JP6893277B1 - Pigment compositions, coloring compositions, and their uses - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment composition containing an isoindrin compound which is excellent in dispersibility, weather resistance and heat resistance, has good storage stability, and can form a highly saturated image or the like. A pigment composition containing an isoindoline compound represented by the formula (1) and an isoindoline compound represented by the formula (2). [In the formula, R1 and R2 are H; A is 2-cyanoacetamide, 2-cyano-N-methylacetamide, 2-cyano-N-phenylacetamide, barbituric acid, 2-cyanomethyl-3H-quinazoline-4. A group derived from on. ] [Selection diagram] None

Description

The present invention relates to a pigment composition containing an isoindoline compound.

Pigments are mainly used as colorants in applications such as plastic products, toners, paints, and printing inks. Pigments are roughly classified into inorganic pigments and organic pigments. Organic pigments are generally superior in color clarity and coloring power to inorganic pigments, but tend to be inferior in weather resistance and heat resistance. Known organic pigments include, for example, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, and quinacridone pigments.

In recent years, from an environmental point of view, there has been an increasing demand for colorants that do not contain aromatic amines and heavy metals. Azo pigments are mainly used as organic pigments having a hue of yellow to crimson, but azo pigments contain aromatic amines in their components due to the raw materials used or decomposition by light or heat. Sometimes. Therefore, in recent years, an isoindoline pigment containing no aromatic amine has attracted attention from the viewpoint of environmental compatibility.

For example, Patent Document 1 discloses an isoindoline pigment for coloring applications of plastics. Further, Patent Document 2 discloses a dispersion for an inkjet ink containing water, a dispersant, and an isoindoline pigment.

Special Table 2009-543917 Gazette Japanese Unexamined Patent Publication No. 10-140066

However, the conventional pigment composition containing an isoindoline compound is difficult to disperse and has poor dispersion stability. Further, a coloring composition containing an isoindoline compound has been required to further improve weather resistance and heat resistance.

In order to solve these problems, for example, a method of using a dye derivative in combination with an isoindoline compound can be considered. However, when a compound having a different color is mixed with an isoindoline compound, the color tone tends to be unclear, and an image, a molded product, etc. There was a problem that the saturation was lowered when it was formed.

An object of the present invention is to provide a pigment composition containing an isoindoline compound which is excellent in dispersibility, weather resistance and heat resistance, has good storage stability, and can form a highly saturated image or the like.

The pigment composition of the present invention contains an isoindoline compound represented by the following formula (1) and an isoindoline compound represented by the following formula (2).

In the formula, R ₁ and R ₂ represent a hydrogen atom, and A represents a group represented by the following formula (3), the following formula (4), or the following formula (5).

In the formula, X represents -O- or -NH-, R ₃ represents an alkyl group or an aryl group, R _{4 to} R ₆ represent a hydrogen atom, and R _{7 to} R ₁₀ are independent hydrogen atoms. Represents an atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group.

According to the above invention, it is possible to provide a pigment composition containing an isoindoline compound which is excellent in dispersibility, weather resistance and heat resistance, has good storage stability, and can form a highly saturated image or the like.

<Pigment composition>
The pigment composition of the present invention contains an isoindoline compound represented by the formula (1) and an isoindoline compound represented by the formula (2).

By containing the two types of isoindoline compounds as described above, the pigment composition of the present invention improves dispersibility, weather resistance, heat resistance, and storage stability, which have been the weak points of the isoindoline compounds in the past. The pigment composition of the present invention can be used in a wide range of applications requiring coloring such as molded products, toners, paints, printing inks, and inkjet inks.

[Isoindoline compound (1)] and [Isoindoline compound (2)]
Hereinafter, the isoindoline compound represented by the formula (1) is referred to as an isoindoline compound (1), and the isoindoline compound represented by the formula (2) is referred to as an isoindoline compound (2).

In formula (2), R ₁ and R ₂ represent a hydrogen atom.
A represents a group represented by the following formula (3), the following formula (4), or the following formula (5).

In formula (3), X represents -O- or -NH-, and R ₃ represents an alkyl group or an aryl group.
In formulas (4) and (5), R _{4 to} R ₆ represent hydrogen atoms.
In formula (5), R _{7 to} R ₁₀ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group.

By containing the isoindoline compound (1) and the isoindoline compound (2), the pigment composition is excellent in weather resistance and heat resistance, and can form a highly saturated image or the like. Furthermore, in aqueous dispersion, it is possible to prepare a dispersion having excellent stability over time and dispersibility.
The reason for these is that both the isoindoline compound (1) and the isoindoline compound (2) have keto-enol tvariability, so that appropriate hydrogen bonds are easily formed between the molecules, and the weather resistance and heat resistance are improved. I guess.
With the isoindoline compound (2) alone, the pigment particles become large due to the extremely strong hydrogen bonds derived from the barbituric acid structure, but the inclusion of the isoindoline compound (1) alleviates the excessive hydrogen bonds. Crystal growth is suppressed, and the enlargement of pigment particles can be suppressed. Further, in the pigment composition, the isoindoline compound (1) has a weak color development by itself, but can be retained without deteriorating the hue of the isoindoline compound (2) due to the intermolecular interaction with the isoindoline compound (2). It is presumed that these factors overlap to form a more saturated image or the like.
The reason why an aqueous dispersion having excellent stability over time and dispersibility can be prepared by using a pigment composition is that the isoindoline compound (2) is much more hydrophilic due to the barbituric acid residue than the dispersant. Has a high affinity with water and cannot adsorb dispersants. However, it is presumed that when used in combination with the isoindoline compound (1), the hydrophilicity of the isoindoline compound (2) is relaxed and the dispersant can be adsorbed, so that an aqueous dispersion can be formed.

The content of the isoindoline compound (1) in 100% by mass of the pigment composition of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 10% by mass.

The content of the isoindoline compound (2) in 100% by mass of the pigment composition of the present invention is preferably 70 to 99.99% by mass, more preferably 90 to 99.95% by mass.

The mass ratio of the isoindoline compound (1) to the isoindoline compound (2) is preferably (1) / (2) = 1/9999 to 3/7, more preferably 1/999 to 1/19.

In the above formula (3), X represents -O- or -NH-, and is preferably -NH-.

In the above formula (3), the _{alkyl group (-R) in R 3} preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 4 carbon atoms, and an alkyl group having 1 or 2 carbon atoms. Most preferred.
The alkyl group may have a linear structure, a branched structure, a monocyclic structure, or a condensed polycyclic structure.
The alkyl group is not particularly limited, and the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, and the like. Isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl Examples thereof include a group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group and the like.

In the above alkyl group, at least one hydrogen atom may be substituted with another substituent such as a fluorine atom. That is, the alkyl group may be a fluoroalkyl group or a perfluoroalkyl group. Examples of the fluoroalkyl group include a monofluoromethyl group, a difluoromethyl group and a trifluoromethyl group.

The alkyl group may have a structure in which two or more alkyl groups (where one becomes an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (-COO-), an ether bond (-O-), and a sulfide bond (-S-). That is, in the present specification, the alkyl group includes, for example, a group represented by "-R'-OR"(R'represents an atomic group obtained by removing one hydrogen atom from the above alkyl group). .. Specific examples include -C ₂ H _4- OC ₂ H ₅ .

In the above formula (3), the aryl group in R ₃ (-Ar) is removing one atomic hydrogen atom from an aromatic hydrocarbon. The number of carbon atoms is preferably 6 to 30, more preferably 6 to 20.
The aryl group is, for example, a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a turnaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group. , Indacenyl group, fluoranthenyl group, acephenanthrylenyl group, acetylenylenyl group, phenylenyl group, fluorenyl group, anthryl group, bianthrasenyl group, taranthrasenyl group, quarter anthrasenyl group, anthracinolyl group, phenylanthryl group , Triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pryadenyl group, pisenyl group, perylenel group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronenyl group, trinaphthylenyl group Examples thereof include a group, a heptaphenyl group, a heptasenyl group, a pyrantrenyl group, an ovalenyl group and the like. Of these, a phenyl group is preferable.

In the formula (5), the _{halogen atom in R 7 to} R ₁₀ is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the formula (5), the _{number of carbon atoms of the alkyl group (-R) in R 7 to} R ₁₀ is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group may have a linear structure, a branched structure, a monocyclic structure, or a condensed polycyclic structure.
The alkyl group is not particularly limited, and the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, an isopropyl group, and the like. Isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl Examples thereof include a group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group and the like.

In the above alkyl group, at least one hydrogen atom may be substituted with another substituent such as a fluorine atom. That is, the alkyl group may be a fluoroalkyl group or a perfluoroalkyl group. Examples of the fluoroalkyl group include a monofluoromethyl group, a difluoromethyl group and a trifluoromethyl group.

The alkyl group may have a structure in which two or more alkyl groups (where one becomes an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (-COO-), an ether bond (-O-), and a sulfide bond (-S-). That is, in the present specification, the alkyl group includes, for example, a group represented by "-R'-OR"(R'represents an atomic group obtained by removing one hydrogen atom from the above alkyl group). .. Specific examples include -C ₂ H _4- OC ₂ H ₅ .

In the present specification, 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 further preferably an alkyl group having 1 or 2 carbon atoms.

In the formula (5), the _{alkoxy group in R 7 to} R ₁₀ is a group (-OR) in which an oxygen atom is bonded to the above-mentioned alkyl group (-R).

In the formula (5), the _{aryl group (-Ar) in R 7 to} R ₁₀ is an atomic group 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.
The aryl group is, for example, a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a turnaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group. , Indacenyl group, fluoranthenyl group, acephenanthrylenyl group, acetylenylenyl group, phenylenyl group, fluorenyl group, anthryl group, bianthrasenyl group, taranthrasenyl group, quarter anthrasenyl group, anthracinolyl group, phenylanthryl group , Triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pryadenyl group, pisenyl group, perylenel group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronenyl group, trinaphthylenyl group Examples thereof include a group, a heptaphenyl group, a heptasenyl group, a pyrantrenyl group, an ovalenyl group and the like. Of these, a phenyl group is preferable.

In the formula (5), the _{aryloxy group in R 7 to} R ₁₀ is a group (-OAr) in which an oxygen atom is bonded to the above-mentioned aryl group (-Ar). In the present specification, the aryloxy group is preferably a phenoxy group.

In the present specification, in the formula (5), R _{7 to} R ₁₀ are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, fluoroalkyl groups having 1 to 6 carbon atoms, and alkoxy groups (alkyl groups). The carbon number of 1 to 6) is preferably selected from the group consisting of a phenyl group and a phenoxy group.

The isoindoline compound (1) and the isoindoline compound (2) can be used alone or in combination of two or more.

The production of the pigment composition containing the isoindolin compound (1) and the isoindolin compound (2) is carried out by (A) a method of synthesizing two kinds at once (co-synthesis method) and (B) an isoindrin compound at the time of preparing a dispersion. Method of mixing (1) and isoindrin compound (2), (C) acid pacing method, acid slurry method, dry milling method, salt milling method of (C) isoindrin compound (1) and isoindrin compound (2) together. , Solvent salt milling method, solvent method (heat treatment in a high boiling point solvent such as alcohol or aromatic solvent), or a method of making a pigment composition by a method combining (A) to (C). And so on. Among these, (A) co-synthesis method, (C) isoindoline compound (1) and isoindoline compound (2) are treated together by acid pacing method, solvent salt milling method, or (A) and (C) are processed. A method of making a pigment composition by a combined method is more preferable.

[Method for producing isoindoline compound (1)]
The isoindoline compound (1) can be synthesized by a known synthetic method. For example, as shown in Scheme 1 below, phthalonitrile represented by the formula (6) (hereinafter referred to as compound (6)) or isoindoline represented by the formula (7) (hereinafter referred to as compound (7)). Can be synthesized as a starting material.
Hereinafter, the synthesis method will be described with reference to specific examples of the isoindoline compound (1). In the following description, the numbers described in each formula will be described as compound numbers.

The isoindoline compound (1) can be produced according to the following scheme 1.
(Scheme 1)

Scheme 1 is a first step (S1) of reacting compound (6) with a base to obtain compound (7) in a solvent; then in the presence of water, compound (7) and compound (8). The second step (S2) of reacting the compound (S2); then, the third step (S3) of reacting the compound (9) with the compound (8) in the presence of acetic acid may be included. The reaction temperature in each step in Scheme 1 is preferably about 10 to 100 ° C.

The solvent used in the first step (S1) is, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and glycol; ethers such as glycol ether and tetrahydrofuran; formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Acyclic or cyclic amides can be mentioned. Among these, acyclic or cyclic amides are preferable, and tetrahydrofuran and formamide are more preferable.

The solvent can be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 15 times by mass, more preferably 5 to 10 times by mass with respect to the mass of compound (6).

The base is, for example, an alkali metal hydroxide, an alkali metal such as lithium, sodium or potassium, an alkali metal amide, an alkali metal hydride; and a primary or primary base having an alkyl chain or an alkylene chain having 1 to 10 carbon atoms. Examples thereof include alkali metal or alkaline earth metal alkoxides derived from secondary or tertiary aliphatic alcohols. Among these, sodium hydroxide or potassium carbonate is preferable.

Further, as another synthetic method, the isoindoline compound (1) can be produced, for example, according to the following scheme 2.
(Scheme 2)

Scheme 2 is a second step (S2) of reacting compound (7) with compound (8) in the presence of aqueous ammonia; then compound (9) and compound (8) in the presence of acetic acid. A third step (S3) of reacting with may be included.
In the second step (S2) of Scheme 2, when a 28% aqueous ammonia solution is used, the amount of the aqueous ammonia solution is preferably 1 to 20 times by mass, preferably 1 to 5 times by mass, based on the mass of the compound (7). Double the amount is more preferred.

Further, the scheme 2 may include a step of continuously reacting the compound (7) with the compound (8) and the compound (9) with the compound (8) in the presence of acetic acid.

In either case, the reaction temperature in each step in Scheme 2 is preferably about 10 to 100 ° C.

[Method for producing isoindoline compound (2)]
The isoindoline compound (2) can be synthesized by a known method. For example, Japanese Patent Application Laid-Open No. 55-157657, Japanese Patent Application Laid-Open No. 56-081369, Japanese Patent Application Laid-Open No. 57-035565, Japanese Patent Application Laid-Open No. 03-153761, Japanese Patent Application Laid-Open No. 54-091532, Japanese Patent Application Laid-Open No. 60-058469 and the like can be mentioned.

Compounds (10) to (18) are exemplified as preferable structures of the isoindoline compound (2). Needless to say, the isoindoline compound (2) is not limited to the following.

The isoindoline compound (1) and the isoindoline compound (2) are preferably used after being finely divided and processed into fine particles, respectively or together, and more preferably treated together. Examples of the miniaturization treatment include a dissolution precipitation method typified by acid pacing, solvent salt milling, and dry milling. The average primary particle size of the pigment particles after miniaturization is preferably 20 to 300 nm, more preferably 50 to 150 nm. Depending on the solvent salt milling conditions, the particle size of the pigment particles may grow.

Micronization by acid pacing causes fine pigment particles to precipitate by dissolving the pigment in concentrated sulfuric acid and mixing it with a large excess of water. Then, filtration and washing with water are repeated and dried to obtain finely divided pigment particles.

Examples of acid pacing include a method in which a pigment is dissolved in 98% sulfuric acid 5 to 30 times by mass, and the obtained sulfuric acid solution is mixed with water 5 to 30 times by mass. The temperature at which the pigment is dissolved in sulfuric acid should be such that reactions such as decomposition and sulfonation of raw materials do not occur. The temperature at the time of melting is preferably, for example, 3 to 40 ° C. Further, the method of mixing the sulfuric acid solution of the pigment and water, and the conditions such as the mixing temperature are not particularly limited. In many cases, the pigment particles that precipitate tend to be fine when mixed at a lower temperature than a high temperature. Therefore, the temperature at the time of mixing is preferably, for example, 0 ° C to 60 ° C. The water used for mixing may be industrially usable water. However, pre-cooled water is preferable from the viewpoint of reducing the temperature rise during precipitation.

The method of mixing the sulfuric acid solution and water is not particularly limited, and any method may be used as long as the pigment can be completely precipitated. For example, pigment particles can be precipitated by a method of injecting a sulfuric acid solution into ice water prepared in advance, or a method of continuously injecting a sulfuric acid solution into running water using an device such as an aspirator.

The slurry obtained by the above method is filtered and washed to remove acidic components, and then dried and pulverized to obtain a pigment adjusted to a desired particle size. When filtering the slurry, the slurry in which the sulfuric acid solution and water are mixed may be filtered as it is, but if the slurry has poor filterability, the slurry may be heated and stirred and then filtered. Alternatively, the slurry may be neutralized with a base and then filtered.

In the micronization by solvent salt milling, a clay-like mixture consisting of at least three components of a pigment, a water-soluble inorganic salt and a water-soluble solvent is strongly kneaded using a kneader or the like. The mixture after kneading is put into water and stirred with various stirrers to form a slurry. The water-soluble inorganic salt and the water-soluble solvent are removed by filtering the obtained slurry. By repeating the above slurrying, filtration, and washing with water, a finely divided pigment can be obtained.

As the water-soluble inorganic salt, sodium chloride, sodium sulfate, potassium chloride and the like can be used. These inorganic salts are used in a range of 1 mass times or more, preferably 20 mass times or less of the pigment. When the amount of the inorganic salt is 1 mass times or more, the pigment can be sufficiently finely divided. Further, when the amount of the inorganic salt is 20 times or less, a large amount of labor for removing the water-soluble inorganic salt and the water-soluble solvent after kneading is not required, and at the same time, the amount of the pigment that can be processed at one time is increased. It is preferable from the viewpoint of productivity because it does not decrease.

Finer pigments often generate heat as they are kneaded. Therefore, from the viewpoint of safety, it is preferable to use a water-soluble solvent having a boiling point of about 120 to 250 ° C. Specific examples of the water-soluble solvent include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, and diethylene glycol mono. Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Examples thereof include monoethyl ether and low molecular weight polypropylene glycol.

The miniaturization by dry milling is performed by dry pulverizing the pigment using various pulverizers. In this method, milling proceeds through collisions or friction between the milling media. The device used for performing dry milling is not particularly limited, and specific examples thereof include a ball mill, an attritor, and a vibration mill, which are dry crushers incorporating a crushing medium such as beads. When dry crushing using these devices, the inside of the crushing container may be depressurized or filled with an inert gas such as nitrogen gas, if necessary. Further, after dry milling, the above-mentioned solvent salt milling and stirring treatment in a solvent may be performed.

[Dye derivative]
The pigment composition can contain a pigment derivative.
The dye derivative is a known compound having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. The dye derivative is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphoric acid group, an amine salt thereof, a sulfonamide group or a compound having a basic substituent such as a tertiary amino group at the terminal. Examples thereof include compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.
Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine. Examples of the dye derivative are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, Patent No. 5735266, and as an anthraquinone-based dye derivative, JP-A-63-264674. Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, WO2009 / 025325 pamphlet, as a quinacridone-based dye derivative, JP-A-48- 54128, 03-9961 and 2000-273383, the dioxazine dye derivative is 2011-162662, and the thiazineindigo dye derivative is 2007-314785. Examples of JP, Triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112, JP-A-2006-291194, and JP-A as quinophthalone-based dye derivatives. 2008-31281, 2012-226110, naphthol dye derivatives are 2012-208329, 2014-5439, and azo dye derivatives are 2001-172520. Japanese Unexamined Patent Publication No. 2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005 as basic substituents. Examples thereof include known dye derivatives described in Japanese Patent Application Laid-Open No. -181383, JP-A-2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a sex group is synonymous with a dye derivative.

The dye derivative can be used alone or in combination of two or more.

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

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

Resin type dispersant, for example BASF Japan Ltd. JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL62J, JONCRYL63J, JONCRYLHPD-96J, JONCRYL501J, JONCRYLPDX-6102B, manufactured by BYK Chemie DISPERBYK, DISPERBYK180, DISPERBYK187, DISPERBYK190, DISPERBYK191, DISPERBYK194, DISPERBYK2010, DISPERBYK2015, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2155, Lubrizol Corp. Japan SOLSPERS24000, SOLSPERS32000, SOLSPERS41000, Sartomer Co., SMA1000H, SMA1440H, SMA2000H, SMA3000H, SMA17352H, and the like.

Examples of the binder resin include polyolefin resins, polyester resins, styrene copolymers, acrylic resins, and modified resins thereof. The binder resin is, for example, a polymer such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), low-density polyethylene (LDPE), a polyolefin resin such as polypropylene; a polyester resin such as polyethylene terephthalate; p-Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methylmethacrylate copolymer 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 copolymers such as coalesced, styrene-acrylonitrile-indene copolymers; acrylic resins such as acrylic resin and methacrylic resin; polyvinyl chloride, phenol resin, naturally modified phenol resin, natural resin modified maleic acid resin, polyvinyl acetate, Examples thereof include silicone resin, polyurethane, polyamide resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, kumaron inden resin, alkyd resin, amino resin, epoxy resin, petroleum resin, and modified resins thereof.

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

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

(Water-based coloring composition)
In the present specification, the coloring composition is preferably used as an aqueous coloring composition.
The water-based coloring composition preferably contains a pigment composition, a resin as a dispersion medium, water, and a water-soluble solvent.
The types of resins include, for example, styrene-acrylic acid copolymer, acrylic acid-acrylic acid acrylic ester copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid copolymer, and styrene-methacryl. Acid-acrylic acid acrylic ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer, polyacrylic acid, polymethacrylic acid, vinyl Naphthalene-acrylic acid copolymer salt, styrene-maleic acid copolymer salt, maleic acid-maleic anhydride copolymer salt, vinyl naphthalene-maleic acid copolymer salt, polyester-modified acrylic acid copolymer, etc. Can be mentioned.

Examples of the resin form include water-soluble resins and emulsions.

The water is preferably ion-exchanged water or distilled water.

The water-soluble solvent is, for example, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono. Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid Polyethylene glycol and the like can be mentioned.

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

Anionic surfactants include, for example, fatty acid salts, alkyl sulfates, alkylaryl sulfonates, alkylnaphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates. , Polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate and the like.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid. Examples thereof include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, glycerol volate fatty acid esters, and polyoxyethylene glycerol fatty acid esters.

The content of the surfactant is preferably 0.3 to 20% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the aqueous coloring composition.

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

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

Preservatives include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethioone-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one. Amine salt and the like can be mentioned.
The content of the preservative is preferably 0.1 to 2% by mass in 100 parts by mass of the aqueous coloring composition.

Examples of the pH adjuster include various amines, inorganic salts, ammonia, various buffer solutions and the like.

The defoaming agent is used to prevent the generation of foam in the production of the water-based coloring composition. Commercially available antifoaming agents include, for example, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol 104BC, Surfinol 104DPM, Surfinol 104PA, Surfinol 104PG-50, Surfinol 420, Surfinol 440, Surfinol. 465, Surfinol 485, Surfinol PSA-336 (all manufactured by Nisshin Kagaku Kogyo Co., Ltd.), ADDITOR VXW 6211, ADDITOR VXW4973, ADDITOR VXW6235, ADDITOR XW375, ADDITOR XW376, ADDITOR VXW6381, ADDITOR VXW6381, ADDITOR ADDITOR VXW6399, ADDITOR XW6544 and the like (all manufactured by Allnex) can be mentioned.

Wetting agents are used to obtain a smooth coating during printing and coating. Commercially available wetting agents include, for example, ADDITOR VXL6237N, ADDITOR XL260N, ADDITOR VXL6212, ADDITOR UVX7301 / 65, ADDITOR XW330, ADDITOR VXW6200, ADDITOR VXW6205, ADDITOR VXW620 Made) and the like.

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

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

The disperser used for the dispersion treatment is, for example, a horizontal sand mill, a vertical sand mill, an annual bead mill, an attritor, a microfluitizer, a high speed mixer, a homomixer, a homogenizer, a high pressure homogenizer, a ball mill, a paint shaker, a roll mill, and a stone mill. Examples include a type mill, an ultrasonic disperser, and a collision type beadless disperser.

It is preferable to perform a heat treatment or a post-treatment after the dispersion treatment because the dispersion stability of the isoindoline compound (1) and the isoindoline compound (2) is improved. The heat treatment is a treatment in which the aqueous coloring composition is heated to 30 to 80 ° C. and held for several hours to one week. For the post-treatment, it is preferable to disperse the aqueous coloring composition using a bead disperser such as a sand mill, an ultrasonic disperser, or a collision-type beadless disperser.

Before the dispersion treatment, the pre-dispersion treatment can be performed without using water or a water-soluble solvent. Examples of the apparatus used for the pre-dispersion treatment include a kneader, a kneaded meat mixer such as a three-roll mill; and a solid disperser such as a two-roll mill.

Aspects of the coloring composition herein include, for example, Aspect 1 containing a pigment composition and a resin (eg, a molding composition, a toner), Aspect 2 containing a pigment composition and an organic solvent (eg, a solvent-based coloring composition). Aspect 3 (for example, a water-based coloring composition) containing the pigment composition, the resin and water described in detail in the upper section, and the like.

Explaining the use of each aspect, the first aspect includes, for example, a molding composition, a toner, a solvent-free inkjet ink, and the like. The second aspect is a solvent-based coloring composition, and examples thereof include paints, printing inks, and inkjet inks. Aspect 3 is a water-based coloring composition, and examples thereof include water-based paints, water-based printing inks, and water-based inkjet inks. In the present specification, when the solvent contains water, it is described as "water-based", but when the solvent is "organic solvent", it is not particularly described as "solvent-based". The water is preferably ion-exchanged water or distilled water from which metal ions and the like have been removed.

<Composition for molding>
The molding composition of the present invention contains a coloring composition (pigment composition, resin). The molding composition preferably contains a thermoplastic resin in the resin. It is preferable that the molding composition containing the thermoplastic resin is melted and kneaded and molded into a desired shape to prepare a molded product. For example, when the molding composition is melted and kneaded at 300 ° C., it contains an isoindoline compound (1) and an isoindoline compound (2) having high heat resistance, so that color change can be suppressed. The resin is not limited to the thermoplastic resin.

Examples of the thermoplastic resin include homopolymers and copolymers using ethylene, propylene, butylene, styrene and the like as monomer components. More specifically, polyethylene such as high density polyethylene (HDPE), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), and polyolefin resins such as polypropylene and polybutylene can be mentioned. Specific examples of other useful resins include polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polystyrene resins, and thermoplastic ionomer resins. Among these, polyolefin resin and polyester resin are preferable. The number average molecular weight of the thermoplastic resin is preferably more than 30,000 and preferably 200,000 or less.

The content of the thermoplastic resin is preferably 10,000 to 1,000,000 parts by mass, preferably 10,000 to 2, with respect to 100 parts by mass of the total of the isoindoline compound (1) and the isoindoline compound (2). Million parts by mass is more preferable.

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

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 appropriately migrates to the surface of the molded product, so that the balance between slidability and bleed-out suppression is excellent.

The melting point of the wax is preferably 60 to 150 ° C, more preferably 70 to 140 ° C. Within this range, the processability when the thermoplastic resin and the wax are melt-kneaded is improved.

The melt flow rate (MFR) obtained in accordance with JIS K-7210 of wax is preferably larger than 100 g / 10 minutes.

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

The molding composition may contain other additives. Other additives are materials generally used in the technical field of molded products, and are antioxidants, light stabilizers, dispersants, metal soaps, antistatic agents, flame retardants, lubricants, fillers, and isoindoline compounds (1). ) And colorants other than the isoindoline compound (2).

The molding composition can be produced, for example, by the composition ratio of the molded product. Alternatively, it can be produced as a master batch containing the isoindoline compound (1) and the isoindoline compound (2) in high concentrations. In the present specification, the masterbatch is preferable in terms of easily uniformly dispersing the isoindoline compound (1) and the isoindoline compound (2) in the molded product.
In the masterbatch, for example, it is preferable that the thermoplastic resin and the pigment composition are melt-kneaded and then molded into an arbitrary shape so as to be easy to use in the next step. Next, the masterbatch and the diluted resin (for example, the thermoplastic resin used in the masterbatch) can be melt-kneaded to form a molded product having a desired shape. Examples of the shape of the masterbatch include pellets, powders, plates and the like. In order to prevent agglomeration of the pigment composition, it is preferable to produce a dispersion in which the pigment composition and wax are melt-kneaded in advance, and then melt-kneaded with the thermoplastic resin to produce a masterbatch. As the apparatus used for the dispersion, for example, a blend mixer, a three-roll mill, or the like is preferable.

When the molding resin composition is produced as a masterbatch, it is preferable to add 1 to 200 parts by mass of the isoindoline compound (1) and the isoindoline compound (2) to 100 parts by mass of the thermoplastic resin. 100 parts by mass is more preferable. The mass ratio of the master batch (X) to the diluted resin (Y) used as the base resin of the molded product is preferably X / Y = 1/1 to 1/100, more preferably 1/3 to 2/100. .. Within this range, the isoindoline compound (1) and the isoindoline compound (2) can be easily dispersed uniformly in the molded product, and good coloring can be easily obtained.

As the diluted resin (Y), it is preferable to use the thermoplastic resin used in the masterbatch, but if there is no problem with compatibility, another thermoplastic resin may be used.

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

Applications of the molding composition include, for example, a molded product, a sheet, a film and the like.

<Toner>
The toner of the present specification contains a coloring composition (pigment composition, resin). As the toner resin, a thermoplastic resin called a binder resin is preferable. Examples of the toner include dry toner and wet toner. Of these, dry toner is preferable. For example, in the dry toner, the pigment composition and the binder resin are melt-kneaded, cooled, and then pulverized and classified. Next, a post-treatment step of blending and mixing the additives can be performed to produce the product.

The binder resin is, for example, a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, a styrene-acrylic acid ester copolymer, or a styrene-methacrylic acid ester copolymer. , Styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene Copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-inden copolymer, polyvinyl chloride, phenol resin, naturally modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone Examples thereof include resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpen resins, kumaron inden resins, petroleum resins and the like.

Among these, polyester resin and styrene-based copolymer are preferable, and polyester resin is more preferable. Since the pigment composition of the present specification is particularly excellent in compatibility with the polyester resin, the isoindoline compound (1) and the isoindoline compound (2) are uniformly and finely dispersed in the toner, so that the quality is high. Toner is obtained.

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

The acid value of the polyester resin is preferably 10 to 60 mgKOH / g, more preferably 15 to 55 mgKOH / g. When a polyester resin having an appropriate acid value is used, it is easy to suppress the release of the release agent, and it is difficult for the image density to decrease in a high humidity environment.

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

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

The toner can further contain a charge control agent. When a charge control agent is used, it is easy to obtain a toner having a stable charge amount. As the charge control agent, a positive or negative charge control agent can be appropriately selected and used.

When the toner is a positively chargeable toner, the positive charge control agent is, for example, a styrene dye having a niglosin dye, a triphenylmethane dye, an organic tin oxide, a quaternary ammonium salt compound, and a quaternary ammonium salt as functional groups. Examples thereof include styrene / acrylic polymers copolymerized with an acrylic resin. Among these, a quaternary ammonium salt compound is preferable. Examples of the quaternary ammonium salt compound include a salt-forming compound of a quaternary ammonium salt and an organic sulfonic acid or molybdic acid. The organic sulfonic acid is preferably naphthalene sulfonic acid.

When the toner is a negatively charged toner, the negative charge control agent is, for example, a metal complex of a monoazo dye, a styrene / acrylic polymer copolymerized with a styrene / acrylic resin using sulfonic acid as a functional group, or an aromatic hydroxycarboxylic acid. Examples thereof include metal salt compounds of the above, metal complexes of aromatic hydroxycarboxylic acids, phenol-based condensates, and phosphonium-based compounds. The aromatic hydroxycarboxylic acid is preferably salicylic acid, 3,5-di-tert-butyl salicylic acid, 3-hydroxy-2-naphthoic acid, or 3-phenylsalicylic acid. Examples of the metal used for the metal salt compound include zinc, calcium, magnesium, chromium, and aluminum.

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

If necessary, a lubricant, a fluidizing agent, an abrasive, a conductivity-imparting agent, an image peeling inhibitor, and the like can be added to the toner.

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

Further, in the present specification, the toner can be used as a one-component developer or a two-component developer. The two-component developer can further contain carriers.

Examples of the carrier include magnetic powders such as iron powder, ferrite powder, and nickel powder, and products whose surfaces are coated with a resin or the like. The resin that coats the carrier surface is, for example, a styrene-acrylic acid ester copolymer, a styrene-methacrylate ester copolymer, an acrylic acid ester copolymer, a methacrylate ester copolymer, a fluorine-containing resin, a silicone-containing resin, and the like. Examples thereof include polyamide resin, ionomer resin, and polyphenylene sulfide resin. Among these, a silicone-containing resin in which less spent toner is formed is preferable. The weight average particle size of the carrier is preferably 30 to 100 μm.

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

<Paint>
The paints herein contain coloring compositions (pigment compositions, resins, solvents).
Examples of the resin include thermosetting resins and thermoplastic resins. The thermosetting resin is preferably a resin having a glass transition temperature of 10 ° C. or higher. Examples of the type of thermosetting resin include acrylic resin, polyester, polyurethane and the like. Further, the thermosetting resin preferably has a functional group capable of reacting with a curing agent. Examples of the functional group include a carboxyl group and a hydroxyl group. Examples of the curing agent include isocyanate curing agents, epoxy curing agents, aziridine curing agents, amine curing agents and the like.
The thermoplastic resin is preferably a resin having a glass transition temperature of 30 ° C. or higher. Examples of the thermoplastic resin include nitrocellulose and polyester. The thermosetting resin and the thermoplastic resin can be used together.

Among the solvents, examples of the water-insoluble solvent include toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons.
Among the solvents, examples of the water-soluble solvent include water, monohydric alcohol, divalent alcohol and glycol. Examples of the water-soluble solvent include ethanol, n-propanol, isopropanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. Also, water-dilutable monoethers derived from polyhydric alcohols can be mentioned. Specific examples thereof include methoxypropanol or methoxybutanol. Further, for example, a water-dilutable glycol ether such as butyl glycol or butyl diglycol can also be mentioned. The paint is called a water-based paint when the solvent contains water as described above.

The paint can further contain known additives.

Applications of the paint include, for example, metal paints, plastic paints and the like.

<Printing ink>
The printing ink of the present specification contains a coloring composition (pigment composition, resin, solvent). The printing ink is an ink other than the injet ink, and examples thereof include an offset printing ink, a flexo printing ink, a gravure printing ink, and a color filter ink. As described above, when the solvent contains water, it is called a water-based printing ink.

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

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

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

The printing ink may further contain a brightening material. The bright material is particles having an average thickness of 0.5 to 10 μm and an average particle diameter of 5 to 50 μm, and examples thereof include metal flakes, mica, and coated glass flakes. Examples of the metal flakes include aluminum flakes and gold powder. Examples of mica include ordinary mica and coated mica. Examples of the coated glass flakes include glass flakes coated with a metal oxide such as titanium oxide.

The content of the bright material is preferably 0.1 to 10% by mass in 100% by mass of the printing ink. In addition, other coloring pigments usually used in the art and various additives may be blended as required. The method for producing the printing ink, the coating method, and the drying method are not particularly limited, and a method well known in the art can be used.

The printing ink can further contain known additives.

<Inkjet ink>
The inkjet ink of the present invention contains a pigment composition and a resin, and preferably further contains a solvent. Inkjet inks can be roughly classified into (solvent-based) inkjet inks, water-based inkjet inks, and ultraviolet-curable inkjet inks, depending on the presence or absence of a solvent and its type. In the present specification, an aqueous inkjet ink in which the isoindoline compound (1) and the isoindoline compound (2) have good dispersibility is preferable. Hereinafter, the water-based inkjet ink will be mainly described.

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

The resin used in the water-based inkjet ink is important for obtaining the fixability of the ink on the printed matter (base material).
Examples of the type of resin include acrylic resin, styrene-acrylic resin, polyester resin, polyamide resin, polyurethane resin and the like. Examples of the resin form include water-soluble resins and emulsion particles. Among these, emulsion particles are preferable. Emulsion particles include single composition particles, core-shell type particles, and the like, and can be arbitrarily selected and used. When emulsion particles are used, it is easy to reduce the viscosity of the water-based inkjet ink, and a recorded material having excellent water resistance can be easily obtained. The resin can be used by neutralizing the acidic functional group with a pH adjusting agent such as ammonia, various amines, and various inorganic alkalis, if necessary.

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

Examples of the solvent include water-insoluble solvents, water, and water-soluble solvents. Examples of water-soluble solvents include glycol ethers and diols. These solvents penetrate very quickly into the substrate, and have low liquid absorption or non-absorption such as coated paper, art paper, vinyl chloride sheet, film, and cloth. It penetrates quickly even into liquid substrates. Therefore, it dries quickly at the time of printing, and accurate printing can be realized. In addition, since it has a high boiling point, it also acts as a wetting agent.

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

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

Inkjet inks can further contain additives. Examples of the additive include a drying accelerator, a penetrant, a preservative, a chelating agent, a pH adjuster and the like.

The drying accelerator is used to accelerate the drying of the water-based inkjet ink after printing. Examples of the drying accelerator include alcohols such as methanol, ethanol and isopropyl alcohol. The content of the drying accelerator is preferably 1 to 50% by mass in 100% by mass of the water-based inkjet ink.

The penetrant is used when the substrate is a permeable material such as paper, to promote the penetration of the ink into the substrate and to accelerate the apparent drying property. Examples of the penetrant include surfactants such as polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium oleate, and sodium dioctyl sulfosuccinate, in addition to the water-soluble solvent. The amount of the penetrant used is preferably 0.1 to 5% by mass based on 100% by mass of the water-based inkjet ink. When an appropriate amount is used, printing bleeding and paper omission are unlikely to occur.

Preservatives include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethioone-1-oxide, 1,2-benzisothiazolin-3-one, 1-benzisothiazolin-3-one. Amine salt and the like can be mentioned. The amount of the preservative used is preferably 0.05 to 1.0% by mass in 100% by mass of the water-based inkjet ink.

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

Examples of the pH adjuster include various amines, inorganic salts, ammonia, various buffer solutions and the like.

Inkjet ink is produced by blending and mixing each material. After mixing, it is preferable to perform filtration to remove coarse particles. Examples of the mixing include a stirrer using wings, various dispersers, an emulsifier and the like. The order of addition of each material and the mixing method are arbitrary.

Inkjet ink is preferably filtered. As a result, the ejection property from the inkjet printer is improved. A known method can be used for filtration.

As the inkjet ink of the present specification, various inkjet methods can be used. Examples of the inkjet method include a charge control type, a continuous injection type such as a spray type, a piezo method, a thermal method, and an electrostatic suction method.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the Examples. In addition, "part" means "part by mass", and "%" means "mass%".

<Manufacturing of isoindoline compounds>
(Example 1-1)
(Step 1)
To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 800 parts of water, 60 parts of 1,3-diiminoisoindoline, and 120 parts of 28% aqueous ammonia were added in this order and stirred. A solution prepared by dissolving 42.58 parts of 2-cyano-N-methylacetamide in 160 parts of water was added dropwise thereto using a dropping funnel for 30 minutes. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. The reaction slurry was filtered using a Buchner funnel. Further, the filter was added to 1600 parts of water, and the mixture was stirred at 40 ° C. for 30 minutes to remove unreacted 2-cyano-N-methylacetamide. The slurry was filtered off to obtain a non-volatile component. The disappearance of 1,3-diiminoisoindoline was confirmed by UPLC (ultra-high performance high performance liquid chromatography Waters).
(Step 2)
To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 60 parts of the non-volatile content, 480 parts of water, and 162 parts of 80% acetic acid were added and stirred. On the other hand, 461 parts of water and 194 parts of 80% acetic acid were added to a glass flask, 6.72 parts of 2-cyano-N-methylacetamide and 31.97 parts of barbituric acid were added thereto, and the mixture was stirred at 65 ° C. did. The heated solution of this mixture was put into the above-mentioned non-volatile stirring solution, and the temperature was raised to 85 ° C. for further completion of the reaction, and the mixture was stirred. The heating and stirring was carried out until the above-mentioned non-volatile component used as a raw material disappeared. The disappearance of the raw material was confirmed by UPLC.
Then, after cooling to room temperature, it was washed with 2400 parts of water three times to obtain a non-volatile component. This non-volatile component was dried in a hot air dryer at 80 ° C. to obtain 85.03 parts of isoindoline compound 1-1.

(Examples 1-2 to 1-5)
Example 1-Except that in step 2 of Example 1-1, 2-cyano-N-methylacetamide was changed to the charges shown in Table 1, and the amount of barbituric acid charged was changed as shown in Table 2. Synthesis was carried out in the same manner as in No. 1, and the amounts shown in Table 1 were obtained.

Table 2 shows the structures contained in the isoindoline compounds obtained in Examples 1-1 to 1-5. In the table, (1) indicates an isoindoline compound (1), and (2) indicates an isoindoline compound (2).

The identification of the obtained isoindoline compound was carried out by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation. Measurement of the molecular ion peak of the mass spectrum was performed using ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Volume 130 Å, 1.7 μm, 2.1 mm × 50 mm) / Ms TAP XEVO TQD manufactured by Waters. Table 2 shows the theoretical molecular weights of the isoindoline compounds (Examples 1-1 to 1-5) and the measured values obtained by mass spectrometry. Due to the nature of the measurement, the H (proton) of the compound is eliminated from the measured value, so if the value has a mass number of the theoretical molecular weight − (minus) 1, the compounds will match.

(Manufacturing Example 1-1)
To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 800 parts of water, 60 parts of 1,3-diiminoisoindoline, and 120 parts of 28% aqueous ammonia were added in this order and stirred. A solution prepared by dissolving 42.58 parts of 2-cyano-N-methylacetamide in 160 parts of water was added dropwise thereto using a dropping funnel for 30 minutes. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. The reaction slurry was filtered using a Buchner funnel. Further, the filter was added to 1600 parts of water, and the mixture was stirred at 40 ° C. for 30 minutes. The slurry was filtered off to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC (ultra-high performance high performance liquid chromatography Waters). To a four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 60 parts of the non-volatile content, 480 parts of water, and 162 parts of 80% acetic acid were added and stirred. On the other hand, 461 parts of water and 194 parts of 80% acetic acid were added to a glass flask, 40.74 parts of barbituric acid was added thereto, and the mixture was stirred at 65 ° C. The heated solution of this mixture was put into the above-mentioned non-volatile stirring solution, and the temperature was raised to 85 ° C. for further completion of the reaction, and the mixture was stirred. The heating and stirring was carried out until the above-mentioned non-volatile component used as a raw material disappeared. The disappearance of the raw material was confirmed by UPLC.
Then, after cooling to room temperature, it was washed with 2400 parts of water three times to obtain a non-volatile component. This non-volatile component was dried in a hot air dryer at 80 ° C. to obtain 84.91 parts of isoindoline compound 2-1.

(Manufacturing Example 1-2-1-6)
Change to raw material B shown in Table 3-1 instead of 1,3-diiminoisoindoline, and change to raw material C shown in Table 3 instead of 42.58 parts of 2-cyano-N-methylacetamide, respectively. The isoindoline compound as shown in Table 3-2 was synthesized in the same manner as in Production Example 1-1 except that the raw material D shown in Table 3 and the amount charged were changed instead of 40.74 parts of barbituric acid. Got the amount.

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

(Example 2-1)
800 parts of water and 800 parts of 80% acetic acid were added to a 4-neck flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the mixture was stirred. 9.72 parts of 2-cyano-N-methylacetamide and 50.79 parts of barbituric acid were added thereto, and the mixture was stirred at 65 ° C. to dissolve 2-cyano-N-methylacetamide and barbituric acid. On the other hand, 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 solution was put into the above-mentioned heat-dissolved solution, and the temperature was raised to 85 ° C. for further completion of the reaction, and the mixture was stirred. The heating and stirring was carried out until the above-mentioned non-volatile component used as a raw material disappeared. The disappearance of the raw material was confirmed by UPLC.
Then, after cooling to room temperature, it was washed with 2000 parts of water three times to obtain a non-volatile component. This non-volatile component was dried in a hot air dryer at 80 ° C. to obtain 139.46 parts of the isoindoline compound 3-1 shown in Table 5.

(Examples 2-2 to 2-3)
9.72 parts of 2-cyano-N-methylacetamide was changed to the raw material E shown in Table 4 and the approximate amount to be charged. Further, the compounds shown in Table 5 were produced in the amounts shown in Table 4 by synthesizing in the same manner as in Example 2-1 except that the raw material F shown in Table 4 and the charged amount were changed instead of barbituric acid. .. In the table, (1) indicates an isoindoline compound (1), and (2) -1 and (2) -2 indicate an isoindoline compound (2).

(Production Examples 2-1 to 2-2)
Instead of 9.72 parts of 2-cyano-N-methylacetamide and 50.79 parts of barbituric acid, the raw material E shown in Table 4 and the amount to be charged were changed, but the compounds were synthesized in the same manner as in Example 2-1. The compounds and amounts as shown in 5 were obtained.

(Example 3-1)
1 part of isoindoline compound (4-2), 99 parts of isoindoline compound (2-1), 1000 parts of sodium chloride, and 150 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. Kneaded for 8 hours (h). Next, the kneaded mixture was put into warm water at about 70 ° C., stirred for 1 hour to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80 ° C. for 24 hours, and pulverized. 95 parts of the finely divided isoindoline compound (5-1) was obtained.

(Examples 3-2, 3-3, Production Examples 3-1 to 3-4)
Except that 1 part of the isoindoline compound (4-2) was changed to the raw material G and the charged amount shown in Table 6, and 99 parts of the isoindoline compound (2-1) was changed to the raw material H and the charged amount shown in Table 6, respectively. Obtained the amounts of the isoindoline compounds (5-2), (5-3), (6-1) to (6-4) shown in Table 6 in the same manner as in Example 3-1.
(Example 3-4)
In the same manner, the isoindoline compound (5-4) was prepared in the same manner except that 1 part of the isoindoline compound (4-2) and 99 parts of the isoindoline compound (2-1) were changed to the raw material G and the charged amount shown in Table 6. Was obtained in the amounts shown in Table 6.

(Example 4-1)
To 1000 parts of 98% sulfuric acid, 0.4 part of isoindoline compound (4-2) and 36.6 parts of isoindoline compound (2-1) were gradually added with stirring, and the mixture was stirred for 4 hours to dissolve. Next, the solution was gradually added dropwise to 8000 parts of water at 10 ° C. over 30 minutes, filtered, washed with warm water, dried at 80 ° C., and refined isoindoline compound (7-1) 38. .5 copies were obtained.

<Coloring composition and its characteristic evaluation>
Using the obtained pigment composition, coloring compositions for various purposes were prepared and their physical properties were evaluated.

<1> Evaluation of molding composition

(Examples A-1 to A-13, Comparative Examples A-1 to A-6)
<Hue evaluation>
Using the obtained isoindoline compound and high-density polyethylene resin (product name: Hizex 2208J, manufactured by Prime Polymer Co., Ltd.), melt kneading was performed with a twin-screw extruder to bring the temperature inside the barrel to 200 ° C. Injection molding was carried out under the above conditions, and the coloring power was adjusted so as to have a concentration of SD1 / 3, and 11 colored plates having a thickness of 3 mm were prepared. The injection molding was carried out under the condition that the residence time of the composition in the barrel was as short as possible. The isoindoline compounds used are shown in Table 7. For the colored plates, in order to detect the average color difference, a color measuring machine (manufactured by Konica Minolta, CM-700d) capable of measuring the total light beam of the 6th to 11th colored plates is used. Then, each color was measured, and the average value of the obtained color measurement values was used as a control (reference value). Each of the color measurement values was compared with a colored plate using only the isoindoline compound (2), a color difference (ΔE *) was obtained, and the color difference was evaluated according to the following criteria. Specifically, Examples A1-1 to A-5, A-9, A-12, and A-13 Comparative Examples A-4 to A-6 are based on Comparative Example A-1 and Example A-11. Was evaluated with reference to Comparative Example A-2, and Example A-10 was evaluated with reference to Comparative Example A-3.

(Evaluation criteria)
5. ΔE * is less than 1.0. Very good 4. ΔE * is 1.0 or more and less than 2.0. Good 3. ΔE * is 2.0 or more and less than 3.0. Practical use 2. ΔE * is 3.0 or more and less than 5.0. Practical use depending on the conditions 1. ΔE * is 5.0 or more. Not practical-. Unmeasured

<Heat resistance test>
The heat resistance test was carried out in accordance with the German industrial standard DIN12877-1. After adjusting the molding conditions so that the residence time in the barrel was 5 minutes, 11 colored plates were molded at 300 ° C. for each. The obtained colored plates, each of which was the 6th to 11th sheets, were color-measured, and the average value of the color measurement values was calculated. The color difference (ΔE *) between the above control and the measured value of the plate molded at 300 ° C. was determined and evaluated according to the following criteria. The results are shown in Table 7. The smaller the color difference, the better the heat resistance.

(Evaluation criteria)
5. ΔE * is less than 2.0. Very good 4. ΔE * is 2.0 or more and less than 4.5. Good 3. ΔE * is 4.5 or more and less than 7.5. Practical use 2. ΔE * is 7.5 or more and less than 10.0. Practical use depending on the conditions 1. ΔE * is 10.0 or more. Not practical-. Unrated

<Evaluation result>
Examples A-1 to A-13 containing the isoindoline compound (1) did not impair the hue of the isoindoline compound (2), and Comparative Examples A-1 to A- of only the isoindoline compound (2). Compared with No. 3, the heat resistance was greatly improved. However, Comparative Examples A-4 to A-6 containing a compound having a structure different from that of the isoindoline compound (1) had a significantly different hue from that of the isoindoline compound (2).
The reason for this is that although the isoindoline compounds 6-2 to 6-4 have a structure similar to that of the isoindoline compound (1), the hue of the pigment composition changes because the compound itself has low saturation. I guess it's gone.

(Example A-14) Preparation of molded product 1 part of isoindoline compound 1-4 and 1000 parts of polypropylene resin (product name: Prime Polypro J105, manufactured by Prime Polymer Co., Ltd.) are melt-mixed at 220 ° C. using a twin-screw extruder. It was smelted and then cut with a pelletizer to obtain a pellet-shaped molding composition. Next, while melt-kneading the obtained molding composition, injection molding was performed using an injection molding machine set at a molding temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a molded product (plate) having a thickness of 1 mm. Got As a result of visually observing the molded product, no coarse particles were observed even in the watermark, and a yellow plate having a good degree of coloring was obtained.

(Example A-15) Preparation of molded product 0.5 parts of isoindoline compound 1-4 and 1000 parts of pre-dried polyethylene terephthalate resin (product name: Vylope EMC-307, manufactured by Toyo Spinning Co., Ltd.) are biaxial. It was melt-kneaded at 275 ° C. with an extruder and then cut with a pelletizer to obtain a pellet-shaped molding composition. Next, while melt-kneading the obtained molding composition, injection molding was performed using an injection molding machine set at a molding temperature of 275 ° C. and a mold temperature of 85 ° C. to obtain a molded product (plate) having a thickness of 3 mm. Obtained. As a result of visually observing the molded product, no coarse particles were observed even in the watermark, and a yellow plate having a good degree of coloring was obtained.

<2> Evaluation of toner A negatively charged toner was prepared and evaluated.
(Example A-16)
2500 parts of isoindoline compound 1-4 and 2500 parts of polyester resin (product name: M-325, manufactured by Sanyo Chemical Industries, Ltd.) were kneaded at 120 ° C. for 15 minutes using a pressure kneader. Next, the obtained kneaded product was taken out from the pressure kneader, and further kneaded using three rolls having a roll temperature of 95 ° C. The obtained kneaded product was cooled and then roughly pulverized to 10 mm or less to obtain a colored composition.
500 parts of the obtained coloring composition, 4375 parts of polyester resin, 50 parts of a calcium salt compound (charge control agent) of 3,5-di-tert-butylsalicylic acid, and an ethylene homopolymer (release agent, molecular weight 850, Mw / 75 parts of Mn = 1.08, melting point 107 ° C.) are mixed (3000 rpm, 3 minutes) using a 20 L volume Henschel mixer, and melt-kneaded at a discharge temperature of 120 ° C. using a twin-screw kneading extruder. went. Then, the kneaded product was cooled and solidified, and then coarsely pulverized with a hammer mill. Next, the obtained coarsely pulverized product was finely pulverized using a type I jet mill (IDS-2 type) and then classified to obtain toner matrix particles.
Next, 2500 parts of the toner mother particles obtained above and 12.5 parts of hydrophobic titanium oxide (manufactured by STT-30A Titan Kogyo Co., Ltd.) were mixed with a Henschel mixer having a volume of 10 L to obtain a negatively charged toner 1.

On the other hand, as a comparison target, a negatively charged toner 2 was obtained in the same manner as in Example A-16, except that the isoindoline compound 1-4 of Example A-16 was changed to the isoindoline compound 2-1.
The obtained negatively charged toner 1 and negatively charged toner 2 were each sliced to a thickness of 0.9 μm using a microtome to form a sample. Next, the dispersed state of the pigment was observed for each sample using a transmission electron microscope. As a result, the pigment is more uniformly distributed in the negatively charged toner 1 using the compound of the isoindoline compound 1-4 than in the negatively charged toner 2 using the isoindoline compound 2-1 and the dispersibility is improved. I was able to confirm that it was good.

<3> Evaluation of paint <3-1> Preparation of solvent-based paint 1. Preparation of base paint (Example B-1) Preparation method of base paint 1 First, the following raw materials and 230 parts of steel beads were placed in a 225 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil. , A mixture was obtained.
-Isoindoline compound 1-1: 19 parts-Acrylic resin (DIC, Acrydic 47-712): 7.7 parts-Dispersion solvent (toluene: xylene: butyl acetate: ENEOS T-SOL150 FLUID mass ratio 3: 3: 2: 2 mixed solvent): 40.7 parts Next, 75.4 parts of acrylic 47-712 and melamine resin (Amidia L-117-60 manufactured by DIC) 17.2 were added to the above mixture. The parts were added and dispersed for another 10 minutes to obtain a dispersion liquid.
Then, the steel beads were removed from the dispersion to obtain the base coating material 1 of the isoindoline compound 1-1.

(Examples B-2 to B-13, Comparative Examples B-1 to B-6) Preparation of Base Paints 2-19 In the method for preparing the base paint 1 described in Example B-1, the isoindoline compound 1-1 The base coating materials 2 to 19 were obtained in the same manner as in Example B-1 except that the compounds were changed to the isoindoline compounds shown in Table 8.

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

3. 3. Preparation of Solid Base Paint (Example C-1) Preparation of Solid Base Paint 1 The following components were stirred using a high-speed stirrer to obtain Solid Base Paint 1.
・ 1:10 parts of base paint prepared in Example B-1 ・ White paint obtained: 31.9 parts

(Examples C-2 to C-13, Comparative Examples C-1 to C-6) Preparation of Solid Base Paints 2 to 19 The fact that the base paint 1 of Example C-1 was changed to the base paints 2 to 19 respectively. Solid base paints 2 to 19 were obtained in the same manner as in Example C-1 except for the above.
The isoindoline compounds of the base paint used in the solid base paints prepared in each Example and each Comparative Example are as shown in Table 9.

4. Preparation of Top Coat Clear Paint The following raw materials were agitated using a high-speed stirrer to obtain a top coat clear paint.
-Acrylic resin (DIC, Acrydic 44-179): 120 parts-Melamine resin (DIC, Amidia L117-60): 30 parts-Diluting solvent (toluene, xylene, ENEOS T-SOL150 FLUID, 3 -Mixed solvent with a mass ratio of ethyl ethoxypropionate and ethyl acetate of 3: 2: 2: 1: 2): 50 parts

5. Preparation of solid base coated plate and evaluation of weather resistance (Example D-1) Preparation of solid base coated plate 1 Solid base paint 1 was sprayed with a spray gun, and a steel plate covered with sandpaper # 1000 was coated. In order to adjust the viscosity so that it is easy to spray, the mass ratio of the diluting solvent (toluene, xylene, T-SOL150FLUID manufactured by ENEOS, ethyl 3-ethoxypropionate, ethyl acetate) is 3: 2 with respect to the solid base paint. : 2: 1: 2 mixed solvent) was appropriately mixed.
The painting was performed in 9 times, and then the top coat clear paint was sprayed in 6 times. Then, after drying at 25 ° C. for 8 hours, it was dried at 140 ° C. for 30 minutes to obtain a solid base coated plate 1.

(Examples D-2 to D-13, Comparative Examples D-1 to D-5) Preparation of solid base coating plates 2 to 19 The solid base coating material 1 of Example D-1 was changed to solid base coating materials 2 to 19, respectively. Solid base coated plates 2 to 19 were obtained in the same manner as in Example D-1 except for the above.

(Hue evaluation)
The solid base coated plate was color-measured using a colorimeter (manufactured by Konica Minolta, CM-700d) capable of measuring the total luminous flux. Further, the color difference (ΔE *) was obtained by comparing with the solid base coated plate using only the isoindoline compound (2), and evaluated according to the following criteria. Specifically, Examples D1-1 to D-5, D-9, D-12, and D-13 Comparative Examples D-4 to D-6 are based on Comparative Example D-1. Example D-11 was evaluated based on Comparative Example D-2, and Example D-10 was evaluated based on Comparative Example D-3. The results are shown in Table 10.

(Evaluation criteria)
5. ΔE * is less than 1.0. Very good 4. ΔE * is 1.0 or more and less than 2.0. Good 3. ΔE * is 2.0 or more and less than 3.0. Practical use 2. ΔE * is 3.0 or more and less than 5.0. Practical use depending on the conditions 1. ΔE * is 5.0 or more. Not practical-. Unmeasured

(Weather resistance evaluation)
The obtained solid base coated plates 1 to 19 were subjected to a weather resistance test according to the following.
The weather resistance test uses an ultra-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151), illuminance 90 mW / cm2, irradiation (daytime) conditions: 12 hours, temperature 63 ° C, humidity 70. %, Irradiation suspension (night) conditions: 12 hours, temperature 70 ° C., humidity 99% as one cycle, under the conditions of 48 hours (2 cycles of 12 hours day and night) and 96 hours (4 cycles of 12 hours day and night). went. The coated plate before and after the weather resistance test was visually observed, and the weather resistance was evaluated according to the following criteria. The results are shown in Table 10. It is considered that the smaller the change in color, the better the weather resistance, and if it is "5", "4", "3" and "2" according to the following evaluation criteria, it is a practical level.

(Evaluation criteria)
5. ΔE * is less than 4.0. Very good 4. ΔE * is 4.0 or more and less than 6.0. Good 3. ΔE * is 6.0 or more and less than 7.5. Practical use 2. ΔE * is 7.5 or more and less than 10.0. Practical use depending on the conditions 1. ΔE * is 10.0 or more. Not practical-. Unmeasured

<Evaluation result>
Examples D-1 to D-13 containing the isoindoline compound (1) did not impair the hue of the isoindoline compound (2), and Comparative Examples D-1 to D- of only the isoindoline compound (2). Compared with 3, the weather resistance was greatly improved. However, Comparative Examples D-4 to D-6, which contained a compound having a structure different from that of the isoindoline compound (1), had a significantly different hue from that of the isoindoline compound (2).
The reason for this is that although the isoindoline compounds 6-2 to 6-4 have a structure similar to that of the isoindoline compound (1), it is presumed that the hue of the pigment composition has changed due to the low saturation of the compound itself. did.

<4> Evaluation of water-based coloring composition 1. Preparation of water-based coloring composition (Example E-1) Preparation of water-based coloring composition E-1 The following raw materials and 70 parts of 1.25 mm diameter zirconia beads were placed in a 70 ml glass bottle, and a paint shaker manufactured by Red Devil Co., Ltd. was used. The mixture was dispersed over 60 minutes using a dispersion to obtain a dispersion.
-Isoindoline compound 1-1: 3.15 parts-Polyester-modified acrylic acid polymer (Allnex, ADDITOR XW 6528): 5.25 parts-Wetting agent (Allnex, ADDITOR XW 6374): 0.95 parts -Antifoaming agent (ADDITOR XW 6211 manufactured by Allnex): 0.63 parts-Ion-exchanged water: 21.52 parts Next, zirconia beads were removed from the above dispersion to obtain an aqueous coloring composition E-1. ..

(Examples E-2 to E-13, Comparative Examples E-1 to E-7) Preparation of water-based coloring compositions E-2 to 20 The isoindoline pigment 1-1 of Example E-1 is as shown in Table 11. Water-based coloring compositions E-2 to 20 were obtained in the same manner as in Example E-1 except that the mixture was changed to.

(Example E-14) Preparation of water-based coloring composition E-21 The isoindoline compound 1-1: 3.15 parts of Example E-1 was added to the isoindoline compound 21: 3.12 parts and the isoindoline compound 4 -2: An aqueous coloring composition E-21 was obtained in the same manner as in Example E-1 except that it was changed to 0.08 part.

2. Evaluation of dispersion stability (evaluation of initial viscosity and viscosity stability)
The initial viscosities of the obtained water-based coloring compositions E-1 to E-17 and E-21 at 25 ° C. were measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosities after aging at 25 ° C. for 1 week and after accelerating at 50 ° C. for 1 week were measured. The rate of increase in viscosity with respect to the initial viscosity was calculated based on the obtained measured values, and the viscosity was evaluated as viscosity stability according to the following evaluation criteria. The results are shown in Table 12. The lower the initial viscosity, the better the dispersibility. Further, the smaller the viscosity increase rate, the better the dispersion stability. According to the following evaluation criteria, "4", "3" and "2" are practical levels.

(Evaluation criteria for initial viscosity)
4. The initial viscosity is less than 10.0 mPa · s. Very good 3. The initial viscosity is 10.0 mPa · s or more and less than 15.0 mPa · s. Good 2. The initial viscosity is 15.0 mPa · s or more and less than 20.0 mPa · s. Practical use 1. The initial viscosity is 20.0 mPa · s or more. Impractical

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

<Evaluation result>
Examples E-1 to E-14 containing the isoindoline compound (1) have more dispersibility and viscosity stability of the aqueous coloring composition than Comparative Examples E-1 to E-3 containing only the isoindoline compound (2). The sex has improved greatly. Further, Comparative Example E-4, which contained a compound having a structure similar to that of the isoindoline compound (1), had poor dispersibility and low viscosity stability.
Isoindoline compounds 2-1 and 2-6, 4-1 are highly hydrophilic and have a very high affinity for water, so that it is usually difficult to disperse them in water. However, it is presumed that the pigment composition containing the isoindoline compound (2) and the isoindoline compound (1) has a relatively hydrophobic surface and can adsorb the dispersant, so that the dispersibility and viscosity stability can be improved. ..
On the other hand, in the isoindoline compound 6-1 containing the isoindoline compound (2) in the highly hydrophilic isoindoline compound 2-2 as in Comparative Example E-4, the dispersibility and viscosity stability should be improved in an aqueous system. It is possible because it cannot be done.

<5> Evaluation of water-based paint A water-based paint was prepared and evaluated using the water-based coloring composition prepared in the upper stage.

<5-1> Preparation of water-based paint (Example F-1)
(1) Preparation of Water-based Paint 1-1 After blending in a solid content so as to have the following composition, the mixture was stirred using a high-speed stirrer to obtain a water-based paint 1-1 (stored at 25 ° C. for 1 week).
-Water-based coloring composition E-1 (stored at 25 ° C for 1 week): 4.8 parts-Watersol S-751 (acrylic resin for baking paint manufactured by DIC): 60.0 parts

-Simel 303 (Melamine resin manufactured by Mitsui Cytec): 45.0 copies

(2) Preparation of Water-based Paint 1-2 The mixture was blended so as to have the following composition in terms of solid content, and then stirred using a high-speed stirrer to obtain water-based paint 1-2 (stored at 50 ° C. for 1 week).
-Water-based coloring composition E-1 (stored at 50 ° C for 1 week): 4.8 parts-Watersol S-751 (acrylic resin for baking paint manufactured by DIC): 60.0 parts-Symel 303 (manufactured by Mitsui Cytec Co., Ltd., Melamine resin): 45.0 parts

(Examples F-2 to F-14, Comparative Examples F-1 to F-7)
All except that the water-based coloring composition E-1 (stored at 25 ° C. for 1 week) of Example F-1 was sequentially changed to the water-based coloring compositions E-2 to 21 (stored at 25 ° C. for 1 week). Water-based coating materials 2-1 to 21-1 were obtained in the same manner as in Example F-1.
Further, the water-based coloring composition E-1 of Example F-1 (stored at 50 ° C. for 1 week) was sequentially changed to the water-based coloring compositions E-2 to 21 (each stored at 50 ° C. for 1 week). A water-based coating material 2-2-21-2 was obtained in the same manner as in Example F-1 except for the above.

<5-2> Preparation of PET film coating (Example G-1) Preparation of PET film coating 1 Using a 6-mil applicator for water-based paint 1-1 and water-based paint 1-2, Lumirror 100T60 (polyethylene terephthalate (PET) ) The film, 100 μm thick) was coated. After the coating, the PET film was dried 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 a PET film coating 1 having a film thickness of 70 μm.

(Examples G-2 to G-14, Comparative Examples G-1 to G-7) Preparation of PET film coating 2 to 25 Water-based paint 1-1 and water-based paint 1-2 of Example G-1 were 2-1. PET film coatings 2 to 21 were obtained in the same manner as in Example G-1 except that they were changed to ~ 21-1 and 2-2-21-2.

<5-3> Evaluation of PET film coating Hue and hue stability of each PET film coating obtained in Examples G-1 to G-14 and Comparative Examples G-1 to G-7 according to the following method. Was evaluated.

(Hue evaluation)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), the color of the PET film coated with the paint of the water-based coloring composition was measured, and the color difference (ΔE *) was determined. Judgment was made based on the following criteria. Each of the color measurement values was compared with a colored plate using only the isoindoline compound (2), a color difference (ΔE *) was obtained, and the color difference was evaluated according to the following criteria. Specifically, Examples G-1 to G-5, G-9, G-12, and G-13 Comparative Examples G-4 to G-7 are based on Comparative Example G-1 and Example G-11. Was evaluated with reference to Comparative Example G-2, and Example G-10 was evaluated with reference to Comparative Example G-3. The results are shown in Table 14. The smaller the color difference, the better. If it is "4", "3" and "2" in the following evaluation criteria, it is a practical level.
(Evaluation criteria)
4. ΔE * is less than 1.0.
3. 3. ΔE * is 1.0 or more and less than 2.0.
2. ΔE * is 2.0 or more and less than 3.0.
1. 1. ΔE * is 3.0 or more.

(Evaluation method of hue stability)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), a PET film coated with a paint of a water-based coloring composition stored at 25 ° C. for 1 week and a paint of a water-based coloring composition stored at 50 ° C. for 1 week was applied. The color was measured, the color difference (ΔE *) was obtained, and the judgment was made according to the following criteria. The results are shown in Table 14. It is considered that the smaller the color difference is, the more excellent the dispersion stability is, and if it is "4", "3" and "2" according to the following evaluation criteria, it is a practical level.
(Evaluation criteria)
4. ΔE * is less than 1.0.
3. 3. ΔE * is 1.0 or more and less than 2.0.
2. ΔE * is 2.0 or more and less than 3.0.
1. 1. ΔE * is 3.0 or more.

<Evaluation result>
Examples G-1 to G-14 containing the isoindoline compound (1) did not impair the hue of the isoindoline compound (2), and Comparative Examples G-1 to G- of only the isoindoline compound (2). Compared with No. 3, the stability of hue was greatly improved. Isoindoline compounds 2-1 and 2-6, 4-1 are highly hydrophilic and have a very high affinity for water, so that it is usually difficult to disperse them in water. However, since the surface of the pigment composition containing the isoindoline compound (2) and the isoindoline compound (1) is relatively hydrophobic, the dispersant is easily adsorbed, and the dispersibility and viscosity stability are improved. I guess it can be done.
On the other hand, Comparative Example G-4, which contained a compound having a structure similar to that of the isoindoline compound (1), did not improve the stability of the hue. Further, the hues of Comparative Examples G-5 to G-7 were significantly different from those of the isoindoline compound (2).

The reason why the hue stability of Comparative Example G-4 was not improved is that the isoindoline compound 6 containing the highly hydrophilic isoindoline compound 2-2 and the isoindoline compound (2), such as Comparative Example G-4. It is presumed that -1 is because the surface does not become relatively hydrophobic and the dispersant could not be adsorbed well.

In Comparative Examples G-5 to G-7, the reason why the hue was significantly different from that of the isoindoline compound (2) is that the isoindoline compounds 6-2 to 6-4 have a structure similar to that of the isoindoline compound (1). However, it is presumed that the hue of the pigment composition has changed due to the low saturation of the compound itself.

<6> Evaluation of gravure ink First, a resin measurement method will be described below.
(Hydroxy group value)
The hydroxyl value is a value obtained by converting the amount of hydroxyl groups in 1 g of the resin, which is calculated by esterifying or acetylating the hydroxyl groups in the resin with an excess anhydrous acid and back titrating the remaining acid with an alkali, to the number of mg of potassium hydroxide. So, it is a value performed according to JISK0070.
(Amine value)
The amine value is the number of mg of potassium hydroxide in the same amount as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin. The amine value was measured by, for example, the following method.
-Measuring method of amine value 0.5 to 2 g of the sample is precisely weighed. (Sample amount: Sg) Add 30 mL of neutral ethanol (BDG neutral) to the precisely weighed sample and dissolve it. The obtained solution is titrated with a 0.2 mol / l ethanolic hydrochloric acid solution (titer: f). With the point where the color of the solution changed from green to yellow as the end point, the amine titer was determined by the following (Equation 2) using the titration amount (AmL) at this time.
(Formula 2) Amine value = (A × f × 0.2 × 56.108) / S
(Weight average molecular weight)
The weight average molecular weight was determined as a polystyrene-equivalent molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (“Shodex GPC System-21” manufactured by Showa Denko Co., Ltd.).

(Synthesis Example 1) [Polyurethane Resin PU1]
160 parts of polyester polyol (hereinafter "PMPA") obtained from adipic acid with a number average molecular weight of 2000 and 3-methyl-1,5-pentanediol, 20 parts of polypropylene glycol (hereinafter "PPG") with a number average molecular weight of 2000, average molecular weight 20 parts of 1000 polypropylene glycol, 53.8 parts of isophorone diisocyanate (hereinafter “IPDI”), and 63.4 parts of ethyl acetate are reacted at 80 ° C. for 4 hours under a nitrogen stream to obtain a solvent solution of the terminal isocyanate prepolymer. It was. Next, 23.1 parts of isophorone diamine (hereinafter "IPDA"), 2.0 parts of iminobispropylamine (hereinafter "IBPA"), 1.0 part of 2-ethanolamine (hereinafter "2EtAm"), ethyl acetate / isopropanol (hereinafter "IBPA"). The obtained terminal isocyanate prepolymer solution was gradually added to a mixture of 589.7 parts of a mixed solvent of "IPA") = 50/50 at 40 ° C., and then reacted at 80 ° C. for 1 hour to obtain a non-volatile component. A polyurethane resin solution PU1 having a amine value of 11.1 mgKOH / g, a hydroxyl value of 3.3 mgKOH / g, and a weight average molecular weight of 35,000 was obtained.

(Example H-1) [Preparation of gravure ink 1]
As the binder resin, 40 parts of polyurethane resin solution PU1 (non-volatile content 30%), 5.0 parts of isoindoline resin (solvine TAO: manufactured by Nisshin Chemical Co., Ltd.), silica particles (P-73 manufactured by Mizusawa Chemical Co., Ltd.) 0 .6 parts, 10 parts of isoindoline compound 1-1 and 45.0 parts of a solution of N-propyl acetate (hereinafter [NPAC]) / IPA = 50/50 (mass ratio) were mixed and dispersed in an Eiger mill for 15 minutes. , Gravure ink 1 was obtained.

(Examples H-2 to 13, Comparative Examples H-1 to 6) [Preparation of gravure inks 2 to 19]
In the method for preparing the gravure ink 1 described in Example H-1, the gravure inks 2 to 19 were prepared in the same manner as in Example H-1 except that the isoindoline compound 1-1 was changed as shown in Table 15. Obtained.

(Example I-1) <Printing of gravure ink>
The gravure ink 1 obtained above is diluted with a mixed solvent (methyl ethyl ketone: NPAC: IPA = 40: 40: 20) so that the viscosity becomes 16 seconds (25 ° C., Zahn cup No. 3), and Helio A 175-line gradation plate (plate type Elongate, 75% solid pattern and 100% to 3% gradation pattern) is used on the corona discharge-treated surface of a 12 μm-thick corona discharge-treated polyester (PET) film (E-5100 manufactured by Toyo Spinning Co., Ltd.). Printing was performed at a printing speed of 100 m / min to obtain a printed matter. The printing conditions were a temperature of 25 ° C. and a humidity of 60%, and the printing distance was 4000 m.

Regarding the obtained printed matter, 1.5 g / m 2 and 1.0 g / m of a polyether urethane-based laminate adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd.) as an ethyl acetate solution having a non-volatile content of 25% by weight and 10% by weight were further added. It was coated and dried so as to be No. 2, and was bonded to aluminum vapor-deposited unstretched polypropylene (VMCP2203, film thickness 25 μm, manufactured by Toray Film Processing Co., Ltd.) and dry-laminated to obtain printed matter I-1.

(Examples I-2 to 13, Comparative Examples I-1 to 6)
The gravure inks 2 to 19 shown in Table 15 were printed according to the printing configuration shown in Table 16 to obtain printed matter I-2 to I-19.

<Evaluation>
The following evaluations were carried out using gravure inks 1 to 19 and printed matter I-1 to I-19.

<Ink stability over time>
Each of the gravure inks 1 to 19 was placed in a closed container and stored at 40 ° C. for 10 days. Then, the viscosity was measured to evaluate the change in viscosity from that before storage. The viscosity was measured at 25 ° C. The number of outflow seconds was 4. The viscosity of each ink in the B-type viscometer before storage was in the range of 40 to 500 cps (25 ° C.). -Has not been measured.
(Evaluation criteria)
5. Viscosity change less than 2 seconds (good)
4. Viscosity change is 2 seconds or more and less than 5 seconds (practical)
3. 3. Viscosity change is 5 seconds or more and less than 10 seconds (slightly defective)
2. Viscosity change is 10 seconds or more and less than 15 seconds (defective)
1. 1. Viscosity change is 15 seconds or more (extremely defective)

<Transparency evaluation>
Regarding the transparency, the printed matter was superposed on a black-belt-colored paper (N2C without Bico-chart coat manufactured by BYK) and compared with the printed matter using only the isoindoline compound (2). Specifically, Examples I-1 to I-5, I-9, I-12, I-13, and Comparative Examples I-4 to I-6 are based on Comparative Example I-1, and Example I- 11 was evaluated based on Comparative Example I-2, and Examples I-6 to I-8 and I-10 were evaluated based on Comparative Example I-3. The results are shown in Table 16.
(Evaluation criteria)
5. Extremely transparent 4. Transparent 3. Equivalent to the standard 2. Opaque 1. Extremely opaque

<Hue evaluation>
Hue is measured by superimposing the printed matter on white bleached paper (BYK Bico-chart uncoated N2C) and using a colorimeter (Konica Minolta, CM-700d) capable of measuring the total luminous flux. Colored. In addition, the color difference (ΔE *) was determined by comparing with the printed matter using only the isoindoline compound (2), and evaluated according to the following criteria. Specifically, Examples I-1 to I-5, I-9, I-12, I-13, and Comparative Examples I-4 to I-6 are based on Comparative Example I-1, and Example I- 11 was evaluated based on Comparative Example I-2, and Example I-10 was evaluated based on Comparative Example I-3. The results are shown in Table 16.
(Evaluation criteria)
5. ΔE * is less than 1.0. Very good 4. ΔE * is 1.0 or more and less than 2.0. Good 3. ΔE * is 2.0 or more and less than 3.0. Practical use 2. ΔE * is 3.0 or more and less than 5.0. Practical use depending on the conditions 1. ΔE * is 5.0 or more. Impractical

<Evaluation result>
Examples H-1 to H-13 and Examples I-1 to I-13, which contain the isoindoline compound (1), do not impair the hue of the isoindoline compound (2), and the isoindoline compound (2) Compared with only Comparative Examples H-1 to H-3 and I-1 to I-3, stability over time and transparency were greatly improved.

The reason for the improvement in stability and transparency over time is not clear, but when the isoindoline compound (1) becomes a pigment together with the isoindoline compound (2), the particles become finer and the surface properties of the pigment change. It is presumed that the stability and transparency over time were greatly improved.

However, Comparative Examples I-4 to I-6, which contained a compound having a structure similar to that of the isoindoline compound (1), had a significantly different hue from that of the isoindoline compound (2).
The reason for this is that although the isoindoline compounds 6-2 to 6-4 have a structure similar to that of the isoindoline compound (1), it is presumed that the hue of the pigment composition has changed due to the low saturation of the compound itself. To do.

<7> Evaluation of water-based inkjet ink

(Example J-1)
(Preparation of Aqueous Coloring Composition for Inkjet (hereinafter referred to as "Aqueous Coloring Composition for IJ"))
-Isoindoline compound (Synthesis Example 1-1): 19.0 parts-Styrene-acrylic acid copolymer (BASF Japan, John Krill 61J): 16.4 parts-Surfactant (Kao, Emargen 420) ): 5.0 parts, ion-exchanged water: 59.6 parts and 200 parts of 1.25 mm diameter zirconia beads were placed in a 200 ml glass bottle and dispersed for 6 hours with a paint shaker manufactured by Red Devil. Then, the zirconia beads were removed from the dispersion to obtain an aqueous coloring composition 1 for IJ.

(Adjustment of water-based inkjet ink (hereinafter referred to as "water-based IJ ink"))
33 parts of aqueous IJ dispersion 1, 5 parts of butyl diglycol, 15 parts of 1,2-propanediol, 8.8 parts of Joncryl HPD96 (manufactured by BASF, water-soluble resin), Chemipearl W400S (manufactured by Mitsui Chemicals) , Reolefin aqueous dispersion) 1.25 parts, Surfinol DF110D (Nissin Chemical Industry Co., Ltd., defoamer) 0.5 parts, BYK-348 (Big Chemie Japan Co., Ltd., silicon-based surfactant) 1 part, triethanolamine 0.1 part, Proxel GXL (manufactured by London, preservative) 0.15 part, ion exchange water 35.2 parts mixed with high speed mixer and filtered with 0.5 μm membrane filter. Then, the water-based IJ ink 1 was obtained.

(Examples J-2 to J-13, Comparative Examples J-1 to J-4) Preparation of Aqueous Coloring Compositions 2 to 17 for IJ and Aqueous IJ Inks 2 to 17 Isoindoline Compound 1 to Example J-1 Aqueous coloring compositions for IJ 2 to 17 and aqueous IJ inks 2 to 17 shown in Table 16 were obtained in the same manner as in Example J-1 except that 1 was changed to the isoindoline compounds shown in Table 16. It was.

(Example J-16) Preparation of Aqueous Coloring Composition 18 for IJ and Aqueous IJ Ink 18 In the method for preparing an aqueous IJ dispersion liquid 1 described in Example J-1, 19 parts of isoindoline compound 1-1 was added to isoindoline. An aqueous coloring composition 18 for IJ and an aqueous IJ ink 18 were obtained in the same manner as in Example J-1 except that they were changed to 2-1 18.81 parts and isoindoline 4-2 0.19 parts.

<Evaluation of water-based IJ ink>
The viscosity stability of the water-based IJ inks 1 to 18 prepared in Examples and Comparative Examples was evaluated according to the following.
(Evaluation method of viscosity stability)
For each water-based inkjet ink, the initial viscosity at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosities after aging at 25 ° C. for 4 weeks and after accelerating at 50 ° C. for 4 weeks were measured. Using each measured value, the rate of increase in viscosity with respect to the initial viscosity was calculated, used as an index of viscosity stability, and evaluated according to the following criteria. The results are shown in Table 17. It is considered that the smaller the viscosity increase rate is, the more excellent the viscosity stability is, and if it is "4", "3" and "2" according to the following evaluation criteria, it is a practical level.

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

<Evaluation result>
Examples J-1 to J-14 containing the isoindoline compound (1) have an ink coating film at the time of long-term storage stability as compared with Comparative Examples J-1 to J-3 containing only the isoindoline compound (2). It can be seen that it is an inkjet ink that can suppress the color change of.
Isoindoline compounds 2-1 and 2-6, 4-1 are highly hydrophilic and have a very high affinity for water, so that it is usually difficult to disperse them in water. However, it is presumed that the pigment composition containing the isoindoline compound (2) and the isoindoline compound (1) has a relatively hydrophobic surface and can adsorb the dispersant, so that the long-term storage stability is improved.
However, the long-term storage stability of Comparative Example J-4, which contained a compound having a structure similar to that of the isoindoline compound (1), was not improved. This is because the isoindoline compound 6-1 containing the isoindoline compound (2) in the highly hydrophilic isoindoline compound 2-2, such as Comparative Example J-4, improves the dispersibility and viscosity stability in an aqueous system. It is thought that this is not possible.

Claims (7)

A pigment composition containing an isoindoline compound represented by the following formula (1) and an isoindoline compound represented by the following formula (2).

[In the formula, R ₁ and R ₂ represent hydrogen atoms,
A represents a group represented by the following formula (3), the following formula (4), or the following formula (5).

In the formula, X represents -O- or -NH- and R ₃ represents an alkyl or aryl group.
R _{4 to} R ₆ represent hydrogen atoms
R _{7 to} R ₁₀ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. ] A coloring composition comprising the pigment composition according to claim 1 and a dispersion medium. A molding composition containing the coloring composition according to claim 2. A toner containing the coloring composition according to claim 2. A paint comprising the coloring composition according to claim 2. A printing ink containing the coloring composition according to claim 2. An inkjet ink containing the coloring composition according to claim 2.