JP2023084180A - Pigment composition, coloring composition, ink, ink set, printed matter, and packaging material - Google Patents

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

The present invention relates to a pigment composition containing a specific azo compound.

In recent years, the demand for organic pigments and colorants that do not contain specific aromatic amines, halogens, heavy metals, and the like has increased from the viewpoint of reducing environmental impact and ensuring safety and health. Under such circumstances, among pigments used for coloring plastic products, toners, paints, printing inks, etc., azo pigments are mainly used as organic pigments having a hue of yellow to red.
Azo pigments may contain a specific aromatic amine derived from raw materials other than the pigment or derived from decomposition of the pigment by light or heat. For example, a representative monoazo yellow pigment, C.I. I. Pigment Yellow 74 is easily decomposed by heat or light to produce a specific aromatic amine, o-anisidine. C.I., a typical disazo yellow pigment, is also used. I. Pigment Yellow 14 uses dichlorobenzidine, which is a specific aromatic amine, as a raw material, and unreacted substances may remain. Also C.I. I. Pigment Yellow 14 may be decomposed by heat or light to produce dichlorobenzidine or o-toluidine.

On the other hand, C.I. I. Pigment Yellow 180 has no specific aromatic amines, halogens, or heavy metals in its structure, and has a benzimidazolone structure, which makes it a disazo pigment with excellent heat resistance and light resistance. Known as an expensive and useful yellow pigment, it is used in a variety of applications.

However, C.I. I. Pigment compositions containing Pigment Yellow 180 had a high degree of difficulty in particle control, and thus a high degree of difficulty in dispersion. In addition, it has poor storage stability and lacks transparency, making it difficult to use.

For example, in Patent Document 1, C.I. I. A crude pigment of Pigment Yellow 180 is disclosed. Moreover, in Patent Document 2, C.I. I. A pigment composition containing Pigment Yellow 180 and a benzimidazolone monoazo pigment is disclosed.

Japanese Patent Application Laid-Open No. 2002-201379 JP 2009-057509 A

However, conventional pigment compositions lack dispersibility and transparency.

An object of the present invention is to provide a pigment composition having good dispersibility and transparency.

The present invention is based on C.I. I. Pigment Yellow 180 and a pigment composition containing an azo compound represented by the following formula (1).
Formula (1)

[In the formula, R ₁ represents —NR ₂ R ₃ or —OR ₄ , and R ₂ to R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. ]

According to the present invention, a pigment composition having good dispersibility and transparency can be provided. In addition, it is possible to provide an ink set, a printed matter, a packaging material, and the like containing a yellow ink excellent in dispersibility and storage stability.

First, the terms used in this specification are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, respectively " acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. "C.I." means a color index (C.I.).

<Pigment composition>
The pigment composition of the present invention contains C.I. I. Pigment Yellow 180 and an azo compound represented by formula (1) are included.

Formula (1)

[In the formula, R ₁ represents —NR ₂ R ₃ or —OR ₄ , and R ₂ to R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. ]

Since the pigment composition of the present invention contains the azo compound represented by formula (1) as described above, conventionally, C.I. I. Dispersibility, storage stability and transparency, which were weak points of Pigment Yellow 180, are improved. INDUSTRIAL APPLICABILITY The pigment composition of the present invention can be used in a wide range of applications requiring coloring, such as molded articles, toners, paints, printing inks and inkjet inks.

[Azo compound (1)]
The azo compound represented by formula (1) is referred to as azo compound (1).

In formula (1), R ₁ represents —NR ₂ R ₃ or —OR ₄ , and R ₂ to R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

The pigment composition of the present invention contains C.I. I. By containing Pigment Yellow 180 and the azo compound (1), a dispersion excellent in dispersibility and stability over time can be produced, and an image with high chroma and transparency can be formed.
For these reasons, in the azo compound (1), one benzimidazolone moiety of the azo group is C.I. I. C.I. Pigment Yellow 180 easily adsorbs to C.I. I. It does not adsorb to Pigment Yellow 180 and can prevent crystal growth of the pigment. This makes it possible to suppress enlargement and aggregation of the pigment particles during preparation of the pigment composition and subsequent dispersion steps. Therefore, it is presumed that inks, paints and the like using the pigment composition have high stability over time. In addition, it is speculated that the presence of the azo compound (1) during preparation of the pigment composition enables adjustment of the pigment particle diameter to an appropriate one, thereby improving dispersibility and transparency.

In the pigment composition of the present invention, C.I. I. The content of the azo compound (1) is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of Pigment Yellow 180. , 1 to 5 parts by weight are particularly preferred.

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

In the alkyl group, at least one hydrogen atom is a halogen atom, a hydroxyl 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, an amido group, or other substituents. may be replaced with Moreover, you may have multiple substituents. In addition, a substituent is not limited to the above.

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 the present specification, an alkyl group includes, 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 -C ₂ H ₄ -OC ₂ H ₅ .

In the above formula (1), the aryl group (--Ar) in R ₂ to R ₄ is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The number of carbon atoms is preferably 6-30, more preferably 6-20.
Examples of the aryl group include phenyl, tolyl, biphenylyl, terphenylyl, quarterphenylyl, pentalenyl, indenyl, naphthyl, binaphthalenyl, ternaphthalenyl, quarternaphthalenyl, azulenyl, and heptalenyl groups. , biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrilenyl group, aceanthrilenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group , phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, pleiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubisenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, or ovalenyl group. Among these, a phenyl group and a tolyl group are preferred.

In the above aryl group, at least one hydrogen atom is a halogen atom, a hydroxyl 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, an amido group, or other substituents. may be replaced with Moreover, you may have multiple substituents. In addition, a substituent is not limited to the above.

In the above formula (1), examples of acyl groups for R ₂ to R ₄ include acetyl group, propioyl group, benzoyl group, acrylyl group, trifluoroacetyl group and the like. Among these, an acetyl group is preferable from the viewpoint of synthetic difficulty.

In the above formula (1), R ₁ is preferably an amino group or a hydroxyl group.

The azo compounds (1) can be used singly or in combination of two or more.

The azo compound (1) can be represented by the following formula (1A), (1B) or (1C). Hereinafter, they are referred to as azo compound (1A), azo compound (1B), and azo compound (1C), respectively.

（１Ａ） （１Ｂ） （１Ｃ）

(1A) (1B) (1C)

R ₅ in the above formula (1A) represents —NR ₆ R ₇ or —OR ₈ , R ₆ to R ₇ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and R ₆ or Either one of _R7 is other than a hydrogen atom, and _R8 represents an alkyl group, an aryl group, or an acyl group.

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. However, the present invention is not limited to these.

[Method for producing azo compound (1)]
Azo compound (1) is obtained 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 and ice-cooling, as shown in Scheme 1 below. , obtained by a coupling reaction of a diazonium salt solution obtained by performing a diazotization reaction and 5-acetoacetylamino-benzimidazolone represented by the formula (4) (hereinafter referred to as compound (4)) be able to. Excess nitrous acid after the diazotization reaction can also be removed by adding an aqueous sulfamic acid solution.

(Scheme 1)

R ₉ in the above formula (3) represents —NR ₁₀ R ₁₁ or —OR ₁₂ , R ₁₀ to R ₁₁ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and R ₁₀ or Either one of R ₁₁ is other than a hydrogen atom, and R ₁₂ represents an alkyl group, an aryl group, or an acyl group.

Further, as shown in Scheme 2 below, 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). Obtainable.

(Scheme 2)

Further, as shown in Scheme 3 below, the azo compound (1) is 1,2-bis(2-aminophenoxy)-ethane (hereinafter referred to as compound (7)) represented by formula (7). It can be obtained by coupling the compound (4) with a diazonium salt solution obtained by adding an aqueous sodium nitrite solution in the presence of an ice-cooled state to carry out a diazotization reaction. At that time, the azo compound (1C) can be obtained by reacting sodium nitrite with the compound (7) equimolarly.

(Scheme 3)

Alternatively, as shown in Scheme 4 below, a diazonium salt solution obtained by diazotizing compound (7) is coupled with an equimolar amount of compound (4) to remove excess diazonium salt. Azo compound (1B) can be obtained by hydrolysis.

(Scheme 4)

Alternatively, the azo compound (1A) can be obtained by alkylating, arylating or acylating the azo compound (1B) or the azo compound (1C).

[Method for producing pigment composition]
C. I. A method for producing a pigment composition containing Pigment Yellow 180 and azo compound (1) is exemplified below.
(I) a method of synthesizing two or more at once (co-synthesis method), (II) C.I. I. Pigment Yellow 180 and the method of mixing the azo compound (1), (III) C.I. I. Pigment Yellow 180 and azo compound (1) are mixed together by acid pasting method, acid slurry method, dry milling method, salt milling method, solvent salt milling method, solvent method (in a high boiling point solvent such as alcohol or aromatic solvent). (IV) A method combining the above methods.
Among them, (I) cosynthesis method, (III) C.I. I. Pigment Yellow 180 and azo compound (1) are combined together to form a pigment using an acid pasting method, a solvent salt milling method, or a solvent method, and (IV) a method combining (I) and (III). .

(I) As for the cosynthesis method, for example, compound (7) and compound (3) are mixed in a desired ratio to form a diazot, and then subjected to a coupling reaction with compound (4) to obtain C.I. I. A co-compound of Pigment Yellow 180 and azo compound (1A) can be obtained. Further, by using compound (6) instead of compound (3), C.I. I. A co-compound of Pigment Yellow 180 and azo compound (1B) can be obtained.

Further, by diazotizing compound (7) to a desired ratio and performing a coupling reaction with compound (4), C.I. I. A co-compound of Pigment Yellow 180 and azo compound (1C) can be obtained.

Alternatively, a diazonium salt solution obtained by diazotizing compound (7) is coupled with compound (4) in a desired ratio to hydrolyze excess diazonium salt to obtain C.I. I. A co-compound of Pigment Yellow 180 and azo compound (1B) can be obtained.

The particle size of the pigment composition of the present invention is preferably adjusted by heating a slurry dispersed in a liquid medium in which the pigment composition is not dissolved. By adjusting the particle size, it can be expected that when the pigment composition of the present invention is used as an ink or the like, the color develops more vividly and the dispersibility and storage stability are improved. As the slurry, the slurry obtained after synthesizing the pigment may be used, the slurry may be obtained by redispersing the wet cake obtained by filtration and washing, or the dried and pulverized product may be redispersed. A slurry may be obtained. It is preferable to use a wet cake as the pigment composition in that dry aggregation does not increase the labor required for pigmentation and the effect of excessive salt can be eliminated.

At this time, water and an organic solvent can be used as the liquid medium. Examples of organic solvents include alcohol solvents such as methanol, ethanol, isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone and acetone; ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; ,4-dioxane, dimethylsulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, hexamethylphosphorus Polar aprotic solvents such as amides, sulfolane are included.

The liquid medium is preferably used in an amount of 300 to 8,000 parts by mass, more preferably 500 to 5,000 parts by mass, and even more preferably 600 to 3,000 parts by mass with respect to 100 parts by mass of the pigment composition.

The temperature of 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, heat treatment may be performed under pressure. Also, a base may be used in combination with the liquid medium.

The pigment composition of the present invention is preferably granulated by solvent salt milling. By narrowing the particle size distribution of the primary particle size by solvent salt milling, when the pigment composition of the present invention is used in an ink or the like, it is possible to develop a more vivid color and improve dispersibility and storage stability. I can expect it. Granulation by solvent salt milling involves vigorously kneading a clay-like mixture comprising at least three components, a pigment, a water-soluble inorganic salt and a water-soluble solvent, using a kneader or the like. The mixture after kneading is put into water and stirred with various stirrers to form a slurry. The resulting slurry is filtered to remove water-soluble inorganic salts and water-soluble solvents. By repeating the slurry formation, filtration, and washing with water, a pigment having a granulated particle size can be obtained.

Water-soluble inorganic salts such as sodium chloride, sodium sulfate, and potassium chloride can be used. These inorganic salts are used in an amount of 1-fold or more, preferably 20-fold or less, of the pigment. When the amount of the inorganic salt is 1-fold or more by mass, the pigment can be sufficiently finely divided. Further, when the amount of the inorganic salt is 20 times by mass or less, a great deal of effort is not required to remove the water-soluble inorganic salt and the water-soluble solvent after kneading, and at the same time, the amount of pigment that can be processed at one time is reduced. Since it does not decrease, it is preferable from the viewpoint of productivity.

Particle size regulation of pigments often generates heat during kneading. Therefore, from the viewpoint of safety, it is preferable to use a water-soluble solvent with a boiling point of about 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 mono Ethyl 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, low molecular weight polypropylene glycol, and the like.

[Dye derivative]
The pigment composition can contain dye derivatives.
A dye derivative is a known compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having an acidic substituent such as a sulfo group, a carboxyl group, and a phosphoric acid group; A compound having a neutral substituent such as a phenyl group or a phthalimidoalkyl group can be mentioned.
Organic dyes include, for example, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazineindigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, benzoiso Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

A dye derivative can be used individually or in mixture of 2 or more types.

<Coloring composition>
The coloring composition of the present invention preferably contains the above pigment composition and a dispersion medium.

[Dispersion medium]
Dispersion media include resins and solvents. Examples of resins include resin-type dispersants and binder resins. Solvents include water and organic solvents. A low-molecular-weight dispersant such as a surfactant can be used as necessary.

The resin-type dispersant has a pigment-affinity site that adsorbs to the pigment, and a relaxation site that has a high affinity with components other than the pigment and causes steric repulsion between dispersed particles. Resin-type dispersants have acidic or basic groups. A carboxy group, a sulfo group, a phosphoric acid group, etc. are mentioned as an acidic group. Basic groups include primary to tertiary amino groups, quaternary ammonium bases, and the like.
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, poly Carboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and salts thereof; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc.; Examples include polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphoric acid esters.
The basic resin-type dispersant is a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. for resin types such as acrylic resin, polyester resin, and urethane resin. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups containing

Resin-type dispersants include, for example, JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL62J, JONCRYL63J, and JONCRYLHPD-9 manufactured by BASF Japan. 6J, JONCRYL501J, JONCRYLPDX-6102B, DISPERBYK180 manufactured by BYK-Chemie, DISPERBYK187, DISPERBYK190, DISPERBYK191, DISPERBYK194, DISPERBYK2010, DISPERBYK2015, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2155, SOLSPERSE24000, SOLSPERSE3 manufactured by Lubrizol Japan 2000, SOLSPERSE41000, Sartomer SMA1000H, SMA1440H, SMA2000H, SMA3000H, SMA17352H, and the like.

Any binder resin may be used as long as it can be coated or molded by printing, molding, or the like, and may be, for example, a polyolefin resin, a polyester resin, a styrene copolymer, an acrylic resin, or a modified resin thereof. Specifically, polyethylene such as high density polyethylene (HDPE), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), polyolefin resin such as polypropylene; polyester resin 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-methyl chloromethacrylate copolymer Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer , Styrene copolymers such as styrene-acrylonitrile-indene copolymers; Acrylic resins such as acrylic resins and methacrylic resins; Polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic acid resins, silicone resins, polyurethane resins , ethylene-vinyl acetate copolymer resin, vinyl acetate resin, nitrocellulose resin, polyamide resin, epoxy resin, xylene resin, polyvinyl butyral resin, polyvinyl acetal resin, cellulose ester resin, alkyd resin, rosin resin, ketone resin, ring chlorinated rubber, chlorinated polyolefin resins, terpene resins, coumarone-indene resins, amino resins, petroleum resins, modified resins thereof, and the like.

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.

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

The coloring composition of the present specification includes, for example, the following aspects. Embodiment 1 (eg molding composition, toner) comprising a pigment composition and a resin. Embodiment 2 comprising a pigment composition and an organic solvent (for example, a solvent-based coloring composition). Embodiment 3 (for example, a water-based coloring composition) comprising a pigment composition, a resin and water.

To explain the use of each aspect, the aspect 1 includes, for example, molding compositions, toners, dope-dyed fibers, solventless printing inks (UV curable offset inks, UV curable inkjet inks, etc.), and the like. Aspect 2 is a solvent-based coloring composition, and includes paints, printing inks (gravure inks, solvent-based inkjet inks, etc.), and the like. Aspect 3 is a water-based coloring composition, and includes water-based paints, water-based printing inks (water-based flexographic inks, water-based inkjet inks, etc.), and the like. When the solvent comprises water, it is described herein as "aqueous," but when the solvent is an "organic solvent," it is not specifically described as "solvent-based." Water is preferably deionized water or distilled water from which metal ions or the like have been removed.

<Molding composition>
The molding composition of the present invention contains a coloring composition (pigment composition, resin). The molding composition preferably contains a thermoplastic resin in the resin. A molding composition containing a thermoplastic resin is preferably melted, kneaded, and molded into a desired shape to produce a molded body. In addition, resin is not limited to a thermoplastic resin.

Thermoplastic resins include, for example, homopolymers or copolymers using ethylene, propylene, butylene, styrene, etc. as monomer components. More specifically, polyethylene such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE) and low-density polyethylene (LDPE), and polyolefin resin such as polypropylene and polybutylene can be used. 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. In addition, the number average molecular weight of the thermoplastic resin is preferably more than 30,000 and 200,000 or less.

The content of the thermoplastic resin is C.I. I. 10,000 to 10,000,000 parts by weight is preferable, and 10,000 to 2,000,000 parts by weight is more preferable with respect to 100 parts by weight of the pigment composition containing Pigment Yellow 180 and the azo compound (1). .

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

The wax has a number average molecular weight of preferably 1,000 to 30,000, more preferably 2,000 to 25,000. Within this range, the wax moderately migrates to the surface of the molded body, so that the balance between slidability and suppression of bleed-out is excellent.

The wax preferably has a melting point of 60 to 150°C, more preferably 70 to 140°C. Within this range, the processability during melt-kneading the thermoplastic resin and the wax is improved. The melt flow rate (MFR) of the wax determined according to JIS K-7210 is preferably greater than 100 g/10 minutes.

The blending amount of the wax is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

The molding composition can contain other additives. Other additives are materials commonly used in the technical field of moldings, such as antioxidants, light stabilizers, dispersants, metallic soaps, antistatic agents, flame retardants, lubricants, fillers, C.I. I. Pigment Yellow 180 and coloring agents other than the pigment composition containing the azo compound (1).

The molding composition can be produced, for example, in the composition ratio of the molding. or C.I. I. Pigment Yellow 180 and the azo compound (1) can be produced as a masterbatch containing a high concentration of the pigment composition. As used herein, C.I. I. A masterbatch is preferable because the pigment composition containing Pigment Yellow 180 and the azo compound (1) can be easily and uniformly dispersed in the molded article.
For the masterbatch, for example, it is preferable to melt-knead a thermoplastic resin and a pigment composition, and then mold it into an arbitrary shape so that it can be easily used in the next step. Next, the masterbatch and a diluent resin (for example, the thermoplastic resin used in the masterbatch) are melt-kneaded to form a molded article having a desired shape. Examples of the shape of the masterbatch include pellets, powders, plates, and the like. In order to prevent agglomeration of the pigment composition, it is preferable to prepare a masterbatch by melt-kneading the pigment composition and the wax together with the thermoplastic resin after preparing a dispersion by melt-kneading in advance. Apparatus used for the dispersion is preferably a blend mixer, a three-roll mill, or the like.

When the resin composition for molding is produced as a masterbatch, C.I. I. Pigment Yellow 180 and the pigment composition containing the azo compound (1) are preferably mixed in a total amount of 1 to 200 parts by mass, more preferably 5 to 100 parts by mass. The mass ratio of the masterbatch (X) and the diluted resin (Y), which is the base material resin of the molded body, is preferably X/Y = 1/1 to 1/100, more preferably 1/3 to 2/100. . Within this range, C.I. I. The pigment composition containing Pigment Yellow 180 and the azo compound (1) is easily dispersed uniformly, and good coloring is easily obtained.

As the diluent resin (Y), the thermoplastic resin used in the masterbatch is preferably used, but other thermoplastic resins may be used as long as there is no problem in compatibility.

Melt-kneading includes, for example, a single-screw kneading extruder, a twin-screw kneading extruder, a tandem-type twin-screw kneading extruder, and the like. The melt-kneading temperature varies depending on the type of thermoplastic resin, but is usually about 150 to 300°C.

Applications of the molding composition include, for example, plastic moldings, sheets, films and the like.

<Toner>
The toner of this specification contains a coloring composition (pigment composition, resin). The resin in the toner is preferably a thermoplastic resin called a binder resin. The toner includes dry toner and liquid toner, and dry toner is preferable. For example, a dry toner is produced by melt-kneading a pigment composition and a binder resin, cooling, pulverizing, and classifying. Then, a post-treatment step of blending and mixing additives can be performed to produce the product.

Binder resins include, for example, styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-(meth)acrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene- Isoprene copolymer, styrene-acrylonitrile-indene copolymer, polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, (meth)acrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane , polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin, and the like.

Among these, polyester resins and styrene copolymers are preferred, and polyester resins are more preferred. Since the pigment composition of the present specification has particularly excellent compatibility with polyester resins, C.I. I. Since the pigment composition containing Pigment Yellow 180 and the azo compound (1) is uniformly and finely dispersed, a high quality toner can be obtained.

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

The acid value of the polyester resin is preferably 10-60 mgKOH/g, more preferably 15-55 mgKOH/g. When a polyester resin having an appropriate acid value is used, release of the releasing agent is easily suppressed, and image density is less likely to decrease in a high-humidity environment.

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 having an appropriate hydroxyl value is used, the image density does not easily decrease in a high humidity environment. Incidentally, the lower limit of the hydroxyl value is 0.1 mgKOH/g.

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

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. A positive or negative charge control agent can be appropriately selected and used as the charge control agent.

When the toner is a positively chargeable toner, the positive charge control agent includes, for example, nigrosine-based dyes, triphenylmethane-based dyes, organic tin oxides, quaternary ammonium salt compounds, and styrene- and quaternary ammonium salt functional groups. Examples include styrene/acrylic polymers copolymerized with acrylic resins. Among these, quaternary ammonium salt compounds are preferred. Examples of quaternary ammonium salt compounds include salt-forming compounds of quaternary ammonium salts and organic sulfonic acids or molybdic acids. Organic sulfonic acid is preferably naphthalenesulfonic acid.

When the toner is a negatively charged toner, the negative charge control agent includes, for example, a metal complex of a monoazo dye, a styrene-acrylic polymer obtained by copolymerizing a styrene-acrylic resin with a sulfonic acid as a functional group, an aromatic hydroxycarboxylic acid. metal salt compounds, metal complexes of aromatic hydroxycarboxylic acids, phenolic condensates, and phosphonium compounds. Preferred aromatic hydroxycarboxylic acids are salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid and 3-phenylsalicylic acid. Metals used in metal salt compounds include zinc, calcium, magnesium, chromium, and aluminum.

The toner can contain a release agent. Examples of the release agent include hydrocarbon waxes such as polypropylene wax, polyethylene wax and Fischer-Tropsch wax, natural ester waxes such as synthetic ester waxes, carnauba wax and rice wax.

To the toner, a lubricant, a fluidizing agent, an abrasive, a conductivity-imparting agent, an image-separation preventing agent, etc., can be added, if necessary.

Lubricants include polyvinylidene fluoride, zinc stearate, and the like. Fluidizing agents include silica, aluminum oxide, titanium oxide, silicon-aluminum co-oxide and silicon-titanium co-oxide produced by a dry method or a wet method, and hydrophobized products thereof. Among them, hydrophobized silica, silicon-aluminum co-oxide, and silicon-titanium co-oxide fine powder are preferred. Examples of the hydrophobizing treatment method for these fine powders include treatment with silicone oil or a silane coupling agent such as tetramethyldisilazane, dimethyldichlorosilane, dimethyldimethoxysilane, or the like. Examples of abrasives include silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, and hydrophobized products thereof. Examples of conductivity-imparting agents include tin oxide and the like.

Also, the toner herein can be used as a one-component developer or a two-component developer. A two-component developer can further contain a carrier.

Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, and products whose surfaces are coated with resin or the like. Examples of resins that coat the surface of the carrier include styrene-(meth)acrylic acid ester copolymers, (meth)acrylic acid ester copolymers, fluorine-containing resins, silicone-containing resins, polyamide resins, ionomer resins, polyphenylene sulfide resins, and the like. is mentioned. Among these, a silicone-containing resin is preferable because it causes little formation of spent toner. The weight average particle size of the carrier is preferably 30-100 μm.

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

<Paint>
The paint herein contains a coloring composition (pigment composition, resin, solvent).
Examples of the resin include thermosetting resins and thermoplastic resins. The thermosetting resin preferably has a glass transition temperature of 10° C. or higher. Types of thermosetting resins include, for example, acrylic resins, polyesters, and polyurethanes. Also, the thermosetting resin preferably has a functional group capable of reacting with the curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Curing agents include, for example, isocyanate curing agents, epoxy curing agents, aziridine curing agents, amine curing agents and the like.
The thermoplastic resin preferably has a glass transition temperature of 30° C. or higher. Examples of thermoplastic resins include nitrocellulose and polyester. A thermosetting resin and a thermoplastic resin can be used together.

Examples of water-insoluble solvents among the solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.
Among the above solvents, water-soluble solvents include, for example, water, monohydric alcohols, dihydric alcohols, and glycols. Water-soluble solvents include, for example, ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Also included are water-dilutable monoethers derived from polyhydric alcohols. Specific examples thereof include methoxypropanol or methoxybutanol. Also included are water-dilutable glycol ethers such as, for example, butyl glycol or butyl diglycol. In addition, as already explained, when the paint contains water in the solvent, it is called a water-based paint.

The paint can further contain known additives.

Applications of the paint include, for example, paints for metals, paints for plastics, and paints for wood.

<Printing ink>
The printing inks herein contain a coloring composition (pigment composition, resin, solvent). Examples of printing inks include offset printing inks, flexographic printing inks, gravure printing inks, inkjet printing inks, silk screen printing inks, color filter inks, and the like. As described above, when the solvent contains water, it is called water-based printing ink.

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, ball mill, pebble mill, attritor, sand mill, or the like.

There are no particular restrictions on the substrate on which the printing ink is printed, and known substrates can be used. Specifically, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate and polylactic acid, polystyrene resins such as polystyrene, AS resin and ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane, Coated paper such as art paper, coated paper, cast paper, non-coated paper such as high-quality paper, medium-quality paper, newsprint, synthetic paper such as Yupo paper, aluminum, etc., or film-like materials made of these composite materials A base material etc. are mentioned. Vapor-deposited substrates obtained by vapor-depositing inorganic compounds such as silica, alumina, and aluminum on polyethylene terephthalate and nylon films are also included. The base material may be coated with polyvinyl alcohol or the like on the surface treated by vapor deposition of an inorganic compound or the like, and may be subjected to surface treatment such as corona treatment.

A method for printing with printing ink is not particularly limited, and a known method can be used. Specific examples include roll coaters, rod coaters, blades, wire bars, doctor knives, spin coaters, screen coaters, gravure coaters, offset gravure coaters, and flexo coaters.
Further, heating may be performed as necessary during printing.

The printing ink can further contain known binder resins, solvents, glittering materials, additives, etc., according to various uses.

Examples of the binder resin include rosin resin, rosin-modified phenol resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, and petroleum resin.

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

Water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Also included are water-dilutable monoethers derived from polyhydric alcohols. Examples include methoxypropanol or methoxybutanol. Also included are water-dilutable glycol ethers such as butyl glycol or butyl diglycol.

The glitter material is particles having an average thickness of 0.5 to 10 μm and an average particle diameter of 5 to 50 μm, and includes metal flakes, mica, and coated glass flakes. Examples of metal flakes include aluminum flakes and gold powder. Examples of mica include ordinary mica and coated mica. Examples of coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide.

The content of the luster material is preferably 0.1 to 10% by mass in 100% by mass of the printing ink. In addition, other color pigments and various additives commonly used in the technical field may be blended as needed.

The printing inks can also contain known additives. Additives include, for example, pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, hydrocarbon waxes, isocyanate curing agents, silane coupling agents, etc. is mentioned.

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

[Polyurethane resin]
The binder resin used in the gravure ink of the present invention is preferably a polyurethane resin. Polyurethane resin includes polyurethane urea resin.
Synthesis of the polyurethane resin is carried out, for example, by (1) synthesizing a urethane prepolymer having terminal isocyanate groups obtained by reacting a polyol and a diisocyanate compound in such a proportion that the isocyanate groups are excessive. (2) polypropylene glycol, polyol, diisocyanate compound, and amino group; A one-step method of reacting a chain extender and/or a terminal blocker having

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 blocking resistance of the ink, the strength of the printed film, and the oil resistance are excellent. , excellent gloss of the printed film.

Moreover, the polyurethane resin preferably has an amine value from the viewpoint of printability and laminate strength. The amine value is preferably 0.5-20 mgKOH/g, more preferably 1-15 mgKOH/g.

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

[Organic solvent]
Organic solvents used in the gravure ink of the present invention include aromatic organic solvents such as toluene and xylene; ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, n-propyl acetate, butyl acetate and propylene. ester-based organic solvents such as glycol monomethyl ether acetate; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol; glycol ether-based solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether; . These organic solvents are preferably used in combination of two or more.
In 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% by mass, more preferably 70 to 85% by mass, based on the mass of the ink.

The viscosity of the gravure ink is preferably 10 mPa·s or more from the viewpoint of preventing sedimentation of the pigment and appropriately dispersing the pigment, and preferably 1,000 mPa·s or less from the viewpoint of work efficiency during ink production and printing. The above viscosity is a value measured at 25° C. with a Brookfield viscometer manufactured by Tokimec.

[water]
The gravure ink of the present invention can further contain water. By including a predetermined amount of water, the pigment dispersibility of the polyurethane resin is improved, and printability such as highlight transfer, plate fogging, and trapping is improved.
The water content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and still more preferably 0.5 to 5% by mass, based on the mass of the gravure ink. Yes, particularly preferably 0.5 to 4% by mass.

[Silica particles]
The gravure ink of the present invention can further contain silica particles. Inclusion of silica particles promotes wetting and spreading of ink during overprinting, improves trapping properties, and maintains highlight transfer properties.
Silica particles may be naturally occurring, synthetic, crystalline, amorphous, hydrophobic or hydrophilic. Synthesis methods of silica particles include dry and wet methods. Known dry methods include combustion method and arc method, and wet methods include sedimentation method and gel method, and silica particles may be synthesized by any method. The silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with an alkylsilane or the like to make it hydrophobic. Hydrophilic silica is preferred.
Examples of such silica particles include the Nip Gel series and Nipsil series manufactured by Tosoh Silica Corporation, and the Mizukasil series manufactured by Mizusawa Chemical.

Silica particles preferably have an average particle diameter of 1 to 10 μm in order to make the surface of the ink layer uneven. It is more preferably 1 to 8 μm, still more preferably 1 to 6 μm. The average particle size of silica particles means the particle size at an integrated value of 50% (D50) in the particle size distribution, and can be obtained by the Coulter counter method.
The specific surface area of the silica particles is preferably 50-600 m ² /g by the BET method. More preferably 100 to 450 m ² /g. Two or more types of silica particles having different average particle sizes or BET specific surface areas can be used in combination for use in the gravure ink of the present invention.

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

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

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

The water-based inkjet ink of the present invention is preferably prepared by first preparing a water-based coloring composition, and then adding a solvent, an additive, and the like to prepare the water-based inkjet ink.

(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 a resin-type dispersant. Types of resins include, 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 , vinyl naphthalene-(meth)acrylic acid copolymer, styrene-maleic acid copolymer, maleic acid-maleic anhydride copolymer, α-olefin-(anhydrous) maleic acid copolymer, α-olefin-(anhydrous) maleic Acid-polyalkylene glycol allyl ether copolymers, vinylnaphthalene-maleic acid copolymers, polyester-modified (meth)acrylic acid polymers, salts thereof, and the like.

The form of the resin includes water-soluble resin, emulsion (water-insoluble resin), and the like.

Water is preferably ion-exchanged water or distilled water.

Water-soluble solvents include, for example, 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl 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, liquid polypropylene glycol and the like.

The aqueous coloring composition can contain a surfactant. Examples of surfactants include anionic surfactants and nonionic surfactants.

Anionic surfactants include, for example, fatty acid salts, alkyl sulfates, alkylarylsulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyldiaryletherdisulfonates, alkylphosphates , polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, naphthalenesulfonic acid formalin condensates, and polyoxyethylene alkyl phosphate salts.

Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethyleneoxypropylene 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, polyoxyethylene glycerol fatty acid esters, and the like.

The content of the surfactant is preferably 0.3 to 20% by mass, more preferably 1 to 10% by mass, in 100 parts by mass of the water-based coloring composition.

The content of the surfactant is preferably 5 to 200 parts by mass, more preferably 25 to 100 parts by mass, based on 100 parts by mass of the pigment.

The water-based coloring composition can contain other additives. Other additives include preservatives, pH adjusters, antifoaming agents, wetting agents and the like.

Preservatives are, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one and amine salts of.
The content of the preservative is preferably 0.1 to 2% by mass in 100 parts by mass of the water-based coloring composition.

Examples of pH adjusters include various amines, inorganic salts, ammonia, and various buffer solutions.

Antifoaming agents are used to prevent foaming during the production of water-based coloring compositions. Commercial 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, Surfynol PSA-336 (all manufactured by Nissin Chemical Industry Co., Ltd.), ADDITOL VXW6211, ADDITOL VXW4973, ADDITOL VXW6235, ADDITOL XW375, ADDITOL XW376, ADDITOL VXW6381, ADDITOL VXW6 386, ADDITOL VXW6392, ADDITOL VXW6393, ADDITOL VXW6399, ADDITOR XW6544, etc. (both manufactured by Allnex) can be mentioned.

Wetting agents are used to obtain smooth films during printing and coating. Commercially available wetting agents are, for example, ADDITOL VXL6237N, ADDITOL XL260N, ADDITOL VXL6212, ADDITOL UVX7301/65, ADDITOL XW330, ADDITOL VXW6200, ADDITOL VXW6205, ADDITOL VXW6394, Additol VXW6208, Additol VXW6208/60, Additol VXW6374 (both Allnex made) and the like.

Each material used for preparing the water-based coloring composition can be used alone or in combination of two or more.

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

The dispersing machine used for the dispersion treatment includes, for example, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, a microfluidizer, a high speed mixer, a homomixer, a homogenizer, a high pressure homogenizer, a ball mill, a paint shaker, a roll mill, and a stone mill. A type mill, an ultrasonic disperser, a facing collision type high pressure disperser, an oblique collision type high pressure disperser, and the like.

More specifically, when a resin-type dispersant that is a water-soluble resin is used as the resin, the method described in the examples described later, that is, after mixing the pigment composition, the resin-type dispersant, water, etc., The water-based coloring composition of the present invention can be obtained by the method of carrying out dispersion treatment using the above dispersing machine.

Further, 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 capable of dissolving the water-insoluble resin, and then mixed with the pigment composition. Then, dispersion processing is performed using the above dispersion machine. Then, after phase inversion emulsification using water, a water-based coloring composition is obtained by a method of distilling off the organic solvent.

On the other hand, it is preferable to crosslink the resin-type dispersant on the surface of the pigment composition from the viewpoint that the dispersibility and dispersion stability of the pigment composition in the water-based coloring composition can be particularly enhanced. Such a water-based inkjet ink using a pigment composition in which a resin-type dispersant present on the surface is crosslinked (hereinafter also referred to as "pigment composition-containing crosslinked resin particles") has poor redispersibility (water-based inkjet ink has By adding water after drying, aggregation and thickening, the pigment composition in the water-based inkjet ink can be dispersed again). ” can be suppressed. Further, by coating the pigment composition with a crosslinked resin-type dispersant, it is possible to improve weather resistance and pH resistance.

Examples of methods for producing a water-based coloring composition containing the pigment composition-containing crosslinked resin particles include the following four methods.

[[Method (i)]]
This is a method for producing pigment composition-containing crosslinked resin particles through the following four steps.
- Step (i-1): a pigment composition; a resin-type dispersant having a crosslinkable functional group and a carboxy group, the carboxy group being neutralized by a basic compound to be hydrophilic; and water A step of performing distributed processing using.
- Step (i-2): adding an acidic compound to the dispersion of the pigment composition prepared in the above step (i-1), and neutralizing or acidifying the pH of the dispersion to obtain the resin-type dispersion A step of depositing and fixing the agent on the surface of the pigment composition.
- Step (i-3): After the above step (i-2), the carboxy group in the resin-type dispersant is replaced with a basic compound (which is the same as the basic compound used in step (i-1) may be different), and redispersing the pigment composition to which the resin-type dispersant is fixed in water.
- Step (i-4): after the above step (i-3), the crosslinkable functional group in the resin-type dispersant is reacted with the crosslinker to crosslink the aqueous system containing the pigment composition-containing crosslinked resin particles. obtaining a colored composition; The cross-linking agent may be added at the start of step (i-4), or may be added at any stage of steps (i-1) to (i-3).

[[Method (ii)]]
As the resin-type dispersant, the steps described above are performed except that a resin-type dispersant having a self-crosslinking functional group and a carboxyl group, which is rendered hydrophilic by neutralization of the carboxyl group with a basic compound, is used. In the same manner as in (i-1) to (i-3), the pigment composition to which the resin-type dispersant is fixed is re-dispersed in water. After that, the resin-type dispersant is allowed to self-crosslink to obtain a water-based coloring composition containing the pigment composition-containing crosslinked resin particles.

[[Method (iii)]]
This is a method for producing pigment composition-containing crosslinked resin particles through the following two steps.
• Step (iii-1): a step of mixing a pigment, a resin having a carboxyl group, a basic compound, and water.
Step (iii-2): After the above step (iii-1), a step of adding a cross-linking agent and performing a cross-linking treatment to obtain a water-based coloring composition containing cross-linked resin particles containing a pigment composition.

[[Method (iv)]]
This is a method for producing pigment composition-containing crosslinked resin particles through the following two steps.
• Step (iv-1): a step of mixing a pigment, a resin having a carboxyl group, and an organic solvent.
Step (iv-2): After the above step (iv-1), water is added and the organic solvent is removed by vacuum distillation or the like.
Step (iv-3): After step (iv-2), a step of adding a cross-linking agent and performing a cross-linking treatment to obtain a water-based coloring composition containing cross-linked resin particles containing a pigment composition.

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

Before dispersion treatment, pre-dispersion treatment can be performed without using water or a water-soluble solvent. Apparatus used for the pre-dispersing treatment includes, for example, a kneader, a kneading mixer such as a three-roll mill; a non-volatile dispersing machine such as a two-roll mill, and a medialess dispersing machine such as an MK mixer.

(water-based inkjet ink)
The content of the pigment composition is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass, based on 100% by mass of the water-based inkjet ink.

The resin used in the water-based inkjet ink is important for obtaining the fixability of the ink to the material to be printed (substrate).
Examples of resin types include acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, and polyurethane resins. Moreover, the form of the resin includes a water-soluble resin, emulsion particles, and the like. Among these, emulsion particles are preferred. Emulsion particles include single-composition particles, core-shell type particles, and the like, and can be used by arbitrarily selecting them. When emulsion particles are used, the viscosity of the water-based inkjet ink can be easily reduced, and recorded matter with excellent water resistance can be easily obtained. The resin can be used after neutralizing the acidic functional groups with a pH adjuster such as ammonia, various amines, various inorganic alkalis, etc., if necessary.

The resin content is preferably 2 to 30% by mass, more preferably 3 to 20% by mass, based on 100% by mass of the non-volatile matter of the inkjet ink. When contained in an appropriate amount, the ejection stability is improved, and the fixability is also improved.

Solvents include water-insoluble solvents, water, and water-soluble solvents. Glycol ethers and diols are examples of water-soluble solvents. Penetrates quickly even into liquid substrates. Therefore, it dries quickly during printing, and accurate printing can be achieved. It also acts as a wetting agent due to its high boiling point.

The water-soluble solvent is important for preventing drying and solidification of the water-based inkjet ink at the nozzle portion of the printer head and for obtaining ink ejection stability. Water-soluble solvents include, for example, 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, 4-methoxy-4methylpentanone and the like.

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

Ink jet inks can further contain additives. Additives include, for example, drying accelerators, penetrants, chelating agents, preservatives, pH adjusters and the like.

Drying accelerators are used to accelerate the drying of water-based 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 in 100% by mass of the water-based inkjet ink.

The penetrant is used to accelerate the penetration of the ink into the substrate and quicken the apparent drying property when the substrate is a permeable material such as paper. Examples of penetrants include surfactants such as polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, and sodium dioctylsulfosuccinate, in addition to water-soluble solvents. The amount of the penetrant to be used is preferably 0.1 to 5% by mass based on 100% by mass of the water-based inkjet ink. When used in an appropriate amount, problems such as bleeding of print and ink dropout are less likely to occur.

A chelating agent is used to capture metal ions contained in the water-based inkjet ink and prevent deposition of insoluble matter in the nozzle or in the ink. Chelating agents include, for example, ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, tetraammonium salt of ethylenediaminetetraacetic acid, and the like. The amount of the chelating agent used is preferably 0.005 to 0.5% by mass based on 100% by mass of the water-based inkjet ink.

The inkjet ink is prepared by blending and mixing each material. For mixing, a stirrer using blades, various dispersers, emulsifiers and the like can be used. The addition order of each material and the mixing method are arbitrary.

After mixing, the inkjet ink is preferably filtered or centrifuged to remove coarse particles. This improves the ejection property from an inkjet printer. A well-known method can be used for filtration and centrifugation.

The inkjet inks herein can use a variety of inkjet systems. Examples of the inkjet method include a charge control type, a continuous injection type such as a spray type, a piezo method, a thermal method, an electrostatic attraction method, and the like.

<Water-based flexographic ink>
The water-based flexographic ink of this specification contains at least a coloring composition (pigment composition, resin) and water. Various types of substrates can be selected, and the method is suitable for printing on impermeable substrates other than general printing paper, such as coated paper and plastic films (including plastic sheets).

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

Each component contained in the water-based flexo ink and, if necessary, a synthesis method thereof will be described below.

(binder resin)
The water-based flexographic ink preferably contains a binder resin. Examples of binder resins include water-based urethane resins, polyester resins, acrylic resins, styrene-acrylic resins, styrene-maleic anhydride resins, rosin-modified maleic acid resins, cellulose resins, and water-based resins such as chlorinated polyolefins. . Among them, it is preferable that at least an aqueous urethane resin is included. Binder resin can be used individually or in combination of 2 or more types.

(Aqueous urethane resin)
A urethane resin is generally a resin obtained by reacting a polyisocyanate having two or more isocyanate groups in one molecule with a hydroxyl group-containing compound having two or more hydroxyl groups in one molecule. The water-based urethane resin of this embodiment has the configuration described below. Such a configuration can be preferably introduced by appropriately selecting the structure, type, etc. of the hydroxyl group-containing compound, as described later.

The number of urethane bonds (mmol/g) of the water-based urethane resin is not particularly limited, but from the viewpoint of adjusting the molecular weight of the resin and the hardness of the coating film, etc., it is preferably 2.2 to 3.0 mmol/g. .3 to 2.9 mmol/g is more preferred. The number of urethane bonds can be set within a desired range by appropriately adjusting the amounts of the hydroxyl group-containing compound and polyisocyanate and the reaction conditions.

The glass transition temperature (Tg) of the water-based urethane resin is not particularly limited, but is preferably -70°C or lower, more preferably -70°C to -90°C. When the Tg of the water-based urethane resin is −70° C. or less, the film-forming property of the ink is improved, and the adhesion of the coating film is improved.

The weight average molecular weight (GPC measurement, standard polystyrene conversion) of the aqueous urethane resin is not particularly limited, but is preferably 10,000 to 100,000, more preferably 30,000 to 70,000.

The hydroxyl value (mgKOH/g) of the water-based urethane resin is not particularly limited, but from the viewpoint of water resistance, etc., it is preferably 0.0 to 3.0 mgKOH/g, more preferably 0.0 to 2.0 mgKOH/g. is more preferable.

The water-based urethane resin is preferably contained in an amount of 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more in the total amount of the water-based flexo ink. On the other hand, the content of the water-based 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 in the total amount of the rotary printing ink.

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

Aqueous flexographic inks contain an aqueous solvent. Aqueous solvents include water and alcohols. Examples of alcohol include n-propanol and isopropyl alcohol.

The content of the aqueous solvent is preferably 40-60% by mass in the aqueous flexographic ink.

(Other ingredients)
The water-based flexographic ink may optionally contain known additives such as antifoaming agents, thickeners, leveling agents, pigment dispersants, and ultraviolet absorbers. Moreover, non-aqueous solvents other than alcohol (for example, ketone-based solvents and ester-based solvents) can be included as long as the problem can be solved. The content of the non-aqueous solvent in the ink is preferably 20% by mass or less, more preferably 10% by mass or less.

<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.

For the active energy ray-curable ink, in addition to the pigment composition of the present invention, any known colorant may be used in combination as needed without departing from 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.

In the following, components contained or possibly contained in the active energy ray-curable ink of the present embodiment will be described.

(Polymerizable compound)
A polymerizable compound is a compound having one or more ethylenically unsaturated bonds in the molecule. Polymerizable compounds include monomers and oligomers.

(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-carboxylethyl (meth) acrylate, 4-tert-butylcyclohequinol (meth) acrylates, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate ) acrylate, 3,3,5-trimethylcyclohexanol (meth)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, monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the molecule such as 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) Acrylates, 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, neopentylglycol hydroxypivalate di(meth)acrylate ) acrylate, 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) Acrylates, (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( Bifunctional (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, dicyclopentanyl di (meth) acrylate, etc. having two (meth) acryloyl groups in the molecule ( meth)acrylate monomers,
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 of
Tetrafunctional (meth)acrylate monomers having four acryloyl groups in the molecule such as pentaerythritol tetra(meth)acrylate, EO-modified (4) pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate,
Pentafunctional (meth)acrylate monomers having five (meth)acryloyl groups in the molecule such as dipentaerythritol penta(meth)acrylate,
A hexafunctional (meth)acrylate monomer having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate, and the like. In addition, vinyl group-containing monomers having no (meth)acryloyl group can also be used.

(oligomer)
Examples of oligomers 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.

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

A polymerizable compound can be used individually or in combination of 2 or more types.

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

(Photoinitiator)
Examples of photopolymerization initiators include benzophenone-based compounds, dialkoxyacetophenone-based compounds, α-hydroxyalkylphenone-based compounds, α-aminoalkylphenone-based compounds, acylphosphine oxide-based compounds, and thioxanthone-based compounds.

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

Examples of the dialkoxyacetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, diethoxyacetophenone, and the like.

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

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-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and the like.

Examples of the above acylphosphine oxide compounds include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like. mentioned.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

A photoinitiator can be used individually or in combination of 2 or more types.

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

The active energy ray-curable ink of the present invention may contain a hydrocarbon wax. From the viewpoint of the balance of abrasion resistance, gloss, and piling, it is preferably 0.5 to 5% by mass, more preferably 0.5 to 4% by mass, relative to the total mass of the active energy ray-curable ink. more preferred.

The active energy ray-curable ink of the present invention may contain a binder resin. By containing the binder resin, curing shrinkage of the coating film that occurs during curing is reduced, curling of the substrate is suppressed, and adhesion to the substrate is improved.

The weight average molecular weight of the binder resin is preferably 10,000 to 100,000. More preferably from 10,000 to 70,000.

The binder resin can be used alone or in combination of two or more. Also, the content of the binder resin is preferably 5 to 15% by mass with respect to the total mass of the ink.

(sensitizer)
The active energy ray-curable ink may contain a sensitizer. Curability can be further improved by including a sensitizer. Examples of sensitizers include triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and dibutylethanolamine. is mentioned.

(Polymerization inhibitor)
The active energy ray-curable ink of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, aluminum salt of N-nitrosophenylhydroxylamine, and the like. mentioned.

The content of the polymerization inhibitor is preferably 0.01 to 2% by mass in the active energy ray-curable ink from the viewpoint of enhancing the storage stability of the active energy ray-curable ink while maintaining curability.

In addition, it is preferable that the active energy ray-curable ink does not substantially contain water. “Contain substantially no” means 3% by mass or less with respect to the total mass of the active energy ray-curable ink.

(Extender pigment)
The active energy ray-curable ink may contain an extender pigment. Extender pigments include clay, talc, barium sulfate, calcium carbonate, ground calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite, and the like.

<Printed matter of active energy ray-curable ink>
The printed matter of the present invention is obtained by printing an active energy ray-curable ink on a substrate and curing it with an active energy ray.

The active energy ray-curable ink can be cured by irradiation with, for example, α-rays, γ-rays, electron beams, X-rays, ultraviolet rays, visible light, or infrared light. Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays are more preferable. The peak wavelength of the active energy ray is preferably 200-600 nm, more preferably 350-420 nm.

Active energy ray sources include, for example, mercury lamps, xenon lamps, metal hydride lamps, LEDs (light emitting diodes) such as ultraviolet light emitting diodes (UV-LED), ultraviolet laser diodes (UV-LD), and gas/solid lasers. be done.

<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, wherein the yellow ink contains the pigment composition of the present invention.

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

The ink set of the present invention can be used for printing ink sets such as offset printing inks, flexographic printing inks, gravure printing inks and screen printing inks, and ink sets for inkjet inks. Among these, a gravure printing ink set and an inkjet ink set used for packaging materials are preferred, and a gravure printing ink set is more preferred.

<Yellow ink>
The yellow ink in the invention contains the above pigment composition and a binder resin.
The yellow ink contains the azo compound (1) as described above, so that C.I. I. Dispersibility and storage stability, which were weak points of Pigment Yellow 180, are improved.

<Binder resin>
Binder resins include, for example, 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, and rosin. rosin-modified maleic acid resin, ketone resin, cyclized rubber, butyral, petroleum resin, and chlorinated polyolefin resin.

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

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

<Cyan ink>
The cyan ink in the present invention is an ink that gives a cyan color and contains a pigment and a binder resin. In addition, binder resin can use already demonstrated resin.

<Magenta ink>
The magenta ink in the present invention is an ink from which a magenta color is obtained, and contains a pigment and a binder resin. As the binder resin, the resins already described can be used.

<Pigment>
Pigments include organic pigments and inorganic pigments. For example, the following pigments can be used herein.

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

Examples of pigments are C.I. I. Indicated by pigment number.

Indigo pigments include, for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60 and the like. Also included are phthalocyanine pigments such as aluminum phthalocyanine (compound (11)) and titanyl phthalocyanine (compound (12)).
The cyan ink preferably contains the indigo pigment. Among these, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4 and C.I. I. Pigment Blue 16 is more preferred.

Red pigments include, for example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 32, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 48:2, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 63:1, C.I. I. Pigment Red 81, C.I. I. Pigment Red 122, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 166, C.I. I. Pigment Red 170, C.I. I. Pigment Red 174, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 188, C.I. I. Pigment Red 190, C.I. I. Pigment Red 202, C.I. I. Pigment Red 207, C.I. I. Pigment Red 208, C.I. I. Pigment Red 209, C.I. I. Pigment Red 214, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 224, C.I. I. Pigment Red 238, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 260, C.I. I. Pigment Red 264, C.I. I. Pigment Red 269, C.I. I. Pigment Red 272, C.I. I. Pigment Violet 19 and the like.
The magenta ink preferably contains the red pigment. Among these, C.I. I. Pigment Red 48:3, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 146, C.I. I. Pigment Red 185, and C.I. I. Pigment Violet 19 is more preferred.

Yellow pigments include, for example, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 234 and the like.
When used for the yellow ink constituting the ink set of the present invention, the yellow pigment may be included.

Purple pigments include, for example, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 37 and the like.

Green pigments include, for example, C.I. I. Pigment Green 7 and the like.

Orange pigments include, for example, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73 and the like.

Examples of special color inks include inks other than cyan, magenta, and yellow, such as purple, grass, and vermilion inks, and preferably contain the above-described purple pigment, green pigment, orange pigment, and the like.

In the ink set of the present invention, for example, C.I. I. Pigment Blue 16 and C.I. for magenta ink. I. Pigment Violet 19 and C.I. I. Pigment Red 122 is preferably included. By including the above pigment, the environmental compatibility and safety and hygiene of the ink can be improved.

[Inorganic pigment]
Inorganic pigments include, for example, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, litbon, antimony white, white inorganic pigments such as gypsum, carbon black, iron black, and copper/chromium composite oxides. black inorganic pigment, aluminum particles, mica (mica), bronze powder, chromium vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine blue, Prussian blue, red iron oxide, yellow iron oxide, zircon and the like.

Carbon black is preferably used for black ink from the viewpoint of excellent coloring power, hiding power, chemical resistance, and weather resistance. I. Pigment Black 7 and the like. Moreover, it is preferable to use titanium oxide for the white ink from the viewpoint of excellent coloring power, hiding power, chemical resistance, and weather resistance. Titanium oxide is preferably surface-treated with silica and/or alumina from the viewpoint of printing performance.

Each ink can use pigments alone or in combination of two or more in order to obtain a desired color tone.

The average primary particle size of the pigment is preferably in the range of 10-200 nm, more preferably in the range of 50-150 nm.
The content of the pigment in the ink is preferably in the range of 1 to 60% by mass based on the mass of the ink in order to ensure the density and tinting strength of the ink, and is preferably in the range of 1 to 60% by mass based on the nonvolatile content mass of the ink. is in the range of 10 to 90% by mass.

<Gravure printing ink set>
The gravure printing ink set of the present invention preferably comprises the ink set described above. The respective color gravure inks constituting the gravure printing ink set of the present invention are as described above.

<Clear ink>
The gravure printing ink set of the present invention can further contain clear ink. The release layer formed from the clear ink has a function of being released from the substrate by being neutralized with an alkaline aqueous solution and dissolved or swollen. This promotes detachment of the printed layer from the base material and promotes recycling of printed matter and packaging materials.
Basic compounds used in the aqueous alkaline solution include, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ), ammonia, and barium hydroxide (Ba(OH) ₂ ). , sodium carbonate (Na ₂ CO ₃ ). More preferably, it 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". A layer that can be detached by alkali treatment is sometimes referred to as a "detachment layer". That is, the printed layer formed with the clear ink corresponds to a layer having releasability (release layer).

[Carboxy group-containing resin]
The clear ink preferably contains a carboxy group-containing resin. For example, it functions as a primer composition that prints onto the substrate prior to the colored inks.
Examples of the carboxy group-containing resin include acrylic resins, polyurethane resins, polyester resins, amino resins, phenol resins, epoxy resins, and cellulose. Among these, polyurethane resins are preferred because of their good lamination suitability.

The hydroxyl value of the carboxy group-containing polyurethane resin is preferably 1 to 35 mgKOH/g, more preferably 10 to 30 mgKOH/g. When it is 1 mgKOH/g or more, the releasability with an alkaline aqueous solution becomes good, and when it is 35 mgKOH/g or less, the substrate adhesion becomes good, so it is preferable.
The acid value of the carboxy group-containing polyurethane resin is preferably 15 mgKOH/g or more, more preferably 15 to 70 mgKOH/g, still more preferably 20 to 50 mgKOH/g. When it is 15 mgKOH/g or more, it is preferable because the removability with an alkaline aqueous solution is improved, and when it is 70 mgKOH/g or less, the adhesion to the substrate is improved, and the retort resistance when used as a packaging material is improved. . Both the hydroxyl value and the acid value are values measured according to JISK0070.

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, still more preferably 15,000 to 50,000.

The molecular weight distribution (Mw/Mn) of the carboxy group-containing polyurethane resin is preferably 6 or less. When the molecular weight distribution is 6 or less, it is possible to avoid the effects of excessive high-molecular-weight components, unreacted components, side-reacted components and other low-molecular-weight components. Retort resistance aptitude is improved.
In addition, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniform the dissolution and peeling action by the alkaline aqueous solution occurs, and the detachability is improved, which is preferable. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. Also, the molecular weight distribution is preferably 1.2 or more, more preferably 1.5 or more.

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

The carboxy group-containing polyurethane resin is not particularly limited, and can be synthesized, for example, by reacting polyol, hydroxy acid and polyisocyanate. By using a hydroxy acid, an acid value can be imparted to the polyurethane resin. It is preferable that the polyurethane resin is further modified into a polyurethane urea resin by reacting with a polyamine.

The clear ink may further contain polyisocyanate as a curing component. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, such as aliphatic polyisocyanates and araliphatic polyisocyanates.
In addition, the clear ink may contain other components other than the carboxy group-containing resin and polyisocyanate, and additives such as organic solvents and antiblocking agents are blended in the same manner as the cyan, yellow, and magenta inks described above. can do.

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

<Printed Matter>
The printed matter of the present invention includes a substrate and a printed layer formed from a gravure printing ink set. The printed layer is formed by printing cyan ink, yellow ink, and magenta ink on the substrate.
The method of gravure printing is not particularly limited, and can be appropriately selected from known methods. The method of gravure printing is roughly divided into surface printing and reverse printing. A printed matter can be obtained by printing in order of black ink.
Further, for example, when the base material is a transparent film in reverse printing, it is preferable to print on the base material in the order of black ink, cyan ink, magenta ink, yellow ink, and white ink to produce a printed matter.
When the ink set of the present invention contains 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 according to the application, the type and number of inks to be used, and the number of times of overprinting, but is usually in the range of 0.5 to 10 μm.

[Base material]
Base materials include, for example, polyolefin base materials such as polyethylene and polypropylene; polycarbonate base materials; polyester base materials such as polyethylene terephthalate and polylactic acid; polystyrene base materials; polystyrene resins such as AS and ABS; polyvinyl chloride substrates; polyvinylidene chloride substrates; cellophane substrates; paper substrates; aluminum foil substrates; The substrate may be either film-like or sheet-like. Among them, a polyester base material and a polyamide base material having a high glass transition point are preferably used.

The surface of the substrate may be vapor-deposited with metal oxide or the like, or may be coated with polyvinyl alcohol or the like. Such surface-treated substrates include, for example, GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., the surface of which is vapor-deposited with aluminum oxide. The substrate may be treated with additives such as antistatic agents and ultraviolet inhibitors, and may be corona treated or low temperature plasma treated, if necessary.

The thickness of the substrate is not particularly limited and is usually in the range of 5-100 μm.

[Detachment layer]
The printed matter of the present invention can contain a release layer. Here, the term "releasing layer" refers to a material having the property of being neutralized with an alkaline aqueous solution, dissolved or swollen, and thereby peeled off from the substrate. The layer having releasability is preferably a layer formed from the above-described clear ink, but other layers may be the release layer.

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

<Packaging material>
The packaging material of the present invention contains printed matter at least in part. The packaging material includes, for example, a structure in which a printed matter, an adhesive layer, and a sealant base material are sequentially laminated. Packaging materials include four-side seal packages, three-side seal packages, pillow packages, stick bags, gusset bags, square-bottom bags, standing pouches, deep-drawn containers, vacuum packages, skin packs, zipper bags, spout pouches, and twist packaging. , packaging, shrink packaging, labels, paper packs for liquids, paper trays, and other packaging bodies having various shapes.

Items to be packaged with packaging materials include, for example, foodstuffs (e.g., rice grains, confectionery, seasonings, edible oils and fats, cooked foods, etc.), beverages (e.g., alcoholic beverages, soft drinks, mineral water, etc.), lifestyle and cultural goods ( (for example, pharmaceuticals, cosmetics, stationery, etc.), electronic parts, and the like.

[Adhesive layer]
Adhesive components that can be used to form the adhesive layer include laminating adhesives, hot-melt adhesives, and thermoplastic resins. Laminate adhesives and hot melt adhesives among adhesive components include, for example, polyether adhesives; polyurethane adhesives; epoxy adhesives; polyvinyl acetate adhesives; cellulose adhesives; agent; Among these adhesive components, polyurethane adhesives are preferably used.

An adhesive component can be used individually or in combination of 2 or more types.
The thickness of the adhesive layer is usually in the range of 1-6 μm.

The polyurethane-based adhesive is a reactive adhesive containing polyol and polyisocyanate, and may have releasability. Releasable polyurethane adhesives include, for example, laminate adhesives described in JP-A-2020-084130.
Such a polyurethane adhesive having releasability preferably has an acid value of 5 to 45 mgKOH/g. Moreover, it is preferable that the polyol constituting the polyurethane-based adhesive includes polyester polyol, and the polyisocyanate includes one selected from the group consisting of aliphatic polyisocyanate and araliphatic polyisocyanate.

[Sealant base material]
The sealant base material is a base material 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 base material include unstretched polypropylene (CPP), vapor-deposited unstretched polypropylene film (VQCPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), and the like. be done.
Although the thickness of the sealant base material is not particularly limited, it is preferably in the range of 10 to 200 μm, more preferably in the range of 15 to 150 μm, in consideration of processability to packaging materials, heat sealability, and the like. In addition, by providing the sealant base material with unevenness having a height difference of 5 to 20 μm, it is possible to impart lubricity to the sealant base material and tearability of the packaging material.
Moreover, the method of laminating the sealant base material is not particularly limited. For example, a method of laminating an adhesive layer and a sealant base film by heat (thermal lamination, dry lamination), or a method of melting the sealant base resin and extruding it onto the adhesive layer, cooling and solidifying it and laminating (extrusion lamination method) and the like.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. "Parts" means "parts by mass" and "%" means "% by mass".

(Method for identifying azo compound (1))
MALDI TOF-MS spectrum measurement was used to identify the azo compound (1) in the pigment composition of the present invention. For MALDI TOF-MS spectrum measurement, a MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics was used, and the molecular ion peak of the obtained mass spectrum and the mass number (theoretical molecular weight) obtained by calculation corresponded to each other. identification of the compound was performed. In the measurement of negative ions, since the H (proton) of the compound is desorbed, the measured value is the mass number of the theoretical molecular weight minus (minus) 1, which means that the compound matches. Also, the composition ratio was calculated from the peak area ratio.

(Measurement of hydroxyl value)
It was obtained according to JIS K0070.

(Measurement of acid value)
It was obtained according to JIS K0070.

(Measurement of amine value)
The amine value was obtained by the following method according to JIS K0070 in terms of mg of potassium hydroxide equivalent to the equivalent of hydrochloric acid required to neutralize the amino groups contained in 1 g of the resin.
0.5 to 2 g of the sample was accurately weighed (sample non-volatile content: Sg). 50 mL of a mixed solution of methanol/methyl ethyl ketone = 60/40 (mass ratio) was added to the accurately weighed sample to dissolve the sample. Bromophenol blue was added to the resulting solution as an indicator, and the resulting solution was titrated with a 0.2 mol/L ethanolic hydrochloric acid solution (potency: f). The point at which the color of the solution changed from green to yellow was defined as the end point, and the titration amount (AmL) at this time was used to determine the amine value by the following formula.
Amine value = (A x f x 0.2 x 56.108) / S [mgKOH/g]

(Measurement of average molecular weight)
The number-average molecular weight and weight-average molecular weight were obtained by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (HLC-8220 manufactured by Tosoh Corporation) and converting the molecular weight using polystyrene as a standard substance. Measurement conditions are shown below.
Column: The following columns were connected in series and used.
Tosoh guard column HXL-H
Tosoh TSKgelG5000HXL
Tosoh TSKgelG4000HXL
Tosoh TSKgelG3000HXL
Tosoh TSKgelG2000HXL
Detector: RI (differential refractometer)
Measurement conditions: Column temperature 40°C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL/min

(Measurement of glass transition temperature)
The glass transition temperature (Tg) was determined by DSC (differential scanning calorimetry measurement). The measuring instrument used was a DSC8231 manufactured by Rigaku, measuring temperature range -70 to 250°C, heating rate 10°C/min. temperature.

<Production of pigment composition>
(Example A-1)
While stirring 1300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after 1 hour, 223.9 parts of 35% hydrochloric acid was added. After further stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 119.6 parts of a 38% sodium nitrite aqueous 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, after dispersing 153.6 parts of 5-acetoacetylamino-benzimidazolone in 1500 parts of methanol, 316.1 parts of 25% aqueous sodium hydroxide solution was added to dissolve, and further sodium dialkylsulfosuccinate (Pelex OT-P, Kao Corporation) was added to obtain a coupler component.
Separately, 500 parts of ice was added to 654.3 parts of an 80% aqueous acetic acid solution, and 223.9 parts of a 25% aqueous sodium hydroxide solution was added with stirring to prepare an acetic acid-sodium acetate buffer solution. A diazo component and a coupler component were added dropwise at the same time to conduct a coupling reaction while stirring a buffer maintained at 20°C. The dropping speed was adjusted so that the dropping of each of the diazo component and the coupler component was completed in 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was contained in the reaction solution, and the reaction solution was heated to 90° C. and held for 30 minutes. Then, it was filtered and washed with water to obtain a water-containing wet cake.
The entire amount of the above wet cake in a wet state was charged into a pressurizable reaction vessel equipped with a stirrer. Water was added to make the mass in the vessel 3500 parts, and the mixture was stirred, and 2100 parts of isobutanol was added, followed by heating at 120° C. for 2 hours in an autoclave under self-pressure. After isobutanol was removed by steam distillation, the residue was filtered, washed with water, dried at 80° C. and pulverized to obtain 257.9 parts of Pigment Composition (A-1). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-2)
In Example A-1, 138.0 parts of 119.6 parts of 38% sodium nitrite aqueous solution prepared as diazo component and 153.6 parts of 5-acetoacetylamino-benzimidazolone prepared as coupler component were added to 177.3 parts. In addition, 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 364.9 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 755.4 parts. The operation was carried out to obtain 282.0 parts of a pigment composition (A-2). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-3)
In Example A-1, 143.2 parts of 119.6 parts of 38% sodium nitrite aqueous solution prepared as diazo component and 153.6 parts of 5-acetoacetylamino-benzimidazolone prepared as coupler component were added to 184.0 parts. 25% sodium hydroxide aqueous solution 316.1 parts to 378.6 parts, except that 80% acetic acid aqueous solution 654.3 parts of buffer solution preparation was changed to 783.7 parts, the same as in Example A-1 The operation was carried out to obtain 289.6 parts of Pigment Composition (A-3). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-4)
In Example A-1, 147.5 parts of 119.6 parts of 38% sodium nitrite aqueous solution prepared as the diazo component, and 189.5 parts of 153.6 parts of 5-acetoacetylamino-benzimidazolone prepared as the coupler component were used. In the same manner as in Example A-1, except that 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 390.0 parts and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 807.4 parts. The operation was carried out to obtain 291.6 parts of Pigment Composition (A-4). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-5)
In Example A-1, 148.5 parts of 119.6 parts of 38% sodium nitrite aqueous solution prepared as the diazo component and 190.8 parts of 153.6 parts of 5-acetoacetylamino-benzimidazolone prepared as the coupler component were used. In addition, 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 392.7 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 812.8 parts. The operation was carried out to obtain 296.6 parts of Pigment Composition (A-5). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-6)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 92.9 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 To 7.5 parts of -(2-aminophenoxy)ethoxy)-N-methylaniline, to 143.4 parts of 119.6 parts of 38% sodium nitrite aqueous solution, 5-acetoacetylamino-benzimidazolone prepared as a coupler component 153.6 parts to 184.2 parts, 316.1 parts of 25% aqueous sodium hydroxide solution to 379.0 parts, 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation were changed to 784.6 parts 285.7 parts of a pigment composition (A-6) was obtained by performing the same operation as in Example A-1. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-7)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 93.4 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 8.1 parts of -(2-aminophenoxy)ethoxy)-N-butylaniline, 119.6 parts of 38% aqueous sodium nitrite solution to 143.8 parts, 5-acetoacetylamino-benzimidazolone prepared as a coupler component Except for changing 153.6 parts to 184.6 parts, 316.1 parts of 25% aqueous sodium hydroxide solution to 380.0 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer preparation to 786.6 parts 287.2 parts of a pigment composition (A-7) was obtained by performing the same operation as in Example A-1. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-8)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 93.6 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 To 8.4 parts of -(2-aminophenoxy)ethoxy)-N-phenoxyaniline, to 143.9 parts of 119.6 parts of 38% sodium nitrite aqueous solution, 5-acetoacetylamino-benzimidazolone prepared as a coupler component Except for changing 153.6 parts to 184.8 parts, 316.1 parts of 25% aqueous sodium hydroxide solution to 380.4 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer preparation to 787.4 parts , to obtain 287.9 parts of a pigment composition (A-8) in the same manner as in Example A-1. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-9)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 93.0 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)-N,N-dimethylaniline To 7.8 parts, 119.6 parts of 38% aqueous sodium nitrite solution to 143.5 parts, 5-acetoacetylamino-benz of the coupler component preparation 153.6 parts of imidazolone was changed to 184.3 parts, 316.1 parts of 25% sodium hydroxide aqueous solution was changed to 379.2 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 785.0 parts. Except for this, the same operations as in Example A-1 were carried out to obtain 286.2 parts of a pigment composition (A-9). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-10)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 60.9 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)phenol 254.2 parts of a pigment composition (A-10) was obtained in the same manner as in Example A-1, except that the content was changed to 39.3 parts. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-11)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 85.7 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)phenol 14.3 parts, 38% aqueous sodium nitrite solution 119.6 parts 138.0 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component was changed to 177.3 parts, 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 364.9 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 755.4 parts. 278.3 parts of pigment composition (A-11) was obtained by performing the same operation as in -1. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-12)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 92.7 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)phenol 7.3 parts, 38% sodium nitrite aqueous solution 119.6 parts 143.2 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component was changed to 184.0 parts, 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 378.6 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 783.7 parts. -1 was carried out to obtain 285.1 parts of a pigment composition (A-12). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-13)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 98.5 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)phenol 1.5 parts, 38% sodium nitrite aqueous solution 119.6 parts 147.5 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component Example A -1 was carried out to obtain 290.7 parts of a pigment composition (A-13). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-14)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 99.9 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)phenol 0.2 parts, 38% aqueous sodium nitrite solution 119.6 parts 148.5 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component Example A -1 was carried out to obtain 292.0 parts of a pigment composition (A-14). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-15)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 92.9 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Methoxyphenoxy)ethoxy)aniline 7.5 parts, 38% aqueous sodium nitrite solution 119.6 parts 143.4 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component Example A -1 was carried out to obtain 285.7 parts of a pigment composition (A-15). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-16)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 93.4 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-butoxyphenoxy)ethoxy)aniline 8.1 parts, 38% sodium nitrite aqueous solution 119.6 parts 143.8 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component Example A -1 was carried out to obtain 287.3 parts of a pigment composition (A-16). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example A-17)
In Example A-1, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation was combined with 93.6 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-phenoxyphenoxy)ethoxy)aniline 8.4 parts, 38% sodium nitrite aqueous solution 119.6 parts 143.9 parts, 5-acetoacetylamino-benzimidazolone 153.6 parts prepared as a coupler component was changed to 184.8 parts, 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 380.4 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 787.4 parts. -1 was carried out to obtain 287.9 parts of a pigment composition (A-17). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example B-1)
While stirring 1300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after 1 hour, 223.9 parts of 35% hydrochloric acid was added. After further stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 143.4 parts of a 38% sodium nitrite aqueous 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, after dispersing 184.1 parts of 5-acetoacetylamino-benzimidazolone in 1500 parts of methanol, 379.0 parts of 25% aqueous sodium hydroxide solution was added to dissolve, and further sodium dialkylsulfosuccinate (Pelex OT-P, Kao Corporation) was added to obtain a coupler component.
Separately, 500 parts of ice was added to 784.5 parts of an 80% aqueous acetic acid solution, and 223.9 parts of a 25% aqueous sodium hydroxide solution was added with stirring to prepare an acetic acid-sodium acetate buffer solution. A diazo component and a coupler component were added dropwise at the same time to conduct a coupling reaction while stirring a buffer maintained at 20°C. The dropping speed was adjusted so that the dropping of each of the diazo component and the coupler component was completed in 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was contained in the reaction solution, and the reaction solution was heated to 90° C. and held for 30 minutes. Next, after filtration and washing with water, N,N-dimethylformamide (hereinafter referred to as DMF) was sprinkled and washed to obtain a DMF-containing wet cake.
The obtained DMF-containing wet cake was put into 1500 parts of DMF and stirred for 1 hour. Furthermore, 4.14 parts of iodomethane and 12.1 parts of potassium carbonate were added and stirred at 30° C. for 6 hours. The reaction solution was poured into 15,000 parts of water, stirred for 1 hour, filtered and washed with water to obtain a water-containing wet cake.
The entire amount of the above wet cake in a wet state was charged into a pressurizable reaction vessel equipped with a stirrer. Water was added to make the mass in the vessel 3500 parts, and the mixture was stirred, and 2100 parts of isobutanol was added, followed by heating at 120° C. for 2 hours in an autoclave under self-pressure. After isobutanol was removed by steam distillation, the residue was filtered, washed with water, dried at 80° C. and pulverized to obtain 286.1 parts of Pigment Composition (B-1). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example B-2)
While stirring 1300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after 1 hour, 223.9 parts of 35% hydrochloric acid was added. After further stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 143.7 parts of a 38% sodium nitrite aqueous 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, after dispersing 184.6 parts of 5-acetoacetylamino-benzimidazolone in 1500 parts of methanol, 380.0 parts of 25% aqueous sodium hydroxide solution was added to dissolve, and further sodium dialkylsulfosuccinate (Pelex OT-P, Kao Corporation) was added to obtain a coupler component.
Separately, 500 parts of ice was added to 786.6 parts of an 80% aqueous acetic acid solution, and 223.9 parts of a 25% aqueous sodium hydroxide solution was added with stirring to prepare an acetic acid-sodium acetate buffer solution. A diazo component and a coupler component were added dropwise at the same time to conduct a coupling reaction while stirring a buffer maintained at 20°C. The dropping speed was adjusted so that the dropping of each of the diazo component and the coupler component was completed in 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was contained in the reaction solution, and the reaction solution was heated to 90° C. and held for 30 minutes. Next, after filtration and washing with water, N,N-dimethylformamide (hereinafter referred to as DMF) was sprinkled and washed to obtain a DMF-containing wet cake.
The obtained DMF-containing wet cake was put into 1500 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 stirred at 60° C. for 6 hours. The reaction solution was poured into 15,000 parts of water, stirred for 1 hour, filtered and washed with water to obtain a water-containing wet cake.
The entire amount of the wet cake in a wet state was charged into a pressurizable reaction vessel equipped with a stirrer. Water was added to make the mass in the vessel 3500 parts, and the mixture was stirred, and 2100 parts of isobutanol was added, followed by heating at 120° C. for 2 hours in an autoclave under self-pressure. After isobutanol was removed by steam distillation, the residue was filtered, washed with water, dried at 80° C. and pulverized to obtain 286.6 parts of a pigment composition (B-2). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example B-3)
While stirring 1300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after 1 hour, 223.9 parts of 35% hydrochloric acid was added. After further stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 143.5 parts of a 38% sodium nitrite aqueous 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, after dispersing 184.3 parts of 5-acetoacetylamino-benzimidazolone in 1500 parts of methanol, 379.3 parts of 25% aqueous sodium hydroxide solution was added to dissolve, and further sodium dialkylsulfosuccinate (Pelex OT-P, Kao Corporation) was added to obtain a coupler component.
Separately, 500 parts of ice was added to 785.2 parts of an 80% aqueous acetic acid solution, and 223.9 parts of a 25% aqueous sodium hydroxide solution was added with stirring to prepare an acetic acid-sodium acetate buffer solution. A diazo component and a coupler component were added dropwise at the same time to conduct a coupling reaction while stirring a buffer maintained at 20°C. The dropping speed was adjusted so that the dropping of each of the diazo component and the coupler component was completed in 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was contained in the reaction solution, and the reaction solution was heated to 90° C. and held for 30 minutes. Next, after filtration and washing with water, N,N-dimethylformamide (hereinafter referred to as DMF) was sprinkled and washed to obtain a DMF-containing wet cake.
The obtained DMF-containing wet cake was put into 1500 parts of DMF and stirred for 1 hour. Further, 8.08 parts of iodomethane and 39.3 parts of potassium carbonate were added and stirred at 30°C for 6 hours. The reaction solution was poured into 15,000 parts of water, stirred for 1 hour, filtered and washed with water to obtain a water-containing wet cake.
The entire amount of the above wet cake in a wet state was charged into a pressurizable reaction vessel equipped with a stirrer. Water was added to make the mass in the vessel 3500 parts, and the mixture was stirred, and 2100 parts of isobutanol was added, followed by heating at 120° C. for 2 hours in an autoclave under self-pressure. After isobutanol was removed by steam distillation, the residue was filtered, washed with water, dried at 80° C. and pulverized to obtain 286.2 parts of a pigment composition (B-3). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example B-4)
While stirring 1300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after 1 hour, 223.9 parts of 35% hydrochloric acid was added. After further stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 143.6 parts of a 38% sodium nitrite aqueous 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, after dispersing 184.5 parts of 5-acetoacetylamino-benzimidazolone in 1500 parts of methanol, 379.7 parts of 25% aqueous sodium hydroxide solution was added to dissolve, and further sodium dialkylsulfosuccinate (Pelex OT-P, Kao Corporation) was added to obtain a coupler component.
Separately, 500 parts of ice was added to 785.9 parts of an 80% aqueous acetic acid solution, and 223.9 parts of a 25% aqueous sodium hydroxide solution was added with stirring to prepare an acetic acid-sodium acetate buffer solution. A diazo component and a coupler component were added dropwise at the same time to conduct a coupling reaction while stirring a buffer maintained at 20°C. The dropping speed was adjusted so that the dropping of each of the diazo component and the coupler component was completed in 2 hours. After completion of the coupling reaction, it was confirmed that no unreacted diazo component was contained in the reaction solution, and the reaction solution was heated to 90° C. and held for 30 minutes. Next, after filtration and washing with water, tetrahydrofuran (hereinafter referred to as THF) was sprinkled and washed to obtain a THF-containing wet cake.
The obtained THF-containing wet cake was put into 1500 parts of THF and stirred for 1 hour. Further, 14.1 parts of triethylamine and 10.9 parts of acetyl chloride were added and stirred at 10°C for 3 hours. The reaction solution was poured into 15,000 parts of water, stirred for 1 hour, filtered and washed with water to obtain a water-containing wet cake.
The entire amount of the above wet cake in a wet state was charged into a pressurizable reaction vessel equipped with a stirrer. Water was added to make the mass in the vessel 3500 parts, and the mixture was stirred, and 2100 parts of isobutanol was added, followed by heating at 120° C. for 2 hours in an autoclave under self-pressure. After isobutanol was removed by steam distillation, the residue was filtered, washed with water, dried at 80° C. and pulverized to obtain 286.4 parts of a pigment composition (B-4). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example B-5)
While stirring 1300 parts of water, 100 parts of 1,2-bis(2-aminophenoxy)-ethane was added and dispersed, and after 1 hour, 223.9 parts of 35% hydrochloric acid was added. After further stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 148.7 parts of a 38% sodium nitrite aqueous 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, after dispersing 184.0 parts of 5-acetoacetylamino-benzimidazolone in 1500 parts of methanol, 378.6 parts of 25% aqueous sodium hydroxide solution was added to dissolve, and further sodium dialkylsulfosuccinate (Pelex OT-P, Kao Corporation) was added to obtain a coupler component.
Separately, 500 parts of ice was added to 783.8 parts of an 80% aqueous acetic acid solution, and 223.9 parts of a 25% aqueous sodium hydroxide solution was added with stirring to prepare an acetic acid-sodium acetate buffer solution. A diazo component and a coupler component were added dropwise at the same time to conduct a coupling reaction while stirring a buffer maintained at 20°C. The dropping speed was adjusted so that the dropping of each of the diazo component and the coupler component was completed in 2 hours. After completion of the coupling reaction, 47.8 parts of a 25% aqueous sodium hydroxide solution was added, and after confirming that no unreacted diazo component was contained in the reaction solution, the reaction solution was heated to 90°C and held for 30 minutes. Then, it was filtered and washed with water to obtain a water-containing wet cake.
The entire amount of the above wet cake in a wet state was charged into a pressurizable reaction vessel equipped with a stirrer. Water was added to make the mass in the vessel 3500 parts, and the mixture was stirred, and 2100 parts of isobutanol was added, followed by heating at 120° C. for 2 hours in an autoclave under self-pressure. After isobutanol was removed by steam distillation, the residue was filtered, washed with water, dried at 80° C. and pulverized to obtain 289.6 parts of a pigment composition (B-5). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example B-6)
In Example B-4, 100 parts of 1,2-bis(2-aminophenoxy)-ethane of the diazo component preparation were combined with 93.2 parts of 1,2-bis(2-aminophenoxy)-ethane and 2-(2 -(2-Aminophenoxy)ethoxy)phenol 285.6 parts of a pigment composition (B-6) was obtained in the same manner as in Example B-4, except that the content was changed to 6.8 parts. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Production Example C-1)
In Example A-1, 148.7 parts of 119.6 parts of 38% sodium nitrite aqueous solution prepared as the diazo component, and 190.9 parts of 153.6 parts of 5-acetoacetylamino-benzimidazolone prepared as the coupler component were used. In addition, 316.1 parts of 25% aqueous sodium hydroxide solution was changed to 393.0 parts, and 654.3 parts of 80% acetic acid aqueous solution for buffer solution preparation was changed to 813.5 parts. The operation was carried out to obtain 296.6 parts of Pigment Composition (C-1). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Production Example C-2)
In Example A-1, 119.6 parts of 38% sodium nitrite aqueous solution was added to 74.3 parts, 153.6 parts of 5-acetoacetylamino-benzimidazolone prepared as a coupler component was added to 95.5 parts, and 25% The same operation as in Example A-1 was performed, except that 316.1 parts of an aqueous sodium hydroxide solution was changed to 196.5 parts and 654.3 parts of an 80% acetic acid aqueous solution for buffer solution preparation was changed to 406.7 parts, 197.8 parts of the pigment composition (C-2) were obtained. Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Production Example C-3)
Except for changing 100 parts of 1,2-bis(2-aminophenoxy)-ethane for preparing the diazo component in Production Example C-2 to 100.4 parts of 2-(2-(2-phenoxyphenoxy)ethoxy)aniline was carried out in the same manner as in Production Example C-2 to obtain 195.2 parts of Pigment Composition (C-3). Table 1 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(Example D-1)
135.0 parts of the pigment composition (C-1), 15.0 parts of the pigment composition (C-2), 1050 parts of sodium chloride, and 250 parts of diethylene glycol are added to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). It was prepared and kneaded at 60° C. for 8 hours. Next, the kneaded mixture is put into hot water of about 70°C, stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and diethylene glycol, dried at 80°C for a whole day and night, and pulverized. 145 parts of pigment composition (D-1) was obtained.

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

(Example E-1)
While stirring and dispersing 271.9 parts of 1,2-bis(2-aminophenoxy)ethane in 2700 parts of water, 645.9 parts of 35% hydrochloric acid was added. After stirring for 1 hour, ice was added to adjust the temperature to 0 to 5° C., and 404.2 g of a 40% sodium nitrite aqueous solution was added to carry out a diazotization reaction. After stirring for 1 hour or longer, 118.1 parts of a 10% aqueous sulfamic acid solution was added to remove excess nitrite, and the mixture was stirred for 30 minutes or longer. was prepared.
On the other hand, after dispersing 539.2 parts of 5-acetoacetylamino-benzimidazolone in 4000 parts of water, 712.9 parts of 25% aqueous sodium hydroxide solution was added and dissolved to obtain a coupler component. Water and ice were added to the diazo component and the coupler component to adjust their liquid volumes to 8100 parts and 5400 parts, respectively.
218.7 parts of the water-containing wet cake (80.8 parts of nonvolatile matter) prepared in Production Example C-3 were charged into a reaction vessel. After adding water to adjust the mass in the container to 8100 parts and dispersing, 35.8 parts of 90% acetic acid was added, and then the temperature of this solution was adjusted to 40°C and the pH to 5.0. For coupling, the diazo component was added at a constant rate while adjusting the pH to 8.0 by adjusting the addition of the coupler component. Coupling was completed in about 3 hours while adding ice or a 5% aqueous sodium hydroxide solution from time to time so as to maintain a temperature of 40° C. and a pH of 8.0 during the coupling. After confirming that no unreacted diazo component was contained in the reaction solution, the reaction solution was heated to 90° C. and held for 1 hour. Then, it was filtered and washed with water to obtain a water-containing wet cake.
101.3 parts of the above water-containing wet cake (20 parts in terms of non-volatile matter) were placed in a pressurizable reactor equipped with a stirrer. After adjusting the mass in the container to 600 parts by adding water, the temperature was raised from room temperature to 140° C. over about 2 hours while stirring, held for 5 hours, cooled to room temperature, and the contents were taken out. The contents were filtered, washed with water, dried at 80° C. and pulverized to obtain 19.5 parts of a pigment composition (E-1). Table 3 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

(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-2009-057509. Table 3 shows the composition ratio calculated from the results of MALDI TOF-MS spectrum measurement.

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

In Table 3, PY151 is C.I. I. Pigment Yellow 151 (formula (13) below), and PY154 is C.I. I. Pigment Yellow 154 (formula (14) below).

<Coloring composition and its property evaluation>
Coloring compositions for various uses were prepared using the resulting pigment compositions, and their physical properties were evaluated.

<1> Production and evaluation of molded product (film)

[Production of molding composition (masterbatch)]
(Example FM-1)
(Manufacturing of masterbatch (FM-1))
100 parts of the pigment composition (A-2) and 100 parts of Mitsui Chemicals high wax (NL-100: decomposition type LDPE-WAX) are mixed and dispersed with three rolls to obtain a masterbatch (F-1). of predispersion was obtained. After that, 10 parts of the pre-dispersion and 90 parts of Novatec LD (LF342M1: film grade low-density polyethylene pellets manufactured by Mitsubishi Chemical Corporation) were added to a tumbler mixer (manufactured by Kawata Co., Ltd.) and stirred at a temperature of 25 ° C. for 3 minutes. After that, it was put into a twin-screw extruder (manufactured by Nippon Placon Co., Ltd.) and melt-kneaded at a temperature of 180° C. to obtain a masterbatch (FM-1).

(Examples FM-2 to FM-13, Comparative Examples FM-1 to FM-3)
(Production of masterbatch (FM-2) to (FM-16))
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 composition shown in Table 4. .

[Production of Molded Body (Film)]
(Example FF-1)
(Production of resin molding (FF-1) made of masterbatch (FM-1))
4 parts of the masterbatch (FM-1) and 100 parts of Novatec LD (LF342M1: film grade low-density polyethylene pellets) similar to the above were placed in a tumbler mixer (manufactured by Kawata Co., Ltd.), and the temperature was 25 ° C. for 3 minutes. After stirring, the mixture was melt-kneaded at a temperature of 180° C. by a T-die extruder, and film-molded to obtain a resin molding (FF-1) (film) composed of the masterbatch (FM-1). The molding temperature at this time was 180° C., and the film was produced so as to have a thickness of 50 μm.

(Examples FF-2 to FF-13, Comparative Examples FF-1 to FF-3)
(Production of resin moldings (FF-2) to (FF-16) composed of masterbatch (FM-2) to (FM-16))
Hereinafter, the resin molded body (FF-1) is performed in the same manner as the resin molded body (FF-1) (film) except that the master batch (FM-1) is changed to the master batches (FM-2) to (FM-16). -2) to (FF-16) (films) were obtained.

[Evaluation of Resin Molded Body (Film) Consisting of Masterbatch]
The dispersibility of the resin moldings (FF-1) to (FF-16) was evaluated by the following method. Table 5 shows the results.

[Dispersibility]
The dispersibility of the pigment in the film was evaluated by observing the surface of the film composed of the obtained masterbatch with an optical microscope. Evaluation criteria are as follows.

(Evaluation criteria)
4: Pigment aggregates are not present and the pigment is very uniformly dispersed. Good 3: Almost no pigment aggregates exist, and the pigment is uniformly dispersed. Practical 2: Pigment aggregates are present and the pigment is not uniformly dispersed. Impractical 1: There are many pigment aggregates, and the pigment is not uniformly dispersed. impractical

Resin molded articles (FF-1) to (FF-13) (films) made of the masterbatch of the present invention are resin molded articles (FF-14) to (FF-16) (films) made of the masterbatch that is not the present invention. Good dispersibility was obtained compared to

<2> Evaluation of molding composition

(Examples FS-1 to FS-13, Comparative Examples FS-1 to FS-3)
[Hue Evaluation]
The obtained pigment composition and high-density polyethylene resin (product name: Hizex 2208J, manufactured by Prime Polymer Co., Ltd.) are melt-kneaded at a temperature of 200 ° C. with a twin-screw extruder, and the temperature in the barrel is was 200° C., and 11 colored plates with a thickness of 3 mm were produced by adjusting the coloring strength to a density of SD1/3. Injection molding was carried out under the condition that the residence time of the composition in the barrel was as short as possible. The resulting pigment compositions used are shown in Table 6. For the colored plates, in order to detect the average color difference, a colorimeter (CM-700d, manufactured by Konica Minolta, Inc.) capable of measuring the total luminous flux is used for the 6th to 11th colored plates. The average value of the obtained colorimetric values was used as a control (reference value). Each colorimetric value was compared with a colored plate using the pigment composition (C-1) to obtain a color difference (ΔE*), which was evaluated according to the following criteria.

(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. Practical.
1. ΔE* is 3.0 or more. Defective.

[Heat resistance test]
The heat resistance test was conducted according to German Industrial Standard DIN12877-1. 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 (6th to 11th) were each subjected to colorimetry, and the average value of the colorimetry values was calculated. The color difference (ΔE*) between the above control and the measured value of the plate molded at 300° C. was determined and evaluated according to the following criteria. Table 6 shows the results. Note that the smaller the color difference, the better the heat resistance.

(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. Practical.
2. ΔE* is 6.0 or more and less than 8.0. Practical.
1. ΔE* is 8.0 or more. Not practical.

A molding composition comprising the pigment composition of the present invention is a C.I. I. Good heat resistance was exhibited without impairing the hue of Pigment Yellow 180.

That is, from the results in Table 6, C.I. I. Pigment Yellow 180 is a C.I. I. Pigment Yellow 180 has improved dispersibility and can be used in molding compositions having good hue and heat resistance.

<3> Production of molding (plate) (Example FP-1) Production of molding 1 part of pigment composition (A-3) and 1000 parts of polypropylene resin (product name: Prime Polypro J105, manufactured by Prime Polymer Co., Ltd.) The mixture was melt-kneaded at 220° C. with a twin-screw extruder, and then cut with a pelletizer to obtain a molding composition in the form of pellets. Next, while melt-kneading the obtained molding composition at a temperature of 220° C., injection molding is performed using an injection molding machine set at a molding temperature of 220° C. and a mold temperature of 40° C. to form a 1 mm thick mold. FP-1 (plate) was obtained. As a result of visual observation of the molded product, no coarse grains or the like were observed even in the watermark, and a yellow plate with a good degree of coloring was obtained.

(Example FP-2) Preparation of Molded Body Example FP except that 1 part of the pigment composition (A-3) used in Example FP-1 was changed to 1 part of the pigment composition (A-12). -1 was performed to obtain a compact FP-2 (plate) having a thickness of 1 mm. As a result of visual observation of the molded product, no coarse grains or the like were observed even in the watermark, and a yellow plate with a good degree of coloring was obtained.

(Example FP-3) Preparation of Molded Body 0.5 parts of the pigment composition (A-3) and 1000 parts of pre-dried polyethylene terephthalate resin (product name: Vylopet EQC-307, manufactured by Toyobo Co., Ltd.) were biaxially The mixture was melt-kneaded by an extruder at 275° C. and then cut by a pelletizer to obtain a molding composition in the form of pellets. Next, while melt kneading the obtained molding composition, injection molding is performed using an injection molding machine set at a molding temperature of 275 ° C. and a mold temperature of 85 ° C., and a molded body FP-3 ( plate) was obtained. As a result of visual observation of the molded product, no coarse grains or the like were observed even in the watermark, and a yellow plate with a good degree of coloring was obtained.

(Example FP-4) Preparation of molded body Except for changing 0.5 parts of the pigment composition (A-3) used in Example FP-3 to 0.5 parts of the pigment composition (A-12) A compact FP-4 (plate) having a thickness of 3 mm was obtained by performing the same operation as in Example FP-3. As a result of visual observation of the molded product, no coarse grains or the like were observed even in the watermark, and a yellow plate with a good degree of coloring was obtained.

<4> Evaluation of Toner A negatively charged toner was prepared and evaluated.

(Example FT-1)
2500 parts of the pigment composition (A-3) and 2500 parts of a polyester resin (product name: M-325, manufactured by Sanyo Kasei Co., Ltd.) were kneaded at 120° C. for 15 minutes using a pressure kneader. Next, the resulting kneaded product was taken out from the pressure kneader and further kneaded using three rolls with a roll temperature of 95°C. After cooling the resulting kneaded product, it was 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 calcium salt compound of 3,5-di-tert-butylsalicylic acid (charge control agent), and ethylene homopolymer (release agent, molecular weight 850, Mw/ Mn = 1.08, melting point 107 ° C.) 75 parts are mixed using a 20 L Henschel mixer (3000 rpm, 3 minutes), and further melt-kneaded at a discharge temperature of 120 ° C. using a twin-screw kneading extruder. gone. Then, the kneaded product was cooled and solidified, and then coarsely pulverized with a hammer mill. Next, the obtained coarsely pulverized product was finely pulverized using an I-type jet mill (IDS-2 type), and then 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.

(Example FT-2)
The same operation as in Example FT-1 was performed except that 2500 parts of the pigment composition (A-3) used in Example FT-1 was changed to 2500 parts of the pigment composition (A-12), and negative charging was performed. Toner FT-2 was obtained.

(Comparative example FT-1)
The same operation as in Example FT-1 was performed except that 2500 parts of the pigment composition (A-3) used in Example FT-1 was changed to 2500 parts of the pigment composition (C-1), and negative charging was performed. Toner FT-3 was obtained.

[Dispersibility evaluation]
Each of the obtained negatively charged toners FT-1 to FT-3 was sliced to a thickness of 0.9 μm using a microtome to form a sample. Next, the dispersion state of the pigment was observed for each sample using a transmission electron microscope. As a result, the negatively charged toner FT-1 using the pigment composition (A-3) and the pigment composition (A-12) were used rather than the negatively charged FT-3 using the pigment composition (C-1). It was confirmed that the negatively-charged toner FT-2, in which the pigment was uniformly distributed, had better dispersibility.

<5> Evaluation of active energy ray-curable ink [Preparation of inert resin varnish]
A 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 heating and mixing (80° C.).

[Preparation of active energy ray-curable ink]
(Example H-1)
(Production of active energy ray-curable ink (H-1))
Pigment composition (A-1) 15 parts, EO (3) modified trimetolpropane triacrylate 9.7 parts, dimethylolpropane tetraacrylate 9.2 parts, dipentaerythritol hexaacrylate 23 parts, Omnirad 369 2 2 parts of Omnirad 907, 2 parts of OmniradDETX, 2 parts of Omnirad EMK, 0.5 parts of solid wax (polytetrafluoroethylene wax), 1 part of talc, 0 parts of polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum) .3 parts and 33.3 parts of resin varnish A were mixed, stirred and mixed using a butterfly mixer, and then dispersed with three rolls so that the maximum particle size was 7.5 μm or less. A curable ink (H-1) was prepared.

Details of the materials used are as follows.

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

[Anti-friction agent]
(solid wax)
・ Teflon (registered trademark) modified polyethylene wax Polytetrafluoroethylene wax, "Fluoroslip 511" manufactured by Shamrock, melting point: 126 ° C.)

[Other ingredients]
(Extender pigment)
・ Talc: High Filler 5000PJ (manufactured by Matsumura Sangyo Co., Ltd.)

(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) and (H-33) to (H-35))
Active energy ray-curable ink H was prepared in the same manner as in Example H-1, except that the pigment composition shown in Table 7 was used instead of the pigment composition (A-1) used in Example H-1. -2) to (H-30) and (H-33) to (H-35) were produced.

(Example H-31)
(Production of active energy ray-curable ink (H-31))
Except for changing 15 parts of the pigment composition (A-1) used in Example H-1 to 14.25 parts of the pigment composition (C-1) and 0.75 parts of the pigment composition (C-2) , and the same operation as in Example H-1 was performed to obtain an active energy ray-curable ink (H-31).

(Example H-32)
(Production of active energy ray-curable ink (H-32))
Except for changing 15 parts of the pigment composition (A-1) used in Example H-1 to 14.25 parts of the pigment composition (C-1) and 0.75 parts of the pigment composition (C-3) , and the same operation as in Example H-1 was performed to obtain an active energy ray-curable ink (H-32).

The performance of the obtained active energy ray-curable ink was evaluated by the following method. Table 7 shows the results.

[Method for preparing test sample]
Using the obtained active energy ray-curable ink, a solid image was printed on Tokubishi art paper as a base material in an amount of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). After that, the ink composition was cured with an LED lamp ("XP-9" manufactured by Air Motion System Co., Ltd., irradiation distance of 10 mm, output of 70%) at a conveyor speed of 60 m/min to prepare a test sample. The RI tester is a tester for printing ink on paper or film, and can adjust the transfer amount of ink and printing pressure.

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

(Evaluation criteria)
5. Less than 40% dispersion time (very good)
4. Dispersion time is 40% or more and less than 60% (good)
3. Dispersion time of 60% or more and less than 80% (slightly good)
2. Dispersion time is 80% or more and less than 100% (Practical)
1. Dispersion time is 100% or more (defective)

[Gloss]
Using the test sample prepared by the above method, the glossiness value (according to 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 Laboratory. bottom. Based on the gloss value of the test sample obtained in Comparative Example H-1, evaluation was made according to the following criteria. It should be noted that the better the pigment is dispersed, the better the gloss.

(Evaluation criteria)
5: Gloss value is 115% or more (very good)
4: The gloss value is 110% or more and less than 115% (good)
3: The gloss value is 105% or more and less than 110% (slightly good)
2: Gloss value is 95% or more and less than 105% (Practical)
1: Gloss value is less than 95% (defective)

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

(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. Practical 1. ΔE* is 3.0 or more. impractical

From the results in Table 7, C.I. I. Pigment Yellow 180, Comparative Example H-1, C.I. I. Pigment Yellow 180, Examples H-1 to H-32, had improved dispersibility and gloss. Further, Comparative Examples H-2 to H-3 had a large effect on the hue, and Examples H-1 to H-32 had improved dispersibility and gloss without adversely affecting the hue.

<6> Evaluation of water-based coloring composition 1. Preparation of water-based coloring composition (Example J-1)
(Preparation of aqueous 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 to obtain a dispersion liquid.
・Pigment composition (A-2): 3.15 parts ・Polyester-modified acrylic acid polymer (ADDITOL XW 6528, manufactured by Allnex): 5.25 parts ・Wetting agent (ADDITOL XW 6374, manufactured by Allnex): 0.25 parts 95 parts Antifoaming agent (ADDITOL XW 6211, manufactured by Allnex): 0.63 parts Ion-exchanged water: 21.52 parts Next, zirconia beads are removed from the dispersion to obtain a water-based coloring composition (J-1 ).

(Examples J-2 to J-13, Comparative Examples J-1 to J-3)
(Preparation of water-based coloring compositions (J-2) to (J-13), (J-16) to (J-18))
The pigment composition (A-2) used in Example J-1 was changed to the pigment composition shown in Table 8, but the same operations as in Example J-1 were performed, and a water-based coloring composition (J -2) ~ (J-13), (J-16) ~ (J-18) were obtained.

(Example J-14)
(Preparation of water-based coloring composition (J-14))
3.15 parts of the pigment composition (A-2) used in Example J-1 was changed to 2.99 parts of the pigment composition (C-1) and 0.16 parts of the pigment composition (C-2) Except for this, the same operations as in Example J-1 were performed to obtain a water-based coloring composition (J-14).

(Example J-15)
(Preparation of water-based coloring composition (J-15))
3.15 parts of the pigment composition (A-2) used in Example J-1 was changed to 2.99 parts of the pigment composition (C-1) and 0.16 parts of the pigment composition (C-3) Except for this, the same operations as in Example J-1 were performed to obtain a water-based coloring composition (J-15).

2. Evaluation of dispersion stability (Evaluation of initial viscosity and viscosity stability)
The initial viscosity at 25° C. of the resulting water-based colored composition was measured using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity was measured after aging at 25° C. for 1 week and after aging at 50° C. for 1 week. Based on the obtained measured values, the rate of increase in viscosity relative to the initial viscosity was calculated and used as an index of viscosity stability, and evaluated according to the following evaluation criteria. Table 8 shows the results. The lower the initial viscosity, the better the dispersibility. Moreover, the smaller the viscosity increase rate, the better the dispersion stability. If it is "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(Evaluation criteria for initial viscosity)
4. Initial viscosity is less than 5.0 mPa·s. Very good 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. Practical 1. Initial viscosity is 10.0 mPa·s or more. impractical

(Evaluation criteria for viscosity stability)
4. Viscosity increase rate is less than 20%. Very good 3. The viscosity increase rate is 20% or more and less than 30%. Good 2. The viscosity increase rate is 30% or more and less than 40%. Practical 1. The viscosity increase rate is 40% or more. impractical

From the results in Table 8, the azo compound (1) of the present invention and C.I. I. A pigment composition containing Pigment Yellow 180 gave good results.

<7> Evaluation of Water-Based Paint Using the water-based coloring composition prepared above, a water-based paint was prepared and evaluated.

<7-1> Preparation of water-based paint (Example JB-1)
(1) Preparation of water-based paint (JB-1-1) After blending so that the non-volatile content has the following composition, stir using a high-speed stirrer, water-based paint (JB-1-1) (1 at 25 ° C. Weekly storage) was obtained.
・ 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 Co., Ltd. made, melamine resin): 45.0 parts

(2) Preparation of water-based paint (JB-1-2) After blending so that the non-volatile content has the following composition, stir using a high-speed stirrer, water-based paint (JB-1-2) (1 at 50 ° C. Weekly storage) was obtained.
・ 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 Co., Ltd. made, melamine resin): 45.0 parts

(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, and the water-based coloring compositions (J-2) to (J-18) (each stored at 25 ° C. for 1 week ) to obtain aqueous paints (JB-2-1) to (JB-18-1).
Further, the water-based coloring composition (J-1) (stored at 50 ° C. for 1 week) used in Example JB-1 was added to the water-based coloring composition (J-2) to (J-18) (each at 50 ° C. 1 Water-based paints (JB-2-2) to (JB-18-2) were obtained in the same manner as in Example JB-1, except that they were sequentially changed to "weekly storage".

<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 (manufactured by Toray Industries, polyester terephthalate (PET) film, 100 μm thick) using a 6 mil applicator. . The coated PET film was dried at room temperature for 18 hours. Then, it was dried at 60° C. for 5 minutes and 140° C. for 20 minutes to obtain a PET film coating (JP-1) having a film thickness of 70 μm.

(Examples JP-2 to JP-15, Comparative Examples JP-1 to JP-3)
(Preparation of PET film coating (JP-2) to (JP-18))
The water-based paint (JB-1-1) used in Example JP-1 is used for water-based paints (JB-2-1) to (JB-18-1), and the water-based paint (JB-1-2) is used for water-based paint ( PET film coating (JP-2) to (JP-18) was obtained by performing the same operation as in Example JP-1 except that JB-2-2) to (JB-18-2) were changed sequentially. .

<7-3> Evaluation of PET Film Coating For each PET film coating obtained in Examples JP-1 to JP-15 and Comparative Examples JP-1 to JP-3, hue stability was evaluated according to the following method. .

(Evaluation method for hue stability)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), each PET film coating (JP-1) to (JP-18) was coated with a water-based coloring composition and stored at 25 ° C. for 1 week. , and the paint of the water-based coloring composition stored at 50°C for 1 week was measured for each color, and the color difference (ΔE*) was determined and judged according to the following criteria. Table 10 shows the results. The smaller the color difference, the more excellent the dispersion stability of the coloring material, and "4" and "3" in the following evaluation criteria 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.

From the results in Table 10, the azo compound (1) of the present invention and C.I. I. A pigment composition containing Pigment Yellow 180 gave good results.

<8> Evaluation of water-based flexo ink

(Synthesis Example 1) (Synthesis of water-based urethane resin B)
82.3 parts of polytetramethylene glycol having a number average molecular weight of 2,000, a number average molecular weight of 000 polyethylene glycol, 13 parts of dimethylolbutanoic acid, and 1.7 parts of 1,4-cyclohexanedimethanol were charged, purged with dry nitrogen, and heated to 100°C. With stirring, 33.3 parts of isophorone diisocyanate was added dropwise over 20 minutes, and the temperature was gradually raised to 140° C. (NCO/OH=0.98). Further reaction was performed for 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: about 40,000, nonvolatile content: 25%, acid value: 36.9). (mgKOH/g), hydroxyl value 11.1 (mgKOH/g)).

[Production of water-based flexographic ink]
(Example K-1)
(Production of water-based flexographic ink (K-1))
Water-based urethane resin B45 parts, pigment composition (A-1) 15 parts, polyethylene wax (W310 manufactured by Mitsui Chemicals, particle diameter 9.5 μm, softening point 132 ° C., needle penetration method hardness 0.8) 2 parts, adipine 0.2 parts of acid dihydrazide, 0.2 parts of aqueous ammonia (28%), 18.8 parts of water, and 18.8 parts of isopropanol are dispersed with an Eiger mill until the particle size becomes 10 μm or less by grind gauge, and aqueous flexographic ink ( K-1) was manufactured.

(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, the same procedure as in Example K-1 was performed except that the pigment composition (A-1) was changed as shown in Table 11. , Aqueous flexographic inks (K-2) to (K-30), (K-33) to (K-35) were obtained

(Example K-31)
(Production of water-based flexographic ink (K-31))
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), 14.25 parts of the pigment composition (C-1) and the pigment composition ( C-2) Water-based flexographic ink (K-31) was obtained in the same manner as in Example K-1, except that the content was changed to 0.75 parts.

(Example K-32)
(Production of water-based flexographic ink (K-32))
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), 14.25 parts of the pigment composition (C-1) and the pigment composition ( C-3) Water-based flexographic ink (K-32) was obtained in the same manner as in Example K-1, except that the content was changed to 0.75 parts.

[Evaluation method and evaluation criteria]
Printing in Examples and Comparative Examples was performed as follows.
Flexo rotary printing: Using a center drum type 6-color flexo printing machine "SOLOFLEX" manufactured by Windmuller & Hoelscher, printing was performed on a plastic film at a speed of 100 m/min and dried at 60 to 70°C to obtain a printed material. As the anilox roll, 350 lines/cm was used, and as the plate cylinder, DuPont "Sirel DPU" (thickness 1.14 mm) was used as a solid plate, and double-sided tape (Toyochem "DF7382T" thickness 0.50 mm).

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

(Evaluation criteria)
5. Less than 40% dispersion time (very good)
4. Dispersion time is 40% or more and less than 60% (good)
3. Dispersion time of 60% or more and less than 80% (slightly good)
2. Dispersion time is 80% or more and less than 100% (Practical)
1. Dispersion time is 100% or more (defective)

(2) Aging stability After storing the ink at a constant temperature of 40°C for 3 months, the Zahn cup No. 4 (25° C.) was used to measure the viscosity over time, and the difference from the finished (initial) viscosity was evaluated. Evaluation criteria are shown below. The practical level is 3 or higher.

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

(3) Hue The ink is spread on a PET film (polyethylene terephthalate film, E-5102 manufactured by Toyobo Co., Ltd., 12 μm) with a Meyer bar, and superimposed on white spread paper (Biko-Chart without coating, N2C manufactured by BYK). The color was measured with a colorimeter capable of measuring luminous flux (CM-700d, manufactured by Konica Minolta), and the color difference (ΔE*) was determined based on Comparative Example K-1, and evaluated according to the following criteria.

(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. Practical 1. ΔE* is 3.0 or more. impractical

From the results in Table 11, C.I. I. Pigment Yellow 180, Comparative Example K-1, C.I. I. Pigment Yellow 180 of Examples K-1 to K-32 had improved dispersibility and stability over time. Further, Comparative Examples K-2 to K-3 had a large effect on the hue, and Examples K-1 to K-32 had improved dispersibility and aging stability without adversely affecting the hue.

<9> Evaluation of water-based inkjet ink <9-1> Preparation of aqueous coloring composition for inkjet (hereinafter “water-based coloring composition for IJ”) (Example L-1)
(Preparation of aqueous coloring composition for IJ (L-1))
Pigment composition (A-1): 19.0 parts Styrene-acrylic acid copolymer (manufactured by BASF Japan, Joncryl 61J): 16.4 parts Surfactant (manufactured by 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 in a paint shaker manufactured by Red Devil for 6 hours. The resulting liquid was diluted with ion-exchanged water, the zirconia beads for dispersion were separated by filtration, and the pigment composition (A-1) was obtained by diluting with ion-exchanged water so that the colorant content was 15%. An aqueous coloring composition for IJ (L-1) was obtained.

(Examples L-2 to L-30, Comparative Examples L-1 to L-3)
(Preparation of aqueous coloring compositions for IJ (L-2) to (L-30) and (L-36) to (L-38))
The same operation as in Example L-1 was performed, except that the pigment composition (A-1) used in Example L-1 was changed to the pigment composition shown in Table 12, and an aqueous coloring composition for IJ was prepared. (L-2) to (L-30) and (L-36) to (L-38) were obtained.

(Example L-31)
(Preparation of aqueous coloring composition for IJ (L-31))
19.0 parts of the pigment composition (A-1) used in Example L-1 was changed to 18.05 parts of the pigment composition (C-1) and 0.95 parts of the pigment composition (C-2). Except for this, the same operations as in Example L-1 were performed to obtain an aqueous coloring composition for IJ (L-31).

(Example L-32)
(Preparation of aqueous coloring composition for IJ (L-32))
19.0 parts of the pigment composition (A-1) used in Example L-1 was changed to 18.05 parts of the pigment composition (C-1) and 0.95 parts of the pigment composition (C-3) Except for this, the same operations as in Example L-1 were performed to obtain an aqueous coloring composition for IJ (L-32).

(Synthesis Example 2) Styrene-acrylic acid ester-methacrylic acid ester copolymer having carboxyl group and hydroxyl group [PA1]
A 3-liter four-necked flask equipped with a dropping funnel, a thermometer, a nitrogen gas inlet tube, a stirrer and a reflux condenser was charged with 1,000 parts of methyl ethyl ketone and heated to 78° C., followed by addition of 100 parts of styrene and n-butyl. A mixture of 538 parts of 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 reacted at the same temperature for 8 hours. After completion of the reaction, methyl ethyl ketone was further added to adjust the nonvolatile content to 50%, and a styrene-acrylic acid ester-methacrylic acid ester copolymer [PA1] solution having an acid value of 70 mgKOH/g and a number average molecular weight of 6,000 was obtained. got

(Example L-33)
(Preparation of aqueous coloring composition for IJ (L-33))
After neutralizing 12.8 parts of styrene-acrylic acid ester-methacrylic acid ester copolymer [PA1] solution (50% non-volatile content) with 0.71 part of dimethylethanolamine, methyl etherified melamine resin (three 2.29 parts of Nikalac MX-041 (manufactured by Wa Chemical Industry Co., Ltd.) (1.6 parts as resin) were mixed. Into this mixed solution, 50 parts of an aqueous slurry (non-volatile content of 16%) of the pigment composition (A-2) prepared in advance was added with stirring. Then, it was charged into a 250 ml glass bottle together with 130 parts of glass beads having a diameter of 1.5 mm, dispersed for 4 hours using a paint shaker manufactured by Red Devil Co., Ltd., and after obtaining a dispersion, ion-exchanged water was added in an amount equal to the mixture. . Thereafter, a 1N hydrochloric acid aqueous solution was added with stirring to deposit and fix the copolymer [PA1] on the surface of the pigment composition (A-2). The pH of the mixed solution after fixing was 3-5.
After that, the mixed solution was subjected to suction filtration and washed with ion-exchanged water until the pH of the washing liquid exceeded 6 to obtain a pigment composition (A-2) to which the copolymer [PA1] was fixed.
Then, water is added until the pigment composition (A-2) to which the copolymer [PA1] is fixed becomes fluid, and then 0.8 parts of dimethylethanolamine is added while stirring with a stirrer. , and the stirring was continued for 1 hour to obtain a redispersion of the pigment composition (A-2) to which the copolymer [PA1] was fixed.
After adding water to this redispersion to adjust the non-volatile content to 19%, an acid crosslinking catalyst (Nacure 2500X, manufactured by Kusumoto Kasei Co., Ltd.) is added to the amount of the copolymer [PA1] contained in the redispersion. By adding 0.5% and performing a crosslinking reaction at 95 ° C. for 1 hour, an aqueous coloring composition containing a pigment composition-containing crosslinked resin particle (IJ aqueous coloring composition (L-33)) was obtained. .

(Synthesis Example 3) Styrene-acrylic acid ester-methacrylic acid ester copolymer having carboxyl group and epoxy group [PA2]
A 3-liter four-necked flask equipped with a dropping funnel, a thermometer, a nitrogen gas inlet tube, a stirrer and a reflux condenser was charged with 1,000 parts of methyl ethyl ketone and heated to 78 ° C., then 100 parts of styrene, n- 476 parts of 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 tertiary butyl peroxy-2-ethylhexanoate. was added dropwise over 4 hours, and the mixture was reacted at the same temperature for 8 hours. After completion of the reaction, methyl ethyl ketone was further added to adjust the non-volatile content to 50%, resulting in a styrene-acrylic acid ester-methacrylic acid ester copolymer [PA2] having an acid value of 70 mgKOH/g and a number average molecular weight of 10,500. A solution was obtained.

(Example L-34)
(Preparation of aqueous coloring composition for IJ (L-34))
16 parts of the resulting styrene-acrylic acid ester-methacrylic acid ester copolymer [PA2] solution (50% non-volatile content), 8 parts of the pigment composition (A-2), and 40 parts of methyl ethyl ketone were placed in a glass with a diameter of 1.5 mm. It was charged into a 250 ml glass bottle together with 130 parts of beads and dispersed for 4 hours using a paint shaker manufactured by Red Devil to obtain a dispersion liquid. Next, 0.8 parts of a hydrophilic epoxy resin (CR-5L, manufactured by DIC) and 24 parts of methyl ethyl ketone were added to this dispersion and stirred, and the glass beads were separated by filtration. 87.2 parts of the dispersion liquid thus obtained was added to a mixed liquid of 1.2 parts of dimethylethanolamine and 100 parts of water with stirring, and then ion-exchanged water was added in the same amount as the mixture. After that, a 1 N phosphoric acid aqueous solution was added with stirring to deposit and fix the copolymer [PA2] on the surface of the pigment composition (A-2). The pH of the mixed solution after the fixation was 5.
After that, the mixed solution was suction-filtered and washed with ion-exchanged water until the pH of the washing exceeded 6 to obtain a pigment composition (A-2) to which the copolymer [PA2] was fixed.
Then, water is added until the pigment composition (A-2) to which the copolymer [PA2] is fixed becomes fluid, and then 0.8 parts of dimethylethanolamine is added while stirring with a stirrer. , and the stirring was continued for 1 hour to obtain a redispersion of the pigment composition (A-2) to which the copolymer [PA2] was fixed.
Water is added to this redispersion to adjust the non-volatile content to 19%, and then the redispersion is heated to 95 ° C. and subjected to a crosslinking reaction for 1 hour to obtain a water-based coloring containing the pigment composition-containing crosslinked resin particles. A composition (aqueous coloring composition for IJ (L-34)) was obtained.

(Synthesis Example 4) Styrene-acrylate copolymer [PA3]
A monomer mixed solution was prepared by mixing 62 parts of acrylic acid, 129 parts of styrene and 9 parts of α-methylstyrene. 20 parts of methyl ethyl ketone, 0.3 parts of 2-mercaptoethanol (polymerization chain transfer agent), and 10% of the above monomer mixture were added and mixed in a reaction vessel, and the mixture was sufficiently replaced with nitrogen gas. Separately, the remaining 90% of the monomer mixture, 0.27 parts of the polymerization chain transfer agent, 60 parts of methyl ethyl ketone, and an azo radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-65, A mixed solution of 2.2 parts of 2,2′-azobis(2,4-dimethylvaleronitrile)) was charged.
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 completion of the dropwise addition, the mixture was allowed to react at 65°C for 1 hour, and then a solution obtained by dissolving 0.3 parts of the polymerization initiator 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 twice, the temperature was raised to 70 ° C. and the reaction was further performed for 1 hour. A styrene-acrylic acid ester copolymer [PA3] solution (nonvolatile content: 40.9%) having a weight average molecular weight of 12,500 was obtained.
This styrene-acrylic acid ester copolymer [PA3] solution was dried under reduced pressure to completely remove the solvent to obtain 32 parts of a resin, which was then mixed with 204 parts of ion-exchanged water. 1 part was added to neutralize about 55 mol % of the carboxy groups in the copolymer [PA3]. This mixed solution was heated to 90° C. and then stirred for 1 hour to obtain an aqueous dispersion of copolymer [PA3] in which copolymer [PA3] was dispersed in water.

(Example L-35)
(Preparation of aqueous coloring composition for IJ (L-35))
After cooling the aqueous dispersion of the copolymer [PA3] to room temperature, 100 parts of the pigment composition (A-2) was added and stirred at 20° C. for 3 hours using a stirrer. After adding 124 parts of ion-exchanged water to this mixed solution, a Microfluidizer (manufactured by Powrex Corporation) was used to perform 15 passes of dispersion treatment at a pressure of 150 MPa. Then, using a high-speed cooling centrifuge (manufactured by Hitachi Koki, himac CR22G), the resulting dispersion was centrifuged at a set temperature of 20 ° C. and 3660 rpm for 20 minutes, and then only the liquid layer was recovered. Filtration was carried out with a 5 μm membrane filter to obtain an aqueous dispersion of pigment composition (A-2) (nonvolatile concentration: 25%).
To 100 parts of the aqueous dispersion of this pigment composition (A-2), 32 parts of ion-exchanged water was added, and 1 part of trimethylolpropane polyglycidyl ether (Denacol EX-321, manufactured by Nagase ChemteX Corporation) was added as a cross-linking agent. 8 parts and heated with stirring at 70° C. for 5 hours. After that, it is cooled to room temperature, filtered through a membrane filter having a pore size of 5 μm, and further added with ion-exchanged water to adjust the non-volatile content to 19%, thereby forming a water-based coloring composition containing crosslinked resin particles containing a pigment composition. A product (aqueous coloring composition for IJ (L-35)) was obtained.

<9-2> Preparation of water-based inkjet ink (hereinafter “water-based IJ ink”) After stirring and mixing each component shown in Tables 13-1 to 13-3, the ink for evaluation test was filtered through a 3 μm membrane filter. Aqueous IJ inks of Examples LB-1 to LB-35 and Comparative Examples LB-1 to LB-3 were obtained. In Tables 13-1 to 13-3, the numerical values indicating the amounts of the components are all "parts", and "-" means that the component is not included. As for "water", ion-exchanged water was used. Other abbreviations in the table have the following meanings.
・PG: propylene glycol ・AMP: 2-amino-2-methyl-1-propanol ・TEA: triethanolamine

(Evaluation method for hue stability)
Hue stability was evaluated according to the following method.

(Hue stability 1)
A mayonnaise bottle was filled with the water-based IJ ink prepared in each example and comparative example, and stored in an oven at 50° C. for two weeks. Using the ink before and after storage of each ink, using the K control coater manufactured by Matsuo Sangyo Co., Ltd., after coating the OK top coat with a wet film thickness of 6 μm, the coated product was dried in an oven at 70 ° C. for 1 minute. A coated product was produced. Using X-rite eXact manufactured by X-Rite, the L*, a*, and b* values of the ink coating film before and after long-term storage of the obtained coated material were measured. From the values, the color difference (ΔE*) before and after storage was calculated and evaluated. If it is "5", "4", "3" and "2" in the following evaluation criteria, it is a practical grade.

(Hue stability 2)
A mayonnaise bottle was filled with the water-based IJ ink prepared in each example and comparative example, stored in an oven at 50° C. for 4 weeks, and evaluated in the same manner as in hue stability 1. If it is "5", "4", "3" and "2" in the following evaluation criteria, it is a practical grade.

(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

From the results of Tables 13-1 to 13-3, the azo compound (1) of the present invention and C.I. I. By using the pigment composition containing Pigment Yellow 180, an inkjet ink was obtained that could suppress the color change of the ink coating film during long-term storage stability. In particular, it was confirmed that the long-term storage stability can be further improved by using the pigment composition-containing crosslinked resin particles.

<10> Evaluation of paint <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 placed in a 225 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil to obtain a mixture.
・Pigment composition (A-2): 19 parts ・Acrylic resin (manufactured by DIC, Acrydic 47-712): 7.7 parts ・Dispersion solvent (toluene: xylene: butyl acetate: T-SOL150 FLUID manufactured by ENEOS Mixed solvent with a mass ratio of 3:3:2:2): 40.7 parts Next, to the above mixture, 75.4 parts of Acrydic 47-712, melamine resin (Amidia L-117-60 manufactured by DIC) 17 .2 parts were added and dispersed for an additional 10 minutes to obtain a dispersion.
Then, the steel beads were removed from the above dispersion to obtain a base paint (M-1) of the pigment composition (A-2).

(Examples M-2 to M-15, Comparative Examples M-1 to M-3)
(Preparation of base paints (M-2) to (M-13) and (M-16) to (M-18))
The same operation as in Example M-1 was performed except that the pigment composition (A-2) used in Example M-1 was changed to the pigment composition shown in Table 14, and a base paint (M-2 ) ~ (M-13), (M-16) ~ (M-18) were obtained.

(Example M-14)
(Preparation of base paint (M-14))
Except for changing 19 parts of the pigment composition (A-2) used in Example M-1 to 18.05 parts of the pigment composition (C-1) and 0.95 parts of the pigment composition (C-2) A base paint (M-14) was obtained by performing the same operation as in Example M-1.

(Example M-15)
(Preparation of base paint (M-15))
Except for changing 19 parts of the pigment composition (A-2) used in Example M-1 to 18.05 parts of the pigment composition (C-1) and 0.95 parts of the pigment composition (C-3) A base paint (M-15) was obtained by performing the same operation as in Example M-1.

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

3. Preparation of Solid Base Paint (Example MS-1)
(Preparation of solid base paint (MS-1))
Using a high-speed stirrer, the following components were stirred 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

(Examples MS-2 to MS-15, Comparative Examples MS-1 to MS-3)
(Preparation of solid base paints (MS-2) to (MS-18))
The same operation as in Example MS-1 was performed except that the base paint (M-1) used in Example MS-1 was changed to base paints (M-2) to (M-18), respectively. Paints (MS-2) to (MS-18) were obtained.
Table 15 shows the pigment compositions of the base paints used in the solid base paints prepared in Examples and Comparative Examples.

4. Preparation of Topcoat Clear Paint Using a high-speed stirrer, the following raw materials were stirred to obtain a topcoat clear paint.
・Acrylic resin (manufactured by DIC, Acrydic 44-179): 120 parts ・Melamine resin (manufactured by DIC, Amidia L117-60): 30 parts ・Dilution solvent (toluene, xylene, ENEOS T-SOL150 FLUID, 3 -mixed solvent in which the mass ratio of ethyl ethoxypropionate and ethyl acetate is 3:2:2:1:2): 50 parts

5. Preparation of solid base coated plate and evaluation of weather resistance (Example MP-1)
(Preparation of solid base coated plate (MP-1))
A solid base paint (MS-1) was sprayed with a spray gun and coated on a steel plate whose surface was adjusted with sandpaper #1000. In order to adjust the viscosity to be easy to spray, dilute solvents (toluene, xylene, T-SOL150 FLUID manufactured by ENEOS, ethyl 3-ethoxypropionate, ethyl acetate with a mass ratio of 3:2 with the same mass as a standard for solid base paint) :2:1:2 mixed solvent) were mixed appropriately.
The coating was carried out in 9 batches, and then the clear topcoat paint was sprayed in 6 batches. After drying at 25° C. for 8 hours, it was dried at 140° C. for 30 minutes to obtain a solid base coated panel (MP-1).

(Examples MP-2 to MP-15, Comparative Examples MP-1 to MP-3)
(Preparation of solid base coated plates (MP-2) to (MP-18))
The same operation as in Example MP-1 was performed 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, Solid base paints (MP-2) to (MP-18) were obtained.

(1) Hue The obtained solid base coated plates (MP-1) to (MP-18) were each measured using a colorimeter (manufactured by Konica Minolta, CM-700d). Color difference (ΔE*) was calculated based on 1 and evaluated according to the following criteria. The results are shown in Table 16. If it is "5", "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(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.

(2) Stability of Hue over Time Coating was carried out in the same manner as MP-1 to MP-3 to obtain solid base coated plates (MP-1b) to (MP-18b). Each color was measured using a colorimeter (Konica Minolta, CM-700d), the color difference (ΔE*) before and after storage over time was determined, and evaluated according to the following criteria. The results are shown in Table 16. If it is "5", "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(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.

(3) Weather Resistance The obtained solid base coated panels (MP-1) to (MP-18) were subjected to a weather resistance test as follows.
The weather resistance test was performed using a super-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151), illumination intensity 90 mW / cm ² , irradiation (daytime) conditions: 12 hours, temperature 63 ° C., humidity 70%, no irradiation (night) conditions: 12 hours, 70° C. temperature, 99% humidity as one cycle, 48 hours (2 cycles of 12 hours day and night). The color of the coated plate before and after the weather resistance test was measured using a colorimeter (CM-700d, manufactured by Konica Minolta Co., Ltd.), and the color difference (ΔE*) was determined and judged according to the following criteria. The results are shown in Table 16. If it is "5", "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(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.

From the results in Table 16, the azo compound (1) of the present invention and C.I. I. Pigment compositions containing Pigment Yellow 180 gave good results in stability over time without impairing hue and weather resistance.

<11> Evaluation of gravure printing ink

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

<11-1> Preparation of gravure printing ink (Example N-1)
(Preparation of gravure printing ink (N-1))
As a binder resin, 30 parts of a polyurethane resin solution [PU1] (30% nonvolatile content), 0.8 parts of polyethylene wax (A-C400A manufactured by Honeywell) as a hydrocarbon wax in terms of nonvolatile content, chlorinated polypropylene resin ( Nippon Paper Industries Product name: 370M chlorine content 30% non-volatile content 50%) in terms of non-volatile content 0.5 parts, pigment composition (A-1) 10 parts, methyl ethyl ketone (hereinafter “MEK”) / acetic acid n 58.7 parts of a solution of -propyl (hereinafter "NPAC")/IPA = 40/40/20 (mass ratio) were mixed and dispersed with an Eiger mill for 15 minutes to obtain a gravure printing ink (N-1).

(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 producing the gravure printing ink (N-1) described in Example N-1, in the same manner as in Example N-1, except that the pigment composition (A-1) was changed as shown in Table 17. , gravure printing inks (N-2) to (N-30) and gravure printing inks (N-33) to (N-35) were obtained.

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

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

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

(Base material)
・ OPP: biaxially oriented polypropylene (OPP) film with corona discharge treatment on one side (Futamura Chemical Co., Ltd. FOR thickness 25 μm)
・ CPP: Unstretched polypropylene (CPP) film without corona treatment (CP-S manufactured by Mitsui Chemicals Tohcello, thickness 30 μm)

(Examples NP-2 to NP-32, Comparative Examples NP-1 to NP-3)
Prints NP2-1 to NP35-1 ( OPP), NP2-2 to NP35-2 (CPP).

<11-3> Evaluation of gravure printing ink The following evaluation was performed using

(Stability of ink over time)
Each of the gravure printing inks (N-1) to (N-35) was 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 to evaluate the viscosity change from before storage. The viscosity was measured at 25°C with a Zahn cup No. A run time of 4 seconds was performed. All inks had a viscosity within the range of 40 to 500 cps (25° C.) measured by a Brookfield viscometer before storage. If it is "5", "4", "3" and "2" in the following evaluation criteria, it is a practical level.

(Evaluation criteria)
5. Viscosity change less than 2 seconds 4 . Viscosity change is 2 seconds or more and less than 3 seconds 3. Viscosity change is 3 seconds or more and less than 4 seconds 2. Viscosity change is 4 seconds or more and less than 5 seconds 1. Viscosity change over 5 seconds

(Transparency evaluation)
Gravure printing inks (N-1) to (N-35) were color-developed on color-developing paper with a black band, and then compared with Comparative Example N-1 to see the degree of transmission on the black band. It was judged.

(Evaluation criteria)
5. 3. Extremely transparent; Transparent 3. Equivalent 2. Opaque 1. extremely opaque

(Scratch resistance)
Using printed matter NP1-1 to NP35-1 (OPP) and printed matter NP1-2 to NP35-2 (CPP), the surface of the printed layer was rubbed with a fingernail at three locations to evaluate the degree of damage to the printed layer. If it is "5" and "4" in the following evaluation criteria, it is a practical level.

(Evaluation criteria)
5. 4. No damage to the printed layer. 3. The printed layer is not scratched, but a slight nail mark remains. 2. The printed layer is scratched and the surface of the printed layer is slightly scooped out. The printed layer is scratched, and the base material is slightly visible. The printed layer is scratched and the base material is clearly visible

(Adhesiveness)
After 3 hours of printing, the printed matter NP1-1 to NP35-1 (OPP) and the printed matter NP1-2 to NP35-2 (CPP) were pasted with an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) with a width of 12 mm on the printed surface, The state of appearance of the printed surface when this was rapidly peeled off was visually evaluated. In addition, the judgment criteria were as follows. If it is "5", "4", and "3" in the following evaluation criteria, it is a practical level.

(Evaluation criteria)
5. 4. No peeling of the ink film on the printed surface. 3. The peeling area of the ink film is 1% or more and less than 3%. 2. The peeling area of the ink film is 3% or more and less than 5%. 1. The peeling area of the ink film is 5% or more and less than 20%. 20% or more of the ink film is peeled off

From the results of Tables 17 and 18, the azo compound (1) of the present invention and C.I. I. Pigment compositions containing Pigment Yellow 180 gave good results in stability over time, transparency, scratch resistance, and adhesion.

<12> Ink set and evaluation of its characteristics An ink set was prepared using the obtained pigment composition, and its characteristics were evaluated.

(Synthesis Example 6) Polyurethane resin solution [PU2]
54.719 parts of a polyester diol having 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 placed under a nitrogen stream. After reacting at 85° C. for 3 hours, 10.0 parts of n-propyl acetate was added and cooled to obtain 78.718 parts of a solvent solution of terminal isocyanate prepolymer. Next, 1.031 parts of isophoronediamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate and 19.6 parts of isopropyl alcohol were mixed, and a solvent solution 78 of the resulting isocyanate-terminated prepolymer was added. 718 parts were gradually added at room temperature and then reacted at 50°C for 1 hour to obtain a polyurethane resin solution [PU2] having a non-volatile content of 30%, a weight average molecular weight of 60,000 and an amine value of 3.0 mgKOH/g. .

(Synthesis Example 7) Polyurethane resin solution [PU3]
PPA (poly(propylene glycol) adipate diol with a number average molecular weight of 2,000) was added to 161 ml while introducing nitrogen gas in a reactor equipped with a reflux condenser, dropping funnel, gas inlet tube, stirrer, and thermometer. 9 parts, 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 form terminal isocyanate groups. A resin solution of a urethane prepolymer having 13.6 parts of 2-(2-aminoethylamino)ethanol (AEA), 0.5 parts of ethanolamine (MEA), and 350 parts of isopropyl alcohol (IPA) are added to the resulting isocyanate-terminated urethane prepolymer resin solution. The mixture was added dropwise at room temperature over 60 minutes, and further reacted at 70° C. for 3 hours. Furthermore, 150 parts of MEK is used to adjust the non-volatile content, and a polyurethane resin having a non-volatile content of 30%, a weight average molecular weight of 35,000, Mw / Mn = 3.0, an acid value of 35.0 mg KOH / g, and a hydroxyl value of 25.7 mg KOH / g A solution [PU3] was obtained.

(Synthesis Example 8) Aluminum phthalocyanine 1250 parts of n-amyl alcohol, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to a reactor and mixed with stirring. To this, 266 parts of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136° C. for 5 hours. The reaction solution cooled to 30° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine represented by the following chemical formula (15).

chemical formula (15)

Next, 1500 parts of concentrated sulfuric acid was added to the reaction vessel, and then 100 parts of the above chloroaluminum phthalocyanine was added in an ice bath, and the mixture was stirred at 25°C for 4 hours. Subsequently, this sulfuric acid solution is poured into 9,000 parts of cold water at 3° C., and the precipitate formed is filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water in that order, dried, and treated with 98 parts of the following. An aluminum phthalocyanine represented by the chemical formula (11) was obtained.

chemical formula (11)

(Synthesis Example 9) Titanyl phthalocyanine 1280 parts of 1-hexanol, 320 parts of quinoline, 320 parts of 1,3-diiminoisoindoline and 206.3 parts of tetrabutyl orthotitanate were added to a reaction vessel and mixed with stirring. The temperature was raised to 155° C. and refluxed for 8 hours. The n-butanol generated from the system was recovered so as not to return to the system. To the reaction solution cooled to 60° C. with stirring, 1000 parts of methanol was added, the slurry was filtered, washed with 1000 parts of methanol, 500 parts of N-methylpyrrolidone and 1000 parts of methanol in that order, dried and dried to 250 parts. A titanyl phthalocyanine crude represented by the following chemical formula (12) was obtained.

chemical formula (12)

Next, 1,500 parts of concentrated sulfuric acid was added to the reaction vessel, and then 100 parts of the titanyl phthalocyanine crude was added 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 precipitate formed was filtered, washed with water, washed with a 1% aqueous sodium hydroxide solution, and washed with water in this order to obtain a cake. Then, 1000 parts of diethylene glycol and the resulting cake were added to the reactor and stirred to form a slurry, which was then stirred at 120° C. for 3 hours. The slurry cooled to 60° C. was filtered, washed with 5000 parts of water and dried to obtain 87 parts of titanyl phthalocyanine.

<12-1> Production of gravure printing ink (Example PY-1)
7.0 parts of the pigment composition (A-1), 34.5 parts of the polyurethane resin solution [PU2], 20 parts of N-propyl acetate, and 5 parts of isopropyl alcohol were stirred and mixed, and after kneading with a sand mill, the polyurethane resin solution was obtained. 20 parts of [PU2], 11 parts of N-propyl acetate and 3 parts of isopropyl alcohol were added to obtain a yellow ink [PY-1].

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

The pigments used in making the inks are shown in Table 20.

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

<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], Each of the magenta inks [PM-1] to [PM-10] was placed in a sealed container and stored at 40° C. for 14 days. After that, the viscosity was measured and evaluated by comparing the change in viscosity with that before storage. The viscosity was measured at 25°C with a Zahn cup No. A run time of 4 seconds was performed. All inks had a viscosity within the range of 40 to 500 cps (25° C.) measured by a Brookfield viscometer before storage. The results are shown in Tables 21-2 and 21-3.

(Evaluation criteria)
○: Viscosity change less than 2 seconds (good)
△: Viscosity change is 2 seconds or more and less than 5 seconds (practical)
×: Viscosity change for 5 seconds or more (defective)

(2) Evaluation of ink set (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 1-97. The obtained ink set was evaluated for trapping property and gamut by the following methods. The results are shown in Tables 21-2 and 21-3.

[Trapping property]
(cyan ink/yellow ink)
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 overprinted 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 printed matter (initial evaluation of trapping properties).
The printing conditions were a temperature of 25° C., a humidity of 60%, a printing speed of 100 m/min, and a printing distance of 4000 m. The cyan ink uses a Helio 175-line gradation plate (plate compression, 75% solid pattern and 100% to 3% gradation pattern), and the yellow ink uses a Helio 175-line gradation plate (plate type elongate, 75% solid pattern and 100% to 100%). 3% gradation pattern) was used.
Cyan ink and yellow ink were each placed in a sealed container, stored at 40° C. for 14 days, diluted and printed in the same manner as above to obtain a printed matter (evaluation of trapping property over time).

(Yellow ink/Magenta ink)
Each of the yellow ink and the magenta ink was diluted with the mixed solvent 1 so as to have a viscosity of 16 seconds (25° C., Zahn cup No. 3).
Yellow and magenta were overprinted 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 printed material (initial evaluation of trapping properties).
The printing conditions were a temperature of 25° C., a humidity of 60%, a printing speed of 100 m/min, and a printing distance of 4000 m. Yellow ink uses a Helio 175-line gradation plate (plate elongate, 75% solid pattern and 100% to 3% gradation pattern), and magenta ink uses a Helio 175-line gradation plate (plate elongate, 75% solid pattern and 100% to 3%). % gradation pattern) was used.
In addition, the yellow ink and the magenta ink were each placed in an airtight container and stored at 40° C. for 14 days, then diluted and printed in the same manner as above to obtain a printed matter (evaluation of trapping property over time).

The gradation overprinted portion of the resulting printed material was observed for trapping properties using a microscope (VHX-5000) manufactured by Keyence Corporation, and evaluated according to the following criteria.

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

[Gamut evaluation]
(Initial evaluation)
Cyan ink, magenta ink, and yellow ink were diluted with the mixed solvent 1 so that the viscosity was 16 seconds (25° C., Zahn cup No. 3). Using each diluted ink, print in the order of cyan, magenta, and yellow, and print the single-color solid area (cyan, magenta, yellow) and the single-color solid overprint area (cyan x magenta, cyan x yellow, yellow x magenta). A printed matter was obtained. The printing conditions are shown below.

(Printing conditions)
Printing press: Fuji Kikai 5-color machine Cyan plate: Helio 175 L/inch, Stylus angle 120°, Elongate Magenta plate: Helio 175 L/inch, Stylus angle 120°, Compress Yellow plate: Helio 175 L/inch, Stylus angle 120°, Compress Printing speed: 150 m/min Substrate: Corona-treated biaxially oriented polypropylene (OPP) film (Pylen P-2161 manufactured by Toyobo Co., Ltd., 20 μm)
Drying temperature: 50°C

The density values of the single-color solid portions (yellow, magenta, and cyan) of the printed matter were measured using Gretag Macbeth D196. In addition, using SpectroEye manufactured by gretagmacbeth as a measuring instrument, the single-color solid area and the overprinted area were measured under the conditions of D50 light source, 2-degree observation field, white background (using a standard white plate), and no filters.
In a two-dimensional space with a* as the horizontal axis and b* as the vertical axis, there are a total of 6 single-color solid areas (yellow, magenta, cyan) and single-color solid overlapping areas (cyan x magenta, cyan x yellow, yellow x magenta). The a* vs. b* values of the color were plotted to create a hexagon and determine the area. The area ratio was obtained when the area of Comparative Example PS-1 used as a reference was taken as 100%, and the area ratio was evaluated according to the following criteria. Note that - indicates that the item is not evaluated.

(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% (cannot be used)

(Evaluation over time)
Cyan ink, magenta ink, and yellow ink were each put in a sealed container, stored at 40° C. for 14 days, diluted and printed in the same manner as in the initial evaluation to obtain a printed material.

Colorimetric measurements were performed on the resulting prints in the same manner as in the initial evaluation described above.
In a two-dimensional space with a* as the horizontal axis and b* as the vertical axis, there are a total of 6 single-color solid areas (yellow, magenta, cyan) and single-color solid overlapping areas (cyan x magenta, cyan x yellow, yellow x magenta). A hexagon plotting the a* vs. b* values of the color was created. The area ratio obtained by dividing the area in the evaluation over time of each example/comparative example by the area in the initial evaluation was obtained, and the area ratio was evaluated according to the following criteria. - indicates unevaluated.

(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% (defective)

From the results in Tables 21-2 and 21-3, the gravure printing ink set of the present invention had a gamut area ratio equal to or higher than that of the conventional ink set, and had good color reproducibility. . In addition, the viscosity stability over time of the yellow ink was improved, and the storage stability as an ink set was good. In addition, the trapping property and color reproducibility (gamut) of each color were evaluated to be good over time, and the storage stability as an ink set was good.

On the other hand, in Comparative Examples PS-1 to PS-16, the viscosity stability of the yellow ink over time was poor, and the trapping properties and color reproducibility (gamut) of each color were also poor in the evaluation over time. The stability is poor and the problem of the present application cannot be solved.

<12-3> Manufacture of packaging materials

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

[Production of Releasable Adhesive]
(Preparation of laminate adhesive solution [1])
A four-necked separable flask was charged with 82 parts of terephthalic acid, 682 parts of isophthalic acid, 236 parts of adipic acid, 236 parts of ethylene glycol, 525 parts of neopentyl glycol, and 405 parts of 1,6-hexanediol. An esterification reaction was carried out. After a predetermined amount of water was distilled off, the pressure was gradually reduced to 1 mmHg or less, and the deglycol reaction was carried out at 240 to 260° C. for 5 hours. After that, 2 parts of isophorone diisocyanate was gradually added, and reaction was carried out at 150° C. for about 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 reacted at 180° C. for about 2 hours. Then, it was diluted with ethyl acetate to a non-volatile content of 50% to obtain a partially acid-modified polyester polyol solution having 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 an ethyl acetate solution of HDI biuret with a non-volatile content of 95% were mixed, and ethyl acetate was added to obtain a laminate adhesive solution [1] having a non-volatile content of 30%.

[Manufacture of packaging materials]
(Example PP-1) Packaging material 1
Cyan ink [PC-1], magenta ink [PM-1], and yellow ink [PY-1] were diluted with the mixed solvent 1 so that the viscosity was 16 seconds (25° C., Zahn cup No. 3). bottom.
Using each diluted ink, a gravure calibration five-color machine equipped with a gravure plate with a plate depth of 20 μm, black ink (Rio Alpha R92 ink (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.)), and an ink set 101 was used to prepare a corona-treated oriented polypropylene film (OPP base material) having a thickness of 20 μm. , black ink, cyan ink [PC-1], magenta ink [PM-1], yellow ink [PY-1], and white ink are printed in this order, and dried at 50°C in each unit. , "OPP substrate/black, cyan, magenta, yellow or white printed layer".
Next, a urethane-based laminate adhesive (TM320/CAT13B manufactured by Toyo-Morton Co., Ltd., non-volatile content 30% ethyl acetate solution) was applied onto the printed layer of the resulting printed material so that the coating amount after drying was 2.0 g/m ² . After coating and drying, an unstretched polyethylene (PE) film with a thickness of 50 μm is laminated on the adhesive layer, and the composition is "OPP base material / 5-color overprint layer / adhesive layer / PE base material". A packaging material 1 was obtained.

(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 set shown in Tables 22-1 and 22-2.

(Example PP-101) Packaging material 101
The above clear ink [1] was diluted with an EA/IPA mixed solvent (mass ratio 70/30) so that the viscosity was 15 seconds (25° C., Zahn cup No. 3).
Cyan ink [PC-1], magenta ink [PM-1], and yellow ink [PY-1] were diluted with the mixed solvent 1 so that the viscosity was 16 seconds (25° C., Zahn cup No. 3). bottom.
Using each diluted ink, a gravure calibration 5-color machine equipped with a gravure plate with a plate depth of 20 μm, clear ink [1], cyan ink [PC-1], magenta ink [PM-1], and yellow ink [ PY-1], clear ink [1], cyan ink [PC-1], magenta ink [PM-1], and yellow ink were applied to a corona-treated oriented polypropylene film having a thickness of 20 μm. [PY-1] is overprinted in order, and each unit is dried at 50 ° C., and has a configuration of "OPP base material / release layer (clear ink) / cyan, magenta or yellow printed layer". , a printed material containing a layer having releasability was obtained.
Next, the laminate adhesive solution [1] is applied on the printed layer of the obtained printed matter using a dry laminator, and the line speed is 40 m / min, and the aluminized unstretched polypropylene (VQCPP) film having a thickness of 25 μm is applied. A packaging material 101 having a configuration of "OPP base material/printing layer having releasability/three-color overprint layer/adhesive layer having releasability/VQCPP base material" and having a release layer. Obtained.

(Examples PP-102 to PP-181) Packaging materials 102 to 181
Packaging materials 102 to 181 having a release layer were prepared 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 set shown in Tables 23-1 and 23-2. got

A packaging material could be made using the gravure printing ink set of the present invention.

<12-4> Production of water-based inkjet ink (Example QY-1)
(Preparation of aqueous coloring composition for inkjet (hereinafter "water-based coloring composition for IJ") [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 (manufactured by BASF Japan, Joncryl 61J): 16.4 parts Surfactant (manufactured by 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 coloring composition for IJ [QY-1].

(Preparation of water-based inkjet ink (hereinafter “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 (manufactured by BASF Japan, water-soluble resin), Chemipearl W400S (Mitsui Chemicals Co., Ltd. Polyolefin aqueous dispersion) 1.25 parts, Surfynol DF110D (manufactured by Nissin Chemical Industry Co., Ltd., antifoaming agent) 0.5 parts, BYK-348 (manufactured by BYK Chemie Japan, silicone surfactant) 1 part, 0.1 part of triethanolamine, 0.15 part of Proxel GXL (manufactured by Lonza, antiseptic), and 35.2 parts of ion-exchanged water were mixed with a high speed mixer and filtered through a 0.5 μm membrane filter. to obtain a water-based IJ ink [QY-1].

(Examples QY-2 to QY-32, Production Examples QY-1 to QY-3, QC-1 to QC-3, QM-1 to QM-6)
(Aqueous coloring compositions for IJ [QY-2] to [QY-35], [QC-1] to [QC-3], [QM-1] to [QM-6], and aqueous IJ ink [QY- 2] to [QY-35], [QC-1] to [QC-3], [QM-1] to [QM-6] Preparation)
Table 24 shows in the same manner as in Example QY-1 except that 19.0 parts of the pigment composition (A-1) of Production Example QY-1 was changed to the pigment shown in Table 24 and the amount shown in Table 24. Aqueous coloring compositions for IJ [QY-2] to [QY-35], [QC-1] to [QC-3], [QM-1] to [QM-6], and aqueous IJ ink [QY-2 ] to [QY-35], [QC-1] to [QC-3], [QM-1] to [QM-6] were obtained.

The pigments used in making the inks are shown in Table 25.

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

(Evaluation criteria for viscosity stability)
4: 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.

(2) Evaluation of ink set [Examples QS-1 to QS-49, Comparative Examples QS-1 to QS-10]
Each of the resulting water-based IJ inks were combined as described in Table 26-1 to form ink sets 301-359. The gamut of the obtained ink set was evaluated by the following method. The results are shown in Table 26-2.

[Gamut evaluation]
(Initial evaluation)
A line-pass type inkjet printer using an inkjet head ("KJ4B series" manufactured by Kyocera Corporation) with a resolution of 600 dpi in the width direction and a maximum ejection frequency of 30 kHz was used to print yellow, magenta, and cyan inks of each ink set. ^The head is filled and a color chart image (X-rite profilemaker chart image "TC3 .5 CQYK i1_i0") was printed to prepare a print for evaluation.

The color chart portion of the obtained evaluation print is measured using a spectrophotometer (i1 i0 Pro manufactured by X-rite) and a colorimetric tool (MeasurementTool and profilemaker manufactured by X-rite), L*a*b* We plotted the color reproduction area in the color space. The measurement conditions were a light source of D50, a field of view of 2 degrees, and measurement optics of 45/0 degrees. The area was determined from each obtained plot. The area ratio when the area of Comparative Example QS-1 used as a reference was taken as 100% was obtained, and the area ratio was evaluated according to the following criteria.

(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% (cannot be used)

(Evaluation over time)
Each water-based IJ ink was placed in a sealed container, stored at 50° C. for 4 weeks, and then printed in the same manner as in the initial evaluation to prepare a print for evaluation. The obtained printed matter was colorimetrically measured in the same manner as in the initial evaluation, and the area was obtained from each obtained plot. The area ratio obtained by dividing the area in the evaluation over time of each example/comparative example by the area in the initial evaluation was obtained, and the area ratio was evaluated according to the following criteria.

(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% (defective)

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. In addition, the viscosity stability over time of the yellow ink was improved, and the storage stability as an ink set was good. Furthermore, the color reproducibility (gamut) was also evaluated as good over time, and the storage stability as an ink set was good.

On the other hand, in Comparative Examples QS-1 to QS-10, the viscosity stability of the yellow ink over time was poor, and the color reproducibility (gamut) was also poor in the evaluation over time, resulting in poor storage stability as an ink set. The problem of the present application cannot be solved.

Claims (14)

C. I. A pigment composition containing Pigment Yellow 180 and an azo compound represented by the following formula (1).
formula (1)

[In the formula, R ₁ represents —NR ₂ R ₃ or —OR ₄ , and R ₂ to R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. ] C. I. 2. The pigment composition according to claim 1, wherein the content of the azo compound represented by formula (1) is 0.1 to 30 parts by mass with respect to 100 parts by mass of Pigment Yellow 180. 3. The pigment composition according to claim ₁ , wherein said R1 is an amino group or a hydroxyl group. A coloring composition comprising the pigment composition according to any one of claims 1 to 3 and a dispersing medium. A molding composition comprising the coloring composition of claim 4 . A toner comprising the coloring composition of claim 4 . A paint comprising the coloring composition according to claim 4 . A printing ink comprising the coloring composition according to claim 4 . An ink set including at least a yellow ink, a cyan ink, and a magenta ink,
An ink set, wherein the yellow ink is an ink containing the coloring composition according to claim 4 . A gravure printing ink set comprising at least a yellow ink, a cyan ink, and a magenta ink,
A gravure printing ink set, wherein the yellow ink is an ink comprising the coloring composition according to claim 4 . 11. The gravure printing ink set of claim 10, further comprising clear ink. A printed article comprising a substrate and a printed layer formed from the gravure printing ink set of claim 10. A printed article comprising a substrate, a printing layer formed from the gravure printing ink set of claim 11, and a release layer formed from a clear ink. A packaging material comprising the printed matter according to claim 12 or 13.