JP2022031604A - Pigment composition, coloring composition, paint, ink, ink set, printed article, and packaging material - Google Patents

Abstract

To provide a pigment composition containing an isoindoline compound that has outstanding dispersion, weather resistance, and heat resistance, also has favorable storage stability, and resists fading over time in a basic atmosphere.SOLUTION: The pigment composition contains an isoindoline compound represented by formula (1) and an isoindoline compound represented by formula (2). [In the formula, R1 to R4 represent H, R5 and R6 each independently represent an alkyl group, and A and A' each represent a specific substituent].SELECTED DRAWING: Figure 3

Description

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

Pigments are a typical colorant used in applications such as plastic products, toners, paints, and printing inks. Pigments are roughly classified into inorganic pigments and organic pigments, and organic pigments generally tend to be inferior in weather resistance and heat resistance as compared with inorganic pigments. However, organic pigments are used in various applications because they are superior to inorganic pigments in terms of color sharpness and coloring power. For example, as organic pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, quinacridone pigments and the like are known.

On the other hand, in recent years, there has been an increasing demand for organic pigments and colorants that do not contain primary aromatic amines and heavy metals from the viewpoint of reducing environmental impacts and ensuring safety and health. Azo pigments are mainly used as organic pigments having a yellow to crimson hue, but the azo pigments are primary aromatic amines in the components due to the raw materials used or decomposition by light or heat. May be included. Therefore, in recent years, from the viewpoint of environmental compatibility and safety and health, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 139, and C.I. I. Isoindoline pigments that do not contain primary aromatic amines, such as Pigment Red 260, are attracting attention.

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, which comprises water, a dispersant, and an isoindoline pigment.

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

However, the conventional isoindoline compound is difficult to disperse and has poor dispersion stability. Further, the coloring composition containing the isoindoline compound has a problem that the weather resistance and the heat resistance are insufficient.
Furthermore, when the isoindoline compound is used for water-based inkjet ink applications, it is necessary to set the pH value of the ink to 7 or more and 10 or less in terms of storage stability, but there is a problem of fading over time in a basic atmosphere. ..

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 suppresses discoloration over time in a basic atmosphere.

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 to R ₄ represent hydrogen atoms, R ₅ and R ₆ each independently represent an alkyl group, and A and A'are the following formulas (3) and (4). Or, it represents a group represented by the following formula (5).

In the formula, X represents —O— or —NH— and R ₇ represents an alkyl or aryl group.
R ₈ to R ₁₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl 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 suppresses fading over time in a basic atmosphere. .. Further, it is possible to provide an ink set, a printed matter, and a packaging material containing yellow ink, which has good dispersibility and storage stability and can form a highly saturated image or the like.

FIG. 1 is an X-ray diffraction spectrum of the isoindoline compound obtained in Production Example 1-1. FIG. 2 is an X-ray diffraction spectrum of the isoindoline compound obtained in Production Example 1-2. FIG. 3 is an X-ray diffraction spectrum of the isoindoline compound obtained in Example 1-1. FIG. 4 is an X-ray diffraction spectrum of the isoindoline compound obtained in Example 1-2. FIG. 5 is an X-ray diffraction spectrum of the isoindoline compound obtained in Example 1-4. FIG. 6 is an X-ray diffraction spectrum of the isoindoline compound obtained in Example 1-5. FIG. 7 is an X-ray diffraction spectrum of the isoindoline compound obtained in Example 1-8. FIG. 8 is an X-ray diffraction spectrum of the isoindoline compound obtained in Example 1-11.

First, the terms used herein are defined. When the terms "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are used, unless otherwise specified, they are "(meth) acrylamide", respectively. It means acryloyl and / or methacrylic, "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". Further, "CI" means a color index (CI).

<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).

As described above, the pigment composition of the present invention contains two types of isoindoline compounds under the dispersibility, weather resistance, heat resistance, storage stability, and basic atmosphere, which have been the weak points of the isoindoline compounds in the past. Can solve the problem of fading over time. The pigment composition of the present invention can be used in a wide range of applications such as plastic molded bodies, 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).

The content of the isoindoline compound (1) in 100% by mass of the pigment composition is preferably 50 to 99% by mass, more preferably 70 to 95% by mass.

In formula (1), R ₁ to R ₄ represent hydrogen atoms.
R ₅ and R ₆ each independently represent an alkyl group.
A and A'represent the 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 _R7 represents an alkyl or aryl group.
In formulas (4) and _{( 5} ), R8 to R14 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl group, respectively. ..

In the above formula (2), R ₅ and R ₆ each independently represent an alkyl group. The number of carbon atoms of the alkyl group (—R) 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.

It is more preferable that R ₅ and R ₆ have the same alkyl group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 or 2 carbon atoms (methyl group, ethyl group) is further preferable.

In the above formula (3), X represents -O- or -NH-, and is preferably -NH-.
In _R7 , the alkyl group and the aryl group are synonymous with the above description. From the viewpoint of heat resistance, weather resistance, and dispersion stability, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms.

In the formulas (4) and (5), the halogen atom _in R8 to _R14 is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine.

In the formulas (4) and (5), the number of carbon atoms of the alkyl group ₍ —R) _in R8 to R14 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 (provided that one is an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (-COO-), an ether bond (-O-), and a sulfide bond (-S-). That is, in the present specification, 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 above formulas (4) and ₍ 5), the alkoxy group _in R8 to R14 is a group (-OR) in which an oxygen atom is bonded to the above-mentioned alkyl group (-R).

In the above formulas (4) and (5), the aryl group ₍ -Ar) _in R8 to R14 is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The number of carbon atoms is preferably 6 to 30, and 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 azrenyl group, a heptalenyl group, or a biphenylenyl group. , Indacenyl group, fluoranthenyl group, acephenanthrylenyl group, aceanthrylenel group, phenylenyl group, fluorenyl group, anthryl group, bianthrasenyl group, taranthrasenyl group, quarter anthrasenyl group, anthracinolyl group, phenylanthril group , Triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pryadenyl group, pisenyl group, perylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronenyl group, trinaphthylenyl Examples thereof include a group, a heptaphenyl group, a heptasenyl group, a pyrandrenyl group, an ovalenyl group and the like. Of these, a phenyl group is preferable.

In the above formulas (4) and (5), the aryloxy group _in R8 to R14 is a group ( _-OAr ) in which an oxygen atom is bonded to the above-mentioned aryl group (-Ar). As used herein, the aryloxy group is preferably a phenoxy group.

In the above formulas (4) and (5), the thioalkyl group _in R8 to R14 is a group ₍ -SR) in which a sulfur atom is bonded to the above-mentioned alkyl group. In one embodiment, the thioalkyl group preferably includes a group in which a sulfur atom is bonded to an alkyl group having a linear structure. The thioaryl group is a group (-SAr) in which a sulfur atom is bonded to the above-mentioned aryl group. Among these, the thioaryl group is preferably a thiophenyl group.

In the present specification, in the above formulas (4) and (5), R ₈ to R ₁₄ are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and fluoroalkyl groups having 1 to 6 carbon atoms, respectively. , Alkoxy group (alkyl group has 1 to 6 carbon atoms), phenyl group, phenoxy group, thioalkyl group (alkyl group has 1 to 6 carbon atoms), and thiophenyl group are preferably selected.

In the above formulas (4) and (5), the aryloxy group _in R8 to R14 is a group ( _-OAr ) in which an oxygen atom is bonded to the above-mentioned aryl group (-Ar). As used herein, the aryloxy group is preferably a phenoxy group.

In the above formulas (4) and (5), the thioalkyl group _in R8 to R14 is a group ₍ -SR) in which a sulfur atom is bonded to the above-mentioned alkyl group. In one embodiment, the thioalkyl group preferably includes a group in which a sulfur atom is bonded to an alkyl group having a linear structure. The thioaryl group is a group (-SAr) in which a sulfur atom is bonded to the above-mentioned aryl group. Among these, the thioaryl group is preferably a thiophenyl group.

In the above formulas (4) and ( ₅ ), R8 to _R14 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 group preferably has 1 to 6 carbon atoms, is preferably selected from the group consisting of a phenyl group, a phenoxy group, a thioalkyl group (the alkyl group has 1 to 6 carbon atoms), and a thiophenyl group.

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

[Method for producing isoindoline compound (1) and isoindoline compound (2)]
The isoindoline compound (1) and the isoindoline compound (2) used in the pigment composition of the present embodiment can be produced 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 1,3-diiminoisoindoline represented by the formula (7) (hereinafter referred to as compound (6)). Compound (7)) can be used as a starting material for synthesis.
Hereinafter, the synthesis method will be described with reference to specific examples of the isoindoline compound (1) and the isoindoline compound (2). In the following description, the numbers described in each formula are described as compound numbers.

(Compounds in which A and A'are formula (3))
In one embodiment, the isoindoline compound (1) and the isoindoline compound (2) can be produced according to the following schemes 1-1 and 1-2.

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

Similarly, in Scheme 1-2, the first step (S1) of reacting compound (6) with a base in a solvent to obtain compound (7); then, in the presence of water, compound (7) and compound (7). A second step (S2) of reacting with (8); then may include a third step (S3) of reacting compound (9) with compound (12) in the presence of acetic acid. The reaction temperature in each step in Scheme 1-2 is preferably about 10 to 100 ° C.

If the relationship between the substituents R5 and R6 of compound _{( 12} ) is asymmetric, the final product is obtained as a mixture containing isomers.
_On the other hand, if the relationship between the substituents R5 and R6 of compound ( ₁₂ ) is all symmetric, the final product is a single compound.
The isoindoline compound (1) and the isoindoline compound (2) constituting the pigment composition may be either a mixture containing an isomer or a single compound, respectively.

The solvent used in the first step (S1) is, for example, alcohol such as methanol, ethanol, isopropanol, butanol, and glycol, glycol ether, ether such as tetrahydrofuran, formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Acyclic or cyclic amides are mentioned. Among these, acyclic or cyclic amides are preferable, and tetrahydrofuran or formamide is 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, more preferably 5 to 10 times, based on 100 parts by mass of the 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 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, an isoindoline compound (1) and an isoindoline compound (2) are used.
) Can be manufactured, for example, according to the following schemes 2-1 and 2-2.

Scheme 2-1 is a second step (S2) of reacting compound (7) with compound (8) in the presence of aqueous ammonia; then compound (9) and compound (9) in the presence of acetic acid. A third step (S3) of reacting with 10) may be included.
Similarly, Scheme 2-2 is a second step (S2) of reacting compound (7) with compound (8) in the presence of aqueous ammonia; then compound (9) in the presence of acetic acid. A third step (S3) of reacting with compound (12) may be included.
In the second step (S2) of Schemes 2-1 and 2-2, the amount of the aqueous ammonia solution used is 1 to 20 times the amount of 100 parts by mass of the compound (7) when the 28% aqueous ammonia solution is used. Is preferable, and an amount of 1 to 5 times is more preferable.
The isoindoline compound (1) and the isoindoline compound (2) are preferably produced according to Schemes 2-1 and 2-2.

(Compounds in which A and A'are formula (4))
In one embodiment, the isoindoline compound (1) and the isoindoline compound (2) can be produced according to the following schemes 3-1 and 3-2.

Scheme 3-1 is a first step (S1) of reacting compound (6) with a base in a solvent to give compound (7); then compound (7) and compound (10) in the presence of acetic acid. ); Then, a third step (S3) of reacting the compound (14) with the compound (10) in the presence of acetic acid may be included. The reaction in each step in Scheme 3-1 is preferably carried out at 10 to 100 ° C.

Similarly, in Scheme 3-2, the first step (S1) of reacting compound (6) with a base in a solvent to obtain compound (7); then in the presence of acetic acid, compound (7) and compound (7). A second step (S2) of reacting with (12); then may include a third step (S3) of reacting compound (16) with compound (17) in the presence of acetic acid. The reaction in each step in Scheme 3-2 is preferably carried out at 10 to 100 ° C.

If the relationship between the substituents R5 and R6 of compound _{( 12} ) is asymmetric, the product is obtained as a mixture containing E and Z isomers. Further, when the relationship between the substituents R ₈ and R ₉ of the compound (17) becomes asymmetric, the product is obtained as a mixture containing the E-form and the Z-form as isomers.
On the other hand, if the relationships of the substituents R ₅ and R ₆ of compound (12) and the substituents R ₈ and R ₉ of compound (17) are all symmetric, the final product is a single compound.
The isoindoline compound (1) and the isoindoline compound (2) constituting the pigment composition may be either a mixture containing an isomer or a single compound.

Solvents used in the first step (S1) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, glycol; ethers such as glycol ether and tetrahydrofuran; and formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Examples include acyclic or cyclic amides. Among these, acyclic or cyclic amides are preferable, and tetrahydrofuran or formamide is 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, more preferably 5 to 10 times, based on 100 parts by mass of the 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, primary having an alkyl or 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.

As another synthetic method, the isoindoline compound (1) and the isoindoline compound (2) can be produced according to the following schemes 4-1 and 4-2.

Scheme 4-1 is a second step (S2) of reacting compound (7) with compound (10) in the presence of acetic acid; then compound (14) and compound (10) in the presence of acetic acid. The third step (S3) for reacting with may be included.

Similarly, scheme 4-2 is a second step (S2) of reacting compound (7) with compound (12) in the presence of acetic acid; then compound (16) and compound (in the presence of acetic acid). A third step (S3) of reacting with 17) may be included.

(Compound in which A is the formula (5))
In one embodiment, the isoindoline compound (1) and the isoindoline compound (2) can be produced according to the following schemes 5-1 and 5-2.

Scheme 5-1 is a first step (S1) of reacting compound (6) with a base in a solvent to give compound (7); then in the presence of water, compound (7) and compound (19). ); Second step (S2); then may include a third step (S3) of reacting compound (20) with compound (10) in the presence of acetic acid. The reaction temperature in each step in Scheme 5-1 is preferably 10 to 100 ° C.

Similarly, in Scheme 5-2, the first step (S1) of reacting compound (6) with a base in a solvent to obtain compound (7); then in the presence of water, compound (7) and compound (7). A second step (S2) of reacting with (19); then may include a third step (S3) of reacting compound (20) with compound (12) in the presence of acetic acid. The reaction temperature in each step in Scheme 5-2 is preferably 10 to 100 ° C.

If the relationship between the substituents R5 and R6 of compound _{( 12} ) is asymmetric, the final product is obtained as a mixture containing isomers.
_On the other hand, if the relationship between the substituents R5 and R6 of compound ( ₁₂ ) is symmetric, the final product is a single compound.
The isoindoline compound (1) and the isoindoline compound (2) constituting the pigment composition may be either a mixture containing an isomer or a single compound.

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, and N-methylpyrrolidone. Acyclic or cyclic amides are mentioned. Among these, acyclic or cyclic amide is preferable, and tetrahydrofuran or formamide is preferable.

It can be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 15 times, more preferably 5 to 10 times, based on 100 parts by mass of the 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 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.

As another synthetic method, the isoindoline compound (1) and the isoindoline compound (2) can be produced according to the following schemes 6-1 and 6-2.

Scheme 6-1 is a second step (S2) of reacting compound (7) with compound (19) in the presence of aqueous ammonia; then compound (20) and compound (20) in the presence of acetic acid. A third step (S3) of reacting with 10) may be included.
In the second step (S2) of Scheme 6-1 the amount of the aqueous ammonia solution used is preferably 1 to 20 times the amount of 100 parts by mass of the compound (7) when the 28% aqueous ammonia solution is used. More preferably, the amount is 1 to 5 times.

Similarly, Scheme 6-2 is a second step (S2) of reacting compound (7) with compound (19) in the presence of aqueous ammonia; then compound (20) in the presence of acetic acid. A third step (S3) of reacting with compound (12) may be included.
In the second step (S2) of Scheme 6-2, the amount of the aqueous ammonia solution used is preferably 1 to 20 times the amount of 100 parts by mass of the compound (7) when the 28% aqueous ammonia solution is used. More preferably, the amount is 1 to 5 times.

In the above-mentioned isoindoline compound (2) used in the pigment composition, R ₅ and R ₆ are alkyl groups in the above-mentioned formula (2). By containing an isoindoline compound having an alkyl group introduced at a predetermined position, in comparison with a conventional isoindoline pigment having no alkyl group at a predetermined position, the dispersibility, weather resistance, heat resistance and basic atmosphere are maintained. Can significantly improve resistance in. Therefore, the pigment composition of the present specification can also be used for applications such as water-based paints, printing inks, and inkjet inks, to which it has been difficult to apply isoindoline pigments in the past. Further, it can be suitably used as a 5-color ink set including white ink in addition to a 4-color ink set combined with cyan ink, magenta ink, and black ink.

Generally, when a pigment composition containing a plurality of pigments shows an X-ray diffraction pattern different from the X-ray diffraction pattern of a physical mixture, the pigment composition is called a solid solution. There are two types of solid solutions that are clearly distinguished: "guest-host type solid solution" and "solid compound type solid solution". A "guest-host type solid solution" is a solid solution in which the X-ray diffraction pattern of the solid solution is substantially the same as the X-ray diffraction pattern of one of the components called the host among the solid solution components. The host component is said to accept other components, or guests, into its crystal lattice. A "solid compound type solid solution" is a solid solution in which two components cooperate with each other to form one X-ray diffraction pattern different from the X-ray diffraction pattern of any component or physical mixture of the two components. ..

In the pigment composition of the present invention, when the isoindoline compound (1) and the isoindoline compound (2) are not a mere mixture but a solid solution, the transparency in the ink composition, the dispersed particle size in the coloring composition and the like are further improved. ..

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.

The method for producing a pigment composition containing an isoindoline compound (1) and an isoindoline compound (2) is exemplified below.
(I) A method of synthesizing two or more kinds at once (co-synthesis method), (II) a method of mixing an isoindoline compound (1) and an isoindoline compound (2) at the time of preparing a dispersion, (III) an isoindoline compound. The acid pacing method, acid slurry method, dry milling method, salt milling method, solvent salt milling method, solvent method (in a high boiling point solvent such as alcohol or aromatic solvent) together with (1) and the isoindoline compound (2). A method of pigmentizing using heat treatment) or the like, and (IV) a method of combining the above methods.
Of these, (I) a co-synthesis method, (III) a method of pigmenting an isoindoline compound (1) and an isoindoline compound (2) together using an acid pacing method or a solvent salt milling method, (IV). This is a method in which (I) and (III) are combined.

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.

As the acid pacing, for example, a method of dissolving a pigment in 98% sulfuric acid 5 to 30 times by mass thereof and mixing the obtained sulfuric acid solution with water 5 to 30 times by mass thereof can be mentioned. 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 at the time of mixing may be any water that can be industrially used. However, pre-cooled water is preferable from the viewpoint of reducing the temperature rise at the time of 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, the pigment particles can be precipitated by a method of injecting a sulfuric acid solution into ice water prepared in advance, a method of continuously injecting a sulfuric acid solution into running water using a device such as an aspirator, or the like.

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.

For miniaturization 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 refined. Further, when the amount of the inorganic salt is 20 times by weight 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.

The miniaturization of pigments often generates heat with kneading. 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.

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 crushing devices having a built-in 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, stirring treatment in a solvent, or the like may be performed.

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

[Distributed 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 small molecule dispersant such as a surfactant can be used.

The resin type dispersants are, for example, JONCRYL67 and JONCRYL manufactured by BASF Japan Ltd.
678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J
、ＪＯＮＣＲＹＬ６２Ｊ、ＪＯＮＣＲＹＬ６３Ｊ、ＪＯＮＣＲＹＬＨＰＤ－９６Ｊ、ＪＯＮＣＲＹＬ５０１Ｊ、ＪＯＮＣＲＹＬＰＤＸ－６１０２Ｂ、ビックケミー社製、ＤＩＳＰＥＲＢＹＫ１８０、ＤＩＳＰＥＲＢＹＫ１８７、ＤＩＳＰＥＲＢＹＫ１９０、ＤＩＳＰＥＲＢＹＫ１９１、ＤＩＳＰＥＲＢＹＫ１９４、ＤＩＳＰＥＲＢＹＫ２０１０、ＤＩＳＰＥＲＢＹＫ２０１５、ＤＩＳＰＥＲＢＹＫ２０９０、ＤＩＳＰＥＲＢＹＫ２０９１、ＤＩＳＰＥＲＢＹＫ２０９５、ＤＩＳＰＥＲＢＹＫ２１５５、日本ルーブリゾール社製ＳＯＬＳＰＥＲＳＥ２４０００、ＳＯＬＳＰＥＲＳＥ３２０００、 Examples thereof include SOLPERSE41000, SMA1000H, SMA1440H, SMA2000H, SMA3000H, SMA17352H manufactured by Sartmer.

The binder resin may be, for example, a polyolefin resin, a polyester resin, a styrene copolymer, an acrylic resin, and a modified resin thereof. Specifically, polyethylene such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE), and low-density polyethylene (LDPE), polymer resins such as polypropylene; polyester resins such as polyethylene terephthalate; styrene-p. -Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylate ester copolymer, styrene-α-chlormethacrylate copolymer Polymers, styrene-acrylonitrile copolymers, styrene-vinylmethyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinylmethylketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers , Stylopolymers such as styrene-acrylonitrile-inden copolymers; acrylic resins such as acrylic resins and methacrylic resins; polyvinyl chlorides, phenolic resins, naturally modified phenolic resins, natural resin modified maleic acid resins, polyvinylacetates, silicones. Resin, polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, nitrocellulose resin, polyamide resin, epoxy resin, xylene resin, polyvinyl butyral resin, polyvinyl acetal resin, cellulose ester resin, alkyd resin, rosin resin, Examples thereof include ketone resins, cyclized rubbers, chlorinated polyolefin resins, terpene resins, kumaron inden resins, alkyd resins, amino resins, petroleum resins, 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)
As used herein, 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 resin used as the dispersion medium is preferably a resin-type dispersant. The type of resin is, for example, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester. Polymer, styrene-α-methylstyrene- (meth) acrylic acid copolymer, styrene-α-methylstyrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, poly (meth) acrylic acid , Vinylnaphthalene- (meth) acrylic acid copolymer, styrene-maleic acid copolymer, maleic acid-anhydrous maleic acid copolymer, α-olefin- (anhydrous) maleic acid copolymer, α-olefin- (anhydrous) malein Examples thereof include acid-polyalkylene glycol allyl ether copolymer vinyl naphthalene-maleic acid copolymer, polyester-modified (meth) acrylic acid polymer, and salts thereof.

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

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 Examples thereof include polypropylene glycol and the like.

The water-based 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 sulfate esters, alkylaryl sulfonates, alkylnaphthalene sulfonates, dialkyl sulfonates, dialkyl sulfosuccinates, alkyldiaryl ether disulfonates, alkyl phosphates. , Polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formarin condensate, polyoxyethylene alkyl phosphate ester salt 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, polyoxyethylene glycerol fatty acid esters, and the like.

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

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

Preservatives include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, zinc pyridinethion-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 water-based 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 VXW6211, ADDITOR VXW4973, ADDITOR VXW6235, ADDITOR XW375, ADDITOR XW376, ADDITOR VXW6381, ADDITOR Examples thereof include VXW6399, ADDITOR XW6544 and the like (all manufactured by Allnex).

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 produced 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 annular 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, a counter-collision type high-pressure disperser, and an oblique collision type high-pressure disperser.

More specifically, when a resin-type dispersant which is a water-soluble resin is used as the resin, the method described in Examples described later, that is, a pigment composition, a resin-type dispersant, water, or the like is mixed, and then the resin is mixed. The aqueous coloring composition of the present invention can be obtained by a method of performing a dispersion treatment using the above disperser.

When a resin-type dispersant, which is a water-insoluble resin, is used as the resin, for example, the resin-type dispersant is dissolved in an organic solvent capable of dissolving the water-insoluble resin, and then mixed with the pigment composition. Then, the dispersion processing is performed using the above-mentioned disperser. Then, the water-based coloring composition of the present invention can be obtained by a method of phase inversion emulsification using water and then distilling off the organic solvent.

On the other hand, it is preferable to crosslink the resin type dispersant on the surface of the pigment composition from the viewpoint that the dispersibility and dispersion stability of the pigment composition in the water-based coloring composition can be particularly improved. In the water-based inkjet ink using such a pigment composition in which the resin-type dispersant present on the surface is cross-linked (hereinafter, also referred to as “pigment composition-containing cross-linked resin particles”), the redispersibility (water-based inkjet ink) is used. By adding water after drying, agglomerating and thickening, the pigment composition in the water-based inkjet ink can be dispersed again). Therefore, for example, nozzle clogging or "blurring" during continuous printing is possible. Can be suppressed. Further, by coating the pigment composition with the crosslinked resin type dispersant, improvement of weather resistance and pH resistance can be realized.

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

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

[[Method (ii)]]
The above-mentioned steps except that a resin-type dispersant having a self-crosslinking functional group and a carboxy group and being hydrophilized by neutralizing the carboxy group with a basic compound is used as the resin-type dispersant. In the same manner as in (i-1) to (i-3), the pigment composition to which the resin-type dispersant is adhered is redispersed in water. Then, the resin type dispersant is self-crosslinked to obtain a water-based coloring composition containing the crosslinked resin particles containing the pigment composition.

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

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

When the water-based coloring composition obtained by the above method is heat-treated or post-treated, the dispersion stability of the isoindoline compound (1) and the isoindoline compound (2) is improved. The heat treatment is a treatment in which the water-based coloring composition is heated to 30 to 80 ° C. and held for several hours to one week. In the post-treatment, the aqueous coloring composition is dispersed using 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 process include a kneader, a kneaded meat mixer such as a 3-roll mill; a non-volatile disperser such as a 2-roll mill, and a medialess disperser such as an MK mixer.

Aspects of the coloring composition herein include, for example, a pigment composition and a resin, embodiment 1 (eg, a molding composition, toner). Aspect 2 (for example, a solvent-based coloring composition) containing a pigment composition and an organic solvent. Examples thereof include the pigment composition described in detail in the upper section, the third aspect (for example, a water-based coloring composition) containing a resin and water, 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 "aqueous", 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.

<Molding composition>
The molding composition of the present invention contains a coloring composition (pigment composition, resin). The molding composition preferably contains a thermoplastic resin in the resin. 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 or 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 10,000,000 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 is appropriately transferred to the surface of the molded body, 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) determined according to JIS K-7210 of the wax is preferably larger than 100 g / 10 minutes.

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

The molding composition 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 masterbatch containing a high concentration of the isoindoline compound (1) and the isoindoline compound (2). In the present specification, the masterbatch is preferable in that the isoindoline compound (1) and the isoindoline compound (2) can be easily dispersed uniformly in the molded product.
In the masterbatch, for example, it is preferable to melt-knead the thermoplastic resin and the pigment composition, and then form the masterbatch into an arbitrary shape so that it can be easily used 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 the 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 in an amount of 5 to 700 parts. Parts by mass are more preferred. 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) are uniformly dispersed 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, plastic molded bodies, sheets, films 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-type toner and wet-type toner, and dry-type 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-chlorstyrene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, a styrene- (meth) acrylic acid ester copolymer, or a styrene-α-chlor. Methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene- Isoprene copolymer, styrene-acrylonitrile-inden copolymer, polyvinyl chloride, phenol resin, naturally modified phenol resin, natural resin modified maleic acid resin, (meth) acrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane , Polypolymer resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, kumaron inden resin, petroleum resin 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 has particularly excellent 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 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. Of these, quaternary ammonium salt compounds are preferred. Examples of the quaternary ammonium salt compound include a salt-forming compound of a quaternary ammonium salt and an organic sulfonic acid or molybdenum acid. The organic sulfonic acid is preferably naphthalene sulfonic acid.

When the toner is a negative chargeable 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 a 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, phenolic condensates, phosphonium-based compounds and the like. The aromatic hydroxycarboxylic acid is preferably salicylic acid, 3,5-di-tert-butylsalicylic 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 mold release agent. Examples of the mold release agent include hydrocarbon waxes such as polypropylene wax, polyethylene wax and Fisher Tropsch wax, synthetic ester waxes, carnauba wax, natural ester waxes such as rice wax and the like.

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

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, silica, silicon-aluminum co-oxide, and silicon-titanium co-oxide fine powder that have been hydrophobized 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 a product whose surface is coated with a resin or the like. The resin that coats the carrier surface is, for example, a styrene- (meth) acrylic acid ester copolymer, a (meth) acrylic acid ester copolymer, a fluorine-containing resin, a silicone-containing resin, a polyamide resin, an ionomer resin, a polyphenylene sulfide resin, or the like. Can be mentioned. Among these, a silicone-containing resin with less formation of spent toner 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 paint of the present specification contains a coloring composition (pigment composition, resin, solvent).
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 the 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 and methoxybutanol. Also mentioned are, for example, water-dilutable glycol ethers such as butyl glycol or butyl diglycol. The paint is called a water-based paint when the solvent contains water as described above.

The paint can further contain known additives.

Examples of the use of the paint include paints for metals and paints for plastics.

<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, a silk screen 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 mentioned 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 the mica include ordinary mica, coated mica, and the like. 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 needed. The method for producing the printing ink, the method for applying the printing ink, and the method for drying the printing ink 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 contains a solvent. Inkjet inks can be roughly classified into (solvent-based) inkjet inks, water-based inkjet inks, and solvent-free inkjet inks depending on the presence or absence of a solvent and its type. In the present specification, the water-based 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 adjuster 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 fixing property is also improved.

Examples of the solvent include water-insoluble solvents, water, and water-soluble solvents. Examples of the water-soluble solvent include glycol ethers and diols as the water-soluble solvent. These solvents penetrate very quickly into the base material and have low absorption such as coated paper, art paper, vinyl chloride sheet, film and cloth. It penetrates quickly even in liquid and non-liquid absorbent 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. Examples of the water-soluble solvent include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether. Examples thereof include 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetraflufuryl 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 adjusting agent 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 to promote the penetration of the ink into the substrate and to accelerate the apparent drying property when the substrate is a permeable material such as paper. 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 in 100% by mass of the water-based inkjet ink. When an appropriate amount is used, problems such as print bleeding and ink omission are unlikely to occur.

Preservatives include, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, zinc pyridinethion-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 the metal ions contained in the aqueous inkjet ink and prevent the 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. 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.

It is preferable that the inkjet ink is mixed and then filtered or centrifuged to remove coarse particles. This improves the ejection property from the inkjet printer. Known methods can be used for filtration and centrifugation.

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.

[Dye derivative]
A dye derivative can be added to the pigment, the coloring composition, and the coloring curable composition used in the present invention, if necessary.

As the dye derivative, a known dye derivative having an acidic group, a basic group, a neutral group or the like as an organic dye residue can be used. 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 compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group or a phthalimide. Examples thereof include compounds having a neutral substituent such as an alkyl 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, and Patent No. 5735266. 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- JP-A-54128, JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 as a dioxazine-based dye derivative, and JP-A-2007-314785 as a thiazineindigo-based dye derivative. Examples of JP-A and 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 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A. 2008-31281, 2012-226110, naphthol-based dye derivatives, 2012-208329, 2014-5439, and azo-based dye derivatives, 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 JP-A-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 may be used alone or in combination of two or more.

<Ink set>
The ink set of the present invention is at least an ink set containing yellow ink, cyan ink, and magenta ink, and it is preferable that the yellow ink contains an ink containing the coloring composition.

The ink set of the present invention may further contain other inks such as black ink (black ink), white ink (white ink), and spot color ink.

The ink set of the present invention can be used for printing ink sets such as offset printing inks, flexo printing inks, gravure printing inks, screen printing inks, and ink sets for inkjet inks. Among these, the gravure printing ink set and the inkjet ink set used for the packaging material are preferable, and the gravure printing ink set is more preferable.

<Yellow ink>
The yellow ink in the present invention contains the above pigment composition and a binder resin.
By containing the two types of isoindoline compounds as described above, the yellow ink improves the dispersibility and storage stability, which have been the weak points of the isoindoline compounds in the past.

<Binder resin>
The binder resin is, for example, polyurethane resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, nitrocellulose resin, polyamide resin, polyvinyl acetal resin, cellulose ester resin, polystyrene resin, acrylic resin, polyester resin, alkyd resin, rosin. Examples thereof include based resins, rosin-modified maleic acid resins, ketone resins, cyclized rubbers, butyral, petroleum resins, and chlorinated polyolefin resins.

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

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

<Cyan ink>
The cyan ink in the present invention is an ink that can obtain a cyan color, and includes a pigment and a binder resin. As the binder resin, the resin already described can be used.

<Magenta ink>
The magenta ink in the present invention is an ink that can obtain a magenta color, and includes a pigment and a binder resin. As the binder resin, the resin already described can be used.

<Pigment>
Examples of the pigment include organic pigments and inorganic pigments. In the present specification, for example, the following pigments can be used.

[Organic pigment]
The pigment is preferably an organic pigment. Organic pigments include, for example, soluble azo-based, insoluble azo-based, azo-based, phthalocyanine-based, halogenated phthalocyanine-based, anthraquinone-based, anthraslon-based, dianthraquinonyl-based, anthrapyrimidine-based, perylene-based, perinone-based, and quinacridone-based. , Thioindigo, dioxazine, isoindolinone, quinophthalone, azomethinazo, flavanthron, diketopyrrolopyrrole, isoindoline, indanslon and the like.

Examples of pigments include C.I. I. Shown by pigment number.

The indigo pigment is, for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60 and the like. Further, phthalocyanine pigments such as aluminum phthalocyanine (compound (30)) and titanyl phthalocyanine (compound (31)) can also be mentioned.
The cyan ink preferably contains the above-mentioned indigo pigment. Among these, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4 and C.I. I. Pigment Blue 16 is more preferred.

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

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

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

The green pigment is, for example, C.I. I. Pigment Green 7 and the like.

The orange pigment is, for example, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64 and the like.

Examples of the spot color ink include inks such as purple, grass, and vermilion other than cyan, magenta, and yellow, and it is preferable to include the above-mentioned purple pigment, green pigment, orange pigment, and the like.

The ink set of the present invention is, for example, Cyan ink. I. Pigment Blue 16, Magenta Ink with C.I. I. Pigment Violet 19 and C.I. I. It is preferable to contain one or more of Pigment Red 122. By including the above pigment, the environmental compatibility and safety and hygiene of the ink can be improved.

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

For the black ink, it is preferable to use carbon black from the viewpoint of excellent coloring power, hiding power, chemical resistance, and weather resistance. For example, C.I. I. Pigment Black 7 and the like. Further, it is preferable to use titanium oxide as the white ink (white ink) from the viewpoint of excellent coloring power, hiding power, chemical resistance and weather resistance. The titanium oxide is preferably surface-treated with silica and / or alumina from the viewpoint of printing performance.

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

The average primary particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably in the range of 50 to 150 nm.
The content of the pigment in the ink is preferably in the range of 1 to 60% by mass based on the mass of the ink and preferably based on the non-volatile content mass of the ink in order to secure the concentration and coloring power of the ink. Is in the range of 10 to 90% by mass.

<Gravure printing ink set>
The gravure printing ink set of the present invention preferably includes the above ink set.

[Polyurethane resin]
The binder resin used in the gravure printing ink set of the present invention is preferably a polyurethane resin. The polyurethane resin includes a polyurethane urea resin.
The polyurethane resin is synthesized, for example, by (1) reacting a polyol with a diisocyanate compound at a ratio of an excess of isocyanate groups to synthesize a urethane prepolymer having an isocyanate group at the terminal. Next, a two-step method for synthesizing a urethane prepolymer having an isocyanate group in a solvent by reacting it with the chain extender having an amino group and / or a terminal blocking agent, (2) polypropylene glycol, polyol, diisocyanate compound, and amino group. Examples thereof include a one-step method in which a chain extender and / or a terminal sealant having the above is reacted at once in an appropriate solvent.
The solvent used for the synthesis is, for example, an ester solvent such as ethyl acetate, propyl acetate or butyl acetate; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an alcohol solvent such as methanol, ethanol, isopropyl alcohol or n-butanol. Solvents; hydrocarbon-based solvents such as methylcyclohexane and ethylcyclohexane; or mixed solvents thereof; can be mentioned.
Among these methods, the two-step method is preferable from the viewpoint of obtaining a more uniform polyurethane resin. When the polyurethane resin is produced by the two-step method, the equivalent ratio of the isocyanate group of the urethane prepolymer to the amino group of the chain extender and the terminal blocker (moll of isocyanate group / mol of amino group) is 1/1. It is preferably 3 to 1 / 0.9. When the equivalent ratio of the isocyanate group to the amino group is 1 / 1.3 or more, the chain extender and / or the terminal sequestering agent remaining unreacted is reduced, and the polyurethane resin is yellowed and has an odor after printing. It can be suppressed. When the equivalent ratio of the isocyanate group to the amino group is 1 / 0.9 or less, the molecular weight of the obtained polyurethane resin becomes appropriate, and a resin having suitable film strength after printing can be obtained.

The weight average molecular weight of the polyurethane resin is preferably in the range of 15,000 to 100,000. When the weight average molecular weight of the polyurethane resin is 15,000 or more, the blocking resistance of the ink, the strength of the printing film, and the oil resistance are excellent, and when it is 100,000 or less, the viscosity of the obtained ink is in an appropriate range. , Excellent gloss of printing film.

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

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

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

The viscosity of each color ink is preferably 10 mPa · s or more from the viewpoint of preventing the pigment from settling and appropriately dispersing, and preferably 1,000 mPa · s or less from the viewpoint of workability efficiency during ink production or printing. The viscosity is a value measured at 25 ° C. with a B-type viscometer manufactured by Tokimec.

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

[Silica particles]
The gravure printing ink set of the present invention can further contain silica particles. By including silica particles, wetting and spreading of the ink during overprinting are promoted, trapping property is improved, and highlight transfer property is maintained.
Examples of the silica particles include natural products, synthetic products, and crystalline, amorphous, hydrophobic, and hydrophilic particles. As a method for synthesizing silica particles, there are a dry method and a wet method. The dry method is known as a combustion method and an arc method, and the wet method is known as a sedimentation method and a gel method, and any method may be used for synthesizing the silica particles. Further, the silica particles may be hydrophilic silica having a hydrophilic functional group on the surface, or hydrophobic silica obtained by modifying the hydrophilic functional group with an alkylsilane or the like to make it hydrophobic. It is preferably hydrophilic silica.
Examples of such silica particles include a nip gel series and a nip sill series manufactured by Tosoh Silica Co., Ltd. and a Mizuka sill series manufactured by Mizusawa Industrial Chemicals Co., Ltd.

Since the silica particles form irregularities on the surface of the ink layer, the average particle diameter is preferably 1 to 10 μm. It is more preferably 1 to 8 μm, still more preferably 1 to 6 μm. The average particle size of the silica particles means the particle size at an integrated value of 50% (D50) in the particle size distribution, and can be obtained by the Coulter counter method.
The specific surface area of the silica particles is preferably 50 to 600 m ² / g by the BET method. More preferably, it is 100 to 450 m ² / g. As the silica particles used in the gravure printing ink of the present invention, two or more kinds of silica particles having different average particle diameters or BET method specific surface areas can be used in combination.

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

[Other additives]
The gravure printing ink set of the present invention may be added with other additives such as extender pigments, pigment dispersants, leveling agents, defoamers, waxes, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, etc., as necessary. Can include agents.

<Clear ink>
The gravure printing ink set of the present invention can further contain clear ink. The desorbed layer formed from the clear ink has a function of being neutralized with an alkaline aqueous solution and being dissolved or swollen to be peeled off from the substrate.
The basic compounds used in the alkaline aqueous solution are, for example, sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂ ), ammonia, barium hydroxide (Ba (OH) ₂ ). , Sodium carbonate (Na ₂ CO ₃ ). More preferably, it is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
In the present specification, the step of neutralizing with an alkaline aqueous solution to dissolve or swell may be referred to as "alkaline treatment". Further, a layer having desorption property by alkaline treatment may be referred to as a "desorption layer". That is, the print layer formed by the clear ink corresponds to a layer having desorption property (detachable layer).

[Carboxy group-containing resin]
The clear ink preferably contains a carboxy group-containing resin. For example, it functions as a primer composition to be printed on a substrate before the color ink.
Examples of the carboxy group-containing resin include acrylic resin, urethane resin, polyester resin, amino resin, phenol resin, epoxy resin, and cellulose. Among these, urethane resin is preferable because it has good laminating suitability.

The hydroxyl value of the carboxy group-containing urethane resin is preferably 1 to 35 mgKOH / g, more preferably 10 to 30 mgKOH / g. When it is 1 mgKOH / g or more, it is preferable because the desorption property by an alkaline aqueous solution is good, and when it is 35 mgKOH / g or less, it is preferable because the substrate adhesion is good.
The acid value of the carboxy group-containing urethane resin is preferably 15 mgKOH / g or more, more preferably 15 to 70 mgKOH / g, and even more preferably 20 to 50 mgKOH / g. When it is 15 mgKOH / g or more, it is preferable because the desorption property by an alkaline aqueous solution is good, and when it is 70 mgKOH / g or less, the adhesion to the substrate is improved and the retort resistance when used as a packaging material is good. .. Both the hydroxyl value and the acid value are values measured according to JIS K0070.

The weight average molecular weight of the carboxy group-containing urethane resin is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, still more preferably 15,000 to 50,000.

The molecular weight distribution (Mw / Mn) of the carboxy group-containing urethane resin is preferably 6 or less. When the molecular weight distribution is 6 or less, the influence caused by the excessive high molecular weight component, the unreacted component, the side reaction component and other low molecular weight components can be avoided, and the desorption property and the drying property of the primer composition can be avoided. Good retort resistance.
Further, the smaller the molecular weight distribution, that is, the sharper the molecular weight distribution, the more uniformly the dissolution / exfoliation action by the alkaline aqueous solution occurs and the desorption property is improved, which is preferable. The molecular weight distribution is more preferably 5 or less, still more preferably 4 or less. The molecular weight distribution is preferably 1.5 or more, more preferably 1.2 or more.

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

The carboxy group-containing urethane resin is not particularly limited, and is preferably a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate, for example. By using a hydroxy acid, an acid value can be imparted to the urethane resin, and the desorption property can be improved. More preferably, it is a resin obtained by reacting a resin obtained by reacting a polyol, a hydroxy acid and a polyisocyanate with a polyamine.

The clear ink may further contain polyisocyanate as a curing component. The polyisocyanate is not particularly limited and can be selected from conventionally known polyisocyanates, and examples thereof include aliphatic polyisocyanates and aromatic aliphatic polyisocyanates.
In addition, the clear ink may contain other components other than the carboxy group-containing resin and polyisocyanate, and like the above-mentioned cyan, yellow, and magenta color inks, it contains additives such as an organic solvent and an anti-blocking agent. can do.

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

<Printed matter>
The printed matter of the present invention includes a substrate and a printed layer formed from a gravure printing ink set. The printing layer is formed by printing cyan ink, yellow ink, and magenta ink on a substrate.
The gravure printing method is not particularly limited and can be appropriately selected from known methods. The gravure printing method is roughly divided into front printing and back printing. For example, when the base material is white paper or white film in front printing, yellow ink, magenta ink, cyan ink, etc. are applied on the base material. A printed matter can be obtained by printing in the order of black ink.
Further, for example, when the base material is a transparent film in back printing, it is preferable to print on the base material in the order of black ink, cyan ink, magenta ink, yellow ink, and white ink to produce a printed matter.
When the ink set of the present invention contains a clear ink, it is preferable that the clear ink is printed on a substrate before the color ink.
The thickness of the print layer can be appropriately selected depending on the intended use, the type and number of inks used, and the number of times of overprinting, but is usually in the range of 0.5 to 10 μm.

[Base material]
The base material is, for example, a polyolefin base material such as polyethylene or polypropylene; a polycarbonate base material; a polyester base material such as polyethylene terephthalate or polylactic acid; a polystyrene base material; a polystyrene resin such as AS or ABS; a polyamide base material such as nylon; Polyvinyl chloride base material; polyvinylidene chloride base material; cellophane base material; paper base material; aluminum foil base material; composite base material composed of these composite materials; The base material may be in the form of a film or a sheet. Of these, polyester base materials and polyamide base materials having a high glass transition point are preferably used.

The surface of the base material may be vapor-filmed with a metal oxide or the like, or may be coated with polyvinyl alcohol or the like. Examples of such a surface-treated substrate include GL-AE manufactured by Toppan Printing Co., Ltd. and IB-PET-PXB manufactured by Dai Nippon Printing Co., Ltd., in which aluminum oxide is vapor-deposited on the surface. The base material may be treated with additives such as an antistatic agent and an ultraviolet protection agent, if necessary, and may be treated with a corona treatment or a low temperature plasma treatment.

[Desorption layer]
The printed matter of the present invention may contain a desorption layer. Here, the "desorption layer" refers to a person having the property of being neutralized with an alkaline aqueous solution and having the property of peeling from the substrate by dissolving or swelling. The layer having desorption property is preferably a layer formed from the above-mentioned clear ink, but other layers may be desorption layers.

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

<Packaging material>
The packaging material of the present invention contains printed matter at least in part thereof. Examples of the packaging material include a structure in which a printed matter, an adhesive layer, and a sealant base material are sequentially laminated. Packaging materials are four-sided seal packaging, three-way seal packaging, pillow packaging, stick bag, gusset bag, square bottom bag, standing pouch, deep squeezed container, vacuum packaging, skin pack, chuck bag, spout pouch, twist packaging. It can be suitably used for packages having various shapes such as wrapping, shrink wrapping, labels, liquid paper packs, and paper trays.

The packaged material of the packaging material is, for example, foodstuffs (for example, rice grains, confectionery, seasonings, edible oils and fats, cooked foods, etc.), beverages (for example, alcoholic beverages, soft drinks, mineral water, etc.), daily life / cultural supplies (for example). For example, pharmaceuticals, cosmetics, stationery, etc.), electronic parts, etc. may be mentioned.

[Adhesive layer]
Examples of the adhesive component that can be used to form the adhesive layer include a thermoplastic resin in addition to a laminate adhesive and a hot melt adhesive. Among the adhesive components, the laminate adhesive and the hot melt adhesive are, for example, a polyether adhesive; a polyurethane adhesive; an epoxy adhesive; a polyvinyl acetate adhesive; a cellulose adhesive; a (meth) acrylic adhesive. Agent; Among these adhesive components, a polyurethane adhesive is preferably used.

The adhesive component can be used alone or in combination of two or more.

The polyurethane-based adhesive is a reactive adhesive containing a polyol and a polyisocyanate, and may be desorbable. Examples of the removable polyurethane adhesive include the laminated adhesive described in JP-A-2020-0841130.
The polyurethane adhesive having such desorption property preferably has an acid value of 5 to 45 mgKOH / g. Further, it is preferable that the polyol constituting the polyurethane-based adhesive contains a polyester polyol, and the polyisocyanate contains one selected from the group consisting of an aliphatic polyisocyanate and an aromatic aliphatic polyisocyanate.
The thickness of the adhesive layer is usually in the range of 1 to 6 μm.

[Sealant base material]
The sealant base material is a base material constituting the innermost layer of the laminated film, and a resin material that can be fused to each other by heat (having heat-sealing property) is used. Examples of the sealant base material include unstretched polypropylene (CPP), vapor-deposited unstretched polypropylene film (VMCPP), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA) and the like. Be done.
The thickness of the sealant base material is not particularly limited, but is preferably in the range of 10 to 200 μm, more preferably in the range of 15 to 150 μm, in consideration of processability to the packaging material, heat sealability, and the like. Further, by providing the sealant base material with irregularities having a height difference of 5 to 20 μm, it is possible to impart slipperiness and tearability of the packaging material to the sealant base material.
Further, the method of laminating the sealant base material is not particularly limited. For example, a method of laminating the adhesive layer and the sealant base film by heat (heat laminating, dry laminating), or a method of melting the sealant base resin, extruding it onto the adhesive layer, cooling and solidifying it, and laminating it (extrusion). Lamination method) and the like.

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)
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% ammonia water 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 over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. This reaction slurry was filtered off using a Büchner funnel to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC (ultra-high-speed high-separation liquid chromatography Waters).
To a 4-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 are added to a glass flask, 36.69 parts of barbituric acid and 4.97 parts of 1,3-dimethylbarbituric acid are added thereto, and the mixture is stirred at 65 ° C. bottom. 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 87.50 parts of isoindoline compound 1-1.

(Example 1-2)
Except for changing 36.69 parts of barbituric acid of Example 1-1 to 40.36 parts and 4.97 parts of 1,3-dimethylbarbituric acid to 0.50 parts, all of them are the same as Example 1-1. The reaction operation was carried out in the same manner to obtain 86.40 parts of isoindoline compound 1-2.

(Example 1-3)
Except for changing 36.69 parts of barbituric acid of Example 1-1 to 28.54 parts and 4.97 parts of 1,3-dimethylbarbituric acid to 14.91 parts, all of them are the same as Example 1-1. The reaction operation was carried out in the same manner to obtain 88.30 parts of isoindoline compound 1-3.

(Example 1-4)
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% ammonia water 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 over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. This reaction slurry was filtered off using a Büchner funnel to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC.
To a 4-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 60 parts of the non-volatile content obtained in the previous preparation, 480 parts of water, and 162 parts of 80% acetic acid were added and stirred as raw materials. On the other hand, 480 parts of water and 162 parts of 80% acetic acid were added to the glass flask, 30.57 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 mixture was stirred at 30 ° C. for 3 hours. To a glass flask prepared separately, 48 parts of water and 16 parts of 80% acetic acid were added, 8.28 parts of 1,3-dimethylbarbituric acid was added thereto, and the mixture was stirred at 65 ° C. The heated solution of this mixture was put into the above reaction 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 86.10 parts of isoindoline compound 1-4.

(Example 1-5)
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% ammonia water 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 over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. This reaction slurry was filtered off using a Büchner funnel to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC.
To a 4-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 60 parts of the non-volatile content obtained in the previous preparation, 480 parts of water, and 162 parts of 80% acetic acid were added and stirred as raw materials. On the other hand, 326 parts of water and 138 parts of 80% acetic acid are added to a glass flask, 27.18 parts of barbituric acid and 2.07 parts of 1,3-dimethylbarbituric acid are added thereto, and the mixture is stirred at 65 ° C. bottom. The heated solution of this mixture was put into the above-mentioned non-volatile stirring solution, and the mixture was stirred at 30 ° C. for 3 hours. To a glass flask prepared separately, 134 parts of water and 57 parts of 80% acetic acid were added, 14.49 parts of 1,3-dimethylbarbituric acid was added thereto, and the mixture was stirred at 65 ° C. The heated solution of this mixture was put into the above reaction 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 88.10 parts of isoindoline compound 1-5.

(Example 1-6)
The reaction operation was carried out in the same manner as in Example 1-4, except that 8.28 parts of 1,3-dimethylbarbituric acid in Example 1-4 was changed to 9.77 parts of 1,3-diethylbarbituric acid. , 86.60 parts of isoindoline compound 1-6 was obtained.

(Example 1-7)
Except that 36.69 parts of barbituric acid of Example 1-1 was changed to 38.73 parts and 4.97 parts of 1,3-dimethylbarbituric acid was changed to 4.65 parts of 1,3-dicyclohexyl barbituric acid. , All the reaction operations were carried out in the same manner as in Example 1-1, and the isoindoline compound 1-7 was added to 89.
.. I got 60 copies.

(Manufacturing Example 1-1)
All the same as in Example 1-1 except that 36.69 parts of barbituric acid and 4.97 parts of 1,3-dimethylbarbituric acid of Example 1-1 were changed to 40.77 parts of barbituric acid. The reaction operation was carried out to obtain 85.80 parts of isoindoline compound 1-8.

(Manufacturing Example 1-2)
All examples 1 except that 36.69 parts of barbituric acid and 4.97 parts of 1,3-dimethylbarbituric acid of Example 1-1 were changed to 49.69 parts of 1,3-dimethylbarbituric acid. The reaction operation was carried out in the same manner as in -1, and 94.20 parts of isoindoline compound 1-9 was obtained.

Table 1 shows the structures contained in the isoindoline compounds obtained in Examples 1-1 to 1-7 and Production Examples 1-1 to 1-2. In the table, (1) indicates an isoindoline compound (1), and (2) indicates an isoindoline compound (2). In the table, H is hydrogen, Me is a methyl group, Et is an ethyl group, and CH is a cyclohexyl group.

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 1 shows the theoretical molecular weights of the isoindoline compounds (Examples 1-1 to 1-7 and Production Examples 1-1 to 1-2) and the measured values obtained by mass spectrometry. Due to the nature of the measurement, the H (proton) of the compound is desorbed from the measured value, so if the value is the mass number of the theoretical molecular weight − (minus) 1, the compounds will match.

(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. 83.39 parts of barbituric acid and 11.29 parts of 1,3-dimethylbarbituric acid were added thereto, and the mixture was stirred at 65 ° C. to dissolve barbituric acid and 1,3-dimethylbarbituric acid. On the other hand, 800 parts of water and 50.00 parts of 1,3-diiminoisoindoline were added to the glass flask, and the mixture was stirred at 30 ° C. This stirring liquid was put into the above-mentioned heating and dissolving liquid, and the temperature was raised to 85 ° C. for further completion of the reaction, and stirring was performed. 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 124.90 parts of isoindoline compound 2-1.

(Example 2-2)
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. 83.39 parts of barbituric acid was added thereto, and the mixture was stirred at 65 ° C. to dissolve the barbituric acid. On the other hand, 720 parts of water and 45.00 parts of 1,3-diiminoisoindoline were added to a glass flask, and the mixture was stirred at 30 ° C. This stirring solution was put into the above-mentioned heat-dissolving solution, and stirring was performed for 1 hour. 11.29 parts of 1,3-dimethylbarbituric acid was added to this reaction solution. On the other hand, 80 parts of water and 5.00 parts of 1,3-diiminoisoindoline were added to a glass flask, and the mixture was stirred at 30 ° C. This stirring solution was put into the above reaction solution, and the temperature was raised to 85 ° C. to complete 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 123.00 parts of isoindoline compound 2-2.

(Manufacturing Example 2-1)
All reactions were the same as in Example 2-1 except that 83.39 parts of barbituric acid and 11.29 parts of 1,3-dimethylbarbituric acid of Example 2-1 were changed to 92.65 parts of barbituric acid. The operation was carried out to obtain 122.90 parts of isoindoline compound 2-3.

(Manufacturing Example 2-2)
All examples 2-except that 83.39 parts of barbituric acid and 11.29 parts of 1,3-dimethylbarbituric acid of Example 2-1 were changed to 112.94 parts of 1,3-dimethylbarbituric acid. The reaction operation was carried out in the same manner as in No. 1, and 141.10 parts of isoindoline compound 2-4 was obtained.

Table 2 shows the structures of the isoindoline compounds obtained in Examples 2-1 to 2-2 and Production Examples 2-1 to 2-2.

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 in the same manner as described above.

(Example 3-1)
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% ammonia water were added in this order and stirred. A solution prepared by dissolving 80.37 parts of 2- (4-oxo-3,4-dihydroquinazoline-2-yl) acetonitrile in 160 parts of water was added dropwise thereto using a dropping funnel in 30 minutes. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. This reaction slurry was filtered off using a Büchner funnel to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC.
To a 4-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 60 parts of the non-volatile content obtained in the previous preparation, 480 parts of water, and 162 parts of 80% acetic acid were added and stirred as raw materials. On the other hand, 461 parts of water and 194 parts of 80% acetic acid are added to a glass flask, 26.49 parts of barbituric acid and 3.59 parts of 1,3-dimethylbarbituric acid are added thereto, and the mixture is stirred at 65 ° C. bottom. 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 73.50 parts of isoindoline compound 3-1.

(Example 3-2)
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% ammonia water were added in this order and stirred. A solution prepared by dissolving 80.38 parts of 2- (4-oxo-3,4-dihydroxoline-2-yl) acetonitrile in 160 parts of water was added dropwise thereto using a dropping funnel in 30 minutes. The mixture was heated and stirred at 30 ° C. until the raw material 1,3-diiminoisoindoline disappeared. This reaction slurry was filtered off using a Büchner funnel to obtain a non-volatile component. The disappearance of the raw material was confirmed by UPLC.
To a 4-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 60 parts of the non-volatile content obtained in the previous preparation, 480 parts of water, and 162 parts of 80% acetic acid were added and stirred as raw materials. On the other hand, 480 parts of water and 162 parts of 80% acetic acid were added to the glass flask, 22.08 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 mixture was stirred at 30 ° C. for 3 hours. To a glass flask prepared separately, 48 parts of water and 16 parts of 80% acetic acid were added, 5.98 parts of 1,3-dimethylbarbituric acid was added thereto, and the mixture was stirred at 65 ° C. The heated solution of this mixture was put into the above reaction 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 74.10 parts of isoindoline compound 3-2.

(Manufacturing Example 3-1)
All reactions were the same as in Example 3-1 except that 26.49 parts of barbituric acid and 3.59 parts of 1,3-dimethylbarbituric acid of Example 3-1 were changed to 29.44 parts of barbituric acid. The operation was carried out to obtain 75.20 parts of isoindoline compound 3-3.

(Manufacturing Example 3-2)
All examples 3-except that 26.49 parts of barbituric acid and 3.59 parts of 1,3-dimethylbarbituric acid of Example 3-1 were changed to 35.88 parts of 1,3-dimethylbarbituric acid. The reaction operation was carried out in the same manner as in No. 1, and 79.70 parts of isoindoline compound 3-4 was obtained.

Table 3 shows the structures of the isoindoline compounds obtained in Examples 3-1 to 3-2 and Production Examples 3-1 to 3-2.

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 in the same manner as described above.

(Example 1-8)
90 parts of the isoindoline compound (1-8) obtained in Production Example 1-1, 10 parts of the isoindoline compound (1-9) obtained in Production Example 1-2, 1000 parts of sodium chloride, and 150 parts of diethylene glycol. , It was charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. 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. overnight, and pulverized. 95.5 parts of the finely divided isoindoline compound (1-10) was obtained.

(Example 1-9)
100 parts of the isoindoline compound (1-3), 500 parts of sodium chloride, and 150 parts of diethylene glycol obtained in Example 1-3 were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and 6 at 75 ° C. Time (h) kneaded. 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. overnight, and pulverized. 96.2 parts of the finely divided isoindoline compound (1-11) was obtained.

(Example 1-10)
95 parts of the isoindoline compound (1-8) obtained in Production Example 1-1, 5 parts of the isoindoline compound (2-4) obtained in Production Example 2-2, 1000 parts of sodium chloride, and 150 parts of diethylene glycol. , It was charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. 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. overnight, and pulverized. 96.0 parts of the finely divided isoindoline compound (1-12) was obtained.

(Example 1-11)
37.0 parts of the isoindoline compound (1-8) obtained in Production Example 1-1 and 3.0 parts of the isoindoline compound (1-9) obtained in Production Example 1-2 were added to 1000 parts of 98% sulfuric acid. The mixture was 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 (1-13) 38. .5 copies were obtained. Obtained.

(Example 2-3)
95 parts of the isoindoline compound (2-3) obtained in Production Example 2-1 and 5 parts of the isoindoline compound (2-4) obtained in Production Example 2-2, 1000 parts of sodium chloride, and 150 parts of diethylene glycol were added. , It was charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. 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. overnight, and pulverized. 96.7 parts of the finely divided isoindoline compound (2-5) was obtained.

(Example 3-3)
90 parts of the isoindoline compound (3-3) obtained in Production Example 3-1, 10 parts of the isoindoline compound (3-4) obtained in Production Example 3-2, 1000 parts of sodium chloride, and 150 parts of diethylene glycol. , It was charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. 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. overnight, and pulverized. 94.7 parts of the finely divided isoindoline compound (3-5) was obtained.

Regarding the obtained isoindoline compound, Production Example 1-1 is shown in FIG. 1, Production Example 1-2 is shown in FIG. 2, Example 1-1 is shown in FIG. 3, Example 1-2 is shown in FIG. 4, and Example 1-4 is shown. 5 is an X-ray diffraction spectrum of Cu—Kα rays measured as shown below, with FIG. 5 for Example 1-5, FIG. 7 for Example 1-8, and FIG. 8 for Example 1-11.

(Method for measuring powder X-ray diffraction of isoindoline compositions (1) and (2))
The powder X-ray diffraction measurement was performed in a range of 3 ° to 35 ° in the diffraction angle (2θ) according to the Japanese Industrial Standards JIS K0131 (general rule of X-ray diffraction analysis).

The measurement conditions were as follows.
X-ray diffractometer: RINT2100 manufactured by Rigaku
Sampling width: 0.02 °
Scan speed: 2.0 ° / min
Divergence slit: 1 °
Divergence vertical limiting slit: 10 mm
Scattering slit: 2 °
Light receiving slit: 0.3 mm
Tube: Cu
Tube voltage: 40kV
Tube current: 40mA

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

<1> Evaluation of molding composition <Heat resistance test>
(Examples A-1 to A-17, Comparative Examples A-1 to A3)
The heat resistance test was carried out in accordance with the German industrial standard DIN12877-1.
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, and the temperature inside the barrel became 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 performed 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 4. For the coloring plate, in order to detect the average color difference, a colorimeter (CM-700d manufactured by Konica Minolta Co., Ltd.) capable of measuring the total light emission of the 6th to 11th coloring plates is used. And each color was measured. The average value of the obtained colorimetric values was used as a control (reference value).

Next, 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 plates, 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 formed at 300 ° C. was obtained and evaluated according to the following criteria. The results are shown in Table 4. The smaller the color difference, the better the heat resistance.

(Evaluation criteria)
4. ΔE * is less than 3.0. Very good 3. ΔE * is 3.0 or more and less than 6.0. Good 2. ΔE * is 6.0 or more and less than 10.0. Practical use 1. ΔE * is 10.0 or more. Impractical

(Example A-18) Preparation of molded product 1 part of isoindoline compound 1-4 and 1000 parts of polypropylene resin (product name: Prime Polypropylene J105, manufactured by Prime Polymer Co., Ltd.) are melt-mixed at 220 ° C. using a twin-screw extruder. After smelting, it was 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 to a molding temperature of 220 ° C. and a mold temperature of 40 ° C., and a molded product (plate) having a thickness of 1 mm was obtained. 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-19) Preparation of molded product 0.5 parts of isoindoline compound 1-4 and 1000 parts of polyethylene terephthalate resin (product name: Vylopet EMC-307, manufactured by Toyobo Co., Ltd.) that has been pre-dried in advance. Melt kneading was carried out at 275 ° C. using a shaft extruder, and then cutting was performed 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 to 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> Toner evaluation Negatively charged toner was prepared and evaluated.
(Example A-20)
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 pressurized 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 / Mn = 1.08, melting point 107 ° C.) 75 parts are mixed (3000 rpm, 3 minutes) using a 20 L volume Henchel mixer, and further melt-kneaded at a discharge temperature of 120 ° C. using a twin-screw kneading extruder. gone. Then, the kneaded product was cooled and solidified, and then coarsely pulverized with a hammer mill. Next, the obtained coarsely pulverized product was finely pulverized using a type I jet mill (IDS-2 type) and then classified to obtain toner mother particles.
Next, 2500 parts of the toner mother particles obtained above and hydrophobic titanium oxide (STT-30A)
12.5 parts (manufactured by 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, negatively charged toner 2 was obtained in the same manner as in Example A-20, except that the isoindoline compound 1-4 of Example A-20 was changed to the isoindoline compound 1-8.
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 1-8, 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 are placed in a 225 ml glass bottle and dispersed over 60 minutes using a paint shaker manufactured by Red Devil. The mixture was obtained.
-Isoindoline compound (1-1): 19 parts-Acrylic resin (DIC, Acridic 47-712): 7.7 parts-Dispersion solvent (toluene: xylene: butyl acetate: ENEOS T-SOL150 FLUID Mixture solvent having a mass ratio of 3: 3: 2: 2): 40.7 parts Next, 75.4 parts of Acridic 47-712 and melamine resin (Amidia L-117-60 manufactured by DIC) 17 were added to the above mixture. .2 parts were added and dispersed for another 10 minutes to obtain a dispersion.
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-17, Comparative Examples B-1 to B-3) Preparation of base coating materials 2 to 20 In the method for preparing the base coating material 1 described in Example B-1, the isoindoline compound 1-1 Is changed to isoindoline 1-2 to 1-8, 1-10 to 1-13, 2-1 to 2-3, 2-5, and 3-1 to 3-3, 3-5, respectively. , The base paints 2 to 20 were obtained in the same manner as in Example B-1.

2. 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 with a paint shaker manufactured by Red Devil for 60 minutes to obtain a dispersion liquid.
-Titanium oxide (Titanium oxide type CR90 manufactured by Ishihara Sangyo Co., Ltd.): 66.6 parts-Acrylic resin (DIC company, Acridic 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 Then, 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.
-Base paint created in Example B-1 1:10 copies-White paint: 31.9 copies

(Examples C-2 to C-17, Comparative Examples C-1 to C-3) -Preparation of solid base paints 2 to 20 The base paint 1 of Example C-1 was changed to the base paints 2 to 20, respectively. The solid base paints 2 to 20 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 6.

4. Preparation of Top Coat Clear Paint The following raw materials were stirred using a high-speed stirrer to obtain a top coat clear paint.
-Acrylic resin (DIC, Acridic 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 painted. In order to adjust the viscosity to be 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, it was dried at 25 ° C. for 8 hours and then dried at 140 ° C. for 30 minutes to obtain a solid base coated plate 1.

(Examples D-2 to D-17, Comparative Examples D-1 to D-3) Fabrication of Solid Base Painted Plates 2 to 20 The solid base paint 1 of Example D-1 was changed to solid base paints 2 to 20, respectively. Solid base coated plates 2 to 20 were obtained in the same manner as in Example D-1 except for the above.

(Weather resistance evaluation)
The obtained solid base coated plates 1 to 20 were subjected to a weather resistance test according to the following.
The weather resistance test is an ultra-accelerated weather resistance tester (manufactured by Iwasaki Electric Co., Ltd., Eye Super Xenon Tester S).
Using UV-W151), illuminance 90 mW / cm ² , irradiation (day) conditions: 12 hours, temperature 63 ° C, humidity 70%, irradiation pause (night) conditions: 12 hours, temperature 70 ° C, humidity 99% Was taken as one cycle, and was carried out 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). The coated plates before and after the weather resistance test were visually observed, and the weather resistance was evaluated according to the following criteria. The results are shown in Table 7. It is considered that the smaller the change in color, the better the weather resistance, and "4", "3" and "2" in the following evaluation criteria are practical levels.

(Evaluation criteria)
4. ΔE * is less than 5.0. Very good 3. ΔE * is 5.0 or more and less than 7.5. Good 2. ΔE * is 7.5 or more and less than 10.0. Practical use 1. ΔE * is 10.0 or more. Impractical

<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 (ADDITOR XW 6528, manufactured by Allnex): 5.25 parts-Wetting agent (ADDITOR XW 6374, manufactured by Allnex): 0. 95 parts ・ Defoaming agent (ADDITOR XW 6211 manufactured by Allnex): 0.63 parts ・ Ion-exchanged water: 21.52 parts Next, the zirconia beads are removed from the above dispersion liquid to obtain the aqueous coloring composition E-1. Obtained.

(Examples E-2 to E-17, Comparative Examples E-1 to E-3) Preparation of water-based coloring compositions E-2 to 20 The isoindoline pigment 1-1 of Example E-1 is as shown in Table 8. Water-based coloring compositions E-2 to 20 were obtained in the same manner as in Example E-1 except that the composition was changed to.

(Example E-18) Preparation of water-based coloring composition E-21 The isoindoline compound 1-1: 3.15 parts of Example E-1 was combined with the isoindoline compound 1-8: 2.84 parts and the isoindoline compound 1. -9: Water-based coloring composition E-21 was obtained in the same manner as in Example E-1 except that the content was changed to 0.32 part.

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

(Evaluation criteria for initial viscosity)
4. The initial viscosity is less than 5.0 mPa · s. Very good 3. The initial viscosity is 5.0 mPa · s or more and less than 7.5 mPa · s. Good 2. The initial viscosity is 7.5 mPa · s or more and less than 10.0 mPa · s. Practical use 1. The initial viscosity is 10.0 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

<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 The following raw materials were stirred using a high-speed stirrer to obtain 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): 1.4 parts-Acrylic resin (acid value 65.0, OH value 50, Mw = 15,000, non-volatile content 35%): 13.6 parts -Melamine resin (manufactured by Allnex, Cymel 325): 3.4 parts

(2) Preparation of Water-based Paint 1-2 The following raw materials were 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): 1.4 parts-Acrylic resin (acid value 65.0, OH value 50, Mw = 15,000, non-volatile content 35%): 13.6 parts -Melamine resin (manufactured by Allnex, Cymel 325): 3.4 parts

(Examples F-2 to F-18, Comparative Examples F-1 to F-3)
All except that the water-based coloring composition E-1 of Example F-1 (stored at 25 ° C. for 1 week) was sequentially changed to the water-based coloring compositions E-2 to 21 (stored at 25 ° C. for 1 week each). Water-based paints 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 (stored at 50 ° C. for 1 week, respectively). Water-based paints 2-2 to 21-2 were 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.
The water-based paint 1-1 and the water-based paint 1-2 were coated on Lumirror 100T60 (PET film, 100 μm thickness) using a 6-mil applicator. After the painting, 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 film 1 having a film thickness of 70 μm.

(Examples G-2 to G-18, Comparative Examples G-1 to G-3) Preparation of pet film coatings 2 to 21 Water-based paint 1-1 and water-based paint 1-2 of Example G-1 are 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, 2-2 to 21-2.

<5-3> Evaluation of Pet Film Coating The hue stability of each of the pet film coatings obtained in Examples G-1 to G-16 and Comparative Examples G-1 to G-3 was evaluated according to the following method. ..

(Evaluation method of hue stability)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), a pet film coated with a water-based coloring composition paint stored at 25 ° C. for 1 week and a water-based coloring composition paint 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 10. 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" 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. 2. ΔE * is 2.0 or more and less than 3.0.
1. 1. ΔE * is 3.0 or more.

<6> Evaluation of gravure ink First, the resin measurement method will be described below.
(Hydroxy group value)
Obtained according to JIS K0070.
(Acid value)
Obtained according to JIS K0070.
(Amine value)
The amine value was determined according to the following method according to JIS K0070 with the same amount of potassium hydroxide as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of the resin.
The sample was precisely weighed in an amount of 0.5 to 2 g (sample non-volatile content: Sg). Methanol in the finely weighed sample /
50 mL of a mixed solution of methyl ethyl ketone = 60/40 (mass ratio) was added and dissolved. Bromophenol blue was added to the obtained solution as an indicator, and the obtained solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid solution (titer: f). Using the titration amount (AmL) at this time as the end point at the point where the color of the solution changed from green to yellow, the amine titer was determined by the following formula.
Amine value = (A × f × 0.2 × 56.108) / S [mgKOH / g]

(Weight average molecular weight)
The weight average molecular weight was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) device (HLC-8220 manufactured by Tosoh Corporation) and using polystyrene as a standard material as a converted molecular weight. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
Tosoh Guard Column HXL-H
Tosoh TSKgelG5000HXL
Tosoh TSKgelG4000HXL
Tosoh TSKgelG3000HXL
Tosoh TSKgelG2000HXL
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

(Glass-transition temperature)
The glass transition temperature (Tg) was determined by DSC (differential scanning calorimetry). The measuring machine used was DSC8231 manufactured by Rigaku Co., Ltd., and the measurement temperature range was -70 to 250 ° C., and the temperature rise rate was 1.
At 0 ° C./min, the midpoint between the heat absorption start temperature and the end temperature based on the glass transition in the DSC curve was defined as the glass transition temperature.

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

(Example H-1) [Preparation of gravure printing ink 1]
30 parts of polyurethane resin solution [PU1] (non-volatile content 30%) as a binder resin, 0.8 part of polyethylene wax (A-C400A manufactured by Honeywell Co., Ltd.) as a hydrocarbon wax, chlorinated polypropylene resin (non-volatile content 30%) Made by Nippon Paper Co., Ltd. Product name: 370M Chlorine content 30% Non-volatile content 50%) in terms of non-volatile content 0.5 parts, Isoindoline compound (1-1) 10 parts, Methyl ethyl ketone (hereinafter "MEK") / n acetate 58.7 parts of a solution of -propyl (hereinafter "NPAC") / IPA = 40/40/20 (mass ratio) was mixed and dispersed with an Eiger mill for 15 minutes to obtain gravure printing ink 1.

(Examples H-2 to 17, Comparative Examples H-1 to 3) [Preparation of gravure printing inks 2 to 20]
In the method for preparing the gravure printing ink 1 described in Example H-1, the isoindoline compound (1-1) was changed as shown in Table 11, but the gravure printing ink was the same as in Example H-1. Obtained 2 to 20.

(Example I-1) <Printing of gravure printing ink>
The gravure printing ink 1 obtained above is mixed with a mixed solvent consisting of MEK / NPAC / IPA = 40/40/20 (mass ratio) so that the viscosity becomes 16 seconds (25 ° C., Zahn cup No. 3). Using a gravure printing machine equipped with a diluted Helio 175-line gradation plate (plate type compressed gradation 100% to 3%), printing is performed on the following substrate (corona discharge processing surface in the case of OPP) at a printing speed of 80 m / min. This was carried out to obtain printed matter I1-1 (OPP) and I1-2 (CPP).
<Base material>
-OPP: Biaxially stretched polypropylene (OPP) film with single-sided corona discharge treatment (FOR thickness 25 μm manufactured by Futamura Chemical Co., Ltd.)
-CPP: Unstretched polypropylene (CPP) film without corona treatment (CP-S thickness 30 μm manufactured by Mitsui Chemicals Tocello Co., Ltd.)

(Examples I-2 to 17, Comparative Examples I-1 to 3)
The gravure inks 2 to 20 shown in Table 11 are printed with the printing configurations shown in Table 12 to obtain printed matter I2-1 to I20-1 (OPP) and I2-2 to I20-2 (CPP). rice field.

<Evaluation>
The following evaluations were performed using gravure inks 1 to 20, printed matter I1-1 to I20-1 (OPP), and printed matter I1-2 to I20-2 (CPP).

<Ink stability over time>
Each of the gravure printing inks 1 to 20 was placed in a closed container and stored at 40 ° C. for 10 days. After that, the viscosity was measured and the change in viscosity from before storage was evaluated. The viscosity was measured at 25 ° C. It was performed in 4 outflow seconds. The viscosity of each ink in the B-type viscometer before storage was in the range of 40 to 500 cps (25 ° C.).
(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. 2. Viscosity change is 10 seconds or more and less than 15 seconds (defective)
1. 1. Viscosity change is 15 seconds or more (extremely poor)
Note that 5 and 4 are ranges in which there is no practical problem.

<Transparency evaluation>
The transparency was judged by spreading the color on a colored paper with a black belt and then observing the degree of transparency on the black belt when compared with the comparative examples having similar hues.
(Evaluation criteria)
5. Extremely transparent 4. Transparent 3. Equivalent 2. Opaque 1. Extremely opaque

<Scratch resistance>
Using the printed matter I1-1 to I20-1 (OPP) and the printed matter I1-2 to I20-2 (CPP), the surface of the printed layer was rubbed with a nail at three places, and the degree of damage to the printed layer was evaluated.
(Evaluation criteria)
5. No scratches on the print layer (good)
4. The print layer is not scratched, but a slight nail mark remains. (Practical)
3. 3. The printed layer is scratched and the surface of the printed layer is slightly scooped out. (Slightly bad)
2. 2. The printed layer is scratched and the substrate is slightly visible. (Defective)
1. 1. The printed layer is scratched and the substrate is clearly visible. (Extremely bad)
Note that 5 and 4 are ranges in which there is no practical problem.

<Adhesiveness>
For the printed matter I1-1 to I20-1 (OPP) and the printed matter I1-2 to I20-2 (CPP), an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) having a width of 12 mm was attached to the printed surface 3 hours after printing. The state of the appearance of the printed surface when this was rapidly peeled off was visually determined. The judgment criteria were as follows.
(Evaluation criteria)
5. The ink film on the printed surface does not peel off at all (good)
4. The peeled area of the ink film is 1% or more and less than 5% (practical)
3. 3. The peeled area of the ink film is 5% or more and less than 20% (slightly defective)
2. 2. The peeled area of the ink film is 20% or more and less than 50% (defective)
1. 1. Ink film peels off by 50% or more (extremely defective)
Note that 5 and 4 are ranges in which there is no practical problem.

<7> Evaluation of Aqueous Ink Ink <7-1> Preparation of Aqueous Coloring Composition for Ink (hereinafter “Aqueous Coloring Composition for IJ”) (Example J-1) Preparation of Aqueous Coloring Composition 1 for IJ ・ Iso Indoline compound (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 in a paint shaker manufactured by Red Devil for 6 hours. The obtained liquid was diluted with ion-exchanged water, the zirconia beads for dispersion were separated by filtration, and diluted with ion-exchanged water so that the colorant content was 15% to obtain the isoindoline compound (1-1). An aqueous coloring composition 1 for IJ was obtained.

(Examples J-2 to J-17, Comparative Examples J-1 to J-3) Preparation of Aqueous Coloring Compositions 2 to 20 for IJ In the method for preparing the aqueous IJ dispersion liquid 1 described in Example J-1, Aqueous coloring compositions 2 to 20 for IJ were obtained in the same manner as in Example J-1 except that the isoindoline compound 1-1 was changed as shown in Table 13.

(Example J-18) Preparation of aqueous coloring composition 21 for IJ In the method for preparing the aqueous IJ dispersion liquid 1 described in Example J-1, 1-1: 19 parts of the isoindoline compound was added to 1-8: isoindoline. An aqueous coloring composition 21 for IJ was obtained in the same manner as in Example J-1 except that it was changed to 17.1 part and 1-9: 1.9 parts of isoindoline.

(Synthesis Example 2) Styrene-acrylic acid ester-methacrylate copolymer having a carboxyl group and a hydroxyl group [PA1]
Put 1,000 parts of methylethylketone in a 3-liter 4-necked flask equipped with a dropping funnel, a thermometer, a nitrogen gas introduction tube, a stirrer and a reflux condenser, raise the temperature to 78 ° C, and then 100 parts of styrene, n-butyl. A mixed solution consisting of 538 parts of methacrylate, 104 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 108 parts of methacrylic acid, and 80 parts of tertiary butylperoxy-2-ethylhexanoate was added dropwise over 4 hours. Then, the reaction was carried out at the same temperature for 8 hours. After completion of the reaction, methyl ethyl ketone was further added to adjust the non-volatile content to 50%, and a styrene-acrylic acid ester-methacrylate copolymer [PA1] solution having an acid value of 70 mgKOH / g and a number average molecular weight of 6,000 was added. Got The acid value is a value measured by the same method as the resin in the gravure printing ink, and the number average molecular weight is the same as the device and method in the case of the weight average molecular weight of the resin in the gravure printing ink described above. It is a polystyrene conversion value measured by.

(Example J-19) Preparation of aqueous coloring composition 22 for IJ 12.8 parts of a styrene-acrylic acid ester-methacrylate copolymer [PA1] solution (nonvolatile content 50%) was added to 0.71 dimethylethanolamine. After neutralizing using the parts, the mixture was mixed with 2.29 parts (1.6 parts as a resin) of a methyl etherified melamine resin (Nikalac MX-041 manufactured by Sanwa Chemical Industry Co., Ltd.). To this mixed solution, 50 parts of an aqueous slurry (nonvolatile content 16%) of the isoindoline compound (1-2) prepared in advance was added with stirring. Then, it was charged into a 250 ml glass bottle together with 130 parts of 1.5 mm diameter glass beads and dispersed over 4 hours using a paint shaker manufactured by Red Devil, and after obtaining a dispersion liquid, an equal amount of ion-exchanged water was added to the mixture. .. Then, a 1N hydrochloric acid aqueous solution was added with stirring, and the copolymer [PA1] was precipitated and fixed on the surface of the isoindoline compound (1-2). The pH of the mixed solution after fixing was 3 to 5.
Then, the mixed solution was suction-filtered and washed with ion-exchanged water until the pH of the washing liquid exceeded 6, to obtain an isoindoline compound (1-2) to which the copolymer [PA1] was adhered.
Next, water was added until the isoindoline compound (1-2) to which the copolymer [PA1] was fixed flowed, and then 0.8 part of dimethylethanolamine was added while stirring with a stirrer. The stirring was continued for 1 hour as it was to obtain a redispersion of the isoindoline compound (1-2) to which the copolymer [PA1] was adhered.
Water was added to this redisperse to adjust the non-volatile content to 19%, and then an acid cross-linking catalyst (Nacure 2500X manufactured by Kusumoto Kasei Co., Ltd.) was added to the amount of the copolymer [PA1] contained in the redispersion. A water-based coloring composition (Aqueous coloring composition 22 for IJ) containing crosslinked resin particles containing a pigment composition was obtained by adding 0.5% to the amount and carrying out a crosslinking reaction at 95 ° C. for 1 hour.

(Synthesis Example 3) Styrene-acrylic acid ester-methacrylate copolymer having a carboxyl group and an epoxy group [PA2]
In a 3-liter 4-necked flask equipped with a dropping funnel, a thermometer, a nitrogen gas introduction tube, a stirrer and a reflux condenser, 1,000 parts of methylethylketone was charged and heated to 78 ° C., and then 100 parts of styrene, n-. A mixed solution consisting of 476 parts of butyl methacrylate, 116 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 50 parts of glycidyl methacrylate, 108 parts of methacrylic acid, and 80 parts of tertiary butylperoxy-2-ethylhexanoate. The mixture was added dropwise over 4 hours and reacted at the same temperature for 8 hours. After completion of the reaction, methyl ethyl ketone was further added to adjust the non-volatile content to 50%, and the styrene-acrylic acid ester-methacrylate copolymer having an acid value of 70 mgKOH / g and a number average molecular weight of 10,500 was [PA2]. A solution was obtained.

(Example J-20) Preparation of Aqueous Coloring Composition 23 for IJ 16 parts of the obtained styrene-acrylic acid ester-methacrylate copolymer [PA2] solution (nonvolatile content 50%), isoindoline compound (1) 8 parts of -2) and 40 parts of methyl ethyl ketone were placed in a 250 ml glass bottle together with 130 parts of glass beads having a diameter of 1.5 mm and dispersed over 4 hours using a paint shaker manufactured by Red Devil to obtain a dispersion solution. Next, 0.8 part of a hydrophilic epoxy resin (CR-5L manufactured by DIC Corporation) and 24 parts of methyl ethyl ketone were added to this dispersion and stirred, and then the glass beads were separated by filtration. 87.2 parts of the dispersion liquid thus obtained was put into a mixed liquid of 1.2 parts of dimethylethanolamine and 100 parts of water with stirring, and then an equal amount of ion-exchanged water was added to the mixture. Then, a 1N aqueous solution of phosphoric acid was added with stirring, and the copolymer [PA2] was precipitated and fixed on the surface of the isoindoline compound (1-2). The pH of the mixed solution after fixing was 5.
Then, the mixed solution was suction-filtered and washed with ion-exchanged water until the pH of the washing liquid exceeded 6, to obtain an isoindoline compound (1-2) to which the copolymer [PA2] was adhered.
Next, water was added until the isoindoline compound (1-2) to which the copolymer [PA2] was fixed flowed, and then 0.8 part of dimethylethanolamine was added while stirring with a stirrer. The stirring was continued for 1 hour as it was to obtain a redispersion of the isoindoline compound (1-2) to which the copolymer [PA2] was adhered.
Water is added to this redisperse to adjust the non-volatile content to 19%, and then the redispersion is heated to 95 ° C. and subjected to a cross-linking reaction for 1 hour to carry out an aqueous-based coloring containing cross-linked resin particles containing a pigment composition. A composition (aqueous coloring composition for IJ 23) was obtained.

(Synthesis Example 4) Styrene-acrylic acid ester copolymer [PA3]
62 parts of acrylic acid, 129 parts of styrene, and 9 parts of α-methylstyrene were mixed to prepare a monomer mixed solution. In the reaction vessel, 20 parts of methyl ethyl ketone, 0.3 part of 2-mercaptoethanol (polymerization chain transfer agent), and 10% of the above-mentioned monomer mixture were put and mixed, and nitrogen gas substitution was sufficiently performed. Separately, in a dropping funnel, the remaining 90% of the monomer mixed solution, 0.27 parts of the polymerization chain transfer agent, 60 parts of methyl ethyl ketone, and an azo radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-65). , 2,2'-azobis (2,4-dimethylvaleronitrile)) 2.2 parts of a mixed solution was charged.
Under a nitrogen atmosphere, the temperature of the mixture in the reaction vessel was raised to 65 ° C. while stirring, and then the mixture in the dropping funnel was added dropwise over 3 hours. After completion of the dropping, the reaction was carried out at 65 ° C. for 1 hour, and then a solution in which 0.3 part of the polymerization initiator was dissolved in 5 parts of methyl ethyl ketone was added, and the reaction was continued at 65 ° C. for 1 hour. After adding the polymerization initiator solution and continuing the reaction twice more, the temperature was raised to 70 ° C. and the reaction was further carried out for 1 hour, and then 200 parts of methyl ethyl ketone was added to obtain an acid value of 240 mgKOH / g and a number average molecular weight. A styrene-acrylic acid ester copolymer [PA3] solution (nonvolatile content concentration 40.9%) having a weight average molecular weight of 5,700 and a weight average molecular weight of 12,500 was obtained.
This styrene-acrylic acid ester copolymer [PA3] solution was dried under reduced pressure to completely remove the solvent to obtain 32 parts of the resin, which was then mixed with 204 parts of ion-exchanged water, and further, triethanolamine 11. One portion was added to neutralize about 55 mol% of the carboxy groups in the copolymer [PA3]. The mixed solution was heated to 90 ° C. and then stirred for 1 hour to obtain an aqueous dispersion of the copolymer [PA3] in which the copolymer [PA3] was dispersed in water.

(Example J-21) Preparation of aqueous coloring composition 24 for IJ After cooling the aqueous dispersion of the copolymer [PA3] to room temperature, add 100 parts of the isoindoline compound (1-2) and use a stirrer. Then, the mixture was stirred at 20 ° C. for 3 hours. After adding 124 parts of ion-exchanged water to this mixed solution, a 15-pass dispersion treatment was performed at a pressure of 150 MPa using a microfluidizer. Next, using a high-speed cooling centrifuge (Himac CR22G, manufactured by Hitachi Koki Co., Ltd.), the obtained dispersion was centrifuged at a set temperature of 20 ° C. and 3,660 rpm for 20 minutes, and then only the liquid layer portion was recovered. , A membrane filter having a pore size of 5 μm was used for filtration to obtain an aqueous dispersion (nonvolatile content concentration of 25%) of the isoindoline compound (1-2).
To 100 parts of the aqueous dispersion of the isoindoline compound (1-2), 32 parts of ion-exchanged water is added, and further, trimethylolpropane polyglycidyl ether (Denacol EX-321 manufactured by Nagase ChemteX Corporation) is added as a cross-linking agent. .8 parts were added and heated at 70 ° C. for 5 hours with stirring. After that, the mixture is cooled to room temperature, filtered through a membrane filter having a pore size of 5 μm, and further added with ion-exchanged water to adjust the non-volatile content to 19%. A product (aqueous coloring composition for IJ 24) was obtained.

<7-1> Preparation of Aqueous Inkjet Ink (hereinafter referred to as "Aqueous IJ Ink") Examples for evaluation test by stirring and mixing each component shown in Tables 14 and 15 and then filtering with a 3 μm membrane filter. Aqueous IJ inks of K-1 to K-23 and Comparative Examples K-1 to K-5 were obtained. In Tables 14 and 15, the numerical values indicating the amounts of the components are all "parts", and those with "-" mean that the components are not included. In addition, "water" used ion-exchanged water. Other abbreviations in the table indicate the following meanings.
・ PG: Propylene glycol ・ TEA: Triethanolamine ・ AMP: 2-Amino-2-methyl-1-propanol ・ NH ₃ 28% aq: 28% aqueous ammonia solution

<Color change during long-term storage>
The water-based IJ ink prepared in each Example and Comparative Example was filled in a mayonnaise bottle and stored in an oven at 50 ° C. for 4 weeks. Using the ink before and after storage of each ink, using a K control coater manufactured by Matsuo Sangyo Co., Ltd., apply the OK top coat with a wet film thickness of 6 μm, and then dry the coated product in an oven at 70 ° C for 1 minute. A coating was made.

Calculation of color difference (ΔE value) before and after storage:
Using the obtained coated product, X-Rite eXact manufactured by X-Rite Co., Ltd. was used, and the L *, a *, and b * values of the ink coating film before and after long-term storage were measured. From the numerical value, the color difference (ΔE value) before and after storage was calculated and evaluated. If it is "4", "3" and "2" in the following evaluation criteria, it is a practical grade.
(Evaluation criteria)
4: Color difference (ΔE value) is less than 2 3: Color difference (ΔE value) is 2 or more and less than 3 2: Color difference (ΔE value) is 3 or more and less than 5 1: Color difference (ΔE value) is 5 or more

From the above results, the effect of the pigment composition containing the isoindoline compound (1) and the isoindoline compound (2) can be understood. For example, from the results in Table 4, a molding composition capable of forming a molded body having excellent heat resistance can be obtained. Further, from the result of the toner, a toner having excellent dispersibility of the pigment can be obtained. Moreover, from the result of the paint, a paint having excellent weather resistance was obtained. In particular, discoloration can be suppressed. Further, from the results of the gravure printing ink, it can be seen that a printing ink having excellent viscosity change and transparency and excellent scratch resistance and adhesiveness can be obtained even in a printed matter. Further, from the results of the water-based coloring composition, it can be seen that the initial viscosity and the storage stability can be improved. Furthermore, from the results of the water-based inkjet ink, it is confirmed that the pH resistance to the coloring material is improved, and it can be seen that an inkjet ink capable of suppressing the color change of the ink coating film at the time of long-term storage stability can be obtained. In particular, it can be confirmed that the pH resistance can be further improved by using the crosslinked resin particles containing the pigment composition.

<Ink set and its characteristic evaluation>
An ink set was prepared using the obtained isoindoline compound, and its characteristics were evaluated.

(Synthesis Example 5) Polyurethane resin solution [PU2]
54.719 parts of polyester diol with a number average molecular weight of 2,000, 3.989 parts of isophorone diisocyanate, and 10.0 parts of n-propyl acetate obtained from adipic acid and 3-methyl-1,5-pentanediol under a nitrogen stream. The reaction was carried out at 85 ° C. for 3 hours, 10.0 parts of n-propyl acetate was added and cooled to obtain 78.718 parts of a solvent solution of the terminal isocyanate prepolymer. Next, a solvent solution 78 of the obtained terminal isocyanate prepolymer was mixed with 1.031 parts of isophorone diamine, 0.261 parts of di-n-butylamine, 30.4 parts of n-propyl acetate and 19.6 parts of isopropyl alcohol. .718 parts were gradually added at room temperature and then reacted at 50 ° C. for 1 hour to obtain a polyurethane resin solution [PU2] having a non-volatile content of 30%, a weight average molecular weight of 60,000 and an amine value of 3.0 mgKOH / g. ..

(Synthesis Example 6) Polyurethane resin solution [PU3]
161 PPA (poly (propylene glycol) adipatediol with a number average molecular weight of 2,000) is introduced while introducing nitrogen gas in a reactor equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer. .9 parts, 2,2-dimethylolbutanoic acid (DMBA) 27.7 parts, isophorone diisocyanate (IPDI) 96.4 parts, methyl ethyl ketone (MEK) 200 parts were charged and reacted at 90 ° C. for 5 hours to form a terminal isocyanate group. A resin solution of a urethane prepolymer having the above was obtained. To the obtained terminal isocyanate group urethane prepolymer resin solution, 13.6 parts of 2- (2-aminoethylamino) ethanol (AEA), 0.5 part of ethanolamine (MEA), and 350 parts of isopropyl alcohol (IPA) were added. The mixture was added dropwise at room temperature over 60 minutes, and further reacted at 70 ° C. for 3 hours. Further, the non-volatile content is adjusted using 150 parts of MEK, and a polyurethane resin having a non-volatile content of 30%, a weight average molecular weight of 35,000, Mw / Mn = 3.0, an acid value of 35.0 mgKOH / g, and a hydroxyl value of 25.7 mgKOH / g. A solution [PU3] was obtained.

(Synthesis Example 7) 1250 parts of n-amyl alcohol, 225 parts of phthalodinitrile, and 78 parts of aluminum chloride anhydride were added to an aluminum phthalocyanine reaction vessel, and the mixture was mixed and stirred. To this, 266 parts of DBU (1,8-diazabicyclo [5.4.0] undec-7-en) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine represented by the following chemical formula (32).

（３２）

(32)

Next, 1500 parts of concentrated sulfuric acid was added to the reaction vessel, then 100 parts of the above chloroaluminum phthalocyanine was added under an ice bath, and the mixture was stirred at 25 ° C. for 4 hours. Subsequently, this sulfuric acid solution is poured into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water, and dried to the following 98 parts. The aluminum phthalocyanine represented by the chemical formula (30) was obtained.

（合成例８）チタニルフタロシアニン 反応容器に、１－ヘキサノール１２８０部、キノリン３２０部、１，３－ジイミノイソインドリン３２０部、及びオルトチタン酸テトラブチル２０６．３部を加えて混合攪拌した。１５５℃まで昇温し、８時間還流した。なお、系内から発生したｎーブタノールは系内に戻らないように回収した。攪拌したまま６０℃まで冷却した反応溶液に、メタノール１０００部を加え、スラリーを濾過し、メタノール１０００部、Ｎ－メチルピロリドン５００部、メタノール１０００部の順で洗浄し、乾燥して、２５０部の下記化学式（３１）で示されるチタニルフタロシアニンクルードを得た。

(Synthesis Example 8) 1280 parts of 1-hexanol, 320 parts of quinoline, 320 parts of 1,3-diiminoisoindoline, and 206.3 parts of tetrabutyl orthotitanium were added to a titanylphthalocyanine reaction vessel, and the mixture was mixed and stirred. The temperature was raised to 155 ° C., and the mixture was refluxed for 8 hours. The n-butanol generated from the system was recovered so as not to return to the system. To the reaction solution cooled to 60 ° C. with stirring, 1000 parts of methanol was added, the slurry was filtered, washed in the order of 1000 parts of methanol, 500 parts of N-methylpyrrolidone, and 1000 parts of methanol, dried, and 250 parts were dried. The titanylphthalocyanine chloride represented by the following chemical formula (31) was obtained.

Next, 1500 parts of concentrated sulfuric acid was added to the reaction vessel, then 100 parts of the above titanylphthalocyanine crude was added under an ice bath, and the mixture was stirred at 25 ° C. for 4 hours. Subsequently, this sulfuric acid solution was poured into 9000 parts of cold water at 3 ° C., and the generated precipitate was treated in the order of filtration, washing with water, washing with 1% sodium hydroxide aqueous solution, and washing with water to obtain a cake. Next, 1000 parts of diethylene glycol and the obtained cake were added to the reaction vessel and stirred to form a slurry, which was stirred at 120 ° C. for 3 hours. The slurry cooled to 60 ° C. was filtered, washed with 5000 parts of water and dried to obtain 87 parts of titanylphthalocyanine.

[Manufacturing of gravure printing ink]
(Example LY-1)
7.0 parts of isoindoline compound (1-1), 34.5 parts of polyurethane resin solution [PU2], 20 parts of N-propyl acetate, and 5 parts of isopropyl alcohol are stirred and mixed, kneaded with a sand mill, and then a polyurethane resin solution. 20 parts of [PU2], 11 parts of N-propyl acetate and 3 parts of isopropyl alcohol were added to obtain a yellow ink [LY-1].

(Examples LY-2 to LY15, Production Examples LY-1 to LY-2, LC-1 to LC-5, LM-1 to LM-10)
The inks shown in Table 16 were obtained in the same manner as in Example LY-1 except that 7.0 parts of the isoindoline compound (1-1) was changed to the compounds shown in Table 16 and the amounts shown in Table 16.

Table 17 shows the pigments used in the production of the ink.

<Evaluation of viscosity stability of ink over time>
Put each of the yellow inks [LY-1] to [LY-17], the cyan inks [LC-1] to [LC-5], and the magenta inks [LM-1] to [LM-10] in a closed container, and 40 It was stored at ° C for 14 days. Then, the viscosity was measured and evaluated by comparing the change in viscosity with that before storage. The viscosity was measured at 25 ° C. It was performed in 4 outflow seconds. The viscosity of each ink in the B-type viscometer before storage was in the range of 40 to 500 cps (25 ° C.). The results are shown in Table 18.
(Evaluation criteria)
◯: Viscosity change is less than 2 seconds (good)
Δ: Viscosity change is 2 seconds or more and less than 5 seconds (practical)
×: Viscosity change is 5 seconds or more (defective)

<Evaluation of Ink Set> (Examples LS-1 to LS-64, Comparative Examples LS-1 to LS-15) The obtained inks were combined as shown in Table 18 to form ink sets 1 to 79.
The obtained ink set was evaluated for trapping property and gamut by the following method. The results are shown in Table 18.

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

(Yellow ink / Magenta ink)
The yellow ink and the magenta ink were each diluted with the above-mentioned mixed solvent 1 so as to have a viscosity of 16 seconds (25 ° C., Zahn cup No. 3).
A printed matter was obtained by overlay printing in the order of yellow and magenta on the corona discharge treated surface of a corona discharge treated polyester film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm (initial evaluation of trapping property).
The printing conditions were a temperature of 25 ° C., a humidity of 60%, a printing speed of 100 m / min, and a printing distance of 4000 m. Yellow ink uses Helio 175 line gradation version (plate type Eron gate, 75% solid pattern and 100% to 3% gradation pattern), and magenta ink uses Helio 175 line gradation version (plate type Eron gate, 75% solid pattern and 100% to 3). % Gradation pattern) was used.
Further, yellow ink and magenta ink were each placed in a closed container and stored at 40 ° C. for 14 days, then diluted and printed in the same manner as described above to obtain a printed matter (evaluation of trapping property over time).

The trapping property of the obtained gradation overprinted portion of the printed matter was observed using a microscope (VHX-5000) manufactured by KEYENCE, and evaluated according to the following criteria.
◯: Printing unevenness occurs at a plate depth of less than 70% (good)
Δ: Printing unevenness occurs when the plate depth is 70% or more and less than 80% (usable).
X: Printing unevenness occurs at a plate depth of 80% or more, or all the overlapping inks become halftone dots and do not spread wet (cannot be used).

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

(Printing conditions)
Printing machine: Fuji Machinery 5-color machine Cyan version: Helio 175L / inch, stylus angle 120 °, Elongate magenta version: Helio 175L / inch, stylus angle 120 °, compressed yellow version: Helio 175L / inch, stylus angle 120 °, Compressed printing speed: 150 m / min Substrate: Corona-treated biaxially stretched polypropylene (OPP) film (Pyrene P-2161, 20 μm manufactured by Toyo Spinning Co., Ltd.)
Drying temperature: 50 ° C

With respect to the obtained printed matter, the density value of the monochromatic solid portion (yellow, magenta, cyan) of the printed matter was measured using Gretag Macbeth D196. In addition, using a SpectroEye manufactured by gretagmacbeth as a measuring device, the monochromatic solid part and the overprinting part were measured under the conditions of a D50 light source, a two-degree observation field of view, a white background (using a standard white plate), and no filters.
In a two-dimensional space with a * as the horizontal axis and b * as the vertical axis, a single-color solid part (yellow, magenta, cyan) and a single-color solid overprint part (cyan x magenta, cyan x yellow, yellow x magenta) total 6 A hexagon was created by plotting the values of a * vs. b * of colors, and the area was calculated. The area ratio when the area of the comparative example as a reference was set to 100% was obtained, and the area ratio was evaluated according to the following criteria. Specifically, Examples LS-1 to LS-12, LS-16 to LS-20, LS-25 to LS-30, and Comparative Examples LS-3 to LS-7 and LS-12 are Comparative Examples LS. -1 was used as the standard. Further, Examples LS-13 to LS-15 were based on Comparative Example LS-2. Further, Examples LS-35 to LS-40 were based on Comparative Example LS-13. -Indicates that it has not been evaluated.
(Evaluation criteria)
◯: Area ratio is 90% or more (good)
Δ: Area ratio is 85% or more and less than 90% (usable)
X: Area ratio is less than 85% (cannot be used)

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

The color of the obtained printed matter was measured in the same manner as in the above initial evaluation.
In a two-dimensional space with a * as the horizontal axis and b * as the vertical axis, a single-color solid part (yellow, magenta, cyan) and a single-color solid overprint part (cyan x magenta, cyan x yellow, yellow x magenta) total 6 A hexagon was created by plotting the a * vs. b * values of the colors. The area ratio of each Example / Comparative Example in the time-dependent evaluation was divided by the area of the initial evaluation, and the area ratio was evaluated according to the following criteria. -Indicates that it has not been evaluated.
(Evaluation criteria)
◯: Area ratio is 98% or more (good)
Δ: Area ratio is 95% or more and less than 98% (practical)
X: Area ratio is less than 95% (defective)

According to Table 18, the gravure printing ink set of the present invention had a gamut ratio equal to or higher than that of the conventional ink set, and had good color reproducibility. In addition, the viscosity stability of the yellow ink over time was improved, and the storage stability of the ink set was good. Further, the trapping property and the color reproducibility (gamut) of each color were also evaluated well over time, and the storage stability as an ink set was also good.

On the other hand, in Comparative Examples LS-1 to LS-15, the viscosity stability of the yellow ink over time was poor, and the trapping property and color reproducibility (gamut) of each color were also poorly evaluated over time, so that they were stored as an ink set. The stability is poor and the problem of the present application cannot be solved.

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

<Manufacturing of adhesive with desorption>
(Preparation of Laminate Adhesive Solution [1])
82 parts of terephthalic acid, 682 parts of isophthalic acid, 236 parts of adipic acid, 236 parts of ethylene glycol, 525 parts of neopentyl glycol and 405 parts of 1,6-hexanediol were placed in a four-neck separable flask at 220 to 260 ° C. An esterification reaction was carried out. After distilling a predetermined amount of water, the pressure was gradually reduced to 1 mmHg or less, and a deglycolation reaction was carried out at 240 to 260 ° C. for 5 hours. Then, 2 parts of isophorone diisocyanate was gradually added, and the reaction was carried out at 150 ° C. for about 2 hours to obtain a polyester polyurethane polyol. To 100 parts of this polyester polyurethane polyol, 2.83 parts of trimellitic anhydride was added, and the mixture was reacted at 180 ° C. for about 2 hours. Then, it was diluted with ethyl acetate to a non-volatile content of 50% to obtain a partially acid-modified polyester polyol solution having a number average molecular weight of 6,000 and an acid value of 16.5 mgKOH / g.
100 parts of the obtained polyol solution and 7.94 parts of HDI Biuret's non-volatile content 95% ethyl acetate solution were mixed, and ethyl acetate was added to obtain a laminated adhesive solution [1] having a non-volatile content of 30%.

<Manufacturing of packaging materials>
(Example LP-1) Packaging material 1
Cyan ink [LC-1], magenta ink [LM-1], and yellow ink [LY-1] are diluted with the above-mentioned mixed solvent 1 so that the viscosity becomes 16 seconds (25 ° C., Zahn cup No. 3). bottom.
Using each diluted ink, a gravure calibration 5-color machine equipped with a gravure plate with a plate depth of 20 μm, black ink (Rio Alpha R92 ink (manufactured by Toyo Ink Co., Ltd.)), cyan ink [LC-1], magenta ink [ A corona-treated stretched polypropylene film (OPP substrate) having a thickness of 20 μm using an ink set 101 containing LM-1], yellow ink [LY-1], and white ink (Rioalpha R631 white (manufactured by Toyo Ink Co., Ltd.)). On the other hand, black ink, cyan ink [LC-1], magenta ink [LM-1], yellow ink [LY-1], and white ink are overprinted in this order, and each unit is dried at 50 ° C. , A printed matter having the composition of "OPP base material / black, cyan, magenta, yellow or white printing layer" was obtained.
Next, a urethane-based laminated adhesive (TM320 / CAT13B manufactured by Toyo Morton Co., Ltd., a non-volatile content 30% ethyl acetate solution) was applied onto the printed layer of the obtained printed matter so that the coating amount after drying was 2.0 g / m ² . After being coated and dried, an unstretched polyethylene (PE) film having a thickness of 50 μm is laminated on the adhesive layer to form an “OPP base material / 5-color layered printing layer / adhesive layer / PE base material”. Obtained a packaging material 1.

(Examples LP-2 to LP-64) Packaging materials 2 to 64
Packaging materials 2 to 64 having a desorption layer were obtained in the same manner as in Example LP-1 except that the ink set 101 used in Example LP-1 was changed to the ink set shown in Table 19.

(Example LP-101) Packaging material 101 The above-mentioned clear ink [1] is prepared to have a viscosity of 15 seconds (25 ° C., Zahn cup No. 3) by using an EA / IPA mixed solvent (mass ratio 70/30). Diluted to.
Cyan ink [LC-1], magenta ink [LM-1], and yellow ink [LY-1] are diluted with the above-mentioned mixed solvent 1 so that the viscosity becomes 16 seconds (25 ° C., Zahn cup No. 3). bottom.
Using each diluted ink, a gravure calibration five-color machine equipped with a gravure plate with a plate depth of 20 μm, clear ink [1], cyan ink [LC-1], magenta ink [LM-1], and yellow ink [ Using the ink set 201 containing LY-1], clear ink [1], cyan ink [LC-1], magenta ink [LM-1], and yellow ink were applied to a corona-treated stretched polypropylene film having a thickness of 20 μm. Overprinting is performed in the order of [LY-1], and each unit is dried at 50 ° C. to form "OPP substrate / desorption layer (clear ink) / cyan, magenta or yellow printing layer". , A printed matter containing a layer having desorption property was obtained.
Next, a laminate adhesive solution [1] was applied onto the printed layer of the obtained printed matter using a dry laminating machine, and an aluminum-deposited unstretched polypropylene (VMCPP) film having a thickness of 25 μm at a line speed of 40 m / min. The packaging material 101 having a detachable layer has a structure of "OPP base material / print layer having desorption property / three-color laminated printing layer / adhesive layer having desorption property / VMCPP base material". Obtained.

(Examples LP-102 to LP-164)
Packaging Materials 102 to 164 In the same manner as in Example LP-101 except that the ink set 201 used in Example LP-101 was changed to the ink set shown in Table 20, the packaging materials 102 to 164 having a desorbing layer were used. Obtained.

By using the gravure printing ink set of the present invention, a packaging material could be produced.

<Manufacturing of water-based inkjet ink> (Example MY-1)
(Preparation of Aqueous Coloring Composition for Inkjet (hereinafter referred to as "Aqueous Coloring Composition for IJ") [MY-1])
The following materials and 200 parts of 1.25 mm diameter zirconia beads were placed in a 200 ml glass bottle and dispersed in a paint shaker manufactured by Red Devil for 6 hours.
-Isoindoline compound (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 Then, the zirconia beads were removed from the above dispersion to obtain an aqueous coloring composition for IJ [MY-1].

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

(Examples MY-2 to MY-15, Production Examples MY-1 to MY-2, MC-1 to MC-3, MM-1 to MM-6)
(Water-based coloring composition for IJ [MY-2] to [MY-17], [MC-1] to [MC-3], [MM-1] to [MM-6], and water-based IJ ink [MY-]. 2]-[MY-17], [MC-1]-[MC-3], [MM-1]-[MM-6] preparation)
19.0 parts of the isoindoline compound (1-1) of Production Example MY-1 is shown in Table 21 in the same manner as in Example MY-1 except that the amounts are changed to the compounds shown in Table 21 and the amounts shown in Table 21. The water-based coloring compositions for IJ [MY-2] to [MY-17], [MC-1] to [MC-3], [MM-1] to [MM-6], and the water-based IJ ink [MY-] shown are shown. 2] to [MY-17], [MC-1] to [MC-3], and [MM-1] to [MM-6] were obtained.

Table 22 shows the pigments used in the production of the ink.

<Evaluation of viscosity stability of ink over time>
Water-based IJ inks [MY-1] to [MY-17], [MC-1] to [MC-3], [MM-1] to [MM-6] E-type viscometer (manufactured by Toki Sangyo Co., Ltd. The initial viscosity at 25 ° C. was measured using an ELD type viscometer "). Similarly, the viscosities after aging at 25 ° C. for 4 weeks and after aging 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 23. It is considered that the smaller the viscosity increase rate is, the better the viscosity stability is, and if it is "4", "3" and "2" in 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 of ink set>
[Examples MS-1 to MS-32, Comparative Examples MS-1 to MS-9]
The obtained water-based IJ inks were combined as shown in Table 23 to form ink sets 301 to 341.
Gamut was evaluated for the obtained ink set by the following method. The results are shown in Table 23.

[Gamut evaluation]
(Initial evaluation)
A line-pass type inkjet printer using an inkjet head (Kyocera's "KJ4B series") with a width resolution of 600 dpi and a maximum ejection frequency of 30 kHz, uses yellow ink, magenta ink, and cyan ink for each ink set. Fill the head and put it on coated paper (OK top coat N manufactured by Oji Paper Co., Ltd., basis weight 104.7 g / m ² ) with a resolution of 600 x 600 dpi, and a color chart image (chart image for profilemaker manufactured by X-rite "TC3". .5 CMYK i1_i0 ") was printed to prepare a printed matter for evaluation.

The color chart portion of the obtained evaluation printed matter was color-measured using a spectrophotometer (X-rite i1 i0 Pro) and a color measurement tool (X-rite Mechanism Tool and profilemaker), and L * a * b * The color reproduction area in the color space was plotted. The measurement conditions were light source D50, 2 degree visual field, and measurement optics 45/0 °. The area was calculated from each of the obtained plots. The area ratio when the area of the comparative example as a reference was set to 100% was obtained, and the area ratio was evaluated according to the following criteria. Specifically, Examples MS-1 to MS-12, MS-16 to MS-26, and Comparative Examples MS-3 to MS-8 were based on Comparative Example MS-1. Further, Examples MS-13 to MS-15 were based on Comparative Example MS-2. Further, Examples MS-27 to MS-32 were based on Comparative Example MS-9.
(Evaluation criteria)
◯: Area ratio is 90% or more (good)
Δ: Area ratio is 85% or more and less than 90% (usable)
X: Area ratio is less than 85% (cannot be used)

(Evaluation over time)
Each water-based IJ ink was placed in a closed container, stored at 50 ° C. for 4 weeks, and then printed in the same manner as in the initial evaluation to prepare a printed matter for evaluation. The color of the obtained printed matter was measured in the same manner as in the initial evaluation, and the area was obtained from each of the obtained plots. The area ratio of each Example / Comparative Example in the time-dependent evaluation was divided by the area of the initial evaluation, and the area ratio was evaluated according to the following criteria.
(Evaluation criteria)
◯: Area ratio is 98% or more (good)
Δ: Area ratio is 95% or more and less than 98% (practical)
X: Area ratio is less than 95% (defective)

According to Table 23, the water-based IJ ink set of the present invention had a gamut ratio of equal to or higher than that of the conventional ink set, and had good color reproducibility. In addition, the viscosity stability of the yellow ink over time was improved, and the storage stability of the ink set was good. Further, in terms of color reproducibility (gamut), the evaluation over time was good, and the storage stability as an ink set was good.

On the other hand, in Comparative Examples MS-1 to MS-9, the viscosity stability over time of the yellow ink was poor, and the color reproducibility (Gamut) was also poorly evaluated over time, so that the storage stability as an ink set was poor. The problem of the present application cannot be solved.

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%". In this specification, Examples 2-2, A-13, B-13, C-13, D-13, E-13, F-13, G-13, H-13, I-13, J- 13, K-14, LY-14, LS-13, LP13, LP-113, MY-14 and MS-13 are reference examples.

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 to R ₄ represent hydrogen atoms.
R ₅ and R ₆ each independently represent an alkyl group.
A and A'represent the 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 ₇ represents an alkyl or aryl group.
R ₈ to R ₁₄ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl group. ] A coloring composition comprising the pigment composition and the dispersion medium according to claim 1. A molding composition comprising 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.

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