3]

[0475] The results in Tables 21-2 and 21-3 show that the gravure printing ink set of the present invention had a gamut area ratio equal to or greater than that of the conventional ink set, and had good color reproducibility. The viscosity stability of the yellow ink over time was also improved, and the ink set had good storage stability. Furthermore, the trapping properties and color reproducibility (gamut) of each color were also evaluated favorably over time, and the ink set had good storage stability.

[0476] On the other hand, in Comparative Examples PS-1 to PS-16, the yellow ink had poor viscosity stability over time, and the trapping properties and color reproducibility (gamut) of each color were also poorly evaluated over time, so the storage stability as an ink set was poor and the problem of the present application could not be solved.

[0477] <12-3> Manufacturing of packaging materials

[0478] [Manufacturing of clear ink] (Preparation of clear ink [1]) 87 parts of polyurethane resin solution [PU3] (non-volatile content 30%), 5 parts of ethyl acetate (EA), 5 parts of IPA, and 3 parts of silica ("P-73" manufactured by Mizusawa Chemical Industries, Ltd., hydrophilic silica particles with an average particle size of 3.8 μm) were mixed and stirred using a disper to obtain clear ink [1].

[0479] [Production of Releasable Adhesive] (Preparation of laminating adhesive solution [1]) A four-neck separable flask was charged with 82 parts terephthalic acid, 682 parts isophthalic acid, 236 parts adipic acid, 236 parts ethylene glycol, 525 parts neopentyl glycol, and 405 parts 1,6-hexanediol, and an esterification reaction was carried out at 220-260°C. After distilling off a predetermined amount of water, the pressure was gradually reduced to 1 mmHg or less, and a deglycolization reaction was carried out at 240-260°C for 5 hours. Then, 2 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150°C for approximately 2 hours to obtain a polyester polyurethane polyol. 2.83 parts of trimellitic anhydride was added to 100 parts of this polyester polyurethane polyol, and the reaction was carried out at 180°C for approximately 2 hours. The mixture was then diluted with ethyl acetate to a nonvolatile content of 50%, yielding a partially acid-modified polyester polyol solution with a number average molecular weight of 6,000 and an acid value of 16.5 mgKOH / g. 100 parts of the obtained polyol solution and 7.94 parts of a 95% nonvolatile ethyl acetate solution of HDI biuret were mixed, and ethyl acetate was added to obtain a laminating adhesive solution [1] with a nonvolatile content of 30%.

[0480] [Manufacturing of packaging materials] (Example PP-1) Packaging Material 1 The cyan ink [PC-1], magenta ink [PM-1], and yellow ink [PY-1] were diluted with the above mixed solvent 1 to a viscosity of 16 seconds (25° C., Zahn cup No. 3). Using each diluted ink, a five-color gravure proofing press equipped with a gravure plate with a 20 μm plate depth and ink set 101 containing black ink (Rio Alpha R92 Black (manufactured by Toyo Ink Co., Ltd.)), cyan ink [PC-1], magenta ink [PM-1], yellow ink [PY-1], and white ink (Rio Alpha R631 White (manufactured by Toyo Ink Co., Ltd.)) was used to print over a 20 μm thick corona-treated stretched polypropylene film (OPP substrate) in the order of black ink, cyan ink [PC-1], magenta ink [PM-1], yellow ink [PY-1], and white ink. Each unit was dried at 50°C to obtain a printed product with a configuration of "OPP substrate / black, cyan, magenta, yellow, or white printed layer." Next, a urethane laminating adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd., 30% non-volatile content ethyl acetate solution) was applied to the printed layer of the obtained printed matter in an amount of 2.0 g / m2 after drying. 2 After coating and drying the mixture, a 50 μm thick unstretched polyethylene (PE) film was laminated onto the adhesive layer to obtain packaging material 1, which had a structure of "OPP substrate / five-color overlapping print layer / adhesive layer / PE substrate."

[0481] (Examples PP-2 to PP-81) Packaging Materials 2 to 81 Packaging materials 2 to 81 were obtained in the same manner as in Example PP-1, except that the ink set 101 used in Example PP-1 was changed to the ink sets shown in Tables 22-1 and 22-2.

[0482] [Table 22-1]

[0483] [Table 22-2]

[0484] (Example PP-101) Packaging Material 101 The above-mentioned clear ink [1] was diluted with an EA / IPA mixed solvent (mass ratio 70 / 30) so that the viscosity became 15 seconds (25°C, Zahn cup No. 3). The cyan ink [PC-1], magenta ink [PM-1], and yellow ink [PY-1] were diluted with the above mixed solvent 1 to a viscosity of 16 seconds (25° C., Zahn cup No. 3). Using each diluted ink, a 5-color gravure proofing machine equipped with a gravure plate with a plate depth of 20 μm and ink set 201 containing clear ink [1], cyan ink [PC-1], magenta ink [PM-1], and yellow ink [PY-1] was used to overprint a 20 μm thick corona-treated stretched polypropylene film in the order of clear ink [1], cyan ink [PC-1], magenta ink [PM-1], and yellow ink [PY-1]. Each unit was dried at 50°C, and a printed matter containing a removable layer was obtained, with a configuration of "OPP substrate / detachable layer (clear ink) / cyan, magenta, or yellow printed layer." Next, a laminating adhesive solution [1] was applied onto the printed layer of the obtained printed matter using a dry laminating machine, and then laminated to a 25 μm thick aluminum-vapor-deposited unoriented polypropylene (VQCPP) film at a line speed of 40 m / min, to obtain a packaging material 101 having a removable layer and configured as "OPP substrate / detachable printed layer / three-color overprinted printed layer / detachable adhesive layer / VQCPP substrate."

[0485] (Examples PP-102 to PP-181) Packaging Materials 102 to 181 Packaging materials 102 to 181 having a release layer were obtained in the same manner as in Example PP-101, except that the ink set 201 used in Example PP-101 was changed to the ink sets shown in Tables 23-1 and 23-2.

[0486] [Table 23-1]

[0487] [Table 23-2]

[0488] Packaging materials could be made using the gravure printing ink set of the present invention.

[0489] <12-4> Manufacturing of water-based inkjet ink (Example QY-1) (Preparation of aqueous inkjet coloring composition (hereinafter referred to as "IJ aqueous coloring composition") [QY-1]) The following materials and 200 parts of zirconia beads with a diameter of 1.25 mm were placed in a 200 ml glass bottle and dispersed for 6 hours using a paint shaker manufactured by Red Devil. Pigment composition (A-1): 19.0 parts Styrene-acrylic acid copolymer (BASF Japan, JONCRYL 61J): 16.4 parts Surfactant (Kao Corporation, Emulgen 420): 5.0 parts Ion-exchanged water: 59.6 parts Next, the zirconia beads were removed from the dispersion to obtain an aqueous inkjet coloring composition [QY-1].

[0490] (Preparation of Water-Based Inkjet Ink (hereinafter referred to as "Water-Based IJ Ink") [QY-1]) 33 parts of aqueous IJ dispersion 1, 5 parts of butyl diglycol, 15 parts of 1,2-propanediol, 8.8 parts of Joncryl HPD96 (a water-soluble resin manufactured by BASF Japan), 1.25 parts of Chemipearl W400S (a polyolefin aqueous dispersion manufactured by Mitsui Chemicals, Inc.), 0.5 parts of Surfynol DF110D (an antifoaming agent manufactured by Nissin Chemical Industry Co., Ltd.), 1 part of BYK-348 (a silicone surfactant manufactured by BYK Japan), 0.1 parts of triethanolamine, 0.15 parts of Proxel GXL (a preservative manufactured by Lonza), and 35.2 parts of ion-exchanged water were mixed in a high-speed mixer and filtered through a 0.5 μm membrane filter to obtain an aqueous IJ ink [QY-1].

[0491] (Examples QY-2 to QY-32, Production Examples QY-1 to QY-3, QC-1 to QC-3, QM-1 to QM-6) (Preparation of aqueous inkjet coloring compositions [QY-2] to [QY-35], [QC-1] to [QC-3], and [QM-1] to [QM-6], and aqueous inkjet inks [QY-2] to [QY-35], [QC-1] to [QC-3], and [QM-1] to [QM-6]) Inkjet aqueous coloring compositions [QY-2] to [QY-35], [QC-1] to [QC-3], and [QM-1] to [QM-6], and water-based inkjet inks [QY-2] to [QY-35], [QC-1] to [QC-3], and [QM-1] to [QM-6] shown in Table 24 were obtained in the same manner as in Example QY-1, except that 19.0 parts of pigment composition (A-1) in Production Example QY-1 was changed to the pigments shown in Table 24 and in the amounts shown in Table 24.

[0492] [Table 24]

[0493] The pigments used in preparing the inks are listed in Table 25.

[0494] [Table 25]

[0495] <12-5> Evaluation of Water-Based IJ Inks and Ink Sets (1) Evaluation of ink viscosity stability over time The initial viscosity of the water-based inkjet inks [QY-1] to [QY-35], [QC-1] to [QC-3], and [QM-1] to [QM-6] was measured at 25°C using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity was measured after 4 weeks of aging at 25°C and after 4 weeks of accelerated aging at 50°C. Using each measured value, the viscosity increase rate relative to the initial viscosity was calculated, which was used as an index of viscosity stability and evaluated according to the following criteria. The results are shown in Table 26-2. The smaller the viscosity increase rate, the better the viscosity stability; a rating of "4," "3," or "2" on the following criteria is considered to be at a practical level.

[0496] (Evaluation criteria for viscosity stability) 4: The viscosity increase rate is less than 15%. 3: The viscosity increase rate is 15% or more and less than 25%. 2: The viscosity increase rate is 25% or more and less than 40%. 1: The viscosity increase rate is 40% or more.

[0497] (2) Ink set evaluation [Examples QS-1 to QS-49, Comparative Examples QS-1 to QS-10] The resulting water-based IJ inks were combined as shown in Table 26-1 to form ink sets 301 to 359. The resulting ink sets were evaluated for gamut using the following method. The results are shown in Table 26-2.

[0498] [Gamut evaluation] (Initial evaluation) Using a line-path inkjet printer with an inkjet head (Kyocera KJ4B series) with a width resolution of 600 dpi and a maximum ejection frequency of 30 kHz, the yellow ink, magenta ink, and cyan ink of each ink set were filled into each head, and printed on coated paper (Oji Paper OK Topcoat N, basis weight 104.7 g / m 2 A color chart image (X-rite ProfileMaker chart image "TC3.5 CQYK i1_i0") was printed on the paper at a resolution of 600 x 600 dpi to prepare a printout for evaluation.

[0499] The color chart portion of the obtained evaluation printout was measured using a spectrophotometer (X-rite i1 i0 Pro) and color measurement tools (X-rite Measurement Tool and ProfileMaker), and the color reproduction range in the L*a*b* color space was plotted. Measurement conditions were a D50 light source, a 2-degree field of view, and measurement optics at 45 / 0°. The area was calculated from each obtained plot. The area ratio was calculated when the area of ​​the comparative example QS-1, which served as the reference, was taken as 100%, and evaluation was performed based on this area ratio using the following criteria.

[0500] (Evaluation criteria) ○: Area ratio is 90% or more (good) △: Area ratio is 85% or more and less than 90% (usable) ×: Area ratio is less than 85% (unusable)

[0501] (Evaluation over time) Each water-based inkjet ink was placed in a sealed container and stored at 50°C for 4 weeks, after which printing was performed in the same manner as in the initial evaluation to produce printed matter for evaluation. The resulting printed matter was colorimetrically measured in the same manner as in the initial evaluation, and the area was calculated from each plot. The area in the aged evaluation of each Example and Comparative Example was divided by the area in the initial evaluation to calculate the area ratio, and the results were evaluated based on the following criteria.

[0502] (Evaluation criteria) ○: Area ratio is 98% or more (good) △: Area ratio is 95% or more and less than 98% (practical) ×: Area ratio is less than 95% (bad)

[0503] [Table 26-1]

[0504] [Table 26-2]

[0505] According to Table 26-2, the water-based IJ ink set of the present invention had a gamut area ratio equal to or greater than that of the conventional ink set, and had good color reproducibility. Furthermore, the viscosity stability of the yellow ink over time was improved, and the ink set had good storage stability. Furthermore, the color reproducibility (gamut) was also evaluated favorably over time, and the ink set had good storage stability.

[0506] On the other hand, in Comparative Examples QS-1 to QS-10, the yellow ink had poor viscosity stability over time, and the color reproducibility (gamut) was also poorly evaluated over time, so the storage stability as an ink set was poor and the problem of the present application could not be solved.

Claims

1. Pigment Yellow 180 and an azo compound represented by the following formula (1): A pigment composition, wherein the content of the azo compound represented by formula (1) is 0.1 to 43 parts by mass relative to 100 parts by mass of C.I. Pigment Yellow 180. Formula (1) 【Chemistry 1】 [In the formula, R １ Ha-NR ２ R ３ Or -OR ４ represents R ２ ~R ４ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

2. The R １ The pigment composition according to claim 1 , wherein is an amino group or a hydroxyl group.

3. A coloring composition comprising the pigment composition according to claim 1 or 2 and a dispersion medium.

4. A molding composition comprising the coloring composition according to claim 3.

5. A toner comprising the coloring composition of claim 3.

6. A paint comprising the coloring composition of claim 3.

7. A printing ink comprising the coloring composition according to claim 3.

8. An ink set including at least a yellow ink, a cyan ink, and a magenta ink, An ink set, wherein the yellow ink comprises the coloring composition according to claim 3.

9. A gravure printing ink set including at least a yellow ink, a cyan ink, and a magenta ink, A gravure printing ink set, wherein the yellow ink comprises the coloring composition of claim 3.

10. The gravure printing ink set of claim 9 further comprising a clear ink.

11. A printed article comprising a substrate and a print layer formed from the gravure printing ink set of claim 9.

12. A printed matter comprising a substrate, a printing layer formed from the gravure printing ink set of claim 10, and a release layer formed from a clear ink.

13. A packaging material comprising the printed matter according to claim 11 or 12.

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