Pigment compositions, coloring compositions, paints, inks, ink sets, printed matter, and packaging materials

Abstract

The present application provides a pigment composition containing isoindoline compounds, which is excellent in dispersibility, weather resistance, and heat resistance, has good storage stability, and can form an image or the like having high chroma, the pigment composition containing an isoindoline compound represented by the following formula (1) and an isoindoline compound represented by the following formula (2). In addition, a colored composition, a paint, an ink, an ink set, a printed matter, and a packaging material using the pigment composition are provided.

Description

Technical Field

[0001] This disclosure relates to pigment compositions comprising isoindoline compounds. Furthermore, this disclosure relates to coloring compositions, coatings, inks, ink groups, printed materials, and packaging materials. Background Technology

[0002] Pigments are primarily used as colorants in applications such as plastics, toners, coatings, and printing inks. Pigments are broadly classified into inorganic and organic pigments. Compared to inorganic pigments, organic pigments generally offer superior color vibrancy and tinting strength, but tend to have poorer weather resistance and heat resistance. Examples of known organic pigments include azo pigments, quinoline pigments, isoindoline pigments, isoindoline ketone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, and quinacridone pigments.

[0003] In recent years, from the perspective of reducing environmental impact and ensuring safety and hygiene, the demand for organic pigments and colorants free of aromatic primary amines and heavy metals has been increasing. Azo pigments are the main type of organic pigment used, ranging from yellow to red. Azo pigments sometimes contain aromatic primary amines from the raw materials used or produced through decomposition caused by light or heat. Therefore, in recent years, from the perspective of environmental suitability and safety and hygiene, isoindoline pigments free of aromatic primary amines, such as CI Pigment Yellow 185, CI Pigment Yellow 139, and CI Pigment Red 260, have attracted attention.

[0004] For example, Patent Document 1 discloses an isoindoline pigment for use in coloring plastics. Additionally, Patent Document 2 discloses a dispersion for inkjet inks comprising water, a dispersant, and the isoindoline pigment.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Publication No. 2009-543917

[0008] Patent Document 2: Japanese Patent Application Publication No. 10-140066 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, conventional pigment compositions containing isoindoline compounds are difficult to disperse and have poor dispersion stability. In addition, coloring compositions containing isoindoline compounds lack sufficient weather resistance and heat resistance.

[0011] The purpose of this invention is to provide a pigment composition containing isoindoline compounds that exhibits excellent dispersibility and storage stability, as well as high weather resistance and heat resistance.

[0012] Methods for solving problems

[0013] As one embodiment of the present invention, the pigment composition comprises an isoindoline compound represented by formula (1) and an isoindoline compound represented by formula (2).

[0014] [Chemistry 1]

[0015]

[0016] In the formula, R1 represents a substituted alkyl group, R2 and R3 each independently represent a hydrogen atom, a substituted alkyl group, or an aryl group, and A represents the group represented by formula (3), formula (4), or formula (5).

[0017] [Chemistry 2]

[0018]

[0019] In the formula, X represents -O- or -NH-, and R4 represents substituted alkyl or aryl groups.

[0020] R5 and R6 each independently represent a hydrogen atom or a substituted alkyl group, while R7 represents a hydrogen atom.

[0021] R8~R 11 Each can independently represent a hydrogen atom, a halogen atom, or a substituted alkyl, alkoxy, aryl, or aryloxy group.

[0022] The disclosures in this application are related to the subject matter described in Japanese Patent Application No. 2021-127080 filed on August 3, 2021 and Japanese Patent Application No. 2022-066765 filed on April 14, 2022, all of which are incorporated herein by reference.

[0023] Invention Effects

[0024] According to the present invention, pigment compositions containing isoindoline compounds can be provided, exhibiting excellent dispersibility and storage stability, as well as high weather resistance and heat resistance. Additionally, ink groups, printed materials, and packaging materials containing yellow inks can also be provided. Detailed Implementation

[0025] First, the terms used in this specification are defined. When expressed as "(meth)acryloyl", "(meth)acrylate", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, they refer to "acryloyl and / or methacryloyl", "acrylate and / or methacrylate", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. Additionally, "CI" refers to the Pigment Index (CI).

[0026] In this specification, "Mw" is the weight-average molecular weight of polystyrene determined by gel permeation chromatography (GPC), and "Mn" is the number-average molecular weight of polystyrene determined by GPC. The amine value is the number of milligrams (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize the amino groups contained in 1g of resin. The acid value and hydroxyl value can be determined according to JIS K0070. The glass transition temperature (Tg) can be determined using a differential scanning calorimeter.

[0027] They can be determined using the methods described in the [Example] section.

[0028] Pigment Composition

[0029] As one embodiment of the present invention, the pigment composition comprises an isoindoline compound represented by formula (1) and an isoindoline compound represented by formula (2).

[0030] The pigment composition of this embodiment, by comprising two isoindoline compounds as described above, can improve the dispersibility, weather resistance, heat resistance, and storage stability that were previously desired to be improved with isoindoline compounds. The pigment composition of this embodiment can be used in a wide range of applications requiring coloring, such as molded articles, toners, coatings, printing inks, and inkjet inks.

[0031] [Isoindolin compound (1)] and [Isoindolin compound (2)]

[0032] Hereinafter, the isoindoline compound represented by formula (1) will be referred to as isoindoline compound (1), and the isoindoline compound represented by formula (2) will be referred to as isoindoline compound (2).

[0033] [Chemistry 3]

[0034]

[0035] In formula (1), R1 represents an alkyl group that can be substituted.

[0036] In formula (2), R2 and R3 each independently represent a hydrogen atom, an alkyl group that can be substituted, or an aryl group.

[0037] A represents the group represented by formula (3), formula (4), or formula (5).

[0038] [Chemistry 4]

[0039]

[0040] In formula (3), X represents -O- or -NH-, and R4 represents an alkyl or aryl group that can be substituted.

[0041] In formulas (4) and (5), R5 and R6 represent hydrogen atoms or alkyl groups that can be substituted, and R7 represents hydrogen atoms.

[0042] In equation (5), R8~R 11 Each can independently represent a hydrogen atom, a halogen atom, or a substituted alkyl, alkoxy, aryl, or aryloxy group.

[0043] The pigment composition, by containing isoindoline compound (1) and isoindoline compound (2), exhibits excellent weather resistance and heat resistance, and is capable of forming images with high chroma. Furthermore, in aqueous dispersion, it is possible to produce dispersions with excellent long-term stability and dispersibility.

[0044] The reason for this is speculated to be that the hydrogen atoms bonded to nitrogen atoms in isoindoline compound (1) form hydrogen bonds with oxygen atoms in isoindoline compound (2). It is speculated that, as mentioned above, hydrogen bonds are formed moderately between molecules, thus improving weather resistance and heat resistance.

[0045] In the case of isoindoline compound (2) monomer, the pigment particles become larger due to the very strong hydrogen bonds originating from the barbituric acid structure. However, by including isoindoline compound (1), the excess hydrogen bonds can be mitigated, thereby inhibiting crystal growth and suppressing pigment particle enlargement. In addition, when formulating pigment compositions, isoindoline compound (1) exhibits weak color development as a monomer, but by utilizing the intermolecular interaction with isoindoline compound (2), the hue of isoindoline compound (2) can be maintained without degradation. It is speculated that the combination of these factors can result in images with higher chroma, etc.

[0046] The reason why the pigment composition can be used to produce an aqueous dispersion with excellent long-term stability and dispersibility is speculated as follows. The isoindoline compound (2) has a very high hydrophilicity due to its barbituric acid residues, and therefore has a higher affinity for water than the dispersant and cannot adsorb the dispersant. However, if it is used in combination with the isoindoline compound (1), the hydrophilicity of the isoindoline compound (2) can be mitigated, the dispersant can be adsorbed, and thus an aqueous dispersion can be formed.

[0047] In one embodiment, the content of isoindoline compound (1) in 100% by mass of the pigment composition is preferably 0.01 to 30% by mass, more preferably 0.05 to 10% by mass.

[0048] In one embodiment, the content of isoindoline compound (2) in 100% by mass of the pigment composition is preferably 70 to 99.99% by mass, more preferably 90 to 99.95% by mass.

[0049] In one embodiment, the content of isoindoline compound (1) in a total of 100% by mass of isoindoline compound (1) and isoindoline compound (2) is preferably 0.01 to 30% by mass, more preferably 0.05 to 10% by mass.

[0050] In one embodiment, the mass ratio of isoindoline compound (1) to isoindoline compound (2) is preferably (1) / (2) = 1 / 9999 to 3 / 7, more preferably 1 / 1999 to 1 / 4, and even more preferably 1 / 999 to 1 / 19.

[0051] In one embodiment, in formula (1) above, the alkyl group (-R) in R1 preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 4, and even more preferably an alkyl group with 1 or 2 carbon atoms.

[0052] Alkyl groups can be any of the following: straight-chain structure, branched-chain structure, monocyclic structure, or condensed polycyclic structure.

[0053] Alkyl groups, for example, include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, 2-ethylhexyl, 2-hexyldodecyl, sec-butyl, tert-butyl, sec-pentyl, tert-pentyl, tert-octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl group, or 4-decylcyclohexyl, etc.

[0054] At least one hydrogen atom of the aforementioned alkyl group may be replaced by a halogen atom, hydroxyl group, alkoxy group, carboxyl group, ester group, sulfonyl group, thioalkyl group, aminosulfonyl group, amino group, alkylamino group, amide group, or other substituents. Furthermore, multiple substituents may be present, and the substituents may further have additional substituents. For example, the aforementioned alkylamino and amide substituents may further have hydroxyl groups or other substituents. It should be noted that the substituents are not limited to those described above.

[0055] The aforementioned alkyl group can have a structure in which two or more alkyl groups (one of which is an alkylene group) are bonded together via a linking group. Specific examples of linking groups include ester bonds (-COO-), ether bonds (-O-), and thioether bonds (-S-). That is, in this specification, the alkyl group can be, for example, a group represented by "-R'-OR" (R' represents the atomic group obtained by removing one hydrogen atom from the aforementioned alkyl group). Specific examples include -C2H4-O-C2H5.

[0056] In equation (2) above, the number of carbon atoms of the alkyl groups (-R) in R2 and R3 is the same as that of the alkyl group in R1.

[0057] In formula (2), the aryl (-Ar) groups in R2 and R3 are atomic groups obtained by removing one hydrogen atom from an aromatic hydrocarbon. The number of carbon atoms is preferably 6 to 30, more preferably 6 to 20.

[0058] Examples of the aryl groups mentioned above include: phenyl, tolyl, biphenyl, terphenyl, tetraphenyl, cyclopentadienyl, indole, naphthyl, binatyl, ternatyl, tetranatyl, azulel, cycloheptatrienyl, biphenylene, dicyclopentadienylphenyl, fluoranthyl, phenanthrenel, phenanthrenel, benzonatyl, fluorenyl, anthracel, bianthrenel, teranethracel, tetraanethracel, anthraquinonel, phenanthrene, triphenylene, pyrene, etc. The group includes phenyl, tetraphenyl, pleiadenyl, picenyl, peryl, pentaphenyl, pentaphenylenyl, tetraphenylenyl, hexaphenyl, hexacenyl, rubicenyl, coronenyl, trinaphthyl, heptaphenyl, pinanthryl, or ovophenyl, etc. Phenyl and tolyl are preferred among these.

[0059] At least one hydrogen atom of the aryl group can be replaced by other substituents such as halogen atom, hydroxyl group, alkoxy group, carboxyl group, ester group, sulfonyl group, thioalkyl group, aminosulfonyl group, amino group, alkylamino group, and amide group. Furthermore, it can have multiple substituents. It should be noted that the substituents are not limited to those described above.

[0060] In the above formula (3), X represents -O- or -NH-, preferably -NH-.

[0061] In formula (3) above, the number of carbon atoms of the alkyl group (-R) in R4 is the same as that of the alkyl group in R1. In addition, the aryl group (-Ar) in R4 in formula (3) above is the same as that of the aryl groups in R2 and R3.

[0062] In equation (4) above, the number of carbon atoms of the alkyl groups (-R) in R5 and R6 is the same as that of the alkyl group in R1.

[0063] In equation (5), R8~R 11 The halogen atom in it is not particularly limited; for example, fluorine, chlorine, bromine, or iodine atoms can be listed.

[0064] In equation (5), R8~R 11 The alkyl group (-R) in R1 has the same number of carbon atoms as the alkyl group in R1.

[0065] In one embodiment, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.

[0066] In equation (5), R8~R 11 The alkoxy group in the figure is a group (-OR) formed by the bonding of an oxygen atom with the above-mentioned alkyl group (-R).

[0067] In equation (5), R8~R 11 The aryl (-Ar) in R2 and R3 are the same.

[0068] In equation (5), R8~R 11 The aryloxy group is a group (-OAr) formed by bonding an oxygen atom to the aforementioned aryl group (-Ar). In one embodiment, the aryloxy group is preferably a phenoxy group.

[0069] In one embodiment, in equation (5), R8~R 11 Each of the following groups is selected independently: free hydrogen atoms, alkyl groups with 1 to 6 carbon atoms, fluoroalkyl groups with 1 to 6 carbon atoms, alkoxy groups (alkyl groups with 1 to 6 carbon atoms), phenyl groups, and phenoxy groups.

[0070] Isoindoline compound (1) and isoindoline compound (2) can be used alone or in combination of two or more.

[0071] The manufacture of a pigment composition comprising isoindoline compound (1) and isoindoline compound (2) can be exemplified by methods for obtaining the pigment composition, such as:

[0072] (A) A method for synthesizing two substances in one step (cosynthesis).

[0073] (B) A method of mixing isoindoline compound (1) and isoindoline compound (2) during the preparation of the dispersion.

[0074] (C) A method for pigmenting isoindoline compound (1) and isoindoline compound (2) together using acid gelatinization, acid slurry method, dry grinding method, solvent grinding method, solvent salt grinding method, or solvent method (heat treatment in high-boiling-point solvents such as alcohols or aromatic solvents), or a method combining (A) to (C). Among these, the pigment composition is preferably prepared by (A) co-synthesis, (C) pigmenting isoindoline compound (1) and isoindoline compound (2) together using acid gelatinization or solvent salt grinding, or by combining (A) and (C).

[0075] [Method for manufacturing isoindoline compound (1)]

[0076] The isoindoline compound (1) can be synthesized by known synthetic methods. For example, as shown in Scheme 1 below, phthalonitrile represented by formula (6) (hereinafter referred to as compound (6)) or 1,3-diiminoisoindoline represented by formula (7) (hereinafter referred to as compound (7)) can be used as starting materials for synthesis.

[0077] The synthesis method will now be described using a specific example of isoindoline compound (1). In the following description, the numbers in each formula will be referred to as the compound numbers.

[0078] The isoindoline compound (1) can be manufactured according to Scheme 1 below.

[0079] (Option 1)

[0080] [Chemistry 5]

[0081]

[0082] Scheme 1 may include: a first step (S1) in which compound (6) reacts with a base in a solvent to obtain compound (7); a second step (S2) in which compound (7) reacts with compound (8) in the presence of water; and a third step (S3) in which compound (9) reacts with compound (10) in the presence of water. The reaction temperature of each step in Scheme 1 is preferably around 10 to 100°C.

[0083] The solvents used in the first step (S1) may include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and ethylene glycol; ethers such as ethylene glycol ethers and tetrahydrofuran; and acyclic or cyclic amides such as formamide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among these, acyclic or cyclic amides are preferred, and tetrahydrofuran and formamide are more preferred.

[0084] The solvent can be used alone or in combination of two or more. The amount of solvent used is preferably 5 to 15 times, more preferably 5 to 10 times, relative to 100 parts by mass of compound (6).

[0085] Examples of alkalis include: alkali metal hydroxides, alkali metals such as lithium, sodium, or potassium, alkali metal carbonates, alkali metal amides, alkali metal hydrides; and alkali metal or alkaline earth metal alkoxides derived from primary, secondary, or tertiary aliphatic alcohols having 1 to 10 carbon atoms. Among these, sodium hydroxide or potassium carbonate are preferred.

[0086] Alternatively, as another synthetic method, isoindoline compound (1) can be manufactured, for example, according to scheme 2 below.

[0087] (Option 2)

[0088] [Chemistry 6]

[0089]

[0090] Scheme 2 may include: a second step (S2) in which compound (7) reacts with compound (8) in the presence of an aqueous ammonia solution; followed by a third step (S3) in which compound (9) reacts with compound (10) in the presence of water.

[0091] In the second step (S2) of Scheme 2, when using a 28% ammonia solution, the amount of ammonia solution used is preferably 1 to 20 times the amount of 100 parts by mass of compound (7), more preferably 1 to 5 times the amount of compound (7).

[0092] Additionally, Scheme 2 may also include a step of continuously reacting compound (7) with compound (8) and compound (9) with compound (10) in the presence of water.

[0093] In any case, the reaction temperature of each step in Scheme 2 is preferably around 10 to 100°C.

[0094] [Method for manufacturing isoindoline compound (2)]

[0095] The isoindoline compound (2) can be synthesized by known methods. For example, the methods described in Japanese Patent Application Publication No. 55-157657, Japanese Patent Application Publication No. 56-081369, Japanese Patent Application Publication No. 57-035565, Japanese Patent Application Publication No. 03-153761, Japanese Patent Application Publication No. 54-091532, and Japanese Patent Application Publication No. 60-058469 are examples.

[0096] The isoindoline compound (1) and the isoindoline compound (2) are preferably processed into fine particles by micronization, either separately or together, and more preferably by micronization together. Examples of micronization processes include solubilization (e.g., acid gelatinization), solvent salt milling, and dry milling. The particle size of the micronized pigment, measured by average primary particle size, is preferably 20–300 nm, and more preferably 50–150 nm. It should be noted that, depending on the conditions of solvent salt milling, the pigment particle size may increase.

[0097] The following illustrates a method for manufacturing a pigment composition comprising isoindoline compound (1) and isoindoline compound (2).

[0098] (A) Methods for synthesizing two or more substances in a single step (cosynthesis method),

[0099] (B) A method of mixing isoindoline compound (1) and isoindoline compound (2) during the preparation of the dispersion.

[0100] (C) Methods for pigmenting isoindoline compound (1) and isoindoline compound (2) together using methods such as acid gelatinization, acid slurry method, dry grinding method, salt grinding method, solvent salt grinding method, and solvent method (heat treatment in high-boiling-point solvents such as alcohols and aromatic solvents).

[0101] (D) A method that combines the methods (A) to (C) above.

[0102] The preferred methods are (A) co-synthesis, (C) pigmentation of isoindoline compound (1) and isoindoline compound (2) together using acid gelatinization or solvent salt grinding, and (D) combination of (A) and (C).

[0103] Micronization using acid gelatinization involves dissolving the pigment in concentrated sulfuric acid and mixing it with a large amount of excess water, causing fine pigment particles to precipitate out. This is then followed by repeated filtration, washing with water, and drying to obtain the micronized pigment particles.

[0104] Acid gelatinization can be exemplified by dissolving the pigment in 5 to 30 times its mass of 98% sulfuric acid, and then mixing the resulting sulfuric acid solution with 5 to 30 times its mass of water. The temperature at which the pigment is dissolved in the sulfuric acid is acceptable as long as no decomposition or sulfonation reactions occur. The preferred dissolution temperature is, for example, 3 to 40°C. Furthermore, there are no particular limitations on the method of mixing the sulfuric acid solution of the pigment with water, or on the mixing temperature. In most cases, there is a tendency that the pigment particles precipitated become finer when mixed at lower temperatures compared to higher temperatures. Therefore, the preferred mixing temperature is, for example, 0°C to 60°C. The water used for mixing can be any industrially usable water. From the viewpoint of reducing the temperature rise during precipitation, pre-cooled water is preferred.

[0105] There are no particular limitations on the method of mixing sulfuric acid solution and water; any method can be used as long as the pigment can be completely precipitated. For example, pigment particles can be precipitated by injecting sulfuric acid solution into pre-prepared ice water or by continuously injecting it into running water using a device such as a suction device.

[0106] The slurry obtained by the above method is filtered and washed to remove acidic components, then dried and pulverized to obtain pigments adjusted to the desired particle size. When filtering the slurry, it can be filtered directly from a mixture of sulfuric acid solution and water. If the slurry has poor filterability, it can be heated and stirred before filtration. Alternatively, the slurry can be neutralized with an alkali before filtration.

[0107] Micronization using solvent salt grinding involves vigorously kneading a clay-like mixture containing at least three components—pigment, water-soluble inorganic salt, and water-soluble solvent—using a kneader or similar apparatus. The kneaded mixture is then placed in water and stirred using various mixers to create a slurry. The resulting slurry is then filtered to remove the water-soluble inorganic salt and solvent. Repeating this slurrying, filtering, and washing process yields a micronized pigment.

[0108] Water-soluble inorganic salts such as sodium chloride, sodium sulfate, and potassium chloride can be used. These inorganic salts are used in amounts at least one times the weight of the pigment, preferably less than 20 times the weight. When the amount of inorganic salt is set at least one times the weight, the pigment can be sufficiently finely refined. Furthermore, when the amount of inorganic salt is set at less than 20 times the weight, it is not necessary to expend considerable labor to remove the water-soluble inorganic salts and water-soluble solvents after mixing. In addition, the amount of pigment that can be processed in one step is not reduced, making it preferable from a productivity point of view. It should be noted that industrially used sodium chloride is sometimes produced from natural sources such as seawater. Therefore, the sodium chloride used may contain approximately 0.01 to 30% by weight of impurities such as potassium chloride, calcium chloride, magnesium chloride, calcium sulfate, and magnesium sulfate.

[0109] The micronization of pigments often involves heating during mixing. Therefore, from a safety perspective, water-soluble solvents with boiling points of around 120–250°C are preferred. Specific examples of water-soluble solvents include 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentoxy)ethanol, 2-(hexoxy)ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 2-ethyl-1,3-hexanediol, diacetate, triacetate, and low molecular weight polypropylene glycol, etc.

[0110] Fine refining using dry grinding can be achieved by dry grinding pigments using various pulverizers. In this method, grinding occurs through the collision or friction of the grinding media against each other. There are no particular limitations on the apparatus used for dry grinding. Specific examples include ball mills, grinding mills, and vibratory mills, which are dry grinding devices containing grinding media such as beads. When using these devices for dry grinding, the internal pressure of the grinding container can be reduced, or inactive gases such as nitrogen can be filled, as needed. Additionally, solvent salt grinding and solvent stirring can be performed after dry grinding.

[0111] [Pigment derivatives]

[0112] Pigment compositions may contain pigment derivatives.

[0113] Pigment derivatives are known compounds that contain acidic, basic, or neutral groups in the residues of organic pigments. Examples of pigment derivatives include: compounds with acidic substituents such as sulfonyl, carboxyl, or phosphate groups and their amine salts; compounds with basic substituents such as sulfonamide groups or tertiary amino groups at the terminal end; and compounds with neutral substituents such as phenyl or phthalimide alkyl groups.

[0114] Organic pigments, for example, include: diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, and diketopyrrolopyrrole pigments. Azide pigments, violet ketone pigments, perylene pigments, thiazide-indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzimidazol, isoindoline pigments, isoindolineone pigments, quinoline ketone pigments, naphthol pigments, reduction pigments, metal complex pigments, azo, diazo, polyazo, and other azo pigments, etc.

[0115] Specifically, the following are examples of well-known pigment derivatives recorded in bulletins and other publications.

[0116] Examples of diketopyrrolopyrrole pigment derivatives include: Japanese Patent Application Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Application Publication No. 2017-156397.

[0117] Examples of phthalocyanine pigment derivatives include: Japanese Patent Application Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Application Publication No. 2017-165820, and Japanese Patent No. 5753266.

[0118] Examples of anthraquinone pigment derivatives include: Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 09-272812, Japanese Patent Application Publication No. 10-245501, Japanese Patent Application Publication No. 10-265697, Japanese Patent Application Publication No. 2007-079094, and brochure No. WO2009 / 025325;

[0119] Examples of quinacridone pigment derivatives include: Japanese Patent Application Publication No. 48-54128, Japanese Patent Application Publication No. 03-9961, and Japanese Patent Application Publication No. 2000-273383.

[0120] As two Azide pigment derivatives, for example: Japanese Patent Application Publication No. 2011-162662;

[0121] Examples of thiazide-indigo pigment derivatives include: Japanese Patent Application Publication No. 2007-314785;

[0122] Examples of triazine pigment derivatives include: Japanese Patent Application Publication No. 61-246261, Japanese Patent Application Publication No. 11-199796, Japanese Patent Application Publication No. 2003-165922, Japanese Patent Application Publication No. 2003-168208, Japanese Patent Application Publication No. 2004-217842, and Japanese Patent Application Publication No. 2007-314681.

[0123] Examples of benzo[i]indole pigment derivatives include: Japanese Patent Application Publication No. 2009-57478;

[0124] Examples of quinoline pigment derivatives include: Japanese Patent Application Publication No. 2003-167112, Japanese Patent Application Publication No. 2006-291194, Japanese Patent Application Publication No. 2008-31281, and Japanese Patent Application Publication No. 2012-226110.

[0125] Examples of naphthol-based pigment derivatives include: Japanese Patent Application Publication No. 2012-208329 and Japanese Patent Application Publication No. 2014-5439.

[0126] Examples of azo pigment derivatives include: Japanese Patent Application Publication No. 2001-172520 and Japanese Patent Application Publication No. 2012-172092.

[0127] Examples of acidic substituents include: Japanese Patent Application Publication No. 2004-307854;

[0128] Examples of basic substituents include: Japanese Patent Application Publication No. 2002-201377, Japanese Patent Application Publication No. 2003-171594, Japanese Patent Application Publication No. 2005-181383, and Japanese Patent Application Publication No. 2005-213404.

[0129] It should be noted that in these documents, pigment derivatives are sometimes referred to as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds. However, compounds with substituents such as acidic groups, basic groups, and neutral groups in the aforementioned organic pigment residues have the same meaning as pigment derivatives.

[0130] Pigment derivatives can be used alone or in combination of two or more.

[0131] <II> Coloring Composition

[0132] As one embodiment of the present invention, the coloring composition preferably comprises the above-described pigment composition and a dispersion medium.

[0133] [Dispersion medium]

[0134] Dispersion media can include resins and solvents. Resins can include resin-type dispersants and adhesive resins. Solvents can include water and organic solvents. It should be noted that low-molecular-weight dispersants such as surfactants can be used as needed.

[0135] Examples of resin-based dispersants include: JONCRYL 67, JONCRYL 678, JONCRYL 586, JONCRYL 611, JONCRYL 683, JONCRYL 690, JONCRYL 57J, JONCRYL 60J, JONCRYL 61J, JONCRYL 62J, JONCRYL 63J, JONCRYL HPD-96J, JONCRYL 501J, and JONCRYL PDX-6102B, all manufactured by BASF Japan.

[0136] BYK Chemicals manufactures the following DISPERBYK products: 180, 187, 190, 191, 194, 2010, 2015, 2090, 2091, 2095, and 2155.

[0137] SOLSPERSE24000, SOLSPERSE32000, SOLSPERSE39000, and SOLSPERSE41000 manufactured by Lubrizol Corporation of Japan.

[0138] SMA1000H, SMA1440H, SMA2000H, SMA3000H, SMA17352H, etc. are manufactured by Sadoma.

[0139] Adhesive resins can be, for example, polyolefin resins, polyester resins, styrene copolymers, acrylic resins, and modified resins thereof. Specifically, examples include polyethylene (HDPE), linear low-density polyethylene (L-LDPE), low-density polyethylene (LDPE), and other polyethylene; polyolefin resins such as polypropylene; polyester resins such as polyethylene terephthalate; styrene-chlorostyrene copolymers, styrene-vinyl toluene copolymers, styrene-vinyl naphthalene copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, and styrene-isoprene copolymers. Styrene copolymers such as olefin copolymers and styrene-acrylonitrile-indene copolymers; acrylic resins such as acrylic resins and methacrylic resins; polyvinyl chloride, phenolic resins, naturally modified phenolic resins, natural resin-modified maleic acid resins, polyvinyl acetate, silicone resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, nitrocellulose resins, polyamide resins, epoxy resins, xylene resins, polyvinyl butyral resins, polyvinyl acetal resins, cellulose ester resins, alkyd resins, rosin-based resins, ketone resins, cyclized rubber, chlorinated polyolefin resins, terpene resins, coumarone-indene resins, alkyd resins, amino resins, petroleum resins, and their modified resins, etc.

[0140] Organic solvents can be classified into water-soluble solvents and non-water-soluble solvents.

[0141] Examples of water-soluble solvents include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol. Examples of non-water-soluble solvents include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0142] The materials constituting the coloring composition can be used individually or in combination of two or more.

[0143] (Water-based coloring composition)

[0144] In one embodiment of the present invention, the coloring composition is preferably used as an aqueous coloring composition.

[0145] The aqueous coloring composition preferably comprises a pigment composition, a resin as a dispersion medium, water, and a water-soluble solvent.

[0146] The resin used as the dispersion medium is preferably a resin-type dispersant. Examples of resins include: styrene-(meth)acrylic acid copolymers, (meth)acrylic acid-(meth)acrylic acid (meth)acrylate copolymers, styrene-(meth)acrylic acid-(meth)acrylate alkyl ester copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylate alkyl ester copolymers, poly(meth)acrylic acid, vinylnaphthalene-(meth)acrylic acid copolymers, styrene-maleic acid copolymers, maleic acid-maleic anhydride copolymers, α-olefin-maleic acid (anhydride) copolymers, α-olefin-maleic acid (anhydride)-polyalkylene glycol allyl ether copolymers, vinylnaphthalene-maleic acid copolymers, polyester-modified (meth)acrylic acid polymers, and their salts.

[0147] In addition, resins can be classified into various forms, such as water-soluble resins and emulsions (water-insoluble resins).

[0148] The water is preferably ion-exchanged water or distilled water.

[0149] Examples of water-soluble solvents include: 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentoxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc.

[0150] Aqueous coloring compositions may contain surfactants. Examples of surfactants include anionic surfactants and nonionic surfactants.

[0151] Examples of anionic surfactants include: fatty acid salts, alkyl sulfates, alkyl aryl sulfonates, alkyl naphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, naphthalene sulfonic acid formaldehyde condensates, and polyoxyethylene alkyl phosphates.

[0152] Examples of nonionic surfactants include: polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, dehydrated sorbitol fatty acid esters, polyoxyethylene dehydrated sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid ester polyoxyethylene alkylamines, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters, etc.

[0153] The surfactant content in the aqueous coloring composition is preferably 0.3 to 20% by mass, more preferably 1 to 10% by mass.

[0154] The surfactant content is preferably 5 to 200 parts by weight relative to 100 parts by weight of the pigment composition, more preferably 25 to 100 parts by weight.

[0155] Aqueous coloring compositions may contain other additives. Other additives include: preservatives, pH adjusters, defoamers, wetting agents, etc.

[0156] Examples of preservatives include: sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, and amine salts of 1-benzisothiazolin-3-one.

[0157] The preservative content is preferably 0.1 to 2% by mass in 100% by mass of the aqueous coloring composition.

[0158] pH adjusters include, for example, various amines, inorganic bases, ammonia, and various buffer solutions.

[0159] Defoamers can be used to prevent foaming during the manufacture of water-based coloring compositions. Commercially available defoamers include, for example: SURFYNOL 104E, SURFYNOL 104H, SURFYNOL 104A, SURFYNOL 104BC, SURFYNOL 104DPM, SURFYNOL 104PA, SURFYNOL 104PG-50, SURFYNOL 420, SURFYNOL 440, SURFYNOL 465, SURFYNOL 485, and SURFYNOL PSA-336 (all manufactured by Nissin Chemical Industries, Ltd.). In addition, ADDITOLVXW6211, ADDITOL VXW4973, ADDITOL VXW6235, ADDITOL XW375, ADDITOL XW376, ADDITOLVXW6381, ADDITOL VXW6386, ADDITOL VXW6392, ADDITOL VXW6393, ADDITOL VXW6399, ADDITOL XW6544, etc. (all manufactured by Allnex Corporation).

[0160] Wetting agents are used to obtain a smooth film during printing or coating. Commercially available wetting agents include, for example: ADDITOL VXL6237N, ADDITOL XL260N, ADDITOL VXL6212, ADDITOL UVX7301 / 65, ADDITOL XW330, ADDITOL VXW6200, ADDITOL VXW6205, ADDITOL VXW6394, ADDITOL VXW6208, ADDITOL VXW6208 / 60, and ADDITOL VXW6374 (all manufactured by Allnex).

[0161] The materials used in the preparation of water-based coloring compositions can be used individually or in combination of two or more.

[0162] Aqueous coloring compositions can be prepared by dispersing materials such as pigment compositions, resins, water, and other additives as needed.

[0163] Examples of dispersers used in the above-mentioned dispersion processes include: horizontal sand mixers, vertical sand mixers, ring bead mills, grinding mills, microfluidizers, high-speed mixers, homogenizers, homogenizers, high-pressure homogenizers, ball mills, paint shakers, roller mills, mortar mills, ultrasonic dispersers, counter-collision high-pressure dispersers, and oblique collision high-pressure dispersers.

[0164] More specifically, when a resin-type dispersant, which is a water-soluble resin, is used as the resin described above, the method described in the examples below can be applied. That is, the aqueous coloring composition of the present invention can be obtained by mixing a pigment composition, a resin-type dispersant, water, etc., and then dispersing it using the above-described disperser.

[0165] Furthermore, when using a resin-type dispersant that is a water-insoluble resin as the aforementioned resin, an aqueous coloring composition can be obtained, for example, by dissolving the resin-type dispersant in an organic solvent capable of dissolving the water-insoluble resin, then mixing it with a pigment composition, and dispersing it using the aforementioned disperser. Then, after phase inversion emulsification with water, the organic solvent is removed by distillation.

[0166] On the other hand, from the perspective of particularly improving the dispersibility and dispersion stability of the pigment composition in the aqueous coloring composition, it is preferable to crosslink the resin-type dispersant on the surface of the pigment composition. In aqueous inkjet inks using a pigment composition crosslinked with such a surface-present resin-type dispersant (hereinafter also referred to as "crosslinked resin particles containing the pigment composition"), excellent redispersibility can be obtained. That is, after the aqueous inkjet ink dries and agglomerates / thickens, the pigment composition in the aforementioned aqueous inkjet ink can be redispersed by adding water. Therefore, for example, nozzle clogging and "ink shortage" during continuous printing can be suppressed. Furthermore, by coating the pigment composition with a crosslinked resin-type dispersant, improvements in weather resistance and pH resistance can also be achieved.

[0167] Methods for manufacturing aqueous coloring compositions comprising crosslinked resin particles containing the above-mentioned pigment composition may include, for example, the following four methods.

[0168] [[Method(i)]]

[0169] This is a method for manufacturing cross-linked resin particles containing a pigment composition through the following four steps.

[0170] • Step (i-1): A step of dispersing a pigment composition; a resin-type dispersant having crosslinking functional groups and carboxyl groups that are hydrophilized by being neutralized by an alkaline compound; and water.

[0171] • Step (i-2): An acidic compound is added to the dispersion of the pigment composition prepared in step (i-1) above to make the pH of the dispersion neutral or acidic, thereby causing the resin-type dispersant to precipitate and adhere to the surface of the pigment composition.

[0172] • Step (i-3): After step (i-2) above, a process is performed to neutralize the carboxyl groups in the resin-type dispersant using an alkaline compound (the alkaline compound may be the same as or different from the alkaline compound used in step (i-1)) and to redisperse the pigment composition with the resin-type dispersant fixed in water.

[0173] • Step (i-4): After step (i-3) above, the crosslinking functional groups in the resin-type dispersant react with the crosslinking agent to crosslink, thereby obtaining an aqueous coloring composition containing crosslinked resin particles of a pigment composition. It should be noted that the crosslinking agent can be added at the beginning of step (i-4) or at any stage of steps (i-1) to (i-3) above.

[0174] [[Method (ii)]]

[0175] The method is as follows: A resin-type dispersant having a self-crosslinking functional group and a carboxyl group, wherein the carboxyl group is neutralized by an alkaline compound and thus hydrophilized, is used as the resin-type dispersant. Otherwise, the pigment composition with the resin-type dispersant immobilized is redispersed in water in the same manner as in steps (i-1) to (i-3) described above. Then, the resin-type dispersant is self-crosslinked to obtain an aqueous coloring composition containing crosslinked resin particles of the pigment composition.

[0176] [[Method (iii)]]

[0177] This is a method for manufacturing cross-linked resin particles containing a pigment composition through the following two steps.

[0178] • Process (iii-1): The process of mixing pigments, carboxyl-containing resins, alkaline compounds, and water.

[0179] • Step (iii-2): After step (iii-1) above, a crosslinking agent is added to perform a crosslinking treatment to obtain an aqueous coloring composition containing crosslinked resin particles of a pigment composition.

[0180] [[Method (iv)]]

[0181] This is a method for manufacturing cross-linked resin particles containing a pigment composition through the following two steps.

[0182] • Process (iv-1): The process of mixing pigments, carboxyl-containing resins, and organic solvents.

[0183] • Step (iv-2): After step (iv-1) above, water is added and organic solvents are removed by vacuum distillation or other means.

[0184] • Step (iv-3): After step (iv-2) above, a crosslinking agent is added to perform a crosslinking treatment to obtain an aqueous coloring composition containing crosslinked resin particles of a pigment composition.

[0185] If the aqueous coloring composition obtained by the above method is subjected to heat treatment and post-treatment, the dispersion stability of isoindoline compound (1) and isoindoline compound (2) is improved. Heat treatment involves heating the aqueous coloring composition to 30-80°C and maintaining it for several hours to about a week. Post-treatment involves dispersing the aqueous coloring composition using an ultrasonic disperser, a collision-type beadless disperser, a high-speed mixer, a homogenizer, a high-pressure homogenizer, a high-shear mixer (Silverson mixer), a planetary mixer, a three-stage mixer, a kneader, an extruder, a horizontal sand mixer, a vertical sand mixer, or / and a ring bead mill, a paint shaker, a ball mill, a high-pressure disperser, a counter-collision disperser, or an oblique collision disperser.

[0186] It should be noted that pre-dispersion can be performed before the dispersion process without the use of water or water-soluble solvents. Equipment used in pre-dispersion includes, for example, kneaders, three-roll mills, and other mixing machines; non-volatile dispersers such as two-roll mills; and media-free dispersers such as MK mixers.

[0187] Examples of the coloring compositions in this embodiment include: Form 1, which comprises a pigment composition and a resin (e.g., a solvent-free coloring composition); Form 2, which comprises a pigment composition and an organic solvent (e.g., a solvent-based coloring composition); and Form 3, which comprises a pigment composition, a resin, and water, as detailed above (e.g., an aqueous coloring composition).

[0188] If the applications of each form are described, examples of Form 1 include molding compositions, toners, solvent-free (reactive energy radiation curable) printing inks, and solvent-free inkjet inks. Form 2 is a solvent-based coloring composition, including coatings, printing inks, and inkjet inks. Form 3 is an aqueous coloring composition, including water-based coatings, water-based printing inks, and water-based inkjet inks. In this specification, when the solvent contains water, it is described as "aqueous," but when the solvent is an "organic solvent," it is not specifically described as "solvent-based." It should be noted that the water is preferably ion-exchanged water or distilled water from which metal ions have been removed.

[0189] <III> Molding Composition

[0190] As one embodiment of the present invention, the molding composition contains a coloring composition (pigment composition, resin).

[0191] The molding composition preferably contains a thermoplastic resin as the resin. The molding composition containing the thermoplastic resin is preferably melt-blended and molded into the desired shape for use in making molded articles. For example, when the molding composition is melt-blended at 300°C, the presence of isoindoline compounds (1) and (2) with high heat resistance can suppress color changes. It should be noted that the resin is not limited to thermoplastic resins.

[0192] Examples of thermoplastic resins include homopolymers or copolymers using ethylene, propylene, butene, styrene, etc., as monomers. More specifically, examples include polyethylene resins such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), as well as polyolefin resins such as polypropylene and polybutene. Other useful examples 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. It should be noted that the number average molecular weight of the thermoplastic resin is preferably greater than 30,000 and less than 200,000.

[0193] The content of thermoplastic resin is preferably 10,000 to 10,000,000 parts by mass relative to a total of 100 parts by mass of isoindoline compound (1) and isoindoline compound (2), and more preferably 10,000 to 2,000,000 parts by mass.

[0194] The molding composition may contain wax. The wax may contain low molecular weight polyolefins. These are polymers of olefin monomers such as ethylene, propylene, and butene, and may also be block copolymers, random copolymers, or terpolymers. Specifically, they may be polymers of α-olefins such as low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP).

[0195] The number-average molecular weight of the wax is preferably 1,000 to 30,000, more preferably 2,000 to 25,000. Within this range, the wax will transfer to the surface of the molded body in a moderate manner, thus achieving an excellent balance between lubrication and exudation suppression.

[0196] The melting point of the wax is preferably 60–150°C, more preferably 70–140°C. By having the melting point within this range, the processability of the thermoplastic resin and wax during melt mixing becomes good.

[0197] It should be noted that the melt flow rate (MFR) of the wax, as determined according to JIS K-7210, is preferably greater than 100 g / 10 minutes.

[0198] The amount of wax incorporated is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of thermoplastic resin.

[0199] The molding composition may contain other additives. Other additives may be materials commonly used in the field of molded articles. Examples include antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and colorants other than isoindoline compounds (1) and (2).

[0200] The molding composition can be manufactured, for example, according to the composition ratio of the molded body. As another example of the molding composition, it can be manufactured as a masterbatch containing a high concentration of isoindoline compound (1) and isoindoline compound (2). In one embodiment, a masterbatch is preferred from the viewpoint that it is easy to uniformly disperse isoindoline compound (1) and isoindoline compound (2) in the molded body.

[0201] Regarding the masterbatch, it is preferable to melt-blend the thermoplastic resin and pigment composition, and then shape it into any shape in a manner that facilitates use in the next process. Next, the masterbatch and diluent resin (e.g., the thermoplastic resin used in the masterbatch) can be melt-blended to form a molded article of the desired shape. Examples of masterbatch shapes include granules, powder, and plates. It should be noted that, to prevent agglomeration of the pigment composition, it is preferable to first prepare a dispersion by melt-blending the pigment composition and wax, and then melt-blend it together with the thermoplastic resin to produce the masterbatch. The apparatus used in the dispersion is preferably, for example, a stirred mixer, a three-roll mill, etc.

[0202] When the molding resin composition is used as a masterbatch, it is preferable to combine 1 to 200 parts by weight of isoindoline compound (1) and isoindoline compound (2) in total, more preferably 5 to 100 parts by weight, relative to 100 parts by weight of the thermoplastic resin. The mass ratio of masterbatch (X) to diluted resin (Y) used as the base resin of the molded body is preferably X / Y = 1 / 1 to 1 / 100, more preferably 1 / 3 to 2 / 100. If it is set within this range, isoindoline compound (1) and isoindoline compound (2) can be easily and uniformly dispersed in the molded body, and good coloring can be easily obtained.

[0203] The diluent (Y) is preferably a thermoplastic resin used in the masterbatch. Other thermoplastic resins may also be used, provided that compatibility is not an issue.

[0204] For melt compounding, single-screw compounding extruders, twin-screw compounding extruders, and tandem twin-screw compounding extruders can be used. The melt compounding temperature varies depending on the type of thermoplastic resin, but is typically around 150–300°C.

[0205] Examples of uses for molding compositions include plastic molded bodies, sheets, films, etc.

[0206] <IV> Toners

[0207] As one embodiment of the present invention, the colorant contains a coloring composition (pigment composition, resin).

[0208] The resin used in the toner is preferably a thermoplastic resin known as a binder resin. Toners can be categorized as dry toners or wet toners, but dry toners are preferred. For example, a dry toner can be manufactured as follows: after melt-blending and cooling the pigment composition and binder resin, a pulverizing and grading process is performed. Next, a post-treatment process involving the addition of additives and mixing is carried out.

[0209] Examples of bonding resins include: styrene-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-(meth)acrylate copolymer, styrene-α-chloromethyl 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)acrylate resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, and petroleum-based resins, etc.

[0210] Among these, polyester resin and styrene copolymer are preferred, and polyester resin is more preferred. The pigment composition of this embodiment has particularly excellent compatibility with polyester resin, so that isoindoline compound (1) and isoindoline compound (2) can be uniformly and finely dispersed in the toner, thus obtaining a high-quality toner.

[0211] The weight-average molecular weight (Mw) of the polyester resin is preferably 5,000 or more, more preferably 10,000 to 1,000,000, and even more preferably 20,000 to 100,000. Using a polyester resin with a suitable Mw yields a toner with good resistance to offset and good low-temperature fixing properties.

[0212] The preferred acid value of the polyester resin is 10–60 mg KOH / g, more preferably 15–55 mg KOH / g. Using a polyester resin with a suitable acid value makes it easier to suppress the release of the release agent and reduces the likelihood of image density reduction under high humidity conditions.

[0213] The hydroxyl value of the polyester resin is preferably below 20 mg KOH / g, more preferably below 15 mg KOH / g. Using a polyester resin with a suitable hydroxyl value reduces image density less likely to occur in high-humidity environments. It should be noted that the lower limit of the aforementioned hydroxyl value is 0.1 mg KOH / g.

[0214] The glass transition temperature (Tg) of the polyester resin is preferably 50–70°C, more preferably 50–65°C. A suitable Tg can suppress the aggregation of the toner. It should be noted that Tg can be measured using a differential scanning calorimeter (DSC-6, manufactured by Shimadzu Corporation).

[0215] Toners can further contain charge control agents. Using charge control agents makes it easier to obtain toners with stable charge. Positive or negative charge control agents can be appropriately selected.

[0216] When the toner is positively charged, a positive charge control agent is used. Examples of positive charge control agents include: aniline black dyes, triphenylmethane dyes, organotin oxides, quaternary ammonium salt compounds, and styrene-acrylic polymers copolymerized with quaternary ammonium salts as functional groups and styrene-acrylic resins. Among these, quaternary ammonium salt compounds are preferred. Examples of quaternary ammonium salt compounds include: salts of quaternary ammonium salts with organic sulfonic acids or molybdic acid. Naphthalene sulfonic acid is preferred.

[0217] When the toner is negatively charged, a negative charge control agent is used. Examples of negative charge control agents include: metal complexes of monoazo dyes, styrene-acrylic polymers copolymerized with sulfonic acid as a functional group and styrene-acrylic resin, metal salt compounds of aromatic hydroxycarboxylic acids, metal complexes of aromatic hydroxycarboxylic acids, phenolic condensates, and phosphonium compounds. Preferably, the aromatic hydroxycarboxylic acid is salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid, or 3-phenylsalicylic acid. Furthermore, metals used in the metal salt compounds include zinc, calcium, magnesium, chromium, and aluminum.

[0218] Colorants may contain mold release agents. Examples of mold release agents include: hydrocarbon waxes such as polypropylene wax, polyethylene wax, and Fischer-Tropsch wax; synthetic ester waxes; and natural ester waxes such as carnauba wax and rice bran wax.

[0219] Toners can contain lubricants, flow agents, abrasives, conductivity enhancers, image peeling inhibitors, etc., as needed.

[0220] Examples of lubricants include polyvinylidene fluoride and zinc stearate. Examples of flow agents include silica, alumina, titanium dioxide, silica-alumina cooxide, and silica-titanium cooxide, as well as their hydrophobically treated derivatives, manufactured by dry or wet methods. Among these, silica, silica-alumina cooxide, and silica-titanium cooxide micropowders that have undergone hydrophobic treatment are preferred. Methods for hydrophobicating these micropowders include treatment using silicone oil or silane coupling agents such as tetramethyldisilazane, dimethyldichlorosilane, and dimethyldimethoxysilane.

[0221] Abrasives include silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, and abrasives made by hydrophobicating these materials. Conductivity-improving agents include tin oxide.

[0222] In addition, in this embodiment, the toner can be used as a one-component developer or a two-component developer. The two-component developer may further contain a carrier.

[0223] Examples of carriers include magnetic powders such as iron powder, ferrite powder, and nickel powder, as well as coated materials whose surfaces are coated with resins, etc. Examples of resins used to coat the carrier surface include styrene-(meth)acrylate copolymers, (meth)acrylate copolymers, fluorinated resins, silicone-containing resins, polyamide resins, ionomer resins, and polyphenylene sulfide resins. Among these, silicone-containing resins that produce less spent toner are preferred. The weight-average particle size of the carrier is preferably 30–100 μm.

[0224] The preferred mixing ratio (mass ratio) of toner and carrier in a two-component developer is toner:carrier = 1:100 to 30:100.

[0225] <V> Coatings

[0226] As one embodiment of the present invention, the coating contains a coloring composition (pigment composition, resin, solvent).

[0227] Examples of the aforementioned resins include thermosetting resins and thermoplastic resins. Thermosetting resins are preferably resins with a glass transition temperature of 10°C or higher. Examples of thermosetting resins include acrylic resins, polyesters, and polyurethanes. Furthermore, thermosetting resins preferably have functional groups capable of reacting with a curing agent. Examples of such functional groups include carboxyl groups and hydroxyl groups. Examples of curing agents include isocyanate curing agents, epoxy curing agents, aziridine curing agents, and amine curing agents.

[0228] Thermoplastic resins are preferably resins with a glass transition temperature of 30°C or higher. Examples of thermoplastic resins include nitrocellulose and polyester. It should be noted that thermosetting resins and thermoplastic resins can be used together.

[0229] Among the solvents mentioned above, non-water-soluble solvents include, for example, toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0230] Among the solvents mentioned above, water-soluble solvents include, for example, water, monohydric alcohols, dihydric alcohols, and ethylene glycol. Other water-soluble solvents include, for example, ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol. Additionally, water-dilutable monoethers derived from polyols can also be listed. Specific examples include methoxypropanol or methoxybutanol. Furthermore, water-dilutable ethylene glycol ethers such as butylethylene glycol or butyl diethylene glycol can also be listed. It should be noted that, as already explained, coatings containing water in their solvents are called water-based coatings.

[0231] Coatings may further contain known additives.

[0232] Examples of applications for coatings include coatings for metals and coatings for plastics.

[0233] <VI> Printing Inks

[0234] The printing ink according to one embodiment of the present invention contains a coloring composition. The forms of the contained coloring composition are as described above, for example: Form 1 containing a pigment composition and a resin; Form 2 containing a pigment composition and an organic solvent; and Form 3 containing a pigment composition, a resin, and water. Solvent-free (reactive energy ray curable) printing ink, (solvent-based) printing ink, and water-based printing ink can be obtained respectively.

[0235] Furthermore, the printing ink in this embodiment is an ink other than inkjet ink. Depending on the printing method, examples include offset printing ink, flexographic printing ink, gravure printing ink, screen printing ink, and color filter ink.

[0236] By combining classifications based on the form of the contained coloring composition and classifications based on the printing method, specific examples of printing inks in this embodiment can be listed, such as the following inks: (solvent-based) offset inks, (solvent-based) gravure inks, (solvent-based) flexographic inks, (solvent-based) screen printing inks, water-based gravure inks, water-based flexographic inks, active energy X-ray curable offset inks, active energy X-ray curable flexographic inks, active energy X-ray curable screen printing inks, etc.

[0237] There are no particular limitations on the manufacturing method (mixing method) of the ink. For example, the ink can be preferably manufactured by mixing using a roller mill, ball mill, pebble mill, grinder, or sand mixer.

[0238] There are no particular restrictions on the substrate for printing inks; known substrates can be used. Specifically, examples include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene, polystyrene-based resins such as AS resin and ABS resin, nylon, polyamide, polyvinyl chloride, polyvinylidene chloride, coated paper such as cellophane, art paper, coated paper, and cast-coated paper, uncoated paper such as high-grade paper, medium-grade paper, and newspaper paper, synthetic paper such as Yupo paper, aluminum, or film-like substrates composed of composites thereof. Additionally, vapor-deposited substrates, formed by depositing inorganic compounds such as silica, alumina, and aluminum onto polyethylene terephthalate or nylon films, can also be used. The substrate can be further coated with polyvinyl alcohol or similar materials on the vapor-deposited surface of the inorganic compound, or further surface-treated with corona treatment or other methods.

[0239] There are no particular restrictions on the methods used for printing printing inks; well-known methods can be used. Specifically, examples include roller coaters, bar coaters, blade coaters, wire bar coaters, doctor knives, spin coaters, screen coaters, gravure coaters, offset gravure coaters, and flexographic coaters.

[0240] In addition, heating can be applied during printing as needed.

[0241] Printing inks may contain known adhesive resins, solvents, glossing materials, additives, etc., depending on their various uses.

[0242] Examples of such adhesive resins include: rosin resin, rosin-modified phenolic resin, polyurethane, nitrocellulose, acrylic resin, styrene-acrylic resin, petroleum resin, etc.

[0243] Examples of non-water-soluble solvents include: toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butanol, and aliphatic hydrocarbons.

[0244] Water-soluble solvents include: ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerol. Additionally, water-dilutable monoethers derived from polyols can also be listed. Examples include methoxypropanol or methoxybutanol. Furthermore, water-dilutable glycol ethers such as butylethylene glycol or butyl diethylene glycol can also be listed.

[0245] Brightening materials are particles with an average thickness of 0.5–10 μm and an average particle size of 5–50 μm, and examples include 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 metal oxides such as titanium dioxide.

[0246] The content of glossy material in 100% by mass of printing ink is preferably 0.1% to 10% by mass. In addition, other coloring pigments and various additives commonly used in this art can be added as needed.

[0247] Printing inks may further contain known additives. Examples of additives include: pigment derivatives, dispersants, wetting agents, adhesive aids, leveling agents, defoamers, antistatic agents, trapping agents, antiblocking agents, hydrocarbon waxes, isocyanate-based curing agents, silane coupling agents, etc.

[0248] As examples of printing inks, embodiments of gravure inks, water-based flexographic inks, and active energy radiation-curable inks will be described in detail, but the present invention is not limited to the following embodiments.

[0249] <Gravure Ink>

[0250] As one embodiment of the present invention, the gravure ink preferably contains a coloring composition (pigment composition and solvent), and more preferably further contains a binder resin.

[0251] The adhesive resin used in the gravure ink of this embodiment is preferably a polyurethane resin. It should be noted that the polyurethane resin includes polyurethane urea resin.

[0252] [Polyurethane resin]

[0253] Examples of polyurethane resin synthesis include: (1) a two-step method, synthesizing a urethane prepolymer with isocyanate groups at the ends by reacting a polyol with a diisocyanate compound in an excess ratio of isocyanate groups. Then, the urethane prepolymer with isocyanate groups is reacted with the aforementioned chain extender and / or capping agent in a solvent to synthesize the prepolymer; (2) a one-step method, reacting polypropylene glycol, a polyol, a diisocyanate compound, and an amino chain extender and / or capping agent in a suitable solvent in a single reaction; etc.

[0254] Solvents used in the synthesis may include, for example, ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, isopropanol, and n-butanol; hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane; or mixtures thereof.

[0255] Among these methods, a two-step method is preferred from the viewpoint of obtaining a more uniform polyurethane resin. In the case of manufacturing polyurethane resin by a two-step method, the equivalence ratio (molar of isocyanate group / molar of amino group) of the isocyanate prepolymer to the amino groups of the chain extender and the capping agent is preferably 1 / 1.3 to 1 / 0.9. If the equivalence ratio of isocyanate group to amino group is 1 / 1.3 or higher, the amount of chain extender and / or capping agent remaining in an unreacted state is reduced, which can suppress yellowing of the polyurethane resin and post-printing odor. If the equivalence ratio of isocyanate group to amino group is 1 / 0.9 or lower, the molecular weight of the obtained polyurethane resin becomes appropriate, and a resin exhibiting suitable film strength after printing can be obtained.

[0256] The weight-average molecular weight of the polyurethane resin is preferably in the range of 15,000 to 100,000. If the weight-average molecular weight of the polyurethane resin is 15,000 or more, the ink has excellent anti-blocking properties, the strength of the printed film, and the oil resistance. If it is 100,000 or less, the viscosity of the obtained ink is within an appropriate range, and the gloss of the printed film is excellent.

[0257] Furthermore, from the viewpoint of printability and lamination strength, the aforementioned polyurethane resin preferably has an amine value. The amine value is preferably 0.5–20 mg KOH / g, more preferably 1–15 mg KOH / g.

[0258] In gravure inks, the content of binder resin is preferably 4 to 25% by mass, more preferably 6 to 20% by mass.

[0259] [Organic solvents]

[0260] Examples of organic solvents used in the gravure inks of this embodiment include: aromatic organic solvents such as toluene and xylene; ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester organic solvents such as ethyl acetate, n-propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; and ethylene glycol ether solvents such as ethylene glycol monopropyl ether and propylene glycol monomethyl ether. Preferably, two or more of these organic solvents are used in combination.

[0261] In gravure inks, a mixture of ester-based and alcohol-based organic solvents is preferred. The mass ratio of ester-based to alcohol-based organic solvents (mass of ester-based organic solvent: mass of alcohol-based organic solvent) is preferably 95:5 to 40:60, more preferably 90:10 to 50:50.

[0262] In gravure inks, the content of organic solvents is preferably 60-90% by mass, more preferably 70-85% by mass, based on the mass of the gravure ink.

[0263] From the viewpoint of preventing pigment sedimentation and ensuring proper dispersion, the viscosity of each color ink is preferably 10 mPa·s or higher; from the viewpoint of workability during ink manufacturing and printing, it is preferably 1,000 mPa·s or lower. It should be noted that the above viscosity values ​​were measured using a TOKIMEC Type B viscometer at 25°C.

[0264] [water]

[0265] The gravure ink of this embodiment may further contain water. By including a predetermined amount of water, the pigment dispersibility based on the polyurethane resin is improved, as are printability characteristics such as highlight transfer, haze properties, and overprinting properties.

[0266] The water content, based on the mass of the gravure ink, is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 4% by mass.

[0267] [Silica particles]

[0268] The gravure ink of this embodiment may further contain silica particles. By including silica particles, ink wetting / spreading is promoted during overprinting, overprinting performance is improved, and high-gloss transfer performance can also be maintained.

[0269] Silica particles can be any of the following: natural or synthetic products, crystalline or amorphous, hydrophobic or hydrophilic. There are dry and wet synthesis methods for silica particles. Known dry methods include combustion and electric arc methods, while known wet methods include sedimentation and gelation methods. Any of these methods can be used for synthesis. Furthermore, the silica particles can be hydrophilic silica with hydrophilic functional groups on the surface, or hydrophobic silica modified by altering the hydrophilic functional groups using alkylsilanes or the like to achieve hydrophobicity. Hydrophilic silica is preferred.

[0270] Commercially available products containing such silica particles include, for example, the NIPGEL series and NIPSIL series manufactured by Tosoh Silica, and the MIZUKASIL series manufactured by Mizusawa Chemical Co., Ltd.

[0271] To create an uneven surface on the ink layer, the average particle size of the silica particles is preferably 1–10 μm. More preferably, it is 1–8 μm, and even more preferably, it is 1–6 μm. The average particle size of the silica particles refers to the cumulative value of 50% (D) of the particle size distribution. 50 The particle size at that time can be determined using the Coulter counter method.

[0272] The specific surface area of ​​silica particles is preferably 50–600 m² / g using the BET method.2 / g. More preferably 100-450m 2 / g. The silica particles used in the gravure ink of this embodiment can be a combination of two or more silica particles with different average particle sizes or BET specific surface areas.

[0273] The content of silica particles is preferably 0.1 to 3% by mass based on the mass of the gravure ink, more preferably 0.2 to 2.5% by mass, even more preferably 0.2 to 2% by mass, and particularly preferably 0.2 to 1.5% by mass.

[0274] [Other Additives]

[0275] The gravure ink of this embodiment may contain extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, and other additives as needed.

[0276] <Water-based flexographic inks>

[0277] As one embodiment of the present invention, the water-based flexographic ink contains a coloring composition (pigment composition, resin, and water). Various substrates can be selected as the substrate type, and it is also suitable for non-permeable substrates other than ordinary printing paper. The water-based flexographic ink is also suitable for printing on coated paper and plastic films (including plastic sheets), for example.

[0278] The content of pigment composition in water-based flexographic inks is not particularly limited, but is preferably 10-30% by mass, more preferably 15-25% by mass.

[0279] The following describes the components contained in water-based flexographic inks and their synthesis methods as needed.

[0280] [Adhesive Resin]

[0281] Water-based flexographic inks preferably contain 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 chlorinated polyolefins. Preferably, at least a water-based urethane resin is included. The binder resin can be used alone or in combination of two or more.

[0282] "Waterborne carbamate resin"

[0283] Uraffinate resins are typically resins obtained by reacting a polyisocyanate having two or more isocyanate groups in one molecule with a hydroxyl-containing compound having two or more hydroxyl groups in one molecule. The aqueous urethane resin of this embodiment has the structure described below. As will be described later, this structure can be preferably introduced by appropriately selecting the structure and type of the hydroxyl-containing compound.

[0284] The number of urethane bonds (mmol / g) in the waterborne 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, it is preferably 2.2 to 3.0 mmol / g, and more preferably 2.3 to 2.9 mmol / g. This number of urethane bonds can be set to the desired range by appropriately adjusting the amount of hydroxyl-containing compound and polyisocyanate, as well as the reaction conditions.

[0285] The glass transition temperature (Tg) of the waterborne urethane resin is not particularly limited, but is preferably below -70°C, and more preferably between -70°C and -90°C. By having the Tg of the waterborne urethane resin below -70°C, the film-forming properties of the ink and the adhesion of the coating are improved.

[0286] The weight-average molecular weight (GPC determination, converted from standard polystyrene) of the waterborne urethane resin is not particularly limited, but is preferably 10,000 to 100,000, and more preferably 30,000 to 70,000.

[0287] The hydroxyl value (mgKOH / g) of the waterborne urethane resin is not particularly limited, but from the viewpoint of water resistance, it is preferably 0.0 to 3.0 mgKOH / g, and more preferably 0.0 to 2.0 mgKOH / g.

[0288] The waterborne urethane resin, based on the waterborne flexographic ink, preferably contains 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. On the other hand, the content of the waterborne urethane resin in the total mass of the waterborne flexographic ink is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less.

[0289] The content of hydrocarbon wax in water-based flexographic inks is preferably 0.5-7% by mass, more preferably 1-4% by mass.

[0290] Water-based flexographic inks preferably contain water-based solvents. Examples of water-based solvents include water and alcohols. Examples of alcohols include n-propanol and isopropanol.

[0291] The content of water-based solvent in water-based flexographic inks is preferably 40-60% by mass.

[0292] [Other ingredients]

[0293] Water-based flexographic inks may also contain known additives such as defoamers, thickeners, leveling agents, pigment dispersants, and UV absorbers, as needed. Furthermore, non-aqueous solvents other than alcohols (e.g., ketone solvents and ester solvents) may be included, provided they address the problem. The content of non-aqueous solvents in water-based flexographic inks is preferably 20% by mass or less, more preferably 10% by mass or less.

[0294] <Active Energy X-ray Curable Ink>

[0295] As one embodiment of the present invention, the active energy ray curable ink contains a coloring composition (pigment composition, resin), a polymerizable compound, and a photopolymerization initiator.

[0296] In addition to the pigment composition of this embodiment, known colorants may be used in any combination as needed without departing from the effects of the present invention in active energy ray curable inks.

[0297] Furthermore, the pigment composition of the present invention is preferably 5 to 30% by mass in the active energy ray curable ink, more preferably 10 to 25% by mass.

[0298] The following describes the components contained in, or that may be contained in, the active energy ray curable ink of this embodiment.

[0299] [Polymerizing compounds]

[0300] Polymerizable compounds are compounds that have one or more vinyl unsaturated bonds within their molecules. As polymerizable compounds, they contain monomers and oligomers.

[0301] (monomer)

[0302] The monomer has polymerizable groups such as (meth)acryloyl, allyl, vinyl, and vinyl ether groups within its molecule. From the perspective of curability, the monomer preferably includes monomers having either (meth)acryloyl or vinyl groups. More preferably, the monomer includes monomers having three or more but less than six (meth)acryloyl groups within its molecule, and even more preferably, monomers having six (meth)acryloyl groups within its molecule.

[0303] Specific examples of monomers containing a (meth)acryloyl group include: 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxyethyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecanyl (meth)acrylate, 3,3,5-trimethylcyclohexanol (methyl)acrylate, etc. Monofunctional (meth)acrylate monomers with one (meth)acrylyl group, such as (meth)acrylate, (meth)cyclohexyl acrylate, (meth)isoborneol acrylate, (meth)norborneol acrylate, (meth)dicyclopentenyl (oxyethyl) acrylate, 1,4-cyclohexanediethanol (meth)acrylate, cyclic trimethylolpropane formaldehyde (meth)acrylate, (meth)benzyl acrylate, EO-modified (2)nonylphenol acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methacrylate, acrylmorpholine, etc.

[0304] 1,3-Butanediol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, 3-Methyl-1,5-pentanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,12-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, Hydroxypentanoic acid neopentyl glycol di(meth)acrylate Ester, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO modified (2) 1,6-hexanediol di(meth)acrylate, PO modified (2) neopentyl glycol di(meth)acrylate, (neopentyl glycol modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO modified (4) bisphenol A di(meth)acrylate, PO modified (4) bisphenol A di(meth)acrylate, cyclohexanediethanol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, dicyclopentyl di(meth)acrylate and other difunctional (meth)acrylate monomers with two (meth)acryloyl groups in the molecule;

[0305] 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 tri(2-acryloyloxyethyl)isocyanurate, ethoxylated isocyanurate tri(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate and other trifunctional (meth)acrylate monomers with three (meth)acryloyl groups in the molecule;

[0306] Pentaerythritol tetra(meth)acrylate, EO-modified (4) pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate and other 4-functional (meth)acrylate monomers with four acryloyl groups in the molecule;

[0307] Dipentaerythritol penta(meth)acrylate and other 5-functional (meth)acrylate monomers with five (meth)acryloyl groups in the molecule;

[0308] Dipentaerythritol hexa(meth)acrylate and other hexafunctional (meth)acrylate monomers with six (meth)acryloyl groups in their molecules.

[0309] Specific examples of monomers containing vinyl groups include N-vinyl-2-pyrrolidone and N-vinylcaprolactam.

[0310] (Oligomers)

[0311] Examples of oligomers include: aliphatic urethane (meth)acrylate oligomers, aromatic urethane (meth)acrylate oligomers, urethane (meth)acrylate oligomers, (meth)acrylate oligomers, polyester (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, etc. The oligomer preferably contains about 2 to 16 vinyl unsaturated bonds. Among these, urethane (meth)acrylate oligomers are preferred, and urethane (meth)acrylate oligomers with 6 to 12 (meth)acryloyl groups are more preferred.

[0312] The weight-average molecular weight (Mw) of the oligomer is preferably 400 to 10,000, more preferably 500 to 5,000, even more preferably 800 to 4,000, and even more preferably 1,000 to 2,000. Here, the "weight-average molecular weight (Mw)" can be obtained by conventional gel permeation chromatography (hereinafter referred to as GPC) as the equivalent molecular weight of polystyrene.

[0313] Specific examples of the aforementioned 6- to 12-functional urethane (meth)acrylate oligomers include EBECRYL1290 (6-functional, Mw 1,000), EBECRYL5129 (6-functional, Mw 800), EBECRYL8254 (6-functional, Mw 1,200), KRM8200 (6-functional, Mw 1,000), KRM8904 (9-functional, Mw 1,800), EBECRYL8602 (9-functional, Mw 2,000), KRM8452 (10-functional, Mw 1,200), EBECRYL225 (10-functional, Mw 1,200), and EBECRYL8415 (10-functional, Mw 1,200), all manufactured by Daicel Allnex Co., Ltd. In addition, examples include Miramer PU5000 (6-functional, Mw1,800), Miramer PU610 (6-functional, Mw1,800), Miramer PU6140 (6-functional, Mw1,500), Miramer MU9800 (9-functional, Mw3,500), and Miramer MU9500 (10-functional, Mw3,200) manufactured by Miwon Specialty Chemical Co., Ltd.

[0314] Polymer compounds can be used alone or in combination of two or more.

[0315] The content of polymeric compounds in the active energy radiation curable ink is preferably 25-90% by mass, more preferably 35-80% by mass.

[0316] (Polymerization initiator)

[0317] In one embodiment, the active energy ray curable ink contains a polymerization initiator. Preferably, the polymerization initiator is a free radical polymerization initiator, and more preferably, it contains a photopolymerization initiator. In this embodiment, the polymerization initiator is a compound that undergoes a chemical change to generate free radicals through the action of light or interaction with the electronically excited state of the sensitized pigment. From the viewpoint that polymerization can be initiated by exposure, a photoradical polymerization initiator is preferred.

[0318] In this embodiment, there are no particular limitations on the photoradical polymerization initiator, and known photoradical polymerization initiators can be used. Specific examples include benzophenone compounds, dialkoxyacetophenone compounds, α-hydroxyalkylphenyl ketone compounds, α-aminoalkylphenyl ketone compounds, acylphosphine oxide compounds, and thioxanthone compounds.

[0319] Examples of the aforementioned benzophenone compounds include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, and [4-(methylphenylthio)phenyl]-phenyl ketone.

[0320] Examples of the aforementioned diekoxyacetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

[0321] Examples of the above-mentioned α-hydroxyalkylphenyl ketone compounds include 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxymethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one.

[0322] Examples of the aforementioned α-aminoalkylphenyl ketone compounds include 2-methyl-1-[4-(methoxythio)-phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0323] Examples of the aforementioned acylphosphine oxide compounds include diphenyl acylphenyl phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.

[0324] Examples of the aforementioned thioxanthone compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

[0325] In this invention, the above-mentioned polymerization initiators can be used alone or in combination of two or more.

[0326] The content of polymerization initiator in the active energy radiation curable ink is preferably 0.5 to 20% by mass, more preferably 5 to 15% by mass.

[0327] [Dispersant]

[0328] In one embodiment, to improve pigment dispersion, the active energy ray curable ink preferably contains a dispersant. There are no particular limitations on the dispersant; known dispersants can be used.

[0329] Specific examples include polymeric dispersants whose main components are polyoxyethylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, and amine polymers. Among these, from the viewpoint of pigment dispersion stability, pigment dispersants containing basic functional groups and having a block or comb-like structure are preferred.

[0330] As commercially available products, they can be obtained from the AJISPER series (AJISPER PB821, PB822, PB824, etc.) manufactured by Ajinomoto Fine Chemicals Co., Ltd., the SOLSPERSE series (SOLSPERSE24000, SOLSPERSE32000, SOLSPERSE38500, SOLSPERSE39000, etc.) manufactured by Lubrizol Corporation, and the DISPERBYK series (BYK-162, BYK-168, BYK-183, etc.) manufactured by BYK Chemical Co., Ltd.

[0331] The content of the above-mentioned dispersant in the active energy ray curable ink is preferably 0.1 to 10% by mass.

[0332] [Polymerization initiator]

[0333] In one embodiment, the active energy ray curable ink may also contain a polymerization initiator. By containing a polymerization initiator, the curability can be further improved. Examples of polymerization initiators include triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and dibutylethanolamine.

[0334] The content of the above-mentioned polymerization initiator in the active energy radiation curable ink is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass.

[0335] [wax]

[0336] In one embodiment, to improve abrasion resistance, anti-blocking properties, smoothness, and scratch resistance, the active energy radiation curable ink preferably contains a wax. There are no particular limitations on the wax used; known waxes can be used. Examples include natural waxes and synthetic waxes. Examples of natural waxes include carnauba wax, wood wax, lanolin, lignite wax, paraffin wax, and microcrystalline wax. Examples of synthetic waxes include Fischer-Tropsch wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compounds.

[0337] From the perspective of balancing abrasion resistance, gloss, and ink buildup, the content of the aforementioned wax in active energy ray curable ink is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass.

[0338] [Adhesive Resin]

[0339] In one embodiment, the active energy ray curable ink may also contain a binder resin. By including a binder resin, the curing shrinkage of the coating film during curing is mitigated, substrate curling is suppressed, and adhesion to the substrate is further improved.

[0340] Examples of adhesive resins include polyvinyl chloride (PVC), poly(meth)acrylate, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, alkyd resin, rosin-modified alkyd resin, petroleum resin, urea resin, and synthetic rubbers such as butadiene-acrylonitrile copolymer. Among these, diallyl phthalate resin and polyester resin are preferred. Diallyl phthalate resin is more preferred.

[0341] The weight-average molecular weight of the adhesive resin is preferably 1,000 to 100,000. More preferably, it is 2,000 to 70,000.

[0342] The aforementioned adhesive resins can be used alone or in combination of two or more. Furthermore, from the viewpoint of curability, the content of the adhesive resin in the active energy ray curable ink is preferably 1 to 15% by mass, more preferably 1 to 5% by mass.

[0343] (polymerization inhibitor)

[0344] In one embodiment, the active energy ray curable ink may contain a polymerization inhibitor. Examples of polymerization inhibitors include 4-methoxyphenol, hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, phenothiazine, aluminum salts of N-nitrosophenylhydroxylamine, etc.

[0345] From the viewpoint of maintaining curability and improving the storage stability of active energy ray-curable inks, the content of the polymerization inhibitor is preferably 0.01 to 2% by mass relative to the total mass of the active energy ray-curable ink.

[0346] [Other ingredients]

[0347] In one embodiment, the active energy ray curable ink may contain extender pigments, leveling agents, antistatic agents, surfactants, defoamers, ultraviolet absorbers, antioxidants, etc., as needed, without reducing the effects brought about by the embodiments of the present invention.

[0348] It should be noted that the active energy radiation curable ink is preferably substantially water-free. "Substantially water-free" means that it is preferably less than 1% by mass relative to the total mass of the active energy radiation curable ink.

[0349] <VII> Inkjet ink

[0350] As one embodiment of the present invention, the inkjet ink preferably contains a pigment composition and a dispersion medium. Inkjet inks can be broadly classified into (solvent-based) inkjet inks, water-based inkjet inks, and solvent-free inkjet inks, depending on the presence or absence of a solvent and its type. In one embodiment, a water-based inkjet ink that provides good dispersibility of isoindoline compound (1) and isoindoline compound (2) is preferred. Hereinafter, the description will focus on water-based inkjet inks.

[0351] The pigment composition content is preferably 0.5 to 30% by mass in 100% by mass of the water-based inkjet ink, more preferably 1 to 15% by mass.

[0352] The resin used in water-based inkjet inks is important for achieving the ink's fixation properties on the printed object (substrate).

[0353] Examples of resin types include acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, and polyurethane resins. Additionally, resin forms include water-soluble resins and emulsion particles. Among these, emulsion particles are preferred. Emulsion particles can be single-component particles, core-shell particles, etc., and can be selected arbitrarily. Using emulsion particles makes it easier to achieve low viscosity in water-based inkjet inks, resulting in recordings with excellent water resistance. The resin can be used after neutralizing acidic functional groups with pH adjusters such as ammonia, various amines, and various inorganic bases, as needed.

[0354] The resin content is preferably 2-30% by mass of the non-volatile components in the inkjet ink, more preferably 3-20% by mass. A moderate resin content improves discharge stability and fixing properties.

[0355] Solvents include non-water-soluble solvents, water, and water-soluble solvents. Water-soluble solvents include glycol ethers and glycols. These solvents penetrate the substrate very quickly, including low-absorbency and non-absorbent substrates such as coated paper, art paper, vinyl chloride sheets, films, and fabrics. Therefore, drying during printing is fast, enabling accurate printing. Additionally, due to their high boiling points, they can also function as wetting agents.

[0356] Water-soluble solvents are important for achieving ink ejection stability by preventing the drying and curing of water-based inkjet inks in the nozzle portion of the printhead. Examples of water-soluble solvents include: ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketols, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidones, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone, etc.

[0357] The water-soluble solvent content, including water, is preferably 15-50% by mass in 100% by mass of the inkjet ink.

[0358] Inkjet inks may further contain additives. Examples of additives include: drying accelerators, penetrants, preservatives, chelating agents, pH adjusters, etc.

[0359] 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 isopropanol. The preferred content of the drying accelerator in 100% by mass of the water-based inkjet ink is 1-50% by mass.

[0360] When the substrate is a permeable raw material such as paper, a penetrant is used to promote ink penetration into the substrate and accelerate apparent drying. Besides water-soluble solvents, penetrants can also include surfactants such as polyethylene glycol monolaurate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, and sodium dioctyl sulfosuccinate. The preferred amount of penetrant used in water-based inkjet inks is 0.1% to 5% by mass. If an appropriate amount of penetrant is used, defects such as ink bleeding and ink seepage into the paper are less likely to occur.

[0361] Examples of preservatives include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, and amine salts of 1-benzisothiazolin-3-one. The amount of preservative used is preferably 0.05 to 1.0% by mass in 100% by mass of the water-based inkjet ink.

[0362] To capture metal ions contained in water-based inkjet inks and prevent the precipitation of insoluble substances from the nozzle or the ink, chelating agents can be used. Examples of chelating agents include ethylenediaminetetraacetic acid (EDTA), sodium salt of EDTA, diammonium salt of EDTA, and tetraammonium salt of EDTA. The amount of chelating agent used is preferably 0.005 to 0.5% by mass of 100% water-based inkjet ink.

[0363] pH adjusters include, for example, various amines, inorganic bases, ammonia, and various buffer solutions.

[0364] Inkjet inks are made by combining various materials. Examples of mixing methods include: blade mixers, various dispersers, emulsifiers, etc. The order of addition and mixing methods of the materials are arbitrary.

[0365] Inkjet inks are preferably manufactured by filtering or centrifuging after mixing to remove coarse particles. This results in good ejection characteristics from the inkjet printer. Filtration and centrifugation can be performed using known methods.

[0366] In one embodiment, the inkjet ink can be used with various inkjet methods. Examples of inkjet methods include: charge-controlled type, continuous jet type such as spray type, piezoelectric type, thermal type, electrostatic attraction type, and single-pass type used in commercial printing applications.

[0367] <VIII> Ink Group

[0368] As one embodiment of the present invention, the ink group is preferably an ink group that includes at least yellow ink, cyan ink, and magenta ink, wherein the yellow ink includes ink containing the above-mentioned coloring composition.

[0369] In one embodiment, the ink group may further contain other inks such as black ink, white ink, and spot color ink.

[0370] The ink set of this embodiment can be used in offset printing inks, flexographic printing inks (flexographic inks), gravure printing inks (gravure inks), screen printing inks (screen printing inks), and other printing ink sets, as well as inkjet ink sets. Among these, flexographic ink sets, gravure ink sets, and inkjet ink sets for packaging materials are preferred, and gravure ink sets are more preferred.

[0371] (Yellow ink)

[0372] The yellow ink in this embodiment comprises the above-described pigment composition and binder resin.

[0373] The aforementioned yellow ink, by containing two isoindoline compounds as described above, is able to improve the dispersibility and storage stability that were previously required for isoindoline compounds.

[0374] [Adhesive Resin]

[0375] Examples of adhesive resins include: polyurethane resins, ethylene-vinyl acetate copolymer resins, vinyl acetate resins, nitrocellulose resins, polyamide resins, polyvinyl alcohol acetal resins, cellulose ester resins, polystyrene resins, acrylic resins, polyester resins, alkyd resins, rosin-based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubber, butyral, petroleum resins, and chlorinated polyolefin resins.

[0376] The content of the adhesive resin in the yellow ink is preferably 4 to 25% by mass, more preferably 6 to 20% by mass.

[0377] Yellow inks may further contain other pigments, resins, organic solvents, other pigment dispersants, leveling agents, defoamers, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, and other additives as needed.

[0378] (Cyan ink)

[0379] The cyan ink in this embodiment is an ink that produces a cyan color and comprises pigment and binder resin. It should be noted that the binder resin can be any of the resins described previously.

[0380] (Magenta ink)

[0381] The magenta ink in this embodiment is an ink that produces a magenta color and comprises pigment and binder resin. It should be noted that the binder resin can be any of the resins described previously.

[0382] The following section explains the pigments that can be used in inks.

[0383] [pigment]

[0384] Pigments can be categorized as organic or inorganic. In this embodiment, for example, the following pigments can be used.

[0385] Organic pigments

[0386] Organic pigments are preferred. Examples of organic pigments include: soluble azo, insoluble azo, azo-based, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthraquinone-based, dianthraquinone-based, anthraquinone-based, perylene-based, violet ketone, quinacridone, indigo-based, and dioxindium-based pigments. Azide series, isoindolineone series, quinolineone series, azomethylazo series, succinyl ketone series, diketopyrrolopyrrole series, isoindoline series, indanone series, etc.

[0387] Examples of pigments are shown using CI pigment codes.

[0388] Examples of blue pigments include CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 60, etc. Additionally, phthalocyanine pigments such as aluminum phthalocyanine (compound (11)) and titanium phthalocyanine (compound (12)) can also be listed.

[0389] The cyan ink preferably contains the aforementioned blue pigments. Among these, CI Pigment Blue 15:3, CI Pigment Blue 15:4, and CI Pigment Blue 16 are more preferred.

[0390] [Chemistry 7]

[0391]

[0392] Examples of red pigments include: CI Pigment 2, CI Pigment Red 32, CI Pigment Red 48:1, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 63:1, CI Pigment Red 81, CI Pigment Red 122, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 166, CI Pigment Red 170, CI Pigment Red 174, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red... Pigment Red 184, CI Pigment Red 185, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 202, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 238, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 260, CI Pigment Red 264, CI Pigment Red 269, CI Pigment Red 272, CI Pigment Violet 19, etc.

[0393] The magenta ink preferably contains the aforementioned red pigments. Among these, CI Pigment Red 48:3, CI Pigment Red 57:1, CI Pigment Red 122, CI Pigment Red 146, CI Pigment Red 185, and CI Pigment Violet 19 are more preferred.

[0394] Examples of yellow pigments include: CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 120, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 151, CI Pigment Yellow 155, CI Pigment Yellow 174, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 234, etc.

[0395] In the case of yellow ink used to constitute the ink group of this embodiment, the aforementioned yellow pigment may be included.

[0396] Examples of purple pigments include CI pigment violet 23, CI pigment violet 32, CI pigment violet 37, etc.

[0397] Examples of green pigments include CI pigment green 7, etc.

[0398] Examples of orange pigments include: CI Pigment Orange 13, CI Pigment Orange 34, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 64, etc.

[0399] As spot color inks, examples include purple, grass, vermilion, etc., in addition to cyan, magenta, and yellow, with purple, green, orange, etc., being preferred.

[0400] Inorganic pigments

[0401] Examples of inorganic pigments include: titanium dioxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silicon dioxide, lithopone, antimony white, gypsum, and other white inorganic pigments; carbon black, iron black, copper-chromium composite oxides and other black inorganic pigments; aluminum particles, mica, bronze powder, chromium vermilion, yellow lead, cadmium yellow, cadmium red, ultramarine, dark blue, red clay, yellow iron oxide, zircon, etc.

[0402] From the viewpoint of excellent tinting strength, hiding power, chemical resistance, and weather resistance, carbon black is preferred for black inks, such as CI Pigment Black 7. Furthermore, from the viewpoint of excellent tinting strength, hiding power, chemical resistance, and weather resistance, titanium dioxide is preferred for white inks. From the viewpoint of printability, titanium dioxide that has undergone surface treatment with silica and / or aluminum oxide is preferred.

[0403] To achieve the desired color tone, each ink can be used with a single pigment or in combination of two or more pigments.

[0404] The average primary particle size of the pigment is preferably in the range of 10 to 200 nm, and more preferably in the range of 50 to 150 nm.

[0405] To ensure the concentration and tinting strength of the ink, the pigment content in the ink is preferably in the range of 1 to 60% by mass, based on the mass of the ink, and preferably in the range of 10 to 90% by mass, based on the amount of non-volatile components in the ink.

[0406] <Gravure Ink Set>

[0407] As an embodiment of the present invention, the gravure ink set preferably includes the above-described ink set. Regarding the various colors of gravure inks constituting the gravure ink set of this embodiment, as described above.

[0408] (Transparent ink)

[0409] In one embodiment, the gravure ink set may further contain a transparent ink. The release layer formed by this transparent ink has the function of being dissolved or swollen by neutralization with an alkaline aqueous solution, thereby peeling it off from the substrate.

[0410] Examples of alkaline compounds used in the above-mentioned alkaline aqueous solutions include: sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH)2), ammonia, barium hydroxide (Ba(OH)2), and sodium carbonate (Na2CO3). More preferably, at least one is selected from the group consisting of sodium hydroxide and potassium hydroxide.

[0411] It should be noted that in this specification, the process of neutralizing, dissolving, or swelling using an alkaline aqueous solution is sometimes referred to as "alkali treatment." Additionally, the layer that becomes releasable through alkali treatment is sometimes referred to as a "release layer." That is, a printing layer formed from a transparent ink with releasable properties is equivalent to a releasable layer (release layer).

[0412] [Carboxyl-containing resins]

[0413] Transparent inks preferably contain carboxyl-containing resins. For example, they function as primer compositions printed onto a substrate prior to colored inks.

[0414] Examples of carboxyl-containing resins include: acrylic resins, urethane resins, polyester resins, amino resins, phenolic resins, epoxy resins, and cellulose. Among these, urethane resins are preferred from the perspective of good lamination adaptability.

[0415] The hydroxyl value of the carboxyl-containing urethane resin is preferably 1 to 35 mg KOH / g, more preferably 10 to 30 mg KOH / g. If it is 1 mg KOH / g or higher, the detachment from alkaline aqueous solution becomes good, and therefore it is preferred; if it is 35 mg KOH / g or lower, the adhesion to the substrate becomes good, and therefore it is preferred.

[0416] The acid value of the carboxyl-containing urethane resin is preferably 15 mg KOH / g or higher, more preferably 15–70 mg KOH / g, and even more preferably 20–50 mg KOH / g. If it is 15 mg KOH / g or higher, the detachment from alkaline aqueous solutions becomes better, therefore it is preferred. If it is 70 mg KOH / g or lower, the substrate adhesion is improved, and the retort resistance when making packaging materials becomes good. It should be noted that both the hydroxyl value and acid value are values ​​measured according to JIS K0070.

[0417] The weight-average molecular weight of the carboxyl-containing urethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and even more preferably 15,000 to 50,000.

[0418] The molecular weight distribution (Mw / Mn) of the carboxyl-containing urethane resin is preferably 6 or less. When the molecular weight distribution is 6 or less, the effects caused by excessive high molecular weight components and low molecular weight components such as unreacted components and by-reacted components can be avoided, and the release properties, drying properties of the primer composition, and boiling resistance become good.

[0419] Furthermore, a smaller molecular weight distribution, i.e., a narrower molecular weight distribution, results in a more uniform dissolution and stripping effect based on the alkaline aqueous solution, thus improving the detachment properties, and is therefore preferred. A molecular weight distribution of 5 or less is more preferred, and 4 or less is even more preferred. Additionally, a molecular weight distribution of 1.2 or more is preferred, and 1.5 or more is even more preferred.

[0420] The above-mentioned carboxyl-containing urethane resins may have an amine value. When the carboxyl-containing urethane resin has an amine value, the amine value is preferably 0.1 to 20 mg KOH / g, more preferably 1 to 10 mg KOH / g.

[0421] There are no particular limitations on carboxyl-containing urethane resins; for example, resins formed by reacting polyols, hydroxy acids, and polyisocyanates are preferred. By using hydroxy acids, an acid value can be imparted to the urethane resin, thereby improving its release properties. More preferably, a resin formed by further reacting a resin formed by reacting polyols, hydroxy acids, and polyisocyanates with a polyamine is preferred.

[0422] Transparent inks may further contain polyisocyanates as a curing agent. There are no particular limitations on the polyisocyanates; they can be selected from conventionally known polyisocyanates, such as aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0423] In addition, transparent inks may also contain other components besides hydroxyl-containing resins and polyisocyanates. Similar to the aforementioned cyan, yellow, and magenta inks, they can be combined with additives such as organic solvents and anti-blocking agents.

[0424] <Flexographic Ink Set>

[0425] As an embodiment of the present invention, the flexographic ink set preferably includes the above-described ink set. Regarding the flexographic inks constituting the flexographic ink set of this embodiment, as described above.

[0426] <Inkjet Ink Group>

[0427] As an embodiment of the present invention, the inkjet ink group preferably includes the above-described ink group. The inkjet inks constituting the inkjet ink group of this embodiment are as described above.

[0428] <IX> Printed Materials

[0429] As one embodiment of the present invention, the printed matter has a substrate and a printing layer formed by the printing ink, inkjet ink, or ink group of the present embodiment. The printing layer is formed by printing each ink onto the substrate.

[0430] The preferred ink group is a gravure ink group, a water-based flexographic ink group, an active energy radiation curable flexographic ink group, and an inkjet ink group, with a more preferred gravure ink group.

[0431] <Intaglio Printed Materials>

[0432] There are no particular restrictions on the methods of gravure printing; any known method can be appropriately selected. Gravure printing methods are broadly divided into surface printing and reverse printing. For example, in surface printing, when the substrate is white paper or white film, the printed material can be obtained by printing on the substrate in the order of yellow ink, magenta ink, cyan ink, and black ink.

[0433] In addition, for example, when the substrate is a transparent film in back printing, it is preferable to print on the substrate in the order of black ink, cyan ink, magenta ink, yellow ink, and white ink to produce the printed material.

[0434] In the case where the ink group in this embodiment includes transparent ink, the transparent ink is preferably printed on the substrate before the colored ink.

[0435] The thickness of the printed layer can be appropriately selected according to the application, the type and quantity of ink used, and the number of overlapping prints, but it is usually in the range of 0.5 to 10 μm.

[0436] [Substrate]

[0437] The substrate can be any of the commonly known substrates. Examples include: polyolefin substrates such as polyethylene and polypropylene; polycarbonate substrates; polyester substrates such as polyethylene terephthalate and polylactic acid; polystyrene substrates; polystyrene-based resins such as AS and ABS; polyamide substrates such as nylon; polyvinyl chloride; polyvinylidene chloride; cellophane substrates; paper substrates; aluminum foil substrates; and composite substrates containing these materials. The substrate can be in film or sheet form. Polyester and polyamide substrates with high glass transition points are particularly suitable.

[0438] The surface of the aforementioned substrate can be treated with vapor deposition of metal oxides or coating with polyvinyl alcohol or the like. Examples of substrates with such surface treatments include GL-AE manufactured by Toppan Printing Co., Ltd., and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., with aluminum oxide vapor deposition on their surfaces. The substrate can be treated with additives such as antistatic agents and UV stabilizers as needed, and can also undergo corona treatment or low-temperature plasma treatment.

[0439] There are no particular restrictions on the thickness of the substrate, which is usually in the range of 5 to 100 μm.

[0440] [Detachment Layer]

[0441] The printed material of this embodiment may contain a release layer. Here, "release layer" refers to a layer that has the property of being dissolved or swollen by neutralization with an alkaline aqueous solution, thereby being peeled off from the substrate. The release layer is preferably a layer formed from the above-described transparent ink, but other layers may also be used as release layers.

[0442] There is no particular limitation on the thickness of the release layer, which is usually in the range of 0.5 to 5 μm.

[0443] <Printed materials using flexographic inks>

[0444] There are no particular limitations on the method of flexographic printing; any known method can be appropriately selected. Examples include the two-roller method, the doctor blade method, and the doctor blade cavity method. In the doctor blade and doctor blade cavity methods, flexographic ink is supplied to an anilox roller with perforations on its surface, and excess flexographic ink is scraped off by a doctor blade, allowing the ink to pass through a resin plate and ultimately be printed onto the substrate.

[0445] As anilox rollers used in flexographic printing, ceramic anilox rollers with engraved meshes and chrome-plated anilox rollers can be used. The mesh shapes include honeycomb patterns, diamond patterns, spiral patterns, etc., and any pattern can be used.

[0446] Examples of printing plates used in flexographic printing include: photosensitive resin plates cured by ultraviolet light using a UV light source, and elastomeric material plates using direct laser engraving. The sleeves and buffer strips used for the printing plates can be any suitable material.

[0447] As flexographic printing presses, there are CI-type multicolor flexographic printing presses, unit-type multicolor flexographic printing presses, etc. Regarding ink supply methods, chamber-type and twin-roll-type ink supply methods can be listed, and appropriate printing presses can be used.

[0448] [Substrate]

[0449] The substrate can be any of the conventionally known substrates. Examples include: polyethylene, polypropylene, polyethylene terephthalate, nylon and other plastic films, cellophane, paper, aluminum foil, or films or sheets made of composites thereof. As a paper substrate, a paper substrate selected from uncoated paper, single-gloss kraft paper with one side treated, bleached kraft paper, unbleached kraft paper, etc., is preferred. Other substrates such as plastic films can use the same substrate as the material printed with gravure ink.

[0450] <Printed materials with active energy radiation curable inks>

[0451] Printed materials of active energy ray curable inks are obtained by printing active energy ray curable inks on a substrate and curing them using active energy rays.

[0452] There are no particular restrictions on the method of printing active energy ray curable inks, and known methods can be used. Offset printing and flexographic printing on the recording medium are particularly preferred. Furthermore, there are no particular restrictions on the recording medium, and known recording media can be used. Specifically, examples include coated paper such as art paper, coated paper, and cast-coated paper; uncoated paper such as high-grade paper, medium-grade paper, and newspaper paper; synthetic paper such as Yupo paper; and plastic films such as PET (polyethylene terephthalate), PP (polypropylene), and OPP (biaxially oriented polypropylene).

[0453] Methods for curing active energy radiation-curable inks include, for example, irradiation with alpha rays, gamma rays, electron beams, X-rays, ultraviolet light, visible light, or infrared light. Ultraviolet light and electron beams are preferred, with ultraviolet light being more preferred. The peak wavelength of the active energy rays is preferably 200–600 nm, more preferably 350–420 nm.

[0454] Examples of active energy radiation sources include: mercury lamps, xenon lamps, metal hydride lamps, ultraviolet light-emitting diodes (UV-LEDs), ultraviolet laser diodes (UV-LDs), and gas / solid-state lasers.

[0455] <X> Packaging Materials

[0456] As one embodiment of the invention, the packaging material includes at least a portion thereof printed material. Examples of packaging materials include those comprising a printed material, an adhesive layer, and a sealing substrate layered sequentially. The packaging material is suitable for use with various shapes of packaging, such as four-side-sealed packages, three-side-sealed packages, pillow-shaped packages, stick bags, corner-supported bags, square-bottom bags, stand-up pouches, deep-draw containers, vacuum packages, patchwork packages, zipper bags, spouted bags, twisted packages, wrap-around packages, shrink wrap, labels, liquid paper packages, and paper pallets.

[0457] Examples of items packaged by packaging materials include: food (e.g., grains, snacks, seasonings, edible oils, cooked foods, etc.), beverages (e.g., alcoholic beverages, soft drinks, mineral water, etc.), daily necessities / cultural products (e.g., pharmaceuticals, cosmetics, stationery, etc.), electronic components, etc.

[0458] [Adhesive layer]

[0459] The adhesive components that can be used in forming the above-mentioned adhesive layer include laminating adhesives, hot melt adhesives, and thermoplastic resins. Examples of laminating adhesives and hot melt adhesives include: polyether-based adhesives; polyurethane-based adhesives; epoxy-based adhesives; polyvinyl acetate-based adhesives; cellulose-based adhesives; and (meth)acrylic adhesives. Among these adhesive components, polyurethane-based adhesives are preferred.

[0460] The adhesive components can be used alone or in combination of two or more.

[0461] The aforementioned polyurethane adhesive is a reactive adhesive containing polyol and polyisocyanate, and can be a polyurethane adhesive with release properties. Examples of polyurethane adhesives with release properties include the laminating adhesive described in Japanese Patent Application Publication No. 2020-084130.

[0462] The acid value of this detachable polyurethane adhesive is preferably 5 to 45 mg KOH / g. Furthermore, the polyol constituting the polyurethane adhesive preferably includes a polyester polyol, and the polyisocyanate preferably includes one selected from the group consisting of aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0463] The thickness of the adhesive layer is typically in the range of 1 to 6 μm.

[0464] [Sealing substrate]

[0465] The sealing substrate is the innermost layer of the laminated film, and it uses a resin material that can fuse together with heat (having heat-sealing properties). Examples of such sealing substrates include unstretched polypropylene (CPP), vapor-deposited unstretched polypropylene film (VMCPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ethylene vinyl acetate copolymer (EVA).

[0466] The thickness of the sealing substrate is not particularly limited. However, considering the processability and heat-sealing properties of the packaging material, a range of 10 to 200 μm is preferred, and a range of 15 to 150 μm is more preferable. Furthermore, by providing unevenness with a height difference of 5 to 20 μm on the sealing substrate, the sealing substrate can be given sliding properties and tear resistance of the packaging material.

[0467] Furthermore, there are no particular limitations on the method of laminating the sealing substrate. Examples include: methods that use heat to laminate the adhesive layer to the sealing substrate film (hot lamination, dry lamination); and methods that melt the sealing substrate resin and extrude it onto the adhesive layer, then cool and solidify it to form a laminate (extrusion lamination).

[0468] Example

[0469] The present invention will be described in detail below through embodiments, but the present invention is not limited to the embodiments. It should be noted that "parts" refers to "parts by mass" and "%" refers to "% by mass".

[0470] It should be noted that the hydroxyl value, acid value, amine value, and weight-average molecular weight of the resins used in the examples and comparative examples were determined by the following method.

[0471] (hydroxyl value)

[0472] Calculated according to JIS K0070.

[0473] (Acid value)

[0474] Calculated according to JIS K0070.

[0475] (amine value)

[0476] The amine value is determined by the number of milligrams (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize the amino group contained in 1g of resin, according to JIS K0070 and the following method.

[0477] Accurately weigh 0.5–2 g of the sample (non-volatile component: Sg). Add 50 mL of a 60 / 40 (mass ratio) methanol / methyl ethyl ketone mixture to the accurately weighed sample and dissolve it. Add bromophenol blue as an indicator to the obtained solution and titrate the solution with 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). Use the point where the solution changes color from green to yellow as the endpoint. Using the titration volume (A mL) at this point, calculate the amine value using the following formula.

[0478] Amine value = (A × f × 0.2 × 56.108) / S [mg KOH / g]

[0479] (weight-average molecular weight)

[0480] The weight-average molecular weight was determined using a GPC (gel permeation chromatography) apparatus (Tosoh HLC-8220) and was used as the converted molecular weight when polystyrene was used as a standard. The determination conditions are shown below.

[0481] Chromatographic column: The following chromatographic columns are connected in series for use.

[0482] HXL-H protective chromatographic column manufactured by Tosoh Corporation

[0483] TSKgel G5000HXL manufactured by Tosoh Corporation

[0484] TSKgel G4000HXL manufactured by Tosoh Corporation

[0485] TSKgel G3000HXL manufactured by Tosoh Corporation

[0486] TSKgel G2000HXL manufactured by Tosoh Corporation

[0487] Detector: RI (Differential Refractometer)

[0488] Determination conditions: Column temperature 40℃

[0489] Eluent: Tetrahydrofuran

[0490] Flow rate: 1.0 mL / min

[0491] (Glass transition temperature)

[0492] The glass transition temperature (Tg) was determined by DSC (differential scanning calorimetry). It should be noted that the measuring instrument used was a Rigaku DSC8231. The glass transition temperature was defined as the midpoint between the endothermic start and end temperatures in the DSC curve, within a temperature range of -70 to 250°C and a heating rate of 10°C / min.

[0493] Evaluation of Pigment Compositions and Their Properties

[0494] <Preparation of isoindoline compounds>

[0495] (Example 1-1)

[0496] (Process 1)

[0497] To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 800 parts water, 60 parts 1,3-diiminoisoindoline, and 120 parts 28% ammonia were added sequentially and stirred. Using a dropping funnel, a solution prepared by dissolving 42.58 parts 2-cyano-N-methylacetamide in 160 parts water was added dropwise over 30 minutes. The mixture was heated and stirred at 30°C until the 1,3-diiminoisoindoline in the starting material disappeared. The reaction slurry was filtered using a Büchner funnel. Further, the filtrate was added to 1600 parts water and stirred at 40°C for 30 minutes to remove unreacted 2-cyano-N-methylacetamide. The slurry was then filtered to obtain the non-volatile component. It should be noted that the disappearance of 1,3-diiminoisoindoline was confirmed by UPLC (Ultra-High Speed, High Separation Liquid Chromatography, Waters Corporation).

[0498] (Process 2)

[0499] To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, add 60 parts of the aforementioned non-volatile component and 480 parts of water, and stir. Then add 4.32 parts of a 40% methylamine aqueous solution and stir at 40°C. Next, add 400 parts of water, 170 parts of 80% acetic acid, and 28.54 parts of barbituric acid to the flask and stir at 65°C. Add the heated solution of this mixture to the stirred liquid containing the aforementioned non-volatile component, and further heat to 85°C and stir to complete the reaction. Heating and stirring continue until the aforementioned non-volatile component used as a starting material disappears. The disappearance of the starting material is confirmed by UPLC.

[0500] Then, the mixture was washed three times with 2400 parts of water to obtain the non-volatile component. The non-volatile component was dried using a hot air dryer at 80°C to obtain 80.09 parts of isoindoline compound (1-1).

[0501] (Examples 1-2)

[0502] In step 2 of Example 1-1, the 40% methylamine aqueous solution was changed from 4.32 parts to 2.16 parts, and the barbituric acid was changed from 28.54 parts to 32.10 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 82.54 parts of isoindoline compound (1-2).

[0503] (Examples 1-3)

[0504] In step 2 of Example 1-1, the 40% methylamine aqueous solution was changed from 4.32 parts to 1.08 parts, and the barbituric acid was changed from 28.54 parts to 33.89 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 83.76 parts of isoindoline compounds (1-3).

[0505] (Examples 1-4)

[0506] In step 2 of Example 1-1, the 40% methylamine aqueous solution was changed from 4.32 parts to 0.22 parts, and the barbituric acid was changed from 28.54 parts to 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 84.74 parts of isoindoline compounds (1-4).

[0507] (Examples 1-5)

[0508] In step 2 of Example 1-1, the 40% methylamine aqueous solution was changed from 4.32 parts to 0.02 parts, and the barbituric acid was changed from 28.54 parts to 35.63 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 84.96 parts of isoindoline compounds (1-5).

[0509] (Examples 1-6)

[0510] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were changed to 0.18 parts of 70% ethylamine aqueous solution, and 28.54 parts of barbituric acid were changed to 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 84.77 parts of isoindoline compounds (1-6).

[0511] (Examples 1-7)

[0512] In step 2 of Example 1-1, the 4.32 parts of 40% methylamine aqueous solution were changed to 0.22 parts, and the 28.54 parts of barbituric acid were changed to 39.18 parts of 1-methylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 88.65 parts of isoindoline compounds (1-7).

[0513] (Examples 1-8)

[0514] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were changed to 0.22 parts, and 28.54 parts of barbituric acid were changed to 43.05 parts of 1,3-dimethylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 91.65 parts of isoindoline compound (1-8).

[0515] (Examples 1-9)

[0516] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were changed to 0.22 parts, and 28.54 parts of barbituric acid were changed to 50.78 parts of 1,3-diethylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 98.63 parts of isoindoline compound (1-9).

[0517] (Examples 1-10)

[0518] In step 2 of Example 1-1, the 4.32 parts of 40% methylamine aqueous solution were changed to 0.22 parts, and the 28.54 parts of barbituric acid were changed to 80.60 parts of 1,3-dicyclohexylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 125.82 parts of isoindoline compound (1-10).

[0519] (Examples 1-11)

[0520] In step 2 of Example 1-1, the 4.32 parts of 40% methylamine aqueous solution were changed to 0.22 parts, and the 28.54 parts of barbituric acid were changed to 77.27 parts of 1,3-diphenylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 122.58 parts of isoindoline compound (1-11).

[0521] (Examples 1-12)

[0522] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.25 parts of N,N-dimethylethylenediamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 84.88 parts of isoindoline compound (1-24).

[0523] (Examples 1-13)

[0524] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.45 parts of N-(3-aminopropyl)diethanolamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 85.07 parts of isoindoline compound (1-25).

[0525] (Examples 1-14)

[0526] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.36 parts of N-octylamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 84.99 parts of isoindoline compound (1-26).

[0527] (Examples 1-15)

[0528] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.75 parts of stearamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 85.34 parts of isoindoline compound (1-27).

[0529] (Examples 1-16)

[0530] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.36 parts of 2-ethylhexylamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 84.99 parts of isoindoline compound (1-28).

[0531] (Examples 1-17)

[0532] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.20 parts of tert-butylamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1, yielding 84.84 parts of isoindoline compound (1-29).

[0533] (Examples 1-18)

[0534] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.28 parts of cyclohexylamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 84.91 parts of isoindoline compound (1-30).

[0535] (Examples 1-19)

[0536] In step 2 of Example 1-1, 4.32 parts of 40% methylamine aqueous solution were replaced with 0.25 parts of 2-ethoxyethylamine, and 28.54 parts of barbituric acid were replaced with 35.31 parts. Otherwise, the reaction was carried out in the same manner as in Example 1-1 to obtain 84.88 parts of isoindoline compound (1-31).

[0537] The structures of the isoindoline compounds obtained in Examples 1-1 to 1-19 are shown in Table 1. It should be noted that in the table, (1) represents isoindoline compound (1), and (2) represents isoindoline compound (2). In the table, H represents hydrogen, Me represents methyl, Et represents ethyl, Cy represents cyclohexyl, Ph represents phenyl, Octe represents n-octyl, OD represents octadecyl, 2EH represents 2-ethylhexyl, and t-Bu represents tert-butyl.

[0538] [Table 1]

[0539]

[0540] In the table, B in Examples 1-12 has the following structure (13), C in Examples 1-13 has the following structure (14), and D in Examples 1-19 has the following structure (15).

[0541] [Chemistry 8]

[0542]

[0543] The identification of the obtained isoindoline compounds was performed by comparing the molecular ion peak of the mass spectrometry with the calculated mass number (theoretical value). The determination of the molecular ion peak of the mass spectrometry was performed using a Waters ACQUITY UPLC H-Class column (ACQUITY UPLC BEH C18 Column). Implemented using 1.7μm, 2.1mm×50mm) / Ms TAP XEVO TQD.

[0544] Regarding the isoindoline compounds (Examples 1-1 to 1-19), the theoretical molecular weights and the measured values ​​obtained from the respective mass analyses are shown in Table 1. In terms of the nature of the measurements, since the H (proton) of the compound is desorbed, if the measured value is the mass number of the theoretical molecular weight minus 1, then the compound is consistent.

[0545] (Manufacturing Example 1-1)

[0546] (Process 1)

[0547] To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 800 parts water, 60 parts 1,3-diiminoisoindoline, and 120 parts 28% ammonia were added sequentially and stirred. Using a dropping funnel, a solution prepared by dissolving 42.58 parts 2-cyano-N-methylacetamide in 160 parts water was added dropwise over 30 minutes. The mixture was heated and stirred at 30°C until the 1,3-diiminoisoindoline in the starting material disappeared. The reaction slurry was filtered using a Büchner funnel. Further, the filtrate was added to 1600 parts water and stirred at 40°C for 30 minutes to remove unreacted 2-cyano-N-methylacetamide. The slurry was then filtered to obtain the non-volatile component. It should be noted that the disappearance of 1,3-diiminoisoindoline was confirmed by UPLC (Ultra-High Speed, High Separation Liquid Chromatography, Waters Corporation).

[0548] (Process 2)

[0549] To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, add 60 parts of the aforementioned non-volatile component and 480 parts of water, and stir. Meanwhile, to a glass flask, add 461 parts of water, 194 parts of 80% acetic acid, and 35.67 parts of barbituric acid, and stir at 65°C. Add this heated solution of the mixture to the stirred liquid containing the aforementioned non-volatile component, and further heat to 85°C and stir to complete the reaction. Heating and stirring continue until the aforementioned non-volatile component used as a starting material disappears. The disappearance of the starting material is confirmed by UPLC.

[0550] Then, the mixture was washed three times with 2400 parts of water to obtain the non-volatile component. The non-volatile component was dried using a hot air dryer at 80°C to obtain 84.91 parts of isoindoline compounds (1-12).

[0551] (Manufacturing Examples 1-2)

[0552] The 43.48 parts of barbituric acid in Preparation Example 1-1 were replaced with 39.57 parts of 1-methylbarbituric acid. All other reaction operations were carried out in the same manner to obtain 88.94 parts of isoindoline compounds (1-13).

[0553] (Manufacturing Examples 1-3)

[0554] The 43.48 parts of barbituric acid in Manufacturing Example 1-1 were replaced with 43.48 parts of 1,3-dimethylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Manufacturing Example 1-1, yielding 91.96 parts of isoindoline compound (1-14).

[0555] (Manufacturing Examples 1-4)

[0556] The 43.48 parts of barbituric acid in Manufacturing Example 1-1 were replaced with 51.29 parts of 1,3-diethylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Manufacturing Example 1-1, yielding 99.02 parts of isoindoline compound (1-15).

[0557] (Manufacturing Examples 1-5)

[0558] The 43.48 parts of barbituric acid in Manufacturing Example 1-1 were replaced with 81.42 parts of 1,3-dicyclohexylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Manufacturing Example 1-1, yielding 126.48 parts of isoindoline compound (1-16).

[0559] (Manufacturing Examples 1-6)

[0560] The 43.48 parts of barbituric acid in Manufacturing Example 1-1 were replaced with 78.05 parts of 1,3-diphenylbarbituric acid. Otherwise, the reaction was carried out in the same manner as in Manufacturing Example 1-1, yielding 123.20 parts of isoindoline compound (1-17).

[0561] The structures contained in the isoindoline compounds obtained in Examples 1-1 to 1-6 are shown in Table 2. It should be noted that in the table, (1) represents isoindoline compound (1), and (2) represents isoindoline compound (2). In the table, H represents hydrogen, Me represents methyl, Et represents ethyl, Cy represents cyclohexyl, and Ph represents phenyl.

[0562] [Table 2]

[0563]

[0564] The identification of the obtained isoindoline compounds was carried out in the same manner as described above, by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation.

[0565] (Manufacturing Examples 1-7)

[0566] 800 parts of water and 800 parts of 80% acetic acid were added to a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the mixture was stirred. 111.18 parts of barbituric acid were then added, and the mixture was stirred at 65°C to obtain a solution containing dissolved barbituric acid. Meanwhile, 800 parts of water and 60.00 parts of 1,3-diiminoisoindoline were added to a glass flask, and the mixture was stirred at 30°C. This stirred mixture was then added to the above solution, and the temperature was further raised to 85°C and stirred to complete the reaction. Heating and stirring continued until the non-volatile components used as starting materials disappeared. The disappearance of the starting materials was confirmed by UPLC.

[0567] Then, the mixture was washed three times with 2000 parts of water to obtain the non-volatile component. The non-volatile component was dried using a hot air dryer at 80°C to obtain 133.59 parts of isoindoline compound (1-18).

[0568] (Manufacturing Examples 1-8)

[0569] The 111.18 parts of barbituric acid in Manufacturing Examples 1-7 were replaced with 135.53 parts of 1,3-dimethylbarbituric acid. Otherwise, all reaction operations were carried out in the same manner as in Manufacturing Examples 1-7, yielding 154.00 parts of isoindoline compounds (1-19).

[0570] The structures contained in the isoindoline compounds obtained in Examples 1-7 and 1-8 are shown in Table 3. It should be noted that in the table, (2) represents isoindoline compound (2). In the table, H represents hydrogen and Me represents methyl.

[0571] [Table 3]

[0572]

[0573] The identification of the obtained isoindoline compounds was carried out in the same manner as described above, by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation.

[0574] (Manufacturing Examples 1-9)

[0575] To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, add 800 parts water, 60 parts 1,3-diiminoisoindoline, and 120 parts 28% ammonia solution sequentially and stir. Using a dropping funnel, add dropwise a solution prepared by dissolving 80.38 parts 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile in 160 parts water over 30 minutes. Heat and stir at 30°C until the 1,3-diiminoisoindoline in the starting material disappears. Filter the reaction slurry using a Büchner funnel to obtain the non-volatile component. Note that the disappearance of the starting material was confirmed by UPLC.

[0576] In a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 480 parts of water and 162 parts of 80% acetic acid were added, relative to 60 parts of the previously prepared non-volatile component used as a starting material, and the mixture was stirred. Meanwhile, another 480 parts of water and 162 parts of 80% acetic acid were added to the flask, along with 29.44 parts of barbituric acid, and the mixture was stirred at 65°C. A heated solution of this mixture was then added to the stirred solution of the aforementioned non-volatile component, and the temperature was further raised to 85°C and stirred to complete the reaction. Heating and stirring continued until the aforementioned non-volatile component used as a starting material disappeared. The disappearance of the starting material was confirmed by UPLC.

[0577] Then, the mixture was washed three times with 2400 parts of water to obtain the non-volatile component. The non-volatile component was dried using a hot air dryer at 80°C to obtain 75.20 parts of isoindoline compound (1-20).

[0578] The structures contained in the isoindoline compounds obtained in Examples 1-9 are shown in Table 4. It should be noted that in the table, (2) represents isoindoline compound (2). In the table, H represents hydrogen.

[0579] [Table 4]

[0580]

[0581] The identification of the obtained isoindoline compounds was carried out in the same manner as described above, by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation.

[0582] (Manufacturing Examples 1-10)

[0583] (Process 1)

[0584] To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, add 800 parts water, 60 parts 1,3-diiminoisoindoline, and 120 parts 28% ammonia solution sequentially and stir. Using a dropping funnel, add dropwise a solution prepared by dissolving 42.58 parts 2-cyano-N-methylacetamide in 160 parts water over 30 minutes. Heat and stir at 30°C until the 1,3-diiminoisoindoline in the starting material disappears. Filter the reaction slurry using a Büchner funnel to obtain the non-volatile component. It should be noted that the disappearance of 1,3-diiminoisoindoline was confirmed by UPLC (Ultra-High Speed, High Separation Liquid Chromatography, Waters Corporation).

[0585] (Process 2)

[0586] Add 60 parts of the aforementioned non-volatile component and 480 parts of water to a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and stir. Add 53.54 parts of a 40% methylamine aqueous solution and stir at 40°C. Stirring continues until the aforementioned non-volatile component used as a raw material disappears. The disappearance of the raw material is confirmed by UPLC.

[0587] Then, the mixture was washed three times with 2400 parts of water to obtain the non-volatile component. The non-volatile component was dried using a hot air dryer at 80°C to obtain 58.62 parts of isoindoline compound (1-21).

[0588] (Manufacturing Example 1-11)

[0589] The same reaction operation as that described in Japanese Patent Application Publication No. 2006-206737, was performed to obtain isoindoline compounds (1-22).

[0590] (Manufacturing Examples 1-12)

[0591] The same reaction operation as that described in Japanese Patent Application Publication No. 2006-206737, was performed to obtain isoindoline compounds (1-23).

[0592] The structures contained in the isoindoline compounds obtained in Manufacturing Examples 1-10 to 1-12 are shown in Table 5.

[0593] [Table 5]

[0594]

[0595] The identification of the obtained isoindoline compounds was carried out in the same manner as described above, by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation.

[0596] (Example 2-1)

[0597] One part of isoindoline compound (1-21), 99 parts of isoindoline compound (1-12), 1000 parts of sodium chloride, and 150 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60°C for 8 hours. Next, the kneaded mixture was placed in warm water at approximately 70°C and stirred for 1 hour to form a slurry. After filtration and washing to remove salt and diethylene glycol, the slurry was dried at 80°C for 24 hours and then pulverized to obtain 95 parts of micronized isoindoline compound (2-1).

[0598] (Examples 2-2 to 2-5)

[0599] One part of isoindoline compound (1-21) was replaced with raw material A and the amount of filling as described in Table 6, and 99 parts of isoindoline compound (1-12) were replaced with raw material B and the amount of filling as described in Table 6. Otherwise, the same procedure as in Example 2-1 was followed to obtain the amounts of isoindoline compounds (2-2) to (2-5) described in Table 6.

[0600] (Manufacturing Examples 2-1 to 2-5)

[0601] One part of isoindoline compound (1-21) and 99 parts of isoindoline compound (1-12) were replaced with the raw material B and the loading amount as shown in Table 6. Otherwise, the same procedure was followed as in Example 2-1 to obtain the amounts of isoindoline compounds (2-6) to (2-10) shown in Table 6.

[0602] [Table 6]

[0603]

[0604] (Example 3-1)

[0605] While stirring, 0.4 parts of isoindoline compound (1-21) and 36.6 parts of isoindoline compound (1-12) were slowly added to 1000 parts of 98% sulfuric acid, and stirred for 4 hours to dissolve. Then, while stirring, the solution was slowly added dropwise to 8000 parts of water at 10°C over 30 minutes, filtered, washed with warm water, and dried at 80°C to obtain 38.5 parts of micronized isoindoline compound (3-1).

[0606] <II> Evaluation of Coloring Compositions and Their Properties

[0607] Using the obtained pigment compositions, coloring compositions for various applications are formulated and their physical properties are evaluated.

[0608] <1> Evaluation of the molding composition

[0609] (Examples A-1 to A-19, Comparative Examples A-1 to A-11)

[0610] [Hue Evaluation]

[0611] Using the obtained isoindoline compound and high-density polyethylene resin (product name: Hizex 2208J, manufactured by Prime Polymer), the mixture was melt-blended using a biaxial extruder at a temperature of 200°C, and injection molded at a barrel temperature of 200°C. The coloring power was adjusted to a concentration of SD1 / 3 to produce 11 colored plates with a thickness of 3 mm. It should be noted that the injection molding was performed with the shortest possible residence time of the composition in the barrel. The isoindoline compound used is shown in Table 7. Regarding the colored plates, in order to detect the average color difference, the 6 colored plates from the 6th to the 11th were measured using a colorimeter capable of full-beam measurement (Konica Minolta, CM-700d), and the average value of the obtained colorimetric values ​​was used as a control (reference value). The color difference (ΔE*) was calculated by comparing the colorimetric value with that of the colored plate using only isoindoline compound (2), and evaluated according to the following criteria. Specifically, the evaluation is conducted according to the criteria listed in Table 7.

[0612] (Evaluation Criteria)

[0613] 5: ΔE* is less than 1.0. Very good.

[0614] 4: ΔE* is greater than 1.0 and less than 2.0. Good.

[0615] 3: ΔE* is greater than 2.0 and less than 3.0. Practical application.

[0616] 2: ΔE* is 3.0 or higher and less than 5.0. Practical application is possible.

[0617] 1: ΔE* is 5.0 or higher. Not practical.

[0618] -: Not measured

[0619] [Heat Resistance Evaluation]

[0620] The heat resistance test was conducted according to German industrial standard DIN12877-1. After adjusting the molding conditions to a residence time of 5 minutes in the barrel, 11 colored plates were formed at 300°C. Color measurements were taken on the 6th to 11th colored plates, and the average value was calculated. The color difference (ΔE*) between the control sample and the plate formed at 300°C was calculated and evaluated according to the following criteria. The results are shown in Table 7. It should be noted that a smaller color difference indicates better heat resistance.

[0621] (Evaluation Criteria)

[0622] 5: ΔE* is less than 2.0. Very good.

[0623] 4: ΔE* is greater than 2.0 and less than 4.5. Good.

[0624] 3: ΔE* is 4.5 or higher and less than 7.5. Practical application is possible.

[0625] 2: ΔE* is 7.5 or higher and less than 10.0. Practical application is possible.

[0626] 1: ΔE* is 10.0 or higher. Not practical.

[0627] -: No rating

[0628] [Table 7]

[0629]

[0630] (Example A-20) [Preparation of the Molded Body]

[0631] One part of isoindoline compounds (1-4) and 1000 parts of polypropylene resin (product name: PrimePolypro J105, manufactured by Prime Polymer) were melt-blended at 220°C using a biaxial extruder. The resulting granules were then cut using a pelletizer to obtain a granular molding composition. Next, while the obtained molding composition was melt-blended at 220°C, injection molding was performed using an injection molding machine with a molding temperature set to 220°C and a mold temperature set to 40°C to obtain a molded body (sheet) with a thickness of 1 mm.

[0632] Visual inspection of the formed body revealed no coarse particles even in the watermark, resulting in a yellow plate with good coloring.

[0633] (Example A-21) [Preparation of the Molded Body]

[0634] Using a biaxial extruder, 0.5 parts of isoindoline compounds (1-4) and 1000 parts of pre-dried polyethylene terephthalate resin (product name: Vylopet EMC-307, manufactured by Toyobo Co., Ltd.) were melt-blended at 275°C. The resulting granules were then cut using a pelletizer to obtain a granular molding composition. Next, while melt-blending the obtained molding composition, injection molding was performed using an injection molding machine with a molding temperature set to 275°C and a mold temperature set to 85°C to obtain a molded body (sheet) with a thickness of 3 mm.

[0635] Visual inspection of the formed body revealed no coarse particles even in the watermark, resulting in a yellow plate with good coloring.

[0636] <2> Evaluation of toners

[0637] (Example A-22) [Preparation of Negatively Electrolyte Toner]

[0638] 2500 parts of isoindoline compounds (1-4) and 2500 parts of polyester resin (product name: M-325, manufactured by Sanyo Chemical Co., Ltd.) were mixed at 120°C for 15 minutes using a pressure kneader.

[0639] Next, the obtained mixture is removed from the pressure kneader and further kneaded using a three-roll mill with a roller temperature of 95°C. After cooling, the obtained mixture is coarsely pulverized to less than 10 mm to obtain the colored composition.

[0640] 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 75 parts of ethylene homopolymer (release agent, molecular weight 850, Mw / Mn = 1.08, melting point 107°C) were mixed using a 20L Henschel mixer (3000 rpm, 3 minutes). The mixture was then melt-kneaded using a twin-screw extruder at an outlet temperature of 120°C. After cooling and solidifying, the mixture was coarsely pulverized using a hammer mill. The coarsely pulverized material was then micronized using an I-type jet mill (IDS-2 type) and classified to obtain colorant masterbatch.

[0641] Next, 2,500 parts of the toner masterbatch obtained above and 12.5 parts of hydrophobic titanium dioxide (manufactured by STT-30A Titanium Industry Co.) were mixed using a 10L Henschel mixer to obtain negatively charged toner 1.

[0642] On the other hand, as a comparison, the isoindoline compounds (1-4) of Example A-22 were changed to isoindoline compounds (1-12), and all other operations were performed in the same manner as in Example A-22 to obtain the negatively charged toner 2.

[0643] The obtained negatively charged toners 1 and 2 were sliced ​​to a thickness of 0.9 μm using a microtome to form samples. Then, the dispersion of the pigments in each sample was observed using a transmission electron microscope. The results confirmed that, compared with negatively charged toner 2 using isoindoline compounds (1-12), negatively charged toner 1 using isoindoline compounds (1-4) exhibited more uniform pigment distribution and better dispersion.

[0644] <3> Evaluation of coatings

[0645] <3-1> Formulation of Solvent-Based Coatings

[0646] 1. Preparation of the base coating

[0647] (Example B-1) [Preparation of Base Coating 1]

[0648] First, put the following raw materials and 230 parts of steel balls into a 225ml glass bottle, and disperse for 60 minutes using a paint shaker made by Red Devil Company to obtain a mixture.

[0649] • Isoindoline compounds (1-1): 19 parts

[0650] • Acrylic resin (manufactured by DIC, ACRYDIC 47-712): 7.7 parts

[0651] • Dispersing solvent (a mixture of toluene, xylene, butyl acetate, and ENEOS T-SOL 150 FLUID in a mass ratio of 3:3:2:2): 40.7 parts

[0652] Next, 75.4 parts of ACRYDIC 47-712 and 17.2 parts of melamine resin (DIC AMIDIR L-117-60) were added to the above mixture, and the mixture was further dispersed for 10 minutes to obtain a dispersion.

[0653] Next, the steel balls were removed from the dispersion to obtain a base coating 1 of isoindoline compound (1-1).

[0654] (Examples B-2 to B-19, Comparative Examples B-1 to B-11) [Preparation of Base Coatings 2 to 30]

[0655] In the method for preparing the base coating 1 described in Example B-1, the isoindoline compound (1-1) was replaced with the isoindoline compound listed in Table 8. Otherwise, the process was the same as in Example B-1 to obtain base coatings 2 to 30.

[0656] [Table 8]

[0657] Table 8 Base Coating Isoindoline compounds Example B-1 Base Coating 1 (1-1) Example B-2 Base Coating 2 (1-2) Example B-3 Base Coating 3 (1-3) Example B-4 Base Coating 4 (1-4) Example B-5 Base Coating 5 (1-5) Example B-6 Base Coating 6 (1-6) Example B-7 Base Coating 7 (1-7) Example B-8 Base Coating 8 (1-8) Example B-9 Base Coating 9 (1-9) Example B-10 Base Coating 10 (1-10) Example B-11 Base Coating 11 (1-11) Example B-12 Base Coating 12 (1-24) Example B-13 Base Coating 13 (1-25) Example B-14 Base Coating 14 (2-1) Example B-15 Base Coating 15 (2-2) Example B-16 Base Coating 16 (2-3) Example B-17 Base Coating 17 (2-4) Example B-18 Base Coating 18 (2-5) Example B-19 Base Coating 19 (3-1) Comparative Example B-1 Base Coating 20 (1-12) Comparative Example B-2 Base Coating 21 (1-13) Comparative Example B-3 Base Coating 22 (1-14) Comparative Example B-4 Base Coating 23 (1-15) Comparative Example B-5 Base Coating 24 (1-16) Comparative Example B-6 Base coating 25 (1-17) Comparative Example B-7 Base Coating 26 (2-6) Comparative Example B-8 Base Coating 27 (2-7) Comparative Example B-9 Base Coating 28 (2-8) Comparative Example B-10 Base Coating 29 (2-9) Comparative Example B-11 Base Coating 30 (2-10)

[0658] 2. Preparation of white paint

[0659] The following are examples of how to prepare white paint for use in light-colored base coatings.

[0660] First, put the following raw materials and 900 parts of steel balls into a 900ml glass bottle and disperse them for 60 minutes using a paint shaker made by Red Devil Company to obtain a dispersion.

[0661] • Titanium oxide (TIPAQUE CR90 titanium oxide manufactured by Ishihara Sangyo Co., Ltd.): 66.6 parts

[0662] • Acrylic resin (manufactured by DIC, ACRYDIC 47-712): 101.7 parts

[0663] • Melamine resin (manufactured by DIC, AMIDIR L-117-60): 21.3 parts

[0664] • Dispersing solvent (a mixture of toluene, xylene, butyl acetate, and ENEOS T-SOL 150 FLUID in a mass ratio of 3:3:2:2): 20.9 parts

[0665] Next, the steel balls are removed from the dispersion to obtain white paint.

[0666] 3. Preparation of light-colored base coatings

[0667] (Example C-1) [Preparation of Light-Colored Base Coating 1]

[0668] Use a high-speed mixer to mix the following components to obtain a light-colored base coating 1.

[0669] • The base coating prepared in Example B-1 was 1:10 parts

[0670] • 31.9 parts of white paint obtained

[0671] (Examples C-2 to C-19, Comparative Examples C-1 to C-11) [Preparation of Light-Colored Base Coatings 2 to 30]

[0672] The base coating 1 of Example C-1 was changed to base coating 2 to 30 respectively. Otherwise, all operations were carried out in the same way as in Example C-1 to obtain light-colored base coating 2 to 30.

[0673] It should be noted that the isoindoline compounds used in the light-colored base coatings prepared in each embodiment and comparative example are shown in Table 9.

[0674] [Table 9]

[0675] Table 9 Light-colored base coating Base Coating Isoindoline compounds Example C-1 Light-colored base coating 1 Base Coating 1 (1-1) Example C-2 Light-colored base coating 2 Base Coating 2 (1-2) Example C-3 Light-colored base coating 3 Base Coating 3 (1-3) Example C-4 Light-colored base coating 4 Base Coating 4 (1-4) Example C-5 Light-colored base coating 5 Base Coating 5 (1-5) Example C-6 Light-colored base coating 6 Base Coating 6 (1-6) Example C-7 Light-colored base coating 7 Base Coating 7 (1-7) Example C-8 Light-colored base coating 8 Base Coating 8 (1-8) Example C-9 Light-colored base coating 9 Base Coating 9 (1-9) Example C-10 Light-colored base coat 10 Base Coating 10 (1-10) Example C-11 Light-colored base coating 11 Base Coating 11 (1-11) Example C-12 Light-colored base coat 12 Base Coating 12 (2-1) Example C-13 Light-colored base coating 13 Base Coating 13 (2-2) Example C-14 Light-colored base coat 14 Base Coating 14 (2-3) Example C-15 Light-colored base coat 15 Base Coating 15 (2-4) Example C-16 Light-colored base coating 16 Base Coating 16 (2-5) Example C-17 Light-colored base coat 17 Base Coating 17 (3-1) Example C-18 Light-colored base coat 18 Base Coating 18 (1-24) Example C-19 Light-colored base coating 19 Base Coating 19 (1-25) Comparative Example C-1 Light-colored base coat 20 Base Coating 20 (1-12) Comparative Example C-2 Light-colored base coating 21 Base Coating 21 (1-13) Comparative Example C-3 Light-colored base coating 22 Base Coating 22 (1-14) Comparative Example C-4 Light-colored base coating 23 Base Coating 23 (1-15) Comparative Example C-5 Light-colored base coat 24 Base Coating 24 (1-16) Comparative Example C-6 Light-colored base coat 25 Base coating 25 (1-17) Comparative Example C-7 Light-colored base coating 26 Base Coating 26 (2-6) Comparative Example C-8 Light-colored base coat 27 Base Coating 27 (2-7) Comparative Example C-9 Light-colored base coat 28 Base Coating 28 (2-8) Comparative Example C-10 Light-colored base coating 29 Base Coating 29 (2-9) Comparative Example C-11 Light-colored base coat 30 Base Coating 30 (2-10)

[0676] 4. Preparation of the topcoat transparent paint

[0677] Use a high-speed mixer to mix the following ingredients to obtain a topcoat clear coating.

[0678] • Acrylic resin (manufactured by DIC, ACRYDIC 44-179): 120 parts

[0679] • Melamine resin (manufactured by DIC, AMIDIR L117-60): 30 parts

[0680] • Diluent (a mixture of toluene, xylene, ENEOS T-SOL 150 FLUID, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2): 50 parts

[0681] 5. Fabrication and weather resistance evaluation of light-colored substrate coated panels

[0682] (Example D-1) [Preparation of light-colored base coating plate 1]

[0683] A light-colored base coat 1 was sprayed onto a steel plate whose surface had been adjusted with #1000 sandpaper using a spray gun. To adjust the viscosity for easy spraying, a suitable diluent (a mixture of toluene, xylene, ENEOS T-SOL 150 Fluid, ethyl 3-ethoxypropionate, and ethyl acetate in a mass ratio of 3:2:2:1:2) was used as the standard, with an equal mass relative to the light-colored base coat.

[0684] The coating is applied in nine coats, followed by six coats of topcoat clear coat.

[0685] Next, after drying at 25°C for 8 hours, the substrate was dried at 140°C for 30 minutes to obtain a light-colored base coating plate 1.

[0686] (Examples D-2 to D-19, Comparative Examples D-1 to D-11) [Preparation of light-colored substrate coating plates 2 to 30]

[0687] The light-colored base coating 1 of Example D-1 was changed to light-colored base coating 2 to 30 respectively. Otherwise, all operations were carried out in the same way as in Example D-1 to obtain light-colored base coated plates 2 to 30.

[0688] [Weather Resistance Evaluation]

[0689] Weather resistance tests were conducted on the obtained light-colored base coated panels 1-30 according to the following procedure.

[0690] The weathering test was conducted using an ultra-accelerated weathering tester (manufactured by Iwasaki Electric Co., Ltd., EYE Super XenonTester SUV-W151) at an illuminance of 90 mW / cm². 2 Irradiation (daytime) conditions: 12 hours, temperature 63℃, humidity 70%; Irradiation rest (nighttime) conditions: 12 hours, temperature 70℃, humidity 99%. One cycle was set, and tests were conducted under 48-hour (two cycles of 12-hour day / night) and 96-hour (four cycles of 12-hour day / night) conditions. The coated panels before and after the weathering resistance test were visually observed, and weather resistance was evaluated according to the following criteria. The results are shown in Table 10. The smaller the color change, the better the weather resistance. A rating of "5", "4", "3", or "2" in the following evaluation criteria indicates a usable level.

[0691] (Evaluation Criteria)

[0692] 5: ΔE* is less than 4.0. Very good.

[0693] 4: ΔE* is 4.0 or higher and less than 6.0. Good.

[0694] 3: ΔE* is 6.0 or higher and less than 7.5. Practical application is possible.

[0695] 2: ΔE* is 7.5 or higher and less than 10.0. Practical application is possible.

[0696] 1: ΔE* is 10.0 or higher. Not practical.

[0697] -: Not measured

[0698] [Table 10]

[0699]

[0700] <4> Evaluation of water-based coloring compositions

[0701] 1. Preparation of water-based coloring compositions

[0702] (Example E-1) Preparation of Aqueous Coloring Composition E-1

[0703] The following raw materials and 70 parts of 1.25mm diameter zirconia beads were placed in a 70ml glass bottle and dispersed for 60 minutes using a Red Devil paint shaker to obtain a dispersion.

[0704] • Isoindoline compound (1-1): 3.15 parts

[0705] • Polyester-modified acrylic polymer (Allnex, ADDITOL XW 6528): 5.25 parts

[0706] • Wetting agent (Allnex, ADDITOL XW 6374): 0.95 parts

[0707] • Defoamer (Allnex, ADDITOL XW 6211): 0.63 parts

[0708] • Ion-exchanged water: 21.52 parts

[0709] Next, the zirconia beads were removed from the dispersion to obtain the aqueous coloring composition E-1.

[0710] (Examples E-2 to E-17, E-20 to E-21, Comparative Examples E-1 to E-11) [Preparation of Aqueous Coloring Compositions E-2 to E-17, Aqueous Coloring Compositions E-20 to E-32]

[0711] The isoindoline compound (1-1) of Example E-1 was changed to the one shown in Table 11. Otherwise, the same procedure as in Example E-1 was followed to obtain aqueous coloring compositions E-2 to 17 and aqueous coloring compositions E-20 to E-32.

[0712] (Example E-18) [Preparation of Aqueous Coloring Composition E-18]

[0713] The isoindoline compound (1-1): 3.15 parts in Example E-1 was changed to isoindoline compound (1-12): 3.12 parts and isoindoline compound (1-21): 0.03 parts. Otherwise, all operations were performed in the same manner as in Example E-1 to obtain the aqueous coloring composition E-18.

[0714] (Example E-19) [Preparation of Aqueous Coloring Composition E-19]

[0715] The isoindoline compound (1-1): 3.15 parts in Example E-1 was changed to isoindoline compound (1-12): 3.06 parts, (1-21): 0.03 parts, (1-22): 0.03 parts and isoindoline compound (1-23): 0.03 parts. Otherwise, all operations were performed in the same manner as in Example E-1 to obtain the aqueous coloring composition E-19.

[0716] (Comparative Example E-12) [Preparation of Aqueous Coloring Composition E-33]

[0717] The isoindoline compound (1-1): 3.15 parts in Example E-1 was changed to isoindoline compound (1-12): 3.09 parts, (1-22): 0.03 parts, and isoindoline compound (1-23): 0.03 parts. Otherwise, all operations were performed in the same manner as in Example E-1 to obtain the aqueous coloring composition E-33.

[0718] 2. Evaluation of Dispersion Stability

[0719] [Evaluation of initial viscosity and viscosity stability]

[0720] For the obtained aqueous coloring composition, the initial viscosity at 25°C was measured using an E-type viscometer (Toki Sangyo Co., Ltd. "ELD type viscometer"). Similarly, the viscosity was measured after one week at 25°C and after one week of accelerated growth at 50°C. Based on the measured values, the viscosity change rate relative to the initial viscosity was calculated and used as an indicator of viscosity stability, evaluated according to the following evaluation criteria. The results are shown in Table 11. Lower initial viscosity indicates better dispersibility. Furthermore, a smaller viscosity change rate indicates better dispersion stability. A value of "4", "3", or "2" in the following evaluation criteria indicates a practically usable level.

[0721] Viscosity change rate (%) = |(Viscosity over time / Initial viscosity) - 1| × 100

[0722] (Evaluation criteria for initial viscosity)

[0723] 4. Initial viscosity less than 5.0 mPa·s. Extremely good.

[0724] 3. Initial viscosity is above 5.0 mPa·s and below 7.5 mPa·s. Good.

[0725] 2. Initial viscosity is above 7.5 mPa·s and below 10.0 mPa·s. Practical application is possible.

[0726] 1. Initial viscosity above 10.0 mPa·s. Not suitable for practical use.

[0727] (Evaluation criteria for viscosity stability)

[0728] 4. Viscosity change rate is less than 20%. Extremely good.

[0729] 3: Viscosity change rate is above 20% and less than 30%. Good.

[0730] 2. Viscosity change rate is above 30% and less than 40%. Practical.

[0731] 1. Viscosity change rate exceeds 40%. Not practical.

[0732] [Table 11]

[0733]

[0734] <5> Evaluation of water-based coatings

[0735] Using the water-based coloring composition prepared in the previous step, water-based coatings were made and evaluated.

[0736] <5-1> Preparation of Water-Based Coatings

[0737] (Example F-1)

[0738] (1) Preparation of water-based coating 1-1

[0739] After mixing the ingredients in the manner described below based on the amount of non-volatile components, stir using a high-speed mixer to obtain water-based coating 1-1 (stored at 25°C for 1 week).

[0740] • Aqueous coloring composition E-1 (stored at 25°C for 1 week): 4.8 parts

[0741] • WATERSOL S-751 (DIC Acrylic Resin for Baking Coatings): 60.0 parts

[0742] • CYMEL 303 (manufactured by Mitsui Cytec, melamine resin): 45.0 parts

[0743] (2) Preparation of water-based coating 1-2

[0744] After mixing the ingredients in the manner described below based on the amount of non-volatile components, stir using a high-speed mixer to obtain water-based coating 1-2 (stored at 50°C for 1 week).

[0745] • Aqueous coloring composition E-1 (stored at 50°C for 1 week): 4.8 parts

[0746] • WATERSOL S-751 (DIC Acrylic Resin for Baking Coatings): 60.0 parts

[0747] • CYMEL 303 (manufactured by Mitsui Cytec, melamine resin): 45.0 parts

[0748] (Examples F-2 to F-21, Comparative Examples F-1 to F-12)

[0749] The aqueous coloring composition E-1 of Example F-1 (stored at 25°C for 1 week) was successively changed to aqueous coloring compositions E-2 to 33 (stored at 25°C for 1 week respectively). Otherwise, all operations were performed in the same manner as in Example F-1 to obtain waterborne coatings 2-1 to 33-1.

[0750] In addition, the water-based coloring composition E-1 of Example F-1 (stored at 50°C for 1 week) was successively changed to water-based coloring compositions E-2 to 33 (stored at 50°C for 1 week respectively). Otherwise, all operations were carried out in the same manner as in Example F-1 to obtain water-based coatings 2-2 to 33-2.

[0751] [Table 12-1]

[0752]

[0753] [Table 12-2]

[0754]

[0755] <5-2> PET Film Coating Process

[0756] (Example G-1) [Preparation of PET film coating 1]

[0757] Water-based coating 1-1 and water-based coating 1-2 were applied together to Lumirror 100T60 (Toray Industries, Inc., polyester terephthalate (PET) film, 100 μm thick) using a 6-mil applicator. After coating, the PET film was allowed to dry at room temperature for 18 hours. Then, it was dried at 60°C for 5 minutes and at 140°C for 20 minutes to obtain PET film coating 1 with a film thickness of 70 μm.

[0758] (Examples G-2 to G-21, Comparative Examples G-1 to G-12) [Preparation of PET film coating 2 to 33]

[0759] The water-based coatings 1-1 and 1-2 of Example G-1 were changed to 2-1 to 33-1 and 2-2 to 33-2, respectively. Otherwise, all operations were performed in the same manner as in Example G-1 to obtain PET film coatings 2 to 33.

[0760] <5-3> Evaluation of PET film coating

[0761] For each PET film coating obtained in Examples G-1 to G-21 and Comparative Examples G-1 to G-12, the hue and hue stability were evaluated according to the following methods.

[0762] [Evaluation of Hue Stability]

[0763] Using a colorimeter (Konica Minolta, CM-700d), colorimetric measurements were performed on coatings 1-33 of PET film, consisting of coatings made from water-based coloring compositions stored at 25°C for one week and coatings made from water-based coloring compositions stored at 50°C for one week. The color difference (ΔE*) was calculated and judged according to the following criteria. The results are shown in Table 13. A smaller color difference indicates better dispersion stability of the colorant. A rating of "4", "3", or "2" in the following evaluation criteria indicates a usable level.

[0764] (Evaluation Criteria)

[0765] 4: ΔE* is less than 1.0.

[0766] 3: ΔE* is greater than 1.0 and less than 2.0.

[0767] 2: ΔE* is greater than 2.0 and less than 3.0.

[0768] 1: ΔE* is 3.0 or higher.

[0769] [Table 13]

[0770]

[0771] <6> Evaluation of Gravure Inks

[0772] (Synthesis Example 1) Polyurethane Resin [PU1]

[0773] 200 parts of polypropylene glycol (hereinafter referred to as "PPG700") with a number average molecular weight of 700, 127 parts of isophorone diisocyanate (hereinafter referred to as "IPDI"), and 81.8 parts of ethyl acetate were reacted at 80°C for 4 hours under a nitrogen atmosphere to obtain a resin solution of terminal isocyanate urethane prepolymer. Next, the obtained resin solution of terminal isocyanate urethane prepolymer was slowly added to a mixture of 49.5 parts of isophorone diamine (hereinafter referred to as "IPDA"), 3 parts of 2-ethanolamine, and 803.9 parts of a mixed solvent of ethyl acetate / isopropanol (hereinafter referred to as "IPA") = 50 / 50 (mass ratio) at 40°C, followed by reaction at 80°C for 1 hour to obtain a polyurethane resin solution [PU1] with 30% non-volatile components, an amine value of 3.5 mgKOH / g, a hydroxyl value of 7.3 mgKOH / g, and a weight average molecular weight of 40,000. The glass transition temperature was -32°C.

[0774] (Example H-1) [Preparation of Gravure Ink 1]

[0775] 30 parts of a polyurethane resin solution [PU1] (30% non-volatile component) as an adhesive resin, 0.8 parts of a polyethylene wax (Honeywell A-C400A) as a hydrocarbon wax (converted to non-volatile component), 0.5 parts of a chlorinated polypropylene resin (Nippon Paper Corporation product name: 370M, 30% chlorine content, 50% non-volatile component) as a non-volatile component, 10 parts of an isoindoline compound (1-1), and 58.7 parts of a solution of methyl ethyl ketone (hereinafter referred to as "MEK") / n-propyl acetate (hereinafter referred to as "NPAC") / IPA = 40 / 40 / 20 (mass ratio) were mixed and dispersed using an Eiger mill for 15 minutes to obtain gravure ink 1.

[0776] (Examples H-2 to 17, H-20 to H-27, Comparative Examples H-1 to 11) [Preparation of Gravure Inks 2 to 17 and 20 to 38]

[0777] In the method for preparing gravure ink 1 described in Example H-1, the isoindoline compound (1-1) was changed to the one shown in Table 14. Otherwise, the same procedure as in Example H-1 was followed to obtain gravure inks 2-17 and gravure inks 20-38.

[0778] (Example H-18) [Preparation of Gravure Ink 18]

[0779] The isoindoline compound (1-1): 10 parts in Example H-1 was changed to isoindoline compound (1-12): 9.9 parts and (1-21): 0.1 parts. Otherwise, all operations were performed in the same manner as in Example H-1 to obtain gravure ink 18.

[0780] (Example H-19) [Preparation of Gravure Ink 19]

[0781] The isoindoline compound (1-1): 10 parts in Example H-1 was changed to isoindoline compounds (1-12): 9.7 parts, (1-21): 0.1 parts, (1-22): 0.1 parts, and (1-23): 0.1 parts. Otherwise, all operations were performed in the same manner as in Example H-1 to obtain gravure ink 19.

[0782] (Comparative Example H-12) [Prepared with Gravure Ink 39]

[0783] The isoindoline compound (1-1): 10 parts in Example H-1 was changed to isoindoline compounds (1-12): 9.8 parts, (1-22): 0.1 parts, and (1-23): 0.1 parts. Otherwise, all operations were performed in the same manner as in Example H-1 to obtain gravure ink 39.

[0784] [Evaluation Methods and Criteria]

[0785] [Time-bound stability evaluation]

[0786] For gravure inks 1–39, they were placed in sealed containers and stored at 40°C for 10 days. The viscosity was then measured and the change from the initial viscosity before storage was evaluated. It should be noted that the viscosity was measured at 25°C using the flow rate in seconds using a Zahn Cup No. 4. It should also be noted that the viscosity of any ink in the Type B viscometer before storage was in the range of 40–500 cps (25°C).

[0787] (Evaluation Criteria)

[0788] 5: Viscosity change less than 2 seconds (Good)

[0789] 4: Viscosity change takes more than 2 seconds but less than 5 seconds (practical)

[0790] 3: Viscosity change takes more than 5 seconds but less than 10 seconds (slightly undesirable)

[0791] 2: Viscosity change takes more than 10 seconds but less than 15 seconds (defective)

[0792] 1. Viscosity change lasting more than 15 seconds (extremely undesirable)

[0793] It should be noted that 5 and 4 represent ranges where there are no practical problems.

[0794] [Table 14]

[0795]

[0796] <Evaluation of Gravure Ink Prints>

[0797] (Example I-1) [Production of printed materials I1-1 and I1-2]

[0798] The gravure ink 1 obtained above was diluted with a mixed solvent containing MEK / NPAC / IPA = 40 / 40 / 20 (mass ratio) to a viscosity of 16 seconds (25°C, Zahn Cup No. 3). The ink was then printed on the following substrate (corona-treated surface in the case of OPP) at a printing speed of 80 m / min using a gravure printing press equipped with a Helio 175-line gradation plate (format compression gradation 100% to 3%) to obtain printed materials I1-1 (OPP) and I1-2 (CPP).

[0799] <Substrate>

[0800] • OPP: Biaxially stretched polypropylene (OPP) membrane treated with single-sided corona discharge (manufactured by Futamura Chemical Co., Ltd., for a thickness of 25 μm)

[0801] • CPP: Unstretched polypropylene (CPP) membrane without corona treatment (Mitsui Chemicals Tosel Cellul., CP-S, 30μm thickness)

[0802] (Examples I-2 to 27, Comparative Examples I-1 to 12) [Preparation of Printed Materials I2-1 to I39-1, I2-2 to I39-2]

[0803] For the gravure inks 2 to 39 listed in Table 14, printing is performed using the printing configuration listed in Table 15 to obtain printed materials I2-1 to I39-1 (OPP) and I2-2 to I39-2 (CPP).

[0804] [Evaluation Methods and Criteria]

[0805] The following evaluation was conducted using printed materials I1-1 to I39-1 (OPP) and printed materials I1-2 to I39-2 (CPP).

[0806] [Transparency Assessment]

[0807] Regarding transparency, after developing the color on the developing paper with black bands, the transmission on the black bands is observed when compared with comparative examples of similar hues to determine transparency.

[0808] (Evaluation Criteria)

[0809] 5: Extremely transparent

[0810] 4: Transparent

[0811] 3: Equal

[0812] 2: Opaque

[0813] 1: Extremely opaque

[0814] [Abrasion Resistance Evaluation]

[0815] Using printed materials I1-1 to I39-1 (OPP) and printed materials I1-2 to I39-2 (CPP), three points on the surface of the printed layer were scratched with a fingernail, and the scratch resistance was evaluated based on the degree of damage to the printed layer.

[0816] (Evaluation Criteria)

[0817] 5: Printed layer undamaged (good)

[0818] 4. The printed layer is undamaged, but may leave slight fingernail marks. (Standard for use)

[0819] 3: The printed layer is damaged, and the surface of the printed layer is slightly dented. (Slight defect)

[0820] 2: The printed layer is damaged, and the substrate is slightly visible. (Defective)

[0821] 1. The printed layer is damaged, and the substrate is clearly visible. (Extremely poor)

[0822] It should be noted that 5 and 4 represent ranges where there are no practical problems.

[0823] [Adhesion Evaluation]

[0824] For printed materials I1-1 to I39-1 (OPP) and I1-2 to I39-2 (CPP), after 3 hours of printing, a 12mm wide adhesive tape (millet tape manufactured by Michelin) was pasted onto the printed surface, and the appearance of the printed surface was visually assessed when it was quickly peeled off. It should be noted that the assessment criteria are as follows.

[0825] (Evaluation Criteria)

[0826] 5: The ink film on the printed surface has not peeled off completely (Good).

[0827] 4. The peeling area of ​​the ink coating is more than 1% and less than 5% (practical).

[0828] 3: The peeling area of ​​the ink coating is more than 5% and less than 20% (slightly undesirable).

[0829] 2: The peeling area of ​​the ink coating is more than 20% but less than 50% (defective)

[0830] 1: More than 50% of the ink coating has been peeled off (extremely poor quality).

[0831] It should be noted that 5 and 4 represent ranges where there are no practical problems.

[0832] [Table 15-1]

[0833]

[0834] [Table 15-2]

[0835]

[0836] <7> Evaluation of water-based flexographic inks

[0837] (Synthesis Example 2) Waterborne carbamate resin [B]

[0838] A 2000 ml four-necked flask equipped with a reflux condenser, dropping funnel, gas inlet tube, stirrer, and thermometer was filled with 82.3 parts of polytetramethylene glycol (number average molecular weight 2,000), 3 parts of polyethylene glycol (number average molecular weight 2,000), 13 parts of dimethylolbutyric acid (DMA), and 1.7 parts of 1,4-cyclohexanediethanol. The flask was purged with dry nitrogen and heated to 100 °C. Under stirring, 33.3 parts of isophorone diisocyanate were added dropwise over 20 minutes, and the temperature was slowly increased to 140 °C (NCO / OH = 0.98). The reaction was further carried out for 30 minutes to obtain a urethane resin. Next, while cooling, 399.8 parts of distilled water containing 5.3 parts of 28% ammonia were added to obtain an aqueous urethane resin [B] (weight average molecular weight of approximately 40,000, non-volatile component of 25%, acid value of 36.9 (mgKOH / g), hydroxyl value of 11.1 (mgKOH / g)).

[0839] (Example P-1) [Preparation of Water-Based Flexographic Ink [P-1]]

[0840] Using an Egger mill, 45 parts of waterborne urethane resin [B], 15 parts of isoindoline compound (1-1), 2 parts of polyethylene wax (W310, manufactured by Mitsui Chemicals, particle size 9.5 μm, softening point 132℃, penetration hardness 0.8), 0.2 parts of adipic dihydrazide, 0.2 parts of ammonia (28%), 18.8 parts of water, and 18.8 parts of isopropanol were dispersed until the particle size was below 10 μm by the grind gauge to obtain waterborne flexographic ink [P-1].

[0841] (Examples P-2 to P-17, P-20 to P-27, Comparative Examples P-1 to P-11) [Preparation of Water-Based Flexographic Inks [P-2] to [P-17], [P-20] to [P-38]]

[0842] In the method for manufacturing the water-based flexographic ink [P-1] described in Example P-1, the isoindoline compound (1-1) was changed to the one shown in Table 16. Otherwise, the same procedure as in Example P-1 was followed to obtain water-based flexographic inks [P-2] to [P-17], [P-20] to [P-38].

[0843] (Example P-18) [Preparation of Water-Based Flexographic Ink [P-18]]

[0844] In the method for manufacturing the water-based flexographic ink [P-1] described in Example P-1, 15 parts of isoindoline compound (1-1) were replaced with 14.85 parts of isoindoline compound (1-12) and 0.15 parts of (1-21). Otherwise, the water-based flexographic ink [P-18] was obtained by operating in the same manner as in Example P-1.

[0845] (Example P-19) [Preparation of Water-Based Flexographic Ink [P-19]]

[0846] In the method for manufacturing the water-based flexographic ink [P-1] described in Example P-1, 15 parts of isoindoline compound (1-1) were replaced with 14.55 parts of isoindoline compounds (1-12), 0.15 parts of (1-21), 0.15 parts of (1-22), and 0.15 parts of (1-23). ​​Otherwise, the same procedure as in Example P-1 was followed to obtain the water-based flexographic ink [P-19].

[0847] (Comparative Example P-12) [Preparation of Water-Based Flexographic Ink [P-39]]

[0848] In the method for manufacturing the water-based flexographic ink [P-1] described in Example P-1, 15 parts of isoindoline compound (1-1) were replaced with 14.7 parts of isoindoline compounds (1-12), 0.15 parts of (1-22), and 0.15 parts of (1-23). ​​Otherwise, the same procedure as in Example P-1 was followed to obtain the water-based flexographic ink [P-39].

[0849] [Evaluation Methods and Criteria]

[0850] <Evaluation of Water-Based Flexographic Inks>

[0851] [Dispersion Assessment]

[0852] The shorter the dispersion time of water-based flexographic inks, the higher their dispersibility. Using the dispersion time of the water-based flexographic ink [P-28] of Comparative Example P-1 as a baseline (100%), the dispersibility of each water-based flexographic ink was evaluated according to the following criteria. Practicality level is 2 or higher.

[0853] (Evaluation Criteria)

[0854] 5: Dispersion time less than 40%

[0855] 4: Dispersion time is above 40% and less than 60%.

[0856] 3: Dispersion time is above 60% and less than 80%.

[0857] 2: Dispersion time is above 80% and less than 100%.

[0858] 1: Dispersion time is over 100%

[0859] [Time-bound stability evaluation]

[0860] Water-based flexographic inks were placed in sealed containers and stored at 40°C for 3 months. The viscosity was then measured and the change from the initial viscosity before storage was evaluated. It should be noted that the viscosity was measured at 25°C using the flow rate in seconds using a Zahn Cup No. 4. It should also be noted that the viscosity of any ink in a Type B viscometer before storage was in the range of 40–500 cps (25°C). The evaluation criteria are shown below. A practical level of 2 or higher is considered satisfactory.

[0861] (Evaluation Criteria)

[0862] 4: Viscosity change less than 2 seconds

[0863] 3: Viscosity change takes more than 2 seconds but less than 4 seconds

[0864] 2: Viscosity change takes more than 4 seconds but less than 6 seconds

[0865] 1: Viscosity change takes more than 6 seconds

[0866] <Evaluation of Printed Materials Using Water-Based Flexographic Inks>

[0867] (The production of printed materials)

[0868] Using the obtained water-based flexographic ink, prints are manufactured by the following method.

[0869] Flexographic rotary printing: A central cylinder type 6-color flexographic printing press "SOLOFLEX" manufactured by Windmoller & Holscher was used to print water-based flexographic inks on plastic film at a speed of 100 m / min and dry at 60-70°C to obtain the printed material. A 350 line / cm anilox roller was used as the printing cylinder. A solid plate was made using DuPont's "Sirel DPU" (1.14 mm thick) and attached using double-sided tape (Toyochem "DF7382T" 0.50 mm thick).

[0870] [Hue Evaluation]

[0871] The obtained printed material was superimposed on white color development paper (Byko-chart uncoated N2C, manufactured by BYK) and measured using a colorimeter capable of full-beam measurement (CM-700d, manufactured by Konica Minolta). The color difference (ΔE*) was calculated based on the comparative examples listed in Table 16, and evaluated according to the following criteria. Practicality level is 2 or higher.

[0872] (Evaluation Criteria)

[0873] 5: ΔE* is less than 0.5.

[0874] 4: ΔE* is greater than 0.5 and less than 1.0.

[0875] 3: ΔE* is greater than 1.0 and less than 1.5.

[0876] 2: ΔE* is greater than 1.5 and less than 3.0.

[0877] 1: ΔE* is 3.0 or higher.

[0878] [Table 16]

[0879]

[0880] <8> Evaluation of Active Energy X-ray Curable Inks

[0881] (Example Q-1) [Preparation of Active Energy Ray Curable Ink [Q-1]]

[0882] The following materials were mixed using a disc mixer and dispersed using a three-roll mill to achieve a maximum particle size of less than 15 μm, thereby obtaining an active energy radiation curable ink [Q-1].

[0883] • Isoindoline compound (1-1): 18.0 parts

[0884] • EBECRYL225: 8.4 parts (5.0 parts based on active ingredient)

[0885] (10-functional urethane acrylate oligomers)

[0886] ·4-Acryloylmorpholine: 15.0 parts (monofunctional monomer)

[0887] • EO-modified trimethylolpropane triacrylate: 20.0 parts

[0888] • Dipentaerythritol pentaacrylate: 5.0 parts

[0889] • Dipentaerythritol hexaacrylate: 16.6 parts

[0890] • IRGACURE 369: 3.0 parts (photopolymerization initiator)

[0891] • Chemrk DEABP: 3.0 parts (photopolymerization initiator)

[0892] • SB-PI718: 4.0 parts (photopolymerization initiator)

[0893] • AJISPER PB821: 3.0 parts (dispersant)

[0894] • T-wax complex: 4.0 parts (wax)

[0895] The details of the materials used are as follows.

[0896] [Acrylate oligomers]

[0897] •EBECRYL225: Manufactured by Daicel Allnex Co., Ltd., a 10-functional aliphatic urethane acrylate oligomer, Mw1,200, active ingredient 60% by mass.

[0898] [Polymerization initiator]

[0899] • IRGACURE 369: Manufactured by BASF, 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl)-1-butanone

[0900] Chemrk DEABP: Manufactured by Sort, 4,4'-bis(diethylamino)benzophenone

[0901] ·SB-PI718: 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide manufactured by Sort.

[0902] [Dispersant]

[0903] • AJISPER PB821: Manufactured by Ajinomoto Fine Chemicals Co., Ltd., a comb-shaped dispersant containing basic functional groups.

[0904] [wax]

[0905] • T-wax complex: Manufactured by Toshin Oils & Fats Co., Ltd., polyethylene wax

[0906] (Examples Q-2 to Q-17, Q-20 to Q-21, Comparative Examples Q-1 to Q-11) [Preparation of Active Energy Ray Curable Inks [Q-2] to [Q-17], [Q-20] to [QP-32]]

[0907] In the method for manufacturing the active energy ray curable ink [Q-1] described in Example Q-1, the isoindoline compound (1-1) was changed to the one shown in Table 17. Otherwise, the active energy ray curable inks [Q-2] to [Q-17] and [Q-20] to [QP-32] were obtained by operating in the same manner as in Example Q-1.

[0908] (Example Q-18) [Preparation of Active Energy Ray Curable Ink [Q-18]]

[0909] In the manufacturing method of the active energy ray curable ink [Q-1] described in Example Q-1, 18.0 parts of isoindoline compound (1-1) were changed to 17.82 parts of isoindoline compound (1-12) and 0.18 parts of (1-21). Otherwise, the active energy ray curable ink [Q-18] was obtained by operating in the same manner as in Example Q-1.

[0910] (Example Q-19) [Preparation of Active Energy Ray Curable Ink [Q-19]]

[0911] In the manufacturing method of the active energy ray curable ink [Q-1] described in Example Q-1, 18.0 parts of isoindoline compound (1-1) were changed to 17.46 parts of isoindoline compounds (1-12), 0.18 parts of (1-21), 0.18 parts of (1-22), and 0.18 parts of (1-23). ​​Otherwise, the active energy ray curable ink [Q-19] was obtained by operating in the same manner as in Example Q-1.

[0912] (Comparative Example Q-12) [Preparation of Active Energy Ray Curable Ink [Q-33]]

[0913] In the manufacturing method of the active energy ray curable ink [Q-1] described in Example Q-1, 18.0 parts of isoindoline compound (1-1) were changed to 17.64 parts of isoindoline compounds (1-12), 0.18 parts of (1-22), and 0.18 parts of (1-23). ​​Otherwise, the active energy ray curable ink [Q-33] was obtained by operating in the same manner as in Example Q-1.

[0914] [Evaluation Methods and Criteria]

[0915] <Evaluation of Active Energy X-ray Curable Inks>

[0916] [Initial Viscosity Evaluation]

[0917] The viscosity of the obtained active energy X-ray curable ink was measured at 25°C and 100 rpm using a Type E viscometer (TVE-25 type, manufactured by Toki Sangyo Co., Ltd.), and evaluated according to the following criteria. Practicality level is 2 or higher.

[0918] (Evaluation Criteria)

[0919] 4: Above 500 mPa·s and below 1400 mPa·s

[0920] 3: 400 mPa·s or higher but less than 500 mPa·s, or 1400 mPa·s or higher but less than 1600 mPa·s

[0921] 2: 200 mPa·s or higher but less than 400 mPa·s, or 1600 mPa·s or higher but less than 2000 mPa·s

[0922] 1: Less than 200 mPa·s, or more than 2000 mPa·s

[0923] [Thixotropic Index (TI) Evaluation]

[0924] The viscosity of the obtained active energy X-ray curable ink was measured at 25°C and 50 rpm and 100 rpm using a Type E viscometer (TVE-25 type, manufactured by Toki Sangyo Co., Ltd.). The Ti value was calculated by dividing the viscosity at 50 rpm by the viscosity at 100 rpm, and evaluated according to the following criteria: Practicality level 2 or higher.

[0925] (Evaluation Criteria)

[0926] 4: 1.00 or higher and less than 1.05

[0927] 3: 1.05 or higher and less than 1.10

[0928] 2: 1.10 or higher and less than 1.15

[0929] 1:1.15 and above

[0930] [Time-bound stability evaluation]

[0931] The obtained active energy X-ray curable inks were placed in sealed containers and stored at 25°C for 10 days. The viscosity (mPa·s) was then measured at 25°C and 100 rpm using a Type E viscometer (TVE-25 type, Type E, manufactured by Toki Sangyo Co., Ltd.). Based on the measured values, the viscosity change rate relative to the initial viscosity (mPa·s) was calculated and evaluated according to the following criteria: Practicality level 2 or higher.

[0932] Viscosity change rate (%) = |(Viscosity over time / Initial viscosity) - 1| × 100

[0933] (Evaluation Criteria)

[0934] 4: Viscosity change rate is less than 2%

[0935] 3: Viscosity change rate is greater than 2% and less than 5%.

[0936] 2: Viscosity change rate is greater than 5% and less than 10%.

[0937] 1: Viscosity change rate is above 10%

[0938] <Evaluation of Printed Materials Using Reactive Energy X-ray Curable Inks>

[0939] (The manufacture of printed materials)

[0940] Using an RI tester (manufactured by TESTER Industrial Co., Ltd.), a solid image was printed on coated paper as a substrate using an energy-curable ink (ERI) at a feed rate of 0.25 ml. The ERI was then cured at a conveyor speed of 60 m / min using an LED lamp (Air Motion System "XP-9", irradiation distance 10 mm, output power 70%) to create a test sample. It should be noted that the RI tester is a testing machine for printing inks on paper and film, capable of adjusting the ink transfer amount and printing pressure.

[0941] [Hue Evaluation]

[0942] The obtained printed materials were measured using a colorimeter capable of full-beam measurement (Konica Minolta, CM-700d). The color difference (ΔE*) was calculated based on the test samples obtained in the comparative examples listed in Table 17, and evaluated according to the following criteria. The practical level is 2 or higher.

[0943] (Evaluation Criteria)

[0944] 4: ΔE* is less than 1.0.

[0945] 3: ΔE* is greater than 1.0 and less than 1.5.

[0946] 2: ΔE* is greater than 1.5 and less than 3.0.

[0947] 1: ΔE* is 3.0 or higher.

[0948] [Table 17]

[0949]

[0950] <9> Evaluation of water-based inkjet inks

[0951] <9-1> Preparation of an inkjet water-based coloring composition (hereinafter referred to as "IJ water-based coloring composition") (Example J-1) [Preparation of IJ water-based coloring composition 1]

[0952] • Isoindoline compounds (1-1): 19.0 parts

[0953] • Styrene-acrylic acid copolymer (manufactured by BASF Japan, JONCRYL 61J): 16.4 parts

[0954] Surfactant (manufactured by Kao Corporation, EMULGEN 420): 5.0 parts

[0955] • Ion-exchanged water: 59.6 parts

[0956] The above ingredients and 200 parts of 1.25mm diameter zirconia beads were placed in a 200ml glass bottle and dispersed for 6 hours using a paint shaker made by Red Devil.

[0957] The obtained liquid was diluted with ion-exchanged water, the dispersion was separated by filtration with zirconia beads, and diluted with ion-exchanged water to a colorant content of 15%, thereby obtaining an aqueous coloring composition 1 of isoindoline compound (1-1).

[0958] (Examples J-2 to J-17, J-20 to J-21, Comparative Examples J-1 to J-11) [Preparation of water-based coloring compositions 2 to 17 and water-based coloring compositions 20 to 32]

[0959] In the preparation method of the aqueous IJ dispersion 1 described in Example J-1, the isoindoline compound (1-1) was changed to those described in Table 18. Otherwise, the same procedure as in Example J-1 was followed to obtain IJ aqueous coloring compositions 2-17 and IJ aqueous coloring compositions 20-32.

[0960] (Example J-18) [Preparation of Water-based Coloring Composition 18]

[0961] In the preparation method of the aqueous IJ dispersion 1 described in Example J-1, the isoindoline compound (1-1): 19 parts was changed to isoindoline (1-12): 18.8 parts and isoindoline (1-21): 0.2 parts. Otherwise, the same procedure as in Example J-1 was followed to obtain the IJ aqueous coloring composition 18.

[0962] (Example J-19) [Preparation of Water-based Coloring Composition 19]

[0963] In the preparation method of the aqueous IJ dispersion 1 described in Example J-1, the isoindoline compound (1-1): 19 parts was changed to isoindoline (1-12): 18.4 parts, isoindoline (1-21): 0.2 parts, isoindoline (1-22): 0.2 parts, and isoindoline (1-23): 0.2 parts. Otherwise, the same procedure as in Example J-1 was followed to obtain the IJ aqueous coloring composition 19.

[0964] (Comparative Example J-12) [Preparation of Water-based Coloring Composition 31]

[0965] In the preparation method of the aqueous IJ dispersion 1 described in Example J-1, the isoindoline compound (1-1): 19 parts was changed to isoindoline (1-12): 18.6 parts, isoindoline (1-22): 0.2 parts, and isoindoline (1-23): 0.2 parts. Otherwise, the same procedure as in Example J-1 was followed to obtain the IJ aqueous coloring composition 33.

[0966] (Synthetic Example 3) Styrene-acrylate-methacrylate copolymer [PA1] containing carboxyl and hydroxyl groups

[0967] 1,000 parts of methyl ethyl ketone were added to a 3-liter four-necked flask equipped with a dropping funnel, thermometer, nitrogen inlet tube, stirrer, and reflux condenser. The temperature was raised to 78°C, and a mixture containing 100 parts of styrene, 538 parts of n-butyl methacrylate, 104 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 108 parts of methacrylic acid, and 80 parts of tert-butyl peroxide-2-ethylhexanoate was added dropwise over 4 hours. The reaction was carried out at this temperature for 8 hours. After the reaction was completed, methyl ethyl ketone was further added to adjust the concentration to 50% non-volatile components, yielding a styrene-acrylate-methacrylate copolymer [PA1] solution with an acid value of 70 mg KOH / g and a number average molecular weight of 6,000.

[0968] (Example J-22) [Preparation of Water-based Coloring Composition 34]

[0969] 0.71 parts of dimethylethanolamine were used to neutralize 12.8 parts of a styrene-acrylate-methacrylate copolymer [PA1] solution (50% non-volatile component), followed by 2.29 parts (1.6 parts based on resin) of methyl etherified melamine resin (Sanwa Chemical Industry Co., Ltd., NIKALACMX-041). While stirring, 50 parts of a pre-prepared aqueous slurry of isoindoline compounds (1-3) (16% non-volatile component) were added to this mixture. Next, 130 parts of 1.5 mm diameter glass beads were placed in a 250 ml glass bottle and dispersed for 4 hours using a Red Devil paint shaker. After obtaining the dispersion, an equal volume of deionized water was added. Then, while stirring, 1 equivalent of hydrochloric acid aqueous solution was added to precipitate and fix the copolymer [PA1] onto the surface of the isoindoline compounds (1-3). It should be noted that the pH of the fixed mixture was 3–5.

[0970] The mixed solution was then filtered by suction and washed with ion-exchanged water until the pH of the washing solution exceeded 6, to obtain isoindoline compounds (1-3) immobilized with copolymer [PA1].

[0971] Next, water was added until the isoindoline compound (1-3) with copolymer [PA1] immobilized flowed. Then, 0.8 parts of dimethylethanolamine were added while stirring with a mixer. Stirring was continued for 1 hour under these conditions to obtain a redispersible mixture of isoindoline compound (1-3) with copolymer [PA1] immobilized.

[0972] Water was added to the redispersible mixture to adjust the non-volatile content to 19%, and then an acid crosslinking catalyst (Nuanben Chemical Co., Ltd., Nacurre 2500X) was added in an amount of 0.5% relative to the copolymer [PA1] contained in the redispersible mixture. The crosslinking reaction was carried out at 95°C for 1 hour to obtain an aqueous coloring composition (IJ Aqueous Coloring Composition 34) containing crosslinked resin particles of a pigment composition.

[0973] (Synthetic Example 4) Styrene-acrylate-methacrylate copolymer [PA2] containing carboxyl and epoxy groups

[0974] 1,000 parts of methyl ethyl ketone were added to a 3-liter four-necked flask equipped with a dropping funnel, thermometer, nitrogen inlet tube, stirrer, and reflux condenser. The temperature was raised to 78°C, and a mixture containing 100 parts of styrene, 476 parts of n-butyl methacrylate, 116 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 50 parts of glycidyl methacrylate, 108 parts of methacrylic acid, and 80 parts of tert-butyl peroxide-2-ethylhexanoate was added dropwise over 4 hours. The reaction was carried out at this temperature for 8 hours. After the reaction was completed, methyl ethyl ketone was further added to adjust the concentration so that the non-volatile component was 50%, resulting in a styrene-acrylate-methacrylate copolymer [PA2] solution with an acid value of 70 mg KOH / g and a number average molecular weight of 10,500.

[0975] (Example J-23) [Preparation of Water-based Coloring Composition 35]

[0976] Sixteen parts of the obtained styrene-acrylate-methacrylate copolymer [PA2] solution (50% non-volatile component), eight parts of isoindoline compounds (1-3), and 40 parts of methyl ethyl ketone were placed together with 130 parts of 1.5 mm diameter glass beads in a 250 ml glass bottle. The mixture was dispersed for 4 hours using a Red Devil paint shaker to obtain a dispersion. Next, 0.8 parts of hydrophilic epoxy resin (DIC, CR-5L) and 24 parts of methyl ethyl ketone were added to the dispersion, and the mixture was stirred. The glass beads were then filtered to separate the dispersion. Eighty-seven parts of the resulting dispersion were added while stirring to a mixture of 1.2 parts of dimethylethanolamine and 100 parts of water, followed by an equal volume of deionized water. Then, while stirring, one equivalent of an aqueous phosphoric acid solution was added to precipitate and fix the copolymer [PA2] onto the surface of the isoindoline compounds (1-3). It should be noted that the pH of the fixed mixture was 5.

[0977] The mixed solution was then filtered by suction and washed with ion-exchanged water until the pH of the washing solution exceeded 6, to obtain isoindoline compounds (1-3) with copolymer [PA2] immobilized.

[0978] Next, water was added until the isoindoline compounds (1-3) with copolymer [PA2] immobilized were flowed. While stirring with a mixer, 0.8 parts of dimethylethanolamine were added, and stirring was continued for 1 hour to obtain a redisperse of isoindoline compounds (1-3) with copolymer [PA2] immobilized.

[0979] Water was added to the redispersible mixture, and the non-volatile content was adjusted to 19%. The redispersible mixture was then heated to 95°C and subjected to a crosslinking reaction for 1 hour to obtain an aqueous coloring composition containing crosslinked resin particles of a pigment composition (IJ Aqueous Coloring Composition 35).

[0980] (Synthesis Example 5) Styrene-acrylate copolymer [PA3]

[0981] Mix 62 parts acrylic acid, 129 parts styrene, and 9 parts α-methylstyrene to prepare a monomer mixture. Add 20 parts methyl ethyl ketone, 0.3 parts 2-mercaptoethanol (polymerization chain transfer agent), and 10% of the above monomer mixture to a reaction vessel and mix thoroughly, then purge with nitrogen. Separately, add the remaining 90% of the above monomer mixture, 0.27 parts of the above polymerization chain transfer agent, 60 parts methyl ethyl ketone, and 2.2 parts of an azo radical polymerization initiator (Wako Pure Chemical Industries Co., Ltd., V-65, 2,2'-azobis(2,4-dimethylpentanonitrile)) to a dropping funnel.

[0982] Under a nitrogen atmosphere, the mixture in the above reaction vessel was stirred and heated to 65°C, and then added dropwise from a dropping funnel over 3 hours. After the addition was complete, the mixture was reacted at 65°C for 1 hour, and then a solution of 0.3 parts of the above polymerization initiator dissolved in 5 parts of methyl ethyl ketone was added, and the reaction was continued at 65°C for 1 hour. After adding the above polymerization initiator solution and continuing the reaction twice more, the temperature was raised to 70°C and the reaction was continued for 1 hour, and then 200 parts of methyl ethyl ketone were added to obtain a styrene-acrylate copolymer [PA3] solution (non-volatile component concentration 40.9%) with an acid value of 240 mg KOH / g, a number average molecular weight of 5,700, and a weight average molecular weight of 12,500.

[0983] The styrene-acrylate copolymer [PA3] solution was subjected to vacuum drying to completely remove the solvent, thereby obtaining 32 parts of resin. This resin was then mixed with 204 parts of deionized water, and 11.1 parts of triethanolamine were further added to neutralize approximately 55 mol% of the carboxyl groups in the copolymer [PA3]. The mixture was heated to 90°C and stirred for 1 hour to obtain an aqueous dispersion of the copolymer [PA3] in water.

[0984] (Example J-24) [Preparation of Water-based Coloring Composition 36]

[0985] After cooling the aqueous dispersion of copolymer [PA3] to room temperature, 100 parts of isoindoline compounds (1-3) were added, and the mixture was stirred at 20°C for 3 hours using a stirrer. Then, 124 parts of deionized water were added to the mixture, and the solution was dispersed 15 times using a microfluidic apparatus at a pressure of 150 MPa. Next, the dispersion was centrifuged at 20°C and 3,660 rpm for 20 minutes using a high-speed refrigerated centrifuge (Hitachi Koki Co., Ltd., Himac CR22G). Only the liquid layer was recovered and further filtered using a 5 μm membrane filter to obtain an aqueous dispersion of isoindoline compounds (1-3) (25% non-volatile component concentration).

[0986] 32 parts of deionized water were added to 100 parts of an aqueous dispersion of the isoindoline compounds (1-3), and 1.8 parts of trimethylolpropane polyglycidyl ether (manufactured by Nagase ChemteX, DENACOL EX-321) as a crosslinking agent were further added. The mixture was heated at 70°C for 5 hours while stirring. Then, it was cooled to room temperature and filtered using a membrane filter with a pore size of 5 μm. Deionized water was added again to adjust the concentration so that the non-volatile component was 19%, thereby obtaining an aqueous coloring composition (IJ Aqueous Coloring Composition 36) containing crosslinked resin particles of a pigment composition.

[0987] [Table 18-1]

[0988]

[0989] [Table 18-2]

[0990]

[0991] <9-2> Formulation of water-based inkjet inks (hereinafter referred to as "water-based inks")

[0992] After mixing the components listed in Table 19, the mixture was filtered using a 3μm membrane filter to obtain the water-based inks for the evaluation tests, Examples K-1 to K-26 and Comparative Examples K-1 to K-12. In Table 19, the numerical values ​​representing the amount of each component are in parts; a "-" indicates that the component is not present. Additionally, "water" refers to ion-exchanged water. Other abbreviations in the table have the following meanings.

[0993] PG: Propylene Glycol

[0994] • TEA: Triethanolamine

[0995] ·AMP: 2-Amino-2-methyl-1-propanol

[0996] ·NH3 28% aq: 28% ammonia solution

[0997] [Evaluation of color change during long-term storage]

[0998] The water-based IJ inks prepared in each example and comparative example were filled into mayonnaise bottles and stored in an oven at 50°C for 4 weeks. Using the inks before and after storage, OK Top Coats were coated with a wet film thickness of 6 μm using a K Control Coater manufactured by Matsuo Sangyo Co., Ltd., and the coatings were dried in an oven at 70°C for 1 minute to prepare the coated products.

[0999] Calculation of color difference (ΔE value) before and after storage:

[1000] Using the obtained coating, the L*, a*, and b* values ​​of the ink film before and after long-term storage were measured using X-rite eXact (X-Rite Corporation). Based on these values, the color difference (ΔE* value) before and after storage was calculated and evaluated. If the evaluation criteria below are "4", "3", or "2", the quality is considered usable.

[1001] (Evaluation Criteria)

[1002] 4: Color difference (ΔE* value) less than 2

[1003] 3: Color difference (ΔE* value) is 2 or higher and less than 3.

[1004] 2: Color difference (ΔE* value) is 3 or higher and less than 5

[1005] 1: Color difference (ΔE* value) is 5 or higher.

[1006] [Table 19-1]

[1007]

[1008] [Table 19-2]

[1009]

[1010] [Table 19-3]

[1011]

[1012] [Table 19-4]

[1013]

[1014] Based on the above results, the effects of pigment compositions containing isoindoline compound (1) and isoindoline compound (2) can be observed. For example, based on the results in Table 7, a molding composition capable of forming molded articles with excellent heat resistance can be obtained. Furthermore, based on the results for toners, a toner with excellent pigment dispersibility can be obtained. Furthermore, based on the results for coatings, a coating with excellent weather resistance can be obtained. In particular, discoloration can be suppressed. Furthermore, based on the results for gravure inks, printing inks with excellent viscosity change, transparency, and even scratch resistance and adhesion in printed materials can be obtained. Furthermore, based on the results for water-based flexographic inks, water-based flexographic inks with improved dispersibility and long-term stability can be obtained. Furthermore, based on the results for active energy ray curable inks, active energy ray curable inks with improved initial viscosity and storage stability can be obtained. Furthermore, based on the results for water-based coloring compositions, initial viscosity and storage stability can be improved. Further, based on the results for water-based inkjet inks, inkjet inks capable of suppressing color changes in the ink film during long-term storage stability can be obtained. In particular, it has been confirmed that long-term storage stability can be further improved by using it as a crosslinked resin particle in a pigment-containing composition. It should be noted that while the examples illustrate coloring compositions and their uses using representative isoindoline compounds, the embodiments of the present invention are not limited to these. Compounds equivalent to isoindoline compound (1) and isoindoline compound (2) can be used in various applications, and the same effects as in the specifically illustrated examples can be obtained by using these compounds. For example, the desired effects can be easily obtained even when using coloring compositions used in gravure inks and water-based flexographic inks to formulate inks of other types, such as water-based inkjet inks.

[1015] <III> Evaluation of Ink Groups and Their Characteristics

[1016] <Gravure Ink Set>

[1017] The obtained isoindoline compounds were used to formulate gravure ink groups, and their properties were evaluated.

[1018] (Synthesis Example 6) Polyurethane Resin Solution [PU2]

[1019] 54.719 parts of polyester diol with a number average molecular weight of 2,000 obtained from adipic acid and 3-methyl-1,5-pentanediol, 3.989 parts of isophorone diisocyanate, and 10.0 parts of n-propyl acetate were reacted at 85°C for 3 hours under a nitrogen atmosphere. Then, 10.0 parts of n-propyl acetate were added and the mixture was cooled to obtain a solvent solution of 78.718 parts of terminal isocyanate prepolymer.

[1020] Next, 78.718 parts of the solvent solution of the obtained terminal isocyanate prepolymer were slowly added to a substance composed of 1.031 parts of isophorone diamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate and 19.6 parts of isopropanol at room temperature. Then, the mixture was reacted at 50°C for 1 hour to obtain a polyurethane resin solution [PU2] with 30% non-volatile components, a weight average molecular weight of 60,000 and an amine value of 3.0 mgKOH / g.

[1021] (Synthesis Example 7) Polyurethane Resin Solution [PU3]

[1022] Nitrogen gas was introduced into a reaction vessel equipped with a reflux cooling pipe, a dropping funnel, a gas inlet pipe, a stirrer, and a thermometer. Simultaneously, 161.9 parts of PPA (poly(propylene glycol) adipate glycol with a number average molecular weight of 2,000), 27.7 parts of 2,2-dimethylolbutyric acid (DMBA), 96.4 parts of isophorone diisocyanate (IPDI), and 200 parts of methyl ethyl ketone (MEK) were added. The mixture was reacted at 90°C for 5 hours to obtain a resin solution of a urethane prepolymer with terminal isocyanate groups.

[1023] A mixture of 13.6 parts of 2-(2-aminoethylamino)ethanol (AEA), 0.5 parts of ethanolamine (MEA), and 350 parts of isopropanol (IPA) was added dropwise over 60 minutes at room temperature relative to the obtained terminal isocyanate-based urethane prepolymer resin solution, and the mixture was further reacted at 70°C for 3 hours. 150 parts of MEK were then used to adjust the non-volatile components to obtain a polyurethane resin solution [PU3] with 30% non-volatile components, a weight-average molecular weight of 35,000, Mw / Mn = 3.0, an acid value of 35.0 mgKOH / g, and a hydroxyl value of 25.7 mgKOH / g.

[1024] (Synthetic Example 8) Aluminum Phthalocyanine

[1025] 1250 parts of n-pentanol, 225 parts of phthalonitrile, and 78 parts of anhydrous aluminum chloride were added to a reaction vessel and mixed with stirring. 266 parts of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) were added, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution, cooled to 30°C under stirring, was injected into a mixed solvent containing 5000 parts of methanol and 10000 parts of water while stirring, to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent containing 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride represented by the following chemical formula (16).

[1026] [Chemistry 9]

[1027]

[1028] Next, 1500 parts of concentrated sulfuric acid were added to the reaction vessel, followed by 100 parts of the above-mentioned aluminum phthalocyanine chloride under ice bath conditions, and the mixture was stirred at 25°C for 4 hours. Then, the sulfuric acid solution was injected into 9000 parts of cold water at 3°C, and the resulting precipitate was treated in the following order: filtration, water washing, washing with 1% sodium hydroxide aqueous solution, and water washing, and then dried to obtain 98 parts of aluminum phthalocyanine represented by the following chemical formula (11).

[1029] [Chemistry 10]

[1030]

[1031] (Synthetic Example 9) Oxytitanium Phthalocyanine

[1032] 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 the reaction vessel and mixed with stirring. The mixture was heated to 155°C and refluxed for 8 hours. It should be noted that the n-butanol produced in the system was recovered to avoid its return to the system. 1000 parts of methanol were added to the reaction solution cooled to 60°C while stirring. The slurry was filtered and washed and dried in the following order: 1000 parts of methanol, 500 parts of N-methylpyrrolidone, and 1000 parts of methanol, to obtain 250 parts of crude oxytitanium phthalocyanine represented by the following chemical formula (12).

[1033] [Chemistry 11]

[1034]

[1035] Next, 1500 parts of concentrated sulfuric acid were added to the reaction vessel, followed by 100 parts of the crude titanium phthalocyanine product mentioned above, under ice bath conditions. The mixture was stirred at 25°C for 4 hours. Then, the sulfuric acid solution was poured into 9000 parts of cold water at 3°C. The resulting precipitate was treated in the following sequence: filtration, washing with water, washing with a 1% sodium hydroxide aqueous solution, and washing with water again to obtain a filter cake. Next, 1000 parts of diethylene glycol and the obtained filter cake were added to the reaction vessel and stirred to form a slurry, which was then stirred at 120°C for 3 hours. The slurry, cooled to 60°C, was filtered, washed with 5000 parts of water, and dried to obtain 87 parts of titanium phthalocyanine.

[1036] (Example LY-1) [Preparation of Yellow Ink [LY-1]]

[1037] 7.0 parts of isoindoline compound (1-1), 34.5 parts of polyurethane resin solution [PU2], 20 parts of N-propyl acetate, and 5 parts of isopropanol were stirred and mixed, and then kneaded using a sand mixer. Finally, 20 parts of polyurethane resin solution [PU2], 11 parts of N-propyl acetate, and 3 parts of isopropanol were added to obtain yellow ink [LY-1].

[1038] (Examples LY-2~LY-20, Manufacturing Examples LY-1~LY-11, LC-1~LC-5, LM-1~LM-10) [Preparation of yellow ink [LY-2]~[LY-31], cyan ink [LC-1]~[LC-6], magenta ink [LM-1]~[LM-10]]

[1039] The 7.0 parts of isoindoline compound (1-1) were changed to the compounds and amounts shown in Table 20, and otherwise operated in the same manner as in Example LY-1 to obtain the ink shown in Table 20.

[1040] [Table 20-1]

[1041]

[1042] [Table 20-2]

[1043]

[1044] The pigments used in the manufacture of the inks are shown in Table 21.

[1045] [Table 21]

[1046] pigment Product Name PB15:3 LIONOL BLUE FG-7358-G (manufactured by Toyo Color Materials Co., Ltd.) PB15:4 LIONOL BLUE FG-7400-G (manufactured by Toyo Color Materials Co., Ltd.) PB16 Heliogen Blue D7490 (manufactured by BASF) Aluminum Phthalocyanine Aluminum Phthalocyanine of Synthetic Example 7 Oxytitanium Phthalocyanine Synthetic Example 8: Oxytitanium Phthalocyanine PR122 Hostaperm Pink E 02 (Made by Clariant) PV19 Hostaperm Red Violet ER02 (Made by Clariant) PR48:3 FUJI Red 5R 763 (manufactured by Fuji Pigment Co., Ltd.) PR57:1 LIONOL RED 6B FG-4306-G (manufactured by Toyo Color Materials Co., Ltd.) PR146 LIONOL RED 5620 (manufactured by Toyo Color Materials Co., Ltd.) PR185 Novoperm Carmine HF4C (manufactured by Clariant) PR144 Cromophtal Red D3890 (manufactured by BASF) PR179 Paliogen Red L3885 (manufactured by BASF) PR255 Irgazin Scarlet L3550HD (BASF) PR264 Irgazin Rubine L4025 (manufactured by BASF)

[1047] [Evaluation Methods and Criteria]

[1048] <Evaluation of Gravure Inks>

[1049] [Viscosity stability over time]

[1050] For the yellow inks [LY-1] to [LY-31], cyan inks [LC-1] to [LC-5], and magenta inks [LM-1] to [LM-10], they were placed in sealed containers and stored at 40°C for 14 days. The viscosity was then measured and compared with the viscosity change before storage for evaluation. It should be noted that the viscosity was measured at 25°C using the flow rate in seconds using a Zahn Cup No. 4. It should also be noted that the viscosity of any ink in the Type B viscometer before storage was in the range of 40–500 cps (25°C). The results are shown in Table 23.

[1051] (Evaluation Criteria)

[1052] ○: Viscosity change less than 2 seconds (Good)

[1053] △: Viscosity change occurs in 2 seconds or more but less than 5 seconds (practical).

[1054] ×: Viscosity change lasting more than 5 seconds (unacceptable)

[1055] <Evaluation of the Ink Group>

[1056] (Examples LS-1 to LS-69, Comparative Examples LS-1 to LS-24) [Preparation of Ink Groups 1 to 93]

[1057] The obtained inks were combined as described in Table 22 to create ink groups 1 through 93. The overprinting properties and gamut of the obtained ink groups were evaluated using the following methods. The results are shown in Table 23.

[1058] [Table 22-1]

[1059] Table 22-1 ink group Yellow ink Cyan ink magenta ink Example LS-1 Ink Group 1 [LY-1] [LC-1] [LM-1] Example LS-2 Ink Group 2 [LY-2] [LC-1] [LM-1] Example LS-3 Ink Group 3 [LY-3] [LC-1] [LM-1] Example LS-4 Ink Group 4 [LY-4] [LC-1] [LM-1] Example LS-5 Ink Group 5 [LY-5] [LC-1] [LM-1] Example LS-6 Ink Group 6 [LY-6] [LC-1] [LM-1] Example LS-7 Ink Group 7 [LY-7] [LC-1] [LM-1] Example LS-8 Ink Group 8 [LY-8] [LC-1] [LM-1] Example LS-9 Ink Group 9 [LY-9] [LC-1] [LM-1] Example LS-10 Ink Group 10 [LY-10] [LC-1] [LM-1] Example LS-11 Ink Group 11 [LY-11] [LC-1] [LM-1] Example LS-12 Ink Group 12 [LY-12] [LC-1] [LM-1] Example LS-13 Ink Group 13 [LY-13] [LC-1] [LM-1] Example LS-14 Ink Group 14 [LY-14] [LC-1] [LM-1] Example LS-15 Ink Group 15 [LY-15] [LC-1] [LM-1] Example LS-16 Ink Group 16 [LY-16] [LC-1] [LM-1] Example LS-17 Ink Group 17 [LY-17] [LC-1] [LM-1] Example LS-18 Ink Group 18 [LY-18] [LC-1] [LM-1] Example LS-19 Ink Group 19 [LY-19] [LC-1] [LM-1] Example LS-20 Ink Group 20 [LY-20] [LC-1] [LM-1] Example LS-21 Ink Group 21 [LY-4] [LC-1] [LM-2] Example LS-22 Ink Group 22 [LY-4] [LC-1] [LM-3] Example LS-23 Ink Group 23 [LY-4] [LC-1] [LM-4] Example LS-24 Ink Group 24 [LY-4] [LC-1] [LM-5] Example LS-25 Ink Group 25 [LY-4] [LC-1] [LM-6] Example LS-26 Ink Group 26 [LY-4] [LC-1] [LM-7] Example LS-27 Ink Group 27 [LY-4] [LC-1] [LM-8] Example LS-28 Ink Group 28 [LY-4] [LC-1] [LM-9] Example LS-29 Ink Group 29 [LY-4] [LC-1] [LM-10] Example LS-30 Ink group 30 [LY-4] [LC-2] [LM-1] Example LS-31 Ink Group 31 [LY-4] [LC-2] [LM-2] Example LS-32 Ink group 32 [LY-4] [LC-2] [LM-3] Example LS-33 Ink Group 33 [LY-4] [LC-2] [LM-4] Example LS-34 Ink group 34 [LY-4] [LC-2] [LM-5] Example LS-35 Ink group 35 [LY-4] [LC-2] [LM-6] Example LS-36 Ink group 36 [LY-4] [LC-2] [LM-7] Example LS-37 Ink Group 37 [LY-4] [LC-2] [LM-8] Example LS-38 Ink group 38 [LY-4] [LC-2] [LM-9] Example LS-39 Ink Group 39 [LY-4] [LC-2] [LM-10] Example LS-40 Ink group 40 [LY-4] [LC-3] [LM-1] Example LS-41 Ink Group 41 [LY-4] [LC-3] [LM-2] Example LS-42 Ink group 42 [LY-4] [LC-3] [LM-3] Example LS-43 Ink Group 43 [LY-4] [LC-3] [LM-4] Example LS-44 Ink group 44 [LY-4] [LC-3] [LM-5] Example LS-45 Ink Group 45 [LY-4] [LC-3] [LM-6]

[1060] [Table 22-2]

[1061] Table 22-2 ink group Yellow ink Cyan ink magenta ink Example LS-46 Ink group 46 [LY-4] [LC-3] [LM-7] Example LS-47 Ink Group 47 [LY-4] [LC-3] [LM-8] Example LS-48 Ink group 48 [LY-4] [LC-3] [LM-9] Example LS-49 Ink Group 49 [LY-4] [LC-3] [LM-10] Example LS-50 Ink Group 50 [LY-4] [LC-4] [LM-1] Example LS-51 Ink Group 51 [LY-4] [LC-4] [LM-2] Example LS-52 Ink Group 52 [LY-4] [LC-4] [LM-3] Example LS-53 Ink Group 53 [LY-4] [LC-4] [LM-4] Example LS-54 Ink Group 54 [LY-4] [LC-4] [LM-5] Example LS-55 Ink Group 55 [LY-4] [LC-4] [LM-6] Example LS-56 Ink Group 56 [LY-4] [LC-4] [LM-7] Example LS-57 Ink Group 57 [LY-4] [LC-4] [LM-8] Example LS-58 Ink Group 58 [LY-4] [LC-4] [LM-9] Example LS-59 Ink Group 59 [LY-4] [LC-4] [LM-10] Example LS-60 Ink Group 60 [LY-4] [LC-5] [LM-1] Example LS-61 Ink Group 61 [LY-4] [LC-5] [LM-2] Example LS-62 Ink group 62 [LY-4] [LC-5] [LM-3] Example LS-63 Ink Group 63 [LY-4] [LC-5] [LM-4] Example LS-64 Ink Group 64 [LY-4] [LC-5] [LM-5] Example LS-65 Ink Group 65 [LY-4] [LC-5] [LM-6] Example LS-66 Ink Group 66 [LY-4] [LC-5] [LM-7] Example LS-67 Ink Group 67 [LY-4] [LC-5] [LM-8] Example LS-68 Ink group 68 [LY-4] [LC-5] [LM-9] Example LS-69 Ink Group 69 [LY-4] [LC-5] [LM-10] Comparative example LS-1 Ink Group 70 [LY-21] [LC-1] [LM-1] Comparative example LS-2 Ink Group 71 [LY-22] [LC-1] [LM-1] Comparative example LS-3 Ink Group 72 [LY-23] [LC-1] [LM-1] Comparative example LS-4 Ink Group 73 [LY-24] [LC-1] [LM-1] Comparative example LS-5 Ink Group 74 [LY-25] [LC-1] [LM-1] Comparative example LS-6 Ink Group 75 [LY-26] [LC-1] [LM-1] Comparative example LS-7 Ink Group 76 [LY-27] [LC-1] [LM-1] Comparative example LS-8 Ink Group 77 [LY-28] [LC-1] [LM-1] Comparative example LS-9 Ink Group 78 [LY-29] [LC-1] [LM-1] Comparative example LS-10 Ink Group 79 [LY-30] [LC-1] [LM-1] Comparative example LS-11 Ink Group 80 [LY-31] [LC-1] [LM-1] Comparative example LS-12 Ink Group 81 [LY-21] [LC-1] [LM-2] Comparative example LS-13 Ink Group 82 [LY-21] [LC-1] [LM-3] Comparative example LS-14 Ink Group 83 [LY-21] [LC-1] [LM-4] Comparative example LS-15 Ink Group 84 [LY-21] [LC-1] [LM-5] Comparative example LS-16 Ink Group 85 [LY-21] [LC-1] [LM-6] Comparative example LS-17 Ink Group 86 [LY-21] [LC-1] [LM-7] Comparative example LS-18 Ink Group 87 [LY-21] [LC-1] [LM-8] Comparative example LS-19 Ink Group 88 [LY-21] [LC-1] [LM-9] Comparative example LS-20 Ink Group 89 [LY-21] [LC-1] [LM-10] Comparative example LS-21 Ink Group 90 [LY-21] [LC-2] [LM-1] Comparative example LS-22 Ink Group 91 [LY-21] [LC-3] [LM-1] Comparative example LS-23 Ink Group 92 [LY-21] [LC-4] [LM-1] Comparative example LS-24 Ink Group 93 [LY-21] [LC-5] [LM-1]

[1062] [Overprint Performance Evaluation]

[1063] (Cyan ink / Yellow ink)

[1064] Cyan and yellow inks were diluted with mixed solvent 1 (methyl ethyl ketone: N-propyl acetate: isopropanol = 40:40:20) at a viscosity of 16 seconds (25°C, Zahn Cup No. 3).

[1065] A cyan-yellow overprint was performed on the corona-treated surface of a 12μm thick corona-treated polyester film (Toyobo Co., Ltd. E-5100) to obtain a printed material (initial evaluation of overprintability).

[1066] The printing conditions were set at a temperature of 25°C, humidity of 60%, printing speed of 100 m / min, and printing distance of 4000 m. Cyan ink was printed using a Helio 175-line gradient plate (format compression, 75% solid image and 100%–3% gradient pattern), while yellow ink was printed using a Helio 175-line gradient plate (format elongation, 75% solid image and 100%–3% gradient pattern).

[1067] In addition, the cyan ink and yellow ink were placed in sealed containers and stored at 40°C for 14 days. Then, they were diluted and printed in the same manner as above to obtain the printed matter (overprint performance evaluation over time).

[1068] (Yellow ink / Magenta ink)

[1069] The yellow ink and magenta ink were diluted with the above-mentioned mixed solvent 1 at a viscosity of 16 seconds (25°C, Zahn Cup No. 3).

[1070] Overlapping printing was performed on the corona-treated surface of a 12μm thick corona-treated polyester film (Toyobo Co., Ltd. E-5100) in the order of yellow and magenta to obtain a printed material (initial evaluation of overprintability).

[1071] The printing conditions were set at a temperature of 25°C, humidity of 60%, printing speed of 100 m / min, and printing distance of 4000 m. Yellow ink was printed using a Helio 175-line gradient plate (with an elongated plate, 75% solid image and 100%–3% gradient image), and magenta ink was printed using a Helio 175-line gradient plate (with an elongated plate, 75% solid image and 100%–3% gradient image).

[1072] In addition, yellow ink and magenta ink were placed in sealed containers and stored at 40°C for 14 days. Then, they were diluted and printed in the same manner as above to obtain printed materials (overprint performance evaluation over time).

[1073] For the overlapping areas of the obtained prints with varying tones, the overprinting properties were observed using a Keyence microscope (VHX-5000) and evaluated according to the following criteria.

[1074] (Evaluation Criteria)

[1075] ○: Uneven printing occurs at areas less than 70% of the plate depth (good).

[1076] △: Uneven printing occurs in areas with a plate depth of 70% or more but less than 80% (can be used).

[1077] ×: Uneven printing occurs at areas with a plate depth of 80% or more, or overlapping ink forms dots without wetting and spreading (not usable).

[1078] [Color Gamut Evaluation]

[1079] (Initial evaluation)

[1080] The cyan, magenta, and yellow inks were diluted using the aforementioned mixed solvent 1 to a viscosity of 16 seconds (25°C, Zahn Cup No. 3). Using the diluted inks, printing was performed in the order of cyan, magenta, and yellow to obtain a print with solid areas (cyan, magenta, yellow) and overlapping solid areas (cyan × magenta, cyan × yellow, yellow × magenta). The printing conditions are shown below.

[1081] (Printing conditions)

[1082] Printing press: Fuji Machinery five-color press

[1083] Cyan version: Helio gravure 175 lines / inch (L / inch), stylus angle 120°, elongated.

[1084] Magenta version: Intaglio 175L / inch, stylus angle 120°, compression.

[1085] Yellow version: Gravure (Helio) 175L / inch, stylus angle 120°, compression.

[1086] Printing speed: 150m / min

[1087] Substrate: Corona-treated biaxially stretched polypropylene (OPP) film (Toyobo Co., Ltd., PYLEN P-2161, 20μm)

[1088] Drying temperature: 50℃

[1089] For the obtained prints, the concentration values ​​of the solid areas (yellow, magenta, and cyan) of the prints were determined using a Gretagmacbeth D196 instrument. Additionally, a Gretagmacbeth SpectroEye instrument was used as the measuring instrument to measure the solid areas and overlapping areas of the prints under conditions of a D50 light source, a 2-degree field of view, a white background (using a standard white plate), and without the use of filters.

[1090] In a two-dimensional space with a* as the horizontal axis and b* as the vertical axis, a hexagon is created by plotting the values ​​of a* versus b* for six colors: solid areas (yellow, magenta, cyan) and overlapping solid areas (cyan × magenta, cyan × yellow, yellow × magenta). The area is then calculated. The area ratio is determined when the area of ​​the comparative example used as a benchmark is set to 100%, and the comparison is performed according to the following criteria based on this area ratio. Specifically, the comparative examples listed in Table 23 are used as benchmarks for comparison. It should be noted that - indicates no evaluation.

[1091] (Evaluation Criteria)

[1092] ○: Area ratio is above 90% (good)

[1093] △: Area ratio of 85% or more but less than 90% (usable)

[1094] ×: Area ratio less than 85% (cannot be used)

[1095] (Evaluation over time)

[1096] Cyan, magenta, and yellow inks were placed in sealed containers and stored at 40°C for 14 days. They were then diluted and printed in the same manner as in the initial evaluation to obtain the printed materials.

[1097] The obtained printed materials were subjected to color measurement in the same manner as the initial evaluation described above.

[1098] In a two-dimensional space with a* as the horizontal axis and b* as the vertical axis, a hexagon is created by plotting the values ​​of a* versus b* for a total of six colors: solid areas (yellow, magenta, cyan) and overlapping solid areas (cyan × magenta, cyan × yellow, yellow × magenta). The area ratio, obtained by dividing the area in the time-lapse evaluation of each embodiment / comparative example by the area in the initial evaluation, is calculated, and the evaluation is performed based on this area ratio according to the following criteria. - indicates no evaluation.

[1099] (Evaluation Criteria)

[1100] ○: Area ratio is above 98% (Good)

[1101] △: Area ratio of 95% or higher and less than 98% (usable)

[1102] ×: Area ratio less than 95% (unacceptable)

[1103] [Table 23-1]

[1104]

[1105] [Table 23-2]

[1106]

[1107] As shown in Table 23, the gravure ink set, as an embodiment of the present invention, has a color gamut area ratio that is equal to or greater than that of conventional ink sets, exhibiting excellent color reproduction. Furthermore, the viscosity stability of the yellow ink is improved over time, resulting in good storage stability as an ink set. Moreover, the overprinting properties and color reproduction (color gamut) of each color are also evaluated well over time, demonstrating good storage stability as an ink set.

[1108] On the other hand, in Comparative Examples LS-1 to LS-24, the yellow ink exhibited poor viscosity stability over time, and its overprinting performance and color reproduction (color gamut) were also poor over time. Therefore, it can be concluded that the poor storage stability of the ink group fails to address the issues raised in this application.

[1109] <Manufacturing of Transparent Inks>

[1110] (Preparation of transparent ink[1])

[1111] Using a disperser, 87 parts of polyurethane resin solution [PU3] (30% non-volatile component), 5 parts of ethyl acetate (EA), 5 parts of IPA, and 3 parts of silica (Mizusawa Chemical Co., Ltd. "P-73", hydrophilic silica particles with an average particle size of 3.8 μm) were stirred and mixed to obtain transparent ink [1].

[1112] <Manufacturing of adhesives with release properties>

[1113] (Preparation of lamination adhesive solution [1])

[1114] An esterification reaction was carried out in a four-necked separable flask containing 82 parts terephthalic acid, 682 parts isophthalic acid, 236 parts adipic acid, 236 parts ethylene glycol, 525 parts neopentyl glycol, and 405 parts 1,6-hexanediol, at 220–260 °C. After distilling off a predetermined amount of water, a de-ethylene glycol removal reaction was carried out slowly under reduced pressure at 240–260 °C (below 1 mmHg) for 5 hours. Then, 2 parts isophorone diisocyanate were slowly added, and the reaction was carried out at 150 °C for approximately 2 hours to obtain a polyester polyurethane polyol.

[1115] 2.83 parts trimellitic anhydride were added to 100 parts of the polyester polyurethane polyol, and the reaction was carried out at 180°C for about 2 hours. Then, the solution was diluted with ethyl acetate to a non-volatile content of 50%, resulting in a partially acid-modified polyester polyol solution with a number average molecular weight of 6,000 and an acid value of 16.5 mgKOH / g.

[1116] 100 parts of the obtained polyol solution were mixed with 7.94 parts of ethyl acetate solution containing 95% non-volatile component of HDI biuret, and ethyl acetate was added to obtain a laminate adhesive solution containing 30% non-volatile component [1].

[1117] <Evaluation of Packaging Materials>

[1118] (Example LP-1) [Preparation of Packaging Material 1]

[1119] The cyan ink [LC-1], magenta ink [LM-1], and yellow ink [LY-1] were diluted using the above-mentioned mixed solvent 1 at a viscosity of 16 seconds (25°C, Zahn Cup No. 3).

[1120] Using diluted inks, a gravure correction five-color press with a 20μm deep gravure plate was prepared, along with ink set 101 containing black ink (LIOALPHA R92 ink (manufactured by Toyo Ink Co., Ltd.)), cyan ink [LC-1], magenta ink [LM-1], yellow ink [LY-1], and white ink (LIOALPHA R631 white (manufactured by Toyo Ink Co., Ltd.)). Using these inks, overlay printing was performed on a 20μm thick corona-treated stretched polypropylene film (OPP substrate) in the following order: black ink, cyan ink [LC-1], magenta ink [LM-1], yellow ink [LY-1], and white ink. Each unit was dried at 50°C to obtain a printed material consisting of "OPP substrate / black, cyan, magenta, yellow, or white printing layers".

[1121] Next, a coating of 2.0 g / m² is applied to the printed layer of the obtained print. 2 A urethane-based laminated adhesive (TM320 / CAT13B manufactured by Toyo Morton, 30% ethyl acetate solution with non-volatile components) was applied and dried. Then, a 50 μm thick unstretched polyethylene (PE) film was laminated onto the adhesive layer to obtain packaging material 1 consisting of "OPP substrate / five-color overlay printing layer / adhesive layer / PE substrate".

[1122] (Examples LP-2 to LP-69) [Preparation of Packaging Materials 2 to 69]

[1123] The ink group 101 used in Example LP-1 was changed to the ink group shown in Table 24. Otherwise, the same procedure as in Example LP-1 was followed to obtain packaging materials 2 to 69.

[1124] [Table 24-1]

[1125]

[1126] [Table 24-2]

[1127]

[1128] (Example LP-101) [Preparation of Packaging Material 101]

[1129] The transparent ink[1] was diluted with EA / IPA mixed solvent (mass ratio 70 / 30) to a viscosity of 15 seconds (25°C, Zahn Cup No. 3).

[1130] The cyan ink [LC-1], magenta ink [LM-1], and yellow ink [LY-1] were diluted using the above-mentioned mixed solvent 1 at a viscosity of 16 seconds (25°C, Zahn Cup No. 3).

[1131] Using diluted inks, a gravure correction five-color press with a gravure plate having a depth of 20 μm and an ink set 201 containing transparent ink [1], cyan ink [LC-1], magenta ink [LM-1], and yellow ink [LY-1] were prepared. Using these inks, corona-treated stretched polypropylene film with a thickness of 20 μm was overprinted in the order of transparent ink [1], cyan ink [LC-1], magenta ink [LM-1], and yellow ink [LY-1]. In each unit, the film was dried at 50°C to obtain a print consisting of "OPP substrate / release layer (transparent ink) / cyan, magenta, or yellow print layer" and including a release layer (a print layer with release properties).

[1132] Next, a laminating adhesive solution was applied to the printed layer of the obtained printed material using a dry laminator [1], and laminated with an aluminum vapor-deposited non-stretched polypropylene (VMCPP) film with a thickness of 25 μm at a line speed of 40 m / min, to obtain a packaging material 101 with a release layer consisting of “OPP substrate / release layer (releaseable printed layer) / three-color overlay printed layer / releaseable adhesive layer / VMCPP substrate”.

[1133] (Examples LP-102 to LP-169) [Preparation of Packaging Materials 102 to 169]

[1134] The ink group 201 used in Example LP-101 was changed to the ink group shown in Table 25. Otherwise, the same procedure as in Example LP-101 was followed to obtain packaging materials 102 to 169 with a release layer.

[1135] [Table 25-1]

[1136]

[1137] [Table 25-2]

[1138]

[1139] Packaging materials can be manufactured by using the gravure ink set of the present invention.

[1140] <Inkjet Ink Group>

[1141] The obtained isoindoline compounds were used to formulate inkjet ink groups, and their properties were evaluated.

[1142] (Example MY-1) [Preparation of Inkjet Water-Based Coloring Composition (hereinafter referred to as "IJ Water-Based Coloring Composition") IJ Water-Based Coloring Composition [MY-1]]

[1143] The following materials were placed in a 200ml glass bottle along with 200 parts of 1.25mm diameter zirconia beads and dispersed for 6 hours using a RedDevil paint shaker.

[1144] • Isoindoline compounds (1-1): 19.0 parts

[1145] • Styrene-acrylic acid copolymer (manufactured by BASF Japan, JONCRYL 61J): 16.4 parts

[1146] Surfactant (manufactured by Kao Corporation, EMULGEN 420): 5.0 parts

[1147] • Ion-exchanged water: 59.6 parts

[1148] Next, the zirconia beads were removed from the dispersion to obtain the IJ waterborne coloring composition [MY-1].

[1149] (Water-based inkjet ink (hereinafter referred to as "water-based IJ ink") [Production of water-based IJ ink [MY-1]]

[1150] 33 parts of aqueous IJ dispersion, 1.5 parts of butyl diethylene glycol, 15 parts of 1,2-propanediol, 8.8 parts of Joncryl HPD96 (manufactured by BASF Japan, water-soluble resin), 1.25 parts of CHEMIPEARL W400S (manufactured by Mitsui Chemicals, a polyolefin aqueous dispersion), 0.5 parts of SURFYNOL DF110D (manufactured by Nissin Chemical Industry Co., Ltd., defoamer), 1 part of BYK-348 (manufactured by BYK Chemicals Japan, a silicone surfactant), 0.1 parts of triethanolamine, 0.15 parts of Proxel GXL (manufactured by Lonza, a preservative), and 35.2 parts of deionized water were mixed using a high-speed mixer and filtered through a 0.5 μm membrane filter to obtain aqueous IJ ink [MY-1].

[1151] (Examples MY-2~MY-20, Manufacturing Examples MY-1~MY-11, MC-1~MC-3, MM-1~MM-6) [Preparation of water-based coloring compositions [MY-2]~[MY-31], [MC-1]~[MC-3], [MM-1]~[MM-6], and water-based inks [MY-2]~[MY-31], [MC-1]~[MC-3], [MM-1]~[MM-6]]

[1152] The 19.0 parts of isoindoline compound (1-1) of manufacturing example MY-1 were changed to the compounds and amounts shown in Table 26. Otherwise, the same procedure was followed as in example MY-1 to obtain the IJ waterborne coloring compositions [MY-2] to [MY-31], [MC-1] to [MC-3], [MM-1] to [MM-6], and waterborne IJ inks [MY-2] to [MY-31], [MC-1] to [MC-3], [MM-1] to [MM-6] shown in Table 26.

[1153] [Table 26-1]

[1154]

[1155] [Table 26-2]

[1156]

[1157] The pigments used in the manufacture of the inks are shown in Table 27.

[1158] [Table 27]

[1159] pigment Product Name PB15:3 LIONOGEN BLUE 7919 (manufactured by Toyo Color Materials Co., Ltd.) PB15:4 LIONOL BLUE FG-7412-J (manufactured by Toyo Color Materials Co., Ltd.) PB16 Heliogen Blue D7490 (manufactured by BASF) PR122 Cinquasia Magenta D4550J (manufactured by BASF) PV19 Cinquasia Magenta E05B (BASF manufactured) PR48:3 FUJI Red 5R 763 (manufactured by Fuji Pigment Co., Ltd.) PR57:1 SYMULER Brilliant Carmine 6B 400S (manufactured by DIC) PR146 LIONOL RED 5620 (manufactured by Toyo Color Materials Co., Ltd.) PR185 Novoperm Carmine HF4C (manufactured by Clariant)

[1160] [Evaluation of Viscosity Stability Over Time]

[1161] For water-based IJ inks [MY-1] to [MY-31], [MC-1] to [MC-3], and [MM-1] to [MM-6], the initial viscosity at 25°C was measured using an E-type viscometer (Toki Sangyo Co., Ltd.'s "ELD type viscometer"). Similarly, the viscosity was measured after 4 weeks at 25°C and after 4 weeks of accelerated viscosity development at 50°C. Using each measured value, the viscosity increase rate relative to the initial viscosity was calculated as an indicator of viscosity stability, and evaluated according to the following criteria. The results are shown in Table 29. A smaller viscosity increase rate indicates better viscosity stability; a value of "4", "3", or "2" in the following evaluation criteria indicates a practically usable level.

[1162] (Evaluation criteria for viscosity stability)

[1163] 4: The viscosity increase rate is less than 15%.

[1164] 3: The viscosity increase rate is more than 15% but less than 25%.

[1165] 2: The viscosity increase rate is greater than 25% but less than 40%.

[1166] 1: The viscosity increase rate is over 40%.

[1167] <Evaluation of the Ink Group>

[1168] (Examples MS-1 to MS-37, Comparative Examples MS-1 to MS-18) [Preparation of Ink Groups 301 to 355]

[1169] Combine the obtained water-based IJ inks as described in Table 28 to produce ink groups 301 to 355.

[1170] [Table 28-1]

[1171]

[1172] [Table 28-2]

[1173]

[1174] The color gamut of the obtained ink groups was evaluated using the following method. The results are shown in Table 29.

[1175] [Color Gamut Evaluation]

[1176] (Initial evaluation)

[1177] In a line-type inkjet printer using a printhead (Kyocera KJ4B series) with a width-direction resolution of 600 dpi and a maximum ejection frequency of 30 kHz, yellow, magenta, and cyan inks from each ink group were filled into each printhead. Using these inks, coated paper (OK TOP COAT N, Oji Paper Co., Ltd., weight 104.7 g / m²) was printed. 2 A color chart image (X-rite profilemaker chart image "TC3.5 CMYK i1 i0") was printed at a resolution of 600×600dpi to produce evaluation materials.

[1178] The color charts of the obtained evaluation prints were measured using a spectrophotometer (X-rite i1 i0 Pro) and colorimetric tools (X-rite Measurement Tool and Profilemaker), and the color reproduction areas in the L*a*b* color space were plotted. Measurements were performed under the following conditions: light source D50, 2-degree field of view, and measurement optics 45 / 0°. The area of ​​each plot was calculated. The area ratio was determined when the area of ​​the comparative examples used as a benchmark was set to 100%, and the evaluation was conducted according to the following criteria based on this area ratio. Specifically, the comparative examples listed in Table 29 were used as benchmarks.

[1179] (Evaluation Criteria)

[1180] ○: Area ratio is above 90% (good)

[1181] △: Area ratio of 85% or more but less than 90% (usable)

[1182] ×: Area ratio less than 85% (cannot be used)

[1183] (Evaluation over time)

[1184] Each water-based ink was placed in a sealed container and stored at 50°C for 4 weeks. Then, it was printed in the same manner as the initial evaluation to produce evaluation prints. Color measurements were performed on the obtained prints in the same manner as the initial evaluation, and the area was calculated based on the obtained drawings. The area ratio, obtained by dividing the area in the time-lapse evaluation of each embodiment / comparative example by the area in the initial evaluation, was calculated. Evaluation was then conducted based on this area ratio according to the following criteria.

[1185] (Evaluation Criteria)

[1186] ○: Area ratio is above 98% (Good)

[1187] △: Area ratio of 95% or higher and less than 98% (usable)

[1188] ×: Area ratio less than 95% (unacceptable)

[1189] [Table 29-1]

[1190]

[1191] [Table 29-2]

[1192]

[1193] As shown in Table 29, the water-based ink group, as an embodiment of the present invention, exhibits a color gamut area ratio equal to or greater than that of conventional ink groups, demonstrating excellent color reproduction. Furthermore, the yellow ink shows improved viscosity stability over time, resulting in good storage stability as an ink group. Moreover, its color reproduction (color gamut) also demonstrates good performance over time, indicating good storage stability as an ink group.

[1194] On the other hand, in Comparative Examples MS-1 to MS-18, the yellow ink exhibited poor viscosity stability over time and also performed poorly in color reproduction (color gamut) over time. Therefore, the poor storage stability of the ink group fails to address the issues raised in this application.

[1195] <Active Energy X-ray Curable Ink Group>

[1196] The obtained isoindoline compounds were used to formulate active energy X-ray curable ink groups, and their properties were evaluated.

[1197] (Example RY-1) [Preparation of Yellow Ink [RY-1]]

[1198] The following materials were mixed using a disc mixer and dispersed using a three-roll mill to produce yellow ink [RY-1] with a maximum particle size of less than 15 μm.

[1199] • Isoindoline compound (1-1): 18.0 parts

[1200] • EBECRYL225: 8.4 parts (5.0 parts based on active ingredient)

[1201] (10-functional urethane acrylate oligomers)

[1202] ·4-Acryloylmorpholine: 15.0 parts (monofunctional monomer)

[1203] • EO-modified trimethylolpropane triacrylate: 20.0 parts

[1204] • Dipentaerythritol pentaacrylate: 5.0 parts

[1205] • Dipentaerythritol hexaacrylate: 16.6 parts

[1206] • IRGACURE 369: 3.0 parts (photopolymerization initiator)

[1207] • Chemrk DEABP: 3.0 parts (photopolymerization initiator)

[1208] • SB-PI718: 4.0 parts (photopolymerization initiator)

[1209] • AJISPER PB821: 3.0 parts (dispersant)

[1210] • T-wax complex: 4.0 parts (wax)

[1211] (Examples RY-2 to RY-20, Manufacturing Examples RY-1 to RY-11, RC-1 to RC-3, RM-1 to RM-6)

[1212] Production of yellow ink [RY-2]~[RY-31], cyan ink [RC-1]~[RC-3], and magenta ink [RM-1]~[RM-6]

[1213] The 18.0 parts of isoindoline compound (1-1) of manufacturing example RY-1 were changed to the compounds and amounts shown in Table 30. Otherwise, the same procedure as in example RY-1 was followed to obtain the yellow inks [RY-2] to [RY-31], cyan inks [RC-1] to [RC-3], and magenta inks [RM-1] to [RM-6] shown in Table 30.

[1214] [Table 30-1]

[1215]

[1216] [Table 30-2]

[1217]

[1218] The pigments used in the manufacture of the inks are shown in Table 31.

[1219] [Table 31]

[1220] pigment Product Name PB15:3 LIONOL BLUE FG-7330 (manufactured by Toyo Color Materials Co., Ltd.) PB15:4 LIONOL BLUE FG-7400-G (manufactured by Toyo Color Materials Co., Ltd.) PB16 Heliogen Blue D7490 (manufactured by BASF) PR122 Hostaperm Pink E02 (Made by Clariant) PV19 Hostaperm Red Violet ER02 (Made by Clariant) PR48:3 FUJI Red 5R 763 (manufactured by Fuji Pigment Co., Ltd.) PR57:1 LIONOL RED 6B FG-4306-G (manufactured by Toyo Color Materials Co., Ltd.) PR146 LIONOL RED 5620 (manufactured by Toyo Color Materials Co., Ltd.) PR185 Novoperm Carmine HF4C (manufactured by Clariant)

[1221] [Evaluation of Viscosity Stability Over Time]

[1222] For yellow inks [RY-1] to [RY-31], cyan inks [RC-1] to [RC-3], and magenta inks [RM-1] to [RM-6], the initial viscosity at 25°C was measured using an E-type viscometer (Toki Sangyo Co., Ltd.'s "ELD type viscometer"). Similarly, the viscosity was measured after 10 days and 20 days at 25°C. Using each measurement, the viscosity increase rate relative to the initial viscosity was calculated and used as an indicator of viscosity stability, evaluated according to the following criteria. The results are shown in Table 32. A smaller viscosity increase rate is considered to indicate better viscosity stability. A practical level of 2 or higher is considered acceptable.

[1223] Viscosity change rate (%) = |(Viscosity over time / Initial viscosity) - 1| × 100

[1224] (Evaluation criteria for viscosity stability)

[1225] 4: Viscosity change rate is less than 2%

[1226] 3: Viscosity change rate is greater than 2% and less than 5%.

[1227] 2: Viscosity change rate is greater than 5% and less than 10%.

[1228] 1: Viscosity change rate is above 10%

[1229] <Evaluation of the Ink Group>

[1230] [Examples RS-1 to RS-37, Comparative Examples RS-1 to RS-18] [Preparation of Ink Groups 401 to 455]

[1231] The obtained active energy ray curable inks were combined as described in Table 32 to obtain ink groups 401 to 455.

[1232] [Table 32-1]

[1233] Table 32-1 ink group Yellow ink Cyan ink magenta ink Example RS-1 Ink Group 401 [RY-1] [RC-1] [RM-1] Example RS-2 Ink Group 402 [RY-2] [RC-1] [RM-1] Example RS-3 Ink Group 403 [RY-3] [RC-1] [RM-1] Example RS-4 Ink Group 404 [RY-4] [RC-1] [RM-1] Example RS-5 Ink Group 405 [RY-5] [RC-1] [RM-1] Example RS-6 Ink Group 406 [RY-6] [RC-1] [RM-1] Example RS-7 Ink Group 407 [RY-7] [RC-1] [RM-1] Example RS-8 Ink Group 408 [RY-8] [RC-1] [RM-1] Example RS-9 Ink Group 409 [RY-9] [RC-1] [RM-1] Example RS-10 Ink Group 410 [RY-10] [RC-1] [RM-1] Example RS-11 Ink Group 411 [RY-11] [RC-1] [RM-1] Example RS-12 Ink group 412 [RY-12] [RC-1] [RM-1] Example RS-13 Ink Group 413 [RY-13] [RC-1] [RM-1] Example RS-14 Ink Group 414 [RY-14] [RC-1] [RM-1] Example RS-15 Ink Group 415 [RY-15] [RC-1] [RM-1] Example RS-16 Ink Group 416 [RY-16] [RC-1] [RM-1] Example RS-17 Ink Group 417 [RY-17] [RC-1] [RM-1] Example RS-18 Ink Group 418 [RY-18] [RC-1] [RM-1] Example RS-19 Ink Group 419 [RY-19] [RC-1] [RM-1] Example RS-20 Ink Group 420 [RY-20] [RC-1] [RM-1] Example RS-21 Ink Group 421 [RY-4] [RC-1] [RM-2] Example RS-22 Ink group 422 [RY-4] [RC-1] [RM-3] Example RS-23 Ink Group 423 [RY-4] [RC-1] [RM-4] Example RS-24 Ink group 424 [RY-4] [RC-1] [RM-5] Example RS-25 Ink Group 425 [RY-4] [RC-1] [RM-6] Example RS-26 Ink group 426 [RY-4] [RC-2] [RM-1] Example RS-27 Ink Group 427 [RY-4] [RC-2] [RM-2] Example RS-28 Ink Group 428 [RY-4] [RC-2] [RM-3] Example RS-29 Ink group 429 [RY-4] [RC-2] [RM-4] Example RS-30 Ink Group 430 [RY-4] [RC-2] [RM-5] Example RS-31 Ink Group 431 [RY-4] [RC-2] [RM-6] Example RS-32 Ink group 432 [RY-4] [RC-3] [RM-1] Example RS-33 Ink Group 433 [RY-4] [RC-3] [RM-2] Example RS-34 Ink Group 434 [RY-4] [RC-3] [RM-3] Example RS-35 Ink Group 435 [RY-4] [RC-3] [RM-4] Example RS-36 Ink group 436 [RY-4] [RC-3] [RM-5] Example RS-37 Ink Group 437 [RY-4] [RC-3] [RM-6]

[1234] [Table 32-2]

[1235] Table 32-2 ink group Yellow ink Cyan ink magenta ink Comparative Example RS-1 Ink group 438 [RY-21] [RC-1] [RM-1] Comparative Example RS-2 Ink Group 439 [RY-22] [RC-1] [RM-1] Comparative Example RS-3 Ink Group 440 [RY-23] [RC-1] [RM-1] Comparative Example RS-4 Ink Group 441 [RY-24] [RC-1] [RM-1] Comparative Example RS-5 Ink group 442 [RY-25] [RC-1] [RM-1] Comparative Example RS-6 Ink Group 443 [RY-26] [RC-1] [RM-1] Comparative Example RS-7 Ink Group 444 [RY-27] [RC-1] [RM-1] Comparative Example RS-8 Ink Group 445 [RY-28] [RC-1] [RM-1] Comparative Example RS-9 Ink group 446 [RY-29] [RC-1] [RM-1] Comparative Example RS-10 Ink Group 447 [RY-30] [RC-1] [RM-1] Comparative Example RS-11 Ink group 448 [RY-31] [RC-1] [RM-1] Comparative Example RS-12 Ink Group 449 [RY-19] [RC-1] [RM-2] Comparative Example RS-13 Ink Group 450 [RY-19] [RC-1] [RM-3] Comparative Example RS-14 Ink Group 451 [RY-19] [RC-1] [RM-4] Comparative Example RS-15 Ink Group 452 [RY-19] [RC-1] [RM-5] Comparative Example RS-16 Ink Group 453 [RY-19] [RC-1] [RM-6] Comparative Example RS-17 Ink Group 454 [RY-19] [RC-2] [RM-1] Comparative Example RS-18 Ink Group 455 [RY-19] [RC-3] [RM-1]

[1236] The color gamut of the obtained ink groups was evaluated using the following method. The results are shown in Table 33.

[1237] [Color Gamut Evaluation]

[1238] (Initial evaluation)

[1239] In the ink group obtained above, an ink with a line count of 800 lpi and a mesh volume of 3.72 cm³ was used. 3 / m 2 After printing cyan ink on coated paper using an anilox roller and flexographic coating machine, the conveyor speed is 50 m / min, and the air-cooled mercury lamp (output power 160 W / cm²) is used. 2 The ink is cured under the same conditions as the cyan ink. Then, magenta ink is printed on the cyan ink layer under the same conditions as the cyan ink, and yellow ink is printed on the magenta ink layer. By doing this, an evaluation print is obtained, which is formed by layering the substrate, cyan ink layer, magenta ink layer, and yellow ink layer in that order.

[1240] For the obtained prints, the concentration values ​​of the solid areas (yellow, magenta, and cyan) of the prints were determined using a Gretagmacbeth D196 instrument. Additionally, a Gretagmacbeth SpectroEye instrument was used as the measuring instrument to measure the solid areas and overlapping areas of the prints under conditions of a D50 light source, a 2-degree field of view, a white background (using a standard white plate), and without the use of filters.

[1241] In a two-dimensional space with a* as the horizontal axis and b* as the vertical axis, a hexagon is created by plotting the values ​​of a* versus b* for six colors: solid areas (yellow, magenta, cyan) and overlapping solid areas (cyan × magenta, cyan × yellow, yellow × magenta). The area is then calculated. The area ratio is determined when the area of ​​the comparative example used as a benchmark is set to 100%, and the comparison is performed according to the following criteria based on this area ratio. Specifically, the comparative examples listed in Table 33 are used as benchmarks for comparison. It should be noted that - indicates no evaluation.

[1242] (Evaluation Criteria)

[1243] ○: Area ratio is above 90% (good)

[1244] △: Area ratio of 85% or more but less than 90% (usable)

[1245] ×: Area ratio less than 85% (cannot be used)

[1246] (Evaluation over time)

[1247] Each active energy ray curable ink was placed in a sealed container and stored at 25°C for 20 days. Then, it was printed in the same manner as the initial evaluation to produce evaluation prints. Color measurements were performed on the obtained prints in the same manner as the initial evaluation, and the area was calculated based on the obtained drawings. The area ratio obtained by dividing the area in the time-lapse evaluation of each example / comparative example by the area in the initial evaluation was calculated, and the evaluation was performed based on this area ratio according to the following criteria.

[1248] (Evaluation Criteria)

[1249] ○: Area ratio is above 98% (Good)

[1250] △: Area ratio of 95% or higher and less than 98% (usable)

[1251] ×: Area ratio less than 95% (unacceptable)

[1252] [Table 33-1]

[1253]

[1254] [Table 33-2]

[1255]

[1256] As shown in Table 33, the active energy ray curable ink group, as one embodiment of the present invention, has a color gamut area ratio that is equal to or greater than that of conventional ink groups, exhibiting excellent color reproduction. Furthermore, the viscosity stability of the yellow ink over time is improved, resulting in good storage stability as an ink group. Moreover, the color reproduction (color gamut) also demonstrates good performance over time, indicating good storage stability as an ink group.

[1257] On the other hand, it can be seen that in comparative examples RS-1 to RS-18, the yellow ink has poor viscosity stability over time and poor color reproduction (color gamut) over time. Therefore, as an ink group, it has poor storage stability and cannot solve the problem of this application.

Claims

1. A pigment composition comprising a compound represented by formula (1) and a compound represented by formula (2), [Chemistry 1] In the formula, R1 represents a substituted alkyl group, which has 1 to 20 carbon atoms. At least one hydrogen atom of the alkyl group can be replaced by an alkylamino group. The alkyl group can also have a structure in which two or more alkyl groups, one of which is an alkylene group, are bonded together via ether bonds. The alkylamino group can further have a hydroxyl group. R2 and R3 each independently represent a hydrogen atom, methyl, ethyl, cyclohexyl, or phenyl atom. A represents the group represented by formula (3), formula (4) or formula (5) below. [Chemistry 2] In the formula, X represents -O- or -NH-, and R4 represents methyl. R5 and R6 each independently represent a hydrogen atom or a methyl group, and R7 represents a hydrogen atom. R8~R 11 Each of them independently represents a hydrogen atom.

2. A coloring composition comprising the pigment composition of claim 1 and a dispersion medium.

3. A molding composition comprising the coloring composition of claim 2.

4. A colorant comprising the coloring composition of claim 2.

5. A coating comprising the coloring composition of claim 2.

6. A printing ink comprising the coloring composition of claim 2.

7. An inkjet ink comprising the coloring composition of claim 2.

8. An ink group comprising at least yellow ink, cyan ink, and magenta ink. The yellow ink is an ink comprising the coloring composition of claim 2.

9. A gravure ink set comprising at least yellow ink, cyan ink, and magenta ink. The yellow ink is an ink comprising the coloring composition of claim 2.

10. The gravure ink set according to claim 9, further comprising a transparent ink.

11. A printed matter comprising a substrate and a printing layer formed by the gravure ink group of claim 9.

12. A printed matter comprising a substrate, a printing layer formed of the gravure ink group of claim 9, and a release layer formed of transparent ink.

13. A packaging material comprising the printout of claim 11 or 12.

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