JP7192639B2 - Isoindoline compound and its use - Google Patents

Description

The present disclosure relates to isoindoline compounds and pigments and coloring compositions comprising the isoindoline compounds. The present disclosure also relates to colorants for plastics, plastic moldings, toners, paints, printing inks, and inkjet inks containing the coloring compositions.

Pigments are typical colorants 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 to inorganic pigments in weather resistance and heat resistance. However, organic pigments are used in various applications because they are superior to inorganic pigments in terms of color vividness and tinting strength. For example, known organic pigments include azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, and quinacridone pigments.

On the other hand, in recent years, from an environmental point of view, there is an increasing demand for organic pigments and colorants that do not contain aromatic amines and heavy metals. Azo pigments are mainly used as organic pigments with hues ranging from yellow to red. Azo pigments contain aromatic amines in their components due to the raw materials used or decomposition due to light or heat. Sometimes. Therefore, in recent years, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 139, and C.I. I. Aromatic amine-free isoindoline pigments, such as Pigment Red 260, are of interest.

For example, Patent Document 1 discloses a method for producing an asymmetric isoindoline pigment. US Pat. No. 6,200,000 discloses isoindoline pigments for plastic coloring applications. US Pat. No. 5,300,000 discloses a dispersion for inkjet inks comprising water, a dispersant, and an isoindoline pigment.

JP-A-5-132630 Japanese Patent Publication No. 2009-543917 (Patent No. 5447833) JP-A-10-140066

When an isoindoline pigment is used to form a colored composition, the isoindoline pigment preferably exhibits excellent dispersibility in a dispersion medium and has excellent heat resistance and weather resistance. Insufficient dispersibility causes problems such as an increase in viscosity and a decrease in dispersion stability. Insufficient heat resistance and weather resistance also cause problems such as discoloration from yellow to black.

However, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 139, and C.I. I. Coloring compositions using conventional isoindoline pigments such as Pigment Red 260 have low dispersibility of the pigment itself, and the weather resistance and heat resistance are not sufficiently satisfactory, and the pigment and composition are limited depending on the application. there is

For example, in Patent Document 2, the dispersibility of an isoindoline pigment is improved by a specific crystallization process during pigment production for use in coloring plastics, but the pigment is C.I. I. Limited to Pigment Yellow 185. In addition, Patent Document 3 discloses a dispersion that requires the use of a dispersant for inkjet ink applications. tend to be poor. In the first place, since the dispersants that can be applied to isoindoline pigments are limited, there is a limit to improvement in dispersibility by dispersants.

Therefore, in view of the above situation, the present invention provides an isoindoline compound that has excellent dispersibility, excellent weather resistance and heat resistance, and can be applied to various uses.

The present inventors conducted various studies on various properties of compounds having an isoindoline structure. As a result, the present inventors have found that the isoindoline compound represented by the following formula (1) can be suitably used as a pigment, and have completed the present invention. That is, embodiments of the present invention relate to: However, the present invention is not limited to the following, and various modifications are possible.

[式中、Ｒ_１～Ｒ_６は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシル基、カルボキシル基、ニトロ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、チオアルキル基、チオアリール基、アミド基、又はスルホンアミド基を表し、
Ｒ_７、Ｒ_８は、それぞれ独立して、水素原子、又はアルキル基を表し、
Ａは、下式（２）、下式（３）、又は下式（４）で表される基を表し、

式中、Ｘは－Ｏ－又は－ＮＨ－を表し、Ｒ_９はアルキル基又はアリール基を表し、
Ｒ_１０、Ｒ_１１は、それぞれ独立して、水素原子、又はアルキル基を表し、
Ｒ_１２～Ｒ_１６は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、又はアリール基を表す。］ One embodiment relates to an isoindoline compound represented by the following formula (1).

[wherein R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, a thioaryl group, represents an amide group or a sulfonamide group,
R ₇ and R ₈ each independently represent a hydrogen atom or an alkyl group,
A represents a group represented by the following formula (2), (3), or (4),

In the formula, X represents -O- or -NH-, R ₉ represents an alkyl group or an aryl group,
R ₁₀ and R ₁₁ each independently represent a hydrogen atom or an alkyl group,
R ₁₂ to R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. ]

One embodiment relates to a coloring composition comprising a pigment comprising an isoindoline compound represented by formula (1) above and a dispersing medium.

One embodiment relates to a coloring composition, wherein the dispersion medium comprises a resin.

One embodiment relates to a plastic colorant comprising the coloring composition of the above embodiments.

One embodiment relates to a molded plastic article containing the colorant for plastics of the above embodiments.

One embodiment relates to a toner comprising the colored composition of the above embodiments.

One embodiment relates to a colored composition, wherein the dispersion medium comprises a resin and a solvent. The solvent preferably contains water.

One embodiment relates to paints or printing inks comprising the colored compositions of the above embodiments.

One embodiment relates to an inkjet ink comprising the colored composition of the above embodiments.

According to the present disclosure, a coloring composition containing an isoindoline compound is provided, which has excellent dispersibility, weather resistance, and heat resistance, and thus can be suitably used in various applications such as coloring of plastics, toners, paints, and printing inks. can do.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and includes various embodiments.
In the present specification, when expressed as "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", especially "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless means. Also, "C.I." described in this specification means color index (C.I.).

<Isoindoline compound (1)>
One embodiment relates to the isoindoline compound (1).

[Isoindoline compound (1)]
As used herein, "isoindoline compound (1)" means a compound having an isoindoline skeleton represented by the following formula (1). The isoindoline compound (1) may contain one or more compounds having an isoindoline skeleton represented by the following formula (1).

式（１）中、Ｒ_１～Ｒ_６は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシル基、カルボキシル基、ニトロ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、チオアルキル基、チオアリール基、アミド基、又はスルホンアミド基を表す。
Ｒ_７、Ｒ_８は、それぞれ独立して、水素原子、又はアルキル基を表す。

In formula (1), R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, or a thioaryl group, amide group, or sulfonamide group.
_R7 and _R8 each independently represent a hydrogen atom or an alkyl group.

式（２）中、Ｘは－Ｏ－又は－ＮＨ－を表し、Ｒ_９はアルキル基又はアリール基を表す。
式（３）中、Ｒ_１０、Ｒ_１１は、それぞれ独立して、水素原子、又はアルキル基を表す。
式（４）中、Ｒ_１２～Ｒ_１６は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、又はアリール基を表す。 A represents a group represented by the following formula (2), the following formula (3), or the following formula (4).

In formula (2), X represents -O- or -NH-, and R ₉ represents an alkyl group or an aryl group.
In formula (3), R ₁₀ and R ₁₁ each independently represent a hydrogen atom or an alkyl group.
In formula (4), R ₁₂ to R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group.

In formula (1), the halogen atoms in R ₁ to R ₆ are not particularly limited, but may be, for example, fluorine, chlorine, bromine, or iodine.

In formula (1), the alkyl group (--R) in R ₁ to R ₆ means an atomic group obtained by removing one hydrogen atom from a hydrocarbon. The number of carbon atoms is preferably 1-20, more preferably 1-10, even more preferably 1-6. Alkyl groups may be straight chain structures, branched structures, monocyclic structures, or condensed polycyclic structures.
Although not particularly limited, the alkyl group includes, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, or 4-decylcyclohexyl group.

At least one hydrogen atom of the alkyl group may be substituted with an amino group or another substituent such as a fluorine atom. That is, the alkyl group may be an alkylamino group, a fluoroalkyl group, or a perfluoroalkyl group. Specific examples of alkylamino groups include -CH ₂ -NH ₂ , -CH ₂ -NHR, -CH ₂ -NRR and the like. Specific examples of fluoroalkyl groups include monofluoromethyl, difluoromethyl, or trifluoromethyl groups.

The alkyl group may have a structure in which two or more alkyl groups (one of which is an alkylene group) are bonded to each other via a linking group. Specific examples of the linking group include an ester bond (--COO--), an ether bond (--O--), and a sulfide bond (--S--). That is, in one embodiment, the alkyl group may be, for example, a group represented by "-R'-OR"(R' represents an atomic group obtained by removing one hydrogen atom from the alkyl group ). A specific example is -C ₂ H ₄ -OC ₂ H ₅ .

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

In the above formula (1), the alkoxy group in R ₁ to R ₆ is a group (-OR) in which an oxygen atom is bonded to the above alkyl group (-R).

In the above formula (1), the aryl group (--Ar) in R ₁ to R ₆ means an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The number of carbon atoms is preferably 6-30, more preferably 6-20.
Although not particularly limited, the aryl group includes, for example, a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentalenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tanaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acephenanthrilenyl group, aceanthrilenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preiadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubisenyl group , a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an ovalenyl group, or the like.
In one embodiment, the aryl group is preferably a phenyl group.

In the above formula (1), the aryloxy group in R ₁ to R ₆ is a group (-OAr) in which an oxygen atom is bonded to the above aryl group (-Ar). In one embodiment, the aryloxy group is preferably a phenoxy group.

In formula (1), the amide group in R ₁ to R ₆ is a group (—CONHR) in which an amide group is linked to the above alkyl group. In one embodiment, the amide group is preferably a group in which an amide group is bonded to an alkyl group having a linear structure.

In formula (1), the sulfonamide group in R ₁ to R ₆ is a group (—SO ₂ NHR) in which a sulfonamide group is linked to the above alkyl group. In one embodiment, the sulfonamide group is preferably a group in which a sulfonamide group is bonded to an alkyl group having a linear structure.

In the above formula (1), the thioalkyl group in R ₁ to R ₆ is a group (-SR) in which a sulfur atom is bonded to the above alkyl group. In one embodiment, the thioalkyl group may preferably be a group in which a sulfur atom is attached to an alkyl group having a linear structure. A thioaryl group is a group (-SAr) in which a sulfur atom is bonded to the above aryl group. In one embodiment, the thioaryl group is preferably a thiophenyl group.

In one embodiment, R ₁ to R ₆ in the above formula (1) are each independently a hydrogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an alkoxy group. (the alkyl group has 1 to 6 carbon atoms), a phenyl group, a phenoxy group, an amide group, a sulfonamide group, a thioalkyl group (the alkyl group has 1 to 6 carbon atoms), and a thiophenyl group. is preferred.

In formula (1), R ₇ and R ₈ each independently represent a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group (-R) is preferably 1-20, more preferably 1-10, even more preferably 1-6. Alkyl groups may be straight chain structures, branched structures, monocyclic structures, or condensed polycyclic structures.

Although not particularly limited, alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl and isobutyl groups. , isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, It may be a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like.

At least one hydrogen atom of the alkyl group may be substituted with an amino group or another substituent such as a fluorine atom. That is, the alkyl group may be an alkylamino group, a fluoroalkyl group, or a perfluoroalkyl group. Specific examples of alkylamino groups include -CH ₂ -NH ₂ , -CH ₂ -NHR, -CH ₂ -NRR and the like. Specific examples of fluoroalkyl groups include monofluoromethyl, difluoromethyl, or trifluoromethyl groups.

From the viewpoint of heat resistance, weather resistance, and dispersion stability, R ₇ and R ₈ are preferably independently selected alkyl groups rather than hydrogen atoms. That is, in one embodiment, at least one of R ₇ and R ₈ is preferably an alkyl group, more preferably both are alkyl groups, and even more preferably the same alkyl group. In one embodiment, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.

In the above formula (2), X represents -O- or -NH-, preferably -NH-.
In R ₉ , the alkyl group and the aryl group are as defined above. 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, more preferably an alkyl group having 1 or 2 carbon atoms.

In formula (3), R ₁₀ and R ₁₁ each independently represent a hydrogen atom or an alkyl group.
The number of carbon atoms in the alkyl group (-R) is preferably 1-20, more preferably 1-10, even more preferably 1-6. Alkyl groups may be straight chain structures, branched structures, monocyclic structures, or condensed polycyclic structures.

Although not particularly limited, the alkyl group includes, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoro methyl group, isopropyl group, 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, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl, 4-decylcyclohexyl and the like.

From the viewpoint of heat resistance, weather resistance, and dispersion stability, R ₁₀ and R ₁₁ are preferably alkyl groups rather than hydrogen atoms. In one embodiment, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.

In the above formula (4), the halogen atom, alkyl group, alkoxy group, or aryl group for R ₁₂ to R ₁₆ has the same meaning as described above for R ₁ to R ₆ .

[Method for producing isoindoline compound (1)]
The isoindoline compound (1) used in this embodiment can be produced by a known synthesis method. For example, as shown in Scheme 1 below, naphthalonitrile represented by formula (5) (hereinafter referred to as compound (5)) or benzoisoindoline represented by formula (6) (hereinafter referred to as compound (6) ) can be synthesized as a starting material.
The synthesis method will be described below along with specific examples of the isoindoline compound (1). In the following explanation, the number described in each formula is described as the number of the compound.

(Compound where A is formula (2))
In one embodiment, isoindoline compound (1) can be prepared according to Scheme 1 below.

Scheme 1 is a first step (S1) in which compound (5) is reacted with a base in a solvent to obtain compound (6); a second step (S2) of reacting; and then a third step (S3) of reacting compounds (8) and (9) with compound (10) in the presence of acetic acid. The reaction in each step in Scheme 1 is preferably carried out at 10-100°C.

When the relationship between the substituents R ₁ and R ₆ , R ₂ and R _{5 ,} and R ₃ and R ₄ of compound (5) used as a starting material is asymmetric, the product resulting from the addition of compound (7) is It is obtained as a mixture of isomers differing in the position of the substituents, represented by compounds (8) and (9). Similarly, the final product is obtained as a mixture of isomers with different substituent positions, as represented by compounds (11) and (12).
Also, when the relationship between the substituents _R7 and R8 of compound ( ₁₀ ) is asymmetrical, the final product is obtained as a mixture of isomers.
On the other hand, the relationship between the substituents R ₁ and R ₆ , R ₂ and R _{5 ,} R ₃ and R ₄ of the compound (5) used as the starting material, and the substituents R ₇ and R ₈ of the compound (10) are all symmetrical. , the final product is a single compound. The isoindoline compound (1) may be either a mixture containing isomers or a single compound.

Solvents used in the first step (S1) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and glycol, ethers such as glycol ethers and tetrahydrofuran, formamide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. may be acyclic or cyclic amides of Among these, acyclic or cyclic amides are preferred, and tetrahydrofuran or formamide is more preferred.

A solvent may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the solvent used is preferably 5 to 15 times, more preferably 5 to 10 times, the amount of 100 parts by mass of compound (5).

Bases are, for example, alkali metal hydroxides, alkali metals such as lithium, sodium or potassium, alkali metal amides, alkali metal hydrides; Alkali metal or alkaline earth metal alkoxides derived from secondary or tertiary fatty alcohols may be mentioned. Among these, sodium hydroxide or potassium carbonate is preferred.

Alternatively, the isoindoline compound (1) can be produced, for example, according to Scheme 2 below.

Scheme 2 is the second step (S2) of reacting compound (6) with compound (7) in the presence of an aqueous ammonia solution; A third step (S3) of reacting with compound (10) may be included.
In the second step (S2) of Scheme 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 (6) when a 28% aqueous ammonia solution is used. Five times the amount is more preferred.
Although not particularly limited, the isoindoline compound (1) used in the pigment of the present embodiment is preferably produced according to Scheme 2.

(Compound where A is formula (3))
In one embodiment, isoindoline compound (1) can be prepared according to Scheme 3 below.

Scheme 3 is a first step (S1) in which compound (5) is reacted with a base in a solvent to obtain compound (6); Second step of reacting (S2); Then, a third step (S3) of reacting compounds (13) and (14) with compound (15) in the presence of acetic acid may be included. The reaction in each step in Scheme 3 is preferably carried out at 10-100°C.

When the relationship between the substituents R ₁ and R ₆ , R ₂ and R _{5 ,} and R ₃ and R ₄ of compound (5) is asymmetric, the products resulting from the addition of compound (10) are compound (13) and As represented by (14), it is obtained as a mixture of isomers with different substituent positions. Similarly, the final product is obtained as a mixture of isomers with different substituent positions, as represented by compounds (16) and (17).
Also, when the relationship between the substituents _R7 and R8 of compound ( ₁₀ ) is asymmetrical, the product is obtained as a mixture of isomers. Furthermore, when the relationship between substituents _R10 and R11 in compound ( ₁₅ ) is asymmetrical, the product is obtained as a mixture of isomers.
On the other hand, substituents R ₁ and R ₆ , R ₂ and R _{5 ,} and R ₃ and R ₄ of compound (5), substituents R ₇ and R ₈ of compound (10), and substituent R of compound (15) If all the relationships between ₁₀ and R ₁₁ are symmetrical, the final product will be a single compound. The isoindoline compound (1) may be either a mixture containing isomers or a single compound.

Solvents used in the first step (S1) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol and glycol; ethers such as glycol ethers and tetrahydrofuran; and formamide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like It may be an acyclic or cyclic amide. Among these, acyclic or cyclic amides are preferred, and tetrahydrofuran or formamide is more preferred.

A solvent may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the solvent used is preferably 5 to 15 times, more preferably 5 to 10 times, the amount of 100 parts by mass of chemical formula (5).

Bases are, for example, alkali metal hydroxides, alkali metals such as lithium, sodium or potassium, alkali metal amides, alkali metal hydrides; Alkali metal or alkaline earth metal alkoxides derived from secondary or tertiary fatty alcohols may be mentioned. Among these, sodium hydroxide or potassium carbonate is preferred.

Alternatively, the isoindoline compound (1) can be produced according to Scheme 4 below.

Scheme 4 shows the second step (S2) of reacting compound (6) with compound (10) in the presence of acetic acid; 15) may include a third step (S3) of reacting with.

(Compound where A is formula (4))
In one embodiment, isoindoline compound (1) can be prepared according to Scheme 5 below.

Scheme 5 is a first step (S1) of reacting compound (5) with a base in a solvent to obtain compound (6); a second step (S2) of reacting; and then a third step (S3) of reacting compounds (19) and (20) with compound (10) in the presence of acetic acid. The reaction in each step in Scheme 5 is preferably carried out at 10-100°C.

When the relationship between the substituents R ₁ and R ₆ , R ₂ and R _{5 ,} and R ₃ and R ₄ of compound (5) used as a starting material is asymmetric, the product resulting from the addition of compound (18) is It is obtained as a mixture of isomers differing in the position of the substituents, represented as compounds (19) and (20). Similarly, as shown by compounds (21) and (22), the final product is also obtained as a mixture of isomers with different substituent positions.
Also, when the relationship between the substituents _R7 and R8 of compound ( ₁₀ ) is asymmetrical, the final product is obtained as a mixture of isomers.
On the other hand, the relationship between the substituents R ₁ and R ₆ , R ₂ and R _{5 ,} R ₃ and R ₄ of the compound (5) used as the starting material, and the substituents R ₇ and R ₈ of the compound (10) are all symmetrical. , the final product is a single compound. The isoindoline compound (1) may be either a mixture containing isomers or a single compound.

Solvents used in the first step (S1) include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and glycol; ethers such as glycol ethers and tetrahydrofuran; formamide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. may be acyclic or cyclic amides of Among these, acyclic or cyclic amides are preferred, and tetrahydrofuran or formamide is preferred.

A solvent may be used individually by 1 type, or may be used in combination of 2 or more type. The amount of the solvent used is preferably 5 to 15 times, more preferably 5 to 10 times, the amount of 100 parts by mass of compound (5).

Bases are, for example, alkali metal hydroxides, alkali metals such as lithium, sodium or potassium, alkali metal amides, alkali metal hydrides; Alkali metal or alkaline earth metal alkoxides derived from secondary or tertiary fatty alcohols may be mentioned. Among these, sodium hydroxide or potassium carbonate is preferred.

Alternatively, the isoindoline compound (1) can be produced according to Scheme 6 below.

Scheme 6 is the second step (S2) of reacting compound (6) with compound (18) in the presence of an aqueous ammonia solution; A third step (S3) of reacting with compound (10) may be included.
In the second step (S2) of Scheme 6, the amount of the aqueous ammonia solution used is preferably 1 to 20 times the amount of 100 parts by mass of the compound (6) when a 28% aqueous ammonia solution is used. Five times the amount is more preferred.

The isoindoline compound (1) is characterized by a benzoisoindoline ring obtained by extending the isoindoline ring. That is, by introducing a benzoisoindoline ring, dispersibility, weather resistance, and heat resistance can be remarkably improved as compared with conventional isoindoline pigments. Therefore, the isoindoline compound (1) can be suitably used in a variety of applications, including water-based paints, printing inks, and inkjet inks for which it has been difficult to apply isoindoline pigments. .
The content of the isoindoline compound (1) is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the pigment. . In one embodiment, the content of the isoindoline compound (1) in the pigment may be 100% by mass.

Although not particularly limited, preferred forms of the isoindoline compound (1) include the following. In addition, when the compounds described in each table have isomers, they may be a mixture containing those isomers. Also, both the C ₆ H ₁₃ group _{and the} Bu (butyl) group are linear.

Specific examples of compounds (11) and (12) shown in schemes 1 and 2

Specific examples of compounds (16) and (17) shown in schemes 3 and 4

Specific examples of compounds (21) and (22) shown in schemes 5 and 6

<Coloring composition>
One embodiment relates to a coloring composition comprising a pigment comprising isoindoline compound (1) and a dispersing medium.

[Dispersion medium]
The dispersion medium in the coloring composition may be a component other than the pigment that constitutes the coloring composition, but in the present specification, the dispersion medium means at least a resin and/or a solvent. The dispersion medium can be appropriately selected according to the application of the coloring composition. Applications of the coloring composition include, for example, coloring agents for plastics, plastic molding materials, plastic moldings, toners, pigment dispersions, paints, printing inks, inkjet inks, and the like. The coloring composition can be obtained by mixing a pigment containing the isoindoline compound (1) with a dispersion medium and subjecting the mixture to a dispersion treatment according to a method known in the art. Hereinafter, the coloring composition will be described in more detail along with specific uses.

(Coloring composition for plastic)
In one embodiment, the coloring composition can be suitably used in plastic coloring applications. In one embodiment, the coloring composition for plastics contains a pigment containing the isoindoline compound (1) and a resin. Coloring compositions for plastics are required to have durability such that they do not discolor even after heating at a high temperature of 300° C., for example. On the other hand, according to the colored composition containing the isoindoline compound (1), excellent weather resistance and heat resistance can be easily obtained.

In the coloring composition for plastics, the resin used as the dispersion medium is not particularly limited, but a partially crystalline resin is preferable. For example, it may be a homopolymer or copolymer using ethylene, propylene, butylene, styrene, or the like as a monomer component. More specifically, polyethylene such as high-density polyethylene (HDPE), linear low-density polyethylene (L-LDPE) and low-density polyethylene (LDPE), and polyolefin resin such as polypropylene and polybutylene can be used. Specific examples of other useful resins include polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polystyrene resins, and thermoplastic ionomer resins.

In one embodiment, the resin preferably contains at least one of polyolefin resin and polyester resin. In one embodiment, the resin preferably contains at least a polyolefin resin. When a polyolefin resin is used, there is a tendency that a more remarkable effect is obtained in improving the dispersibility, weather resistance, and heat resistance of the coloring composition.

As one embodiment of the coloring composition for plastics, a so-called masterbatch or a pellet-like form called a color chip containing a high concentration of the isoindoline compound (1) functioning as a pigment (hereinafter referred to as a coloring agent for plastics Also called).

(Plastic molding material)
As another embodiment, a coloring composition for forming a plastic molded article (hereinafter also referred to as a plastic molding material) by adding a resin to a plastic coloring agent containing a high concentration of the isoindoline compound (1). can also be configured. Accordingly, one embodiment may be a plastic molding compound comprising the plastic colorant described above. In the plastic molding material, the resin (base resin) added to the plastic colorant is not particularly limited, and can be selected from resins known in the art according to the use of the plastic molded product. The same resin as that used for the colorant for plastics may be used.

In one embodiment, a polyolefin resin can also be suitably used as the base resin of the plastic molding material. The polyolefin resin to be used preferably has an MFR (melt flow rate, so-called melt viscosity) in the range of 0.001 to 30. If the MFR is 0.001 or more, the molding processability of the plastic molding material is good, and weld marks or flow marks are less likely to occur in the molded product. On the other hand, when the MFR is 30 or less, excellent mechanical properties can be easily obtained in the molded product. In particular, when using high density polyethylene (HDPE), the MFR is preferably in the range of 0.005 to 10. Also, when low-density polyethylene (LDPE), polypropylene, or polybutene is used, the MFR is preferably in the range of 0.005 to 20.

The plastic coloring agent and plastic molding material may further contain other additive components within a range that does not impair the desired effect and that does not pose a sanitary problem.
Additives include waxes or derivatives thereof; heavy metal deactivators, alkali metals, alkaline earth metals or zinc metal soaps; hydrotalcite; nonionic surfactants, cationic surfactants, anionic surfactants, antistatic agents consisting of amphoteric surfactants; flame retardants such as halogen-based, phosphorus-based or metal oxides; lubricants such as ethylenebisalkylamide; antioxidants and UV absorbers; Examples include various additives for polymers. For the purpose of adjusting the color tone, an inorganic pigment or an organic pigment other than the isoindoline compound (1) may be added, if necessary.

(Plastic molded product)
In one embodiment, a molding method for obtaining a plastic molded article made of a plastic coloring agent such as a color chip and a plastic molding material is not particularly limited. Examples of molding methods include blow molding, inflation molding, extrusion molding, Engel molding, and vacuum molding. Due to the improved dispersibility and heat resistance of the isoindoline compound (1) contained in the colorant for plastics and the plastic molding material, discoloration does not occur even after heating at a high temperature during molding, and the desired hue is maintained well. Plastic moldings can be obtained.

(toner)
In one embodiment, the coloring composition can be suitably used in toner applications. The coloring composition for toner contains a pigment containing the isoindoline compound (1) and a binder resin. When the coloring composition is used as a toner, it is preferable that the coloring composition does not discolor under a use environment involving heating and irradiation with UV light, for example. On the other hand, the colored composition containing the isoindoline compound (1) has excellent weather resistance and heat resistance, so discoloration is suppressed and the desired hue can be maintained.

The toner may be either dry toner or liquid toner. For example, a dry toner can be produced by melting and kneading a toner coloring composition containing the isoindoline compound (1) and a binder resin, cooling, pulverizing, and classifying. It can be manufactured through a post-treatment process of adding and mixing components. Toners can also be manufactured using the toner coloring composition according to other methods known in the art.

The binder resin constituting the coloring composition for toner is not particularly limited, but examples include styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid. Ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer , styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin, etc. good.

In one embodiment, the binder resin preferably contains a polyester resin or a styrenic copolymer, and preferably contains at least a polyester resin. Among the above binder resins, the isoindoline compound (1) has particularly excellent suitability for polyester resins. Therefore, in one embodiment, the coloring composition for toner preferably contains the isoindoline compound (1) and a binder resin containing a polyester resin. In such a toner coloring composition, the isoindoline compound is uniformly and finely dispersed in the binder resin containing the polyester resin, so that a high-quality toner can be provided.

The polyester resin used as the binder resin may be a resin obtained by reaction between an alcohol component and an acid component. Examples of alcohol components constituting the polyester resin include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1, 4-butenediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, bisphenol A, hydrogenated bisphenol A, 1, 4-bis(hydroxymethyl)cyclohexane, glycerol, diglycerol, sorbitol, sorbitan, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol, and represented by the following formula (D) Polyhydric alcohols such as bisphenol derivatives can be used. One of these may be used alone, or two or more may be used in combination.

In the formula, R _A is an ethylene group or a propylene group, x and y are each integers of 1 or more, and x+y is 2-10.

The acid component that constitutes the polyester resin may be a divalent carboxylic acid. Examples of divalent carboxylic acids include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or their anhydrides; aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; Acids or anhydrides thereof; succinic acid substituted with an alkyl group having 16 to 18 carbon atoms or anhydrides thereof; aliphatic unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof; mentioned.

As the acid component, a carboxylic acid having a valence of 3 or higher, which is effective as a cross-linking component, may be used. For example, trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, butanetricarboxylic acid, hexanetricarboxylic acid, benzophenonetetracarboxylic acid, tetra(methylenecarboxyl)methane, octanetetracarboxylic acid, and benzophenonetetracarboxylic acid and their anhydrides etc.
As the acid component, one of the exemplified compounds may be used alone, or two or more may be used in combination.

The polyester resin may be either a homopolyester or a copolyester obtained by reacting an alcohol component and an acid component. One type of polyester resin may be used alone, or two or more types may be used in combination.

In one embodiment, the weight average molecular weight (Mw) of the polyester resin is preferably 5,000 or more, and more preferably in the range of 10,000 to 1,000,000, from the standpoint of offset resistance and low-temperature fixability of the toner. , 20,000 to 100,000 is more preferred. The weight average molecular weight means a molecular weight measured by gel permeation chromatography (GPC). When the weight average molecular weight is 5,000 or more, the toner can easily have excellent offset resistance. Also, when the weight average molecular weight is 1,000,000 or less, excellent fixability can be easily obtained.

In one embodiment, the acid value of the polyester resin is preferably in the range of 10-60 mgKOH/g, more preferably in the range of 15-55 mgKOH/g. When the acid value is adjusted to 10 mgKOH/g or more, liberation of the release agent can be easily suppressed. Further, when the acid value is adjusted to 60 mgKOH/g or less, it is possible to suppress the increase in hydrophilicity of the resin and prevent the decrease in image density in a high-humidity environment.

In one embodiment, the hydroxyl value of the polyester resin is preferably 20 mgKOH/g or less, more preferably 15 mgKOH/g or less. When the hydroxyl value is adjusted to 20 mgKOH/g or less, it is possible to suppress an increase in the hydrophilicity of the resin and suppress a decrease in image density in a high-humidity environment.

From the viewpoint of preventing aggregation of the toner, the polyester resin preferably has a glass transition temperature (Tg) of 50 to 70° C. measured by a differential scanning calorimeter (device: DSC-6, manufactured by Shimadzu Corporation). It is more preferably 50 to 65°C.

A charge control agent may be added to the toner coloring composition, if necessary. When a charge control agent is used, a toner with a stable charge amount can be easily obtained. The charge control agent added to the toner coloring composition may be any of conventionally known positive or negative charge control agents.

In one embodiment, when the toner is a positively charged toner, specific examples of positive charge control agents that can be used include nigrosine-based dyes, triphenylmethane-based dyes, organic tin oxides, quaternary ammonium salt compounds, and quaternary ammonium salt compounds. Examples include styrene-acrylic polymers obtained by copolymerizing styrene-acrylic resins with polyammonium salts as functional groups. Among them, quaternary ammonium salt compounds are preferred. Specific examples of quaternary ammonium salt compounds that can be used include salt-forming compounds comprising a quaternary ammonium salt and an organic sulfonic acid or molybdic acid. As the organic sulfonic acid, naphthalenesulfonic acid is preferably used.

On the other hand, when the toner is a negatively charged toner, specific examples of negative charge control agents that can be used include a metal complex of a monoazo dye, and a styrene-acrylic polymer copolymerized with a styrene-acrylic resin using sulfonic acid as a functional group. , metal salt compounds of aromatic hydroxycarboxylic acids, metal complexes of aromatic hydroxycarboxylic acids, phenolic condensates, and phosphonium compounds. Preferred aromatic hydroxycarboxylic acids are salicylic acid, 3,5-di-tert-butylsalicylic acid, 3-hydroxy-2-naphthoic acid and 3-phenylsalicylic acid. Moreover, zinc, calcium, magnesium, chromium, aluminum, etc. are mentioned as a metal used for a metal salt compound.

Further, a releasing agent can be used for the coloring composition for toner. Examples of release agents include hydrocarbon waxes such as polypropylene wax, polyethylene wax and Fischer-Tropsch wax, natural ester waxes such as synthetic ester waxes, carnauba wax and rice wax.

Furthermore, external additives such as a lubricant, a fluidizing agent, an abrasive, a conductivity imparting agent, and an image peeling preventive agent may be added to the toner coloring composition, if necessary. These external additives can be selected from known external additives conventionally used for producing toners.

Specific examples of external additives include the following.
Lubricants may be polyvinylidene fluoride, zinc stearate, and the like. The fluidizing agent may be silica, aluminum oxide, titanium oxide, silicon-aluminum co-oxide, silicon-titanium co-oxide, produced by a dry method or a wet method, or those obtained by hydrophobilizing them. The abrasive may be silicon nitride, cerium oxide, silicon carbide, strontium titanate, tungsten carbide, calcium carbonate, or those obtained by hydrophobizing them. The conductivity imparting agent may be tin oxide or the like.

Among the fluidizing agents exemplified above, at least one of hydrophobized silica, silicon-aluminum co-oxide, and silicon-titanium co-oxide fine powder is preferably used in the toner coloring composition. Examples of the hydrophobizing treatment method for these fine powders include treatment with silicone oil or a silane coupling agent such as tetramethyldisilazane, dimethyldichlorosilane, dimethyldimethoxysilane, or the like.

In one embodiment, the toner formed from the toner coloring composition can be used as a one-component developer. In other embodiments, the toner can also be used as a two-component developer. When the toner is used as a two-component developer, the toner coloring composition further contains a carrier. Carriers for toners used as two-component developers can be any material known in the art.

Examples of materials that can be used as carriers include magnetic powders such as iron powder, ferrite powder, and nickel powder, and those whose surfaces are treated with resin or the like. Examples of resins that coat the surface of the carrier include styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, fluorine-containing resins, silicone-containing resins, polyamides. Resins, ionomer resins, polyphenylene sulfide resins, etc., or mixtures thereof can be used. Among these, silicone-containing resins are particularly preferred because they are less likely to form spent toner. The weight average particle size of these carriers is preferably in the range of 30 to 100 μm.

(Pigment dispersion)
In one embodiment, the coloring composition may be a pigment dispersion suitable for making paints, printing inks, inkjet inks, and the like. That is, in one embodiment, the coloring composition may be a pigment dispersion containing a pigment containing the isoindoline compound (1), and a resin and a solvent as dispersion media.

It is preferable that the coloring composition configured as a pigment dispersion is less likely to increase in viscosity after the dispersion treatment and has excellent dispersion stability of the pigment. For example, when it is assumed to be used as a film-forming material such as paint and printing ink, it is preferable that a film having excellent light resistance can be formed and that the initial viscosity and storage stability are good.
However, since conventional isoindoline pigments themselves have low dispersibility, they are often used in combination with dispersants of polymer compounds. Therefore, pigment dispersions using conventional isoindoline pigments tend to have high initial viscosities and poor storage stability. On the other hand, when a pigment dispersion is formed using a coloring composition containing the isoindoline compound (1), it is possible to provide a pigment dispersion excellent in dispersibility, initial viscosity and storage stability.

(Paints, printing inks)
In one embodiment, the coloring composition can be used as a pigment dispersion to form a composition that makes up a paint or printing ink. The forms of paints and printing inks are not particularly limited, and various general paints for automobiles, wood, metals, etc., magnetic tape backcoat paints, radiation cure inks, color filter inks, and ink jet printers described later. It may be ink or the like. The printing inks may be in the form of inks usable in offset, flexographic and gravure printing.

The solvent may be water and/or an organic solvent, and can be appropriately selected according to the desired form of paint or printing ink. In one implementation, the pigment dispersion comprises a pigment comprising isoindoline compound (1), and a resin and water as dispersion media. In another embodiment, the pigment dispersion contains a pigment containing the isoindoline compound (1), and a resin, water and an organic solvent as dispersion media. In the above embodiment, the water and organic solvent used as the dispersion medium can also be used as a diluent solvent in order to obtain the desired viscosity according to the application of the pigment dispersion. As an example, paint and printing ink will be specifically described below.

In the above embodiment, the resin is preferably a polymer capable of forming a coating film (hereinafter referred to as a coating film-forming polymer).
A film-forming polymer functions as a vehicle component. For example, the main component of the vehicle component can be selected from acrylic resins, alkyd resins, polyester resins, amino resins, epoxy resins, modified resins thereof, and the like. Furthermore, as a vehicle component, if necessary, it is preferable to use a curing agent or cross-linking agent for an amino resin, an isocyanate compound, a blocked isocyanate compound, a polyamide resin, a melamine resin, or the like.

For example, in the case of non-aqueous paints or printing inks, toluene, xylene, butyl acetate, methyl acetate, methyl ethyl ketone, methyl isobutyl ketone, butyl alcohol, and aliphatic hydrocarbons can be used as solvents. In addition, solvents commonly used in the technical field of paints or printing inks can also be used.

In the case of water-based paints or printing inks, water or water-dilutable monohydric or dihydric alcohols and glycols can be used as solvents. Specific examples include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin. As solvents it is also possible to use water-dilutable monoethers derived from polyhydric alcohols. Specific examples include methoxypropanol or methoxybutanol. Additionally, water-dilutable glycol ethers such as, for example, butyl glycol or butyl diglycol can be used. These may be used alone or in combination of two or more.

In one embodiment, the paint or printing ink may be composed of a pigment containing the isoindoline compound (1), a film-forming polymer, and a solvent, and if necessary, other components may be added. good.

For example, in one embodiment, metal flakes, mica, and coated glass flakes having an average thickness of 0.5 to 10 μm and an average particle size of 5 to 50 μm may be added as glittering materials. Commonly used metal flakes and mica can be used. Examples of metal flakes include aluminum flakes and gold powder, examples of mica include ordinary mica and coated mica, and examples of coated glass flakes include those coated with a metal oxide such as titanium oxide. Glass flakes can be exemplified.

The amount of the glitter material is 0.1 to 10% by mass based on the total mass of the pigment containing the isoindoline compound (1), the film-forming polymer, and the paint or printing ink containing the solvent. A range is preferred. In addition, other color pigments and various additives commonly used in the technical field may be blended as needed. There are no particular restrictions on the method of producing the paint or printing ink, or the methods of coating and drying, and methods well known in the art can be applied.

(Aqueous pigment dispersion)
Conventional isoindoline pigments have poor dispersibility and are difficult to use in aqueous systems. On the other hand, according to the coloring composition containing the isoindoline compound (1) of the above embodiment, dispersibility can be improved. Therefore, even when water is used as a dispersion medium, it is possible to provide an aqueous pigment dispersion that is excellent in dispersibility, suppresses an increase in viscosity, and has excellent dispersion stability. Therefore, one preferred embodiment relates to a water-based pigment dispersion constructed using the coloring composition. In water-based pigment dispersions, the solvent may be water and/or an organic solvent. Water-based pigment dispersions can be suitably used in applications such as water-based paints, printing inks, and inkjet inks. The water-based pigment dispersion will be described in more detail below.

In one embodiment, the aqueous pigment dispersion comprises an isoindoline compound (1), a resin, and water.
The resin constituting the water-based pigment dispersion preferably contains a water-soluble resin. Examples of water-soluble resins include styrene-acrylic acid copolymer, acrylic acid-acrylic acid acrylic ester copolymer, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid Acid-acrylic acid acrylic ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer, polyacrylic acid, polymethacrylic acid, vinyl Naphthalene-acrylic acid copolymer salts, styrene-maleic acid copolymer salts, maleic acid-maleic anhydride copolymer salts, vinylnaphthalene-maleic acid copolymer salts, and polyester-modified acrylic acid polymers etc. can be mentioned.

Moreover, when preparing the water-soluble resin, a resin obtained by copolymerizing monomers such as acrylonitrile, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride, ethylene, and hydroxyethyl acrylate may be used. One type of these exemplified resins may be used alone, or two or more types may be used in combination.
The above resin can be used in an amount of 0.1 to 30% by weight, preferably 1 to 15% by weight, based on the total weight of the aqueous pigment dispersion.

The water-based pigment dispersion may further contain a surfactant, if necessary. Surfactants may be either anionic or nonionic, and any compound capable of functioning as a dispersant can be used without particular limitation.

Examples of anionic surfactants include fatty acid salts, alkyl sulfates, alkylarylsulfonates, alkylnaphthalenesulfonates, dialkylsulfonates, dialkylsulfosuccinates, alkyldiaryletherdisulfonates, and alkylphosphates. , polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphate ester salts, glycerol borate fatty acid esters, and polyoxyethylene glycerol fatty acid esters. can be done.

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethyleneoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, Examples include polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.
One of these surfactants may be used alone, or two or more may be used in combination.

The surfactant can be used in an amount of 0.3 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the aqueous pigment dispersion.

The aqueous pigment dispersion can be configured using a pigment containing the isoindoline compound (1) and a coloring composition containing a resin and water as a dispersion medium, but preferably further contains a pigment dispersant. A diluting solvent may be added to the water-based pigment dispersion to obtain the desired viscosity. An aqueous solvent is preferably used as the diluent solvent. In order to obtain desired ink properties and film properties, it is preferable to add a resin as a vehicle component, if necessary.

In one embodiment, the water-based pigment dispersion comprises a pigment containing the isoindoline compound (1), a pigment dispersion containing a resin and a solvent as a dispersion medium, and optionally a diluent solvent containing an aqueous solvent, the pigment Dispersants, resins as vehicle components, surfactants, and the like may be included. The water-based pigment dispersion can be prepared by subjecting the mixture of the raw materials to dispersion treatment using various dispersers. In addition, if necessary, various additives may be added to the above raw materials and subjected to dispersion treatment. In the preparation of the water-based pigment dispersion, the addition order or addition method of each raw material is not particularly limited, and methods known in the art can be applied.

In the water-based pigment dispersion, the amount of the pigment containing the isoindoline compound (1) (also referred to as a pigment composition) is not particularly limited. In one embodiment, the content of the pigment composition is desirably adjusted within the range of 5 to 40% by mass based on the total mass of film-forming components in the aqueous pigment dispersion. Particularly preferably, the content may be between 10 and 25% by weight.

Although the type of diluent solvent used for producing the water-based pigment dispersion is not particularly limited, water-based solvents are preferred. Among them, it is preferable to use ion-exchanged water or distilled water from which metal ions and the like have been removed. Although the content of the aqueous solvent in the aqueous pigment dispersion is not particularly limited, it is preferably 30 to 95% by mass.

Water and/or water-soluble solvents can be used as the aqueous solvent. Water-soluble solvents include, but are not limited to, 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. One of these may be used alone, or two or more may be used in combination. When using these water-soluble solvents, the content of the water-soluble solvent in the water-based pigment dispersion is preferably 1 to 50% by mass.

The resin used as the vehicle component for producing the aqueous pigment dispersion is not particularly limited as long as it can disperse the pigment containing the isoindoline compound (1) in an aqueous medium (aqueous solvent). For example, resins exemplified as water-soluble resins that can be used when producing a pigment dispersion can be used. One of these water-soluble resins may be used alone, or two or more of them may be used in combination. Although the amount of the resin used in the water-based pigment dispersion is not particularly limited, it is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass.

If necessary, a surfactant may be used to produce the water-based pigment dispersion. The surfactant is not particularly limited as long as it can disperse the pigment containing the isoindoline compound (1) in the aqueous medium. For example, compounds exemplified as surfactants that can be used in the production of pigment dispersions can be used. One of these surfactants may be used alone, or two or more may be used in combination. The amount of surfactant used in the water-based pigment dispersion is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

Furthermore, additives such as preservatives, pH adjusters, antifoaming agents, wetting agents and the like can be used as necessary to produce the aqueous pigment dispersion.

Preservatives are used to prevent the development of mold and bacteria in aqueous pigment dispersions. The type of antiseptic is not particularly limited, but for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1- and amine salts of benzisothiazolin-3-one. These are preferably used in the range of 0.1 to 2% by mass in the pigment dispersion.

A pH adjuster is used to adjust the pH of the aqueous pigment dispersion to a desired value. Although the type of pH adjuster is not particularly limited, for example, various amines, inorganic salts, ammonia, various buffers and the like can be used.

Antifoaming agents are used to prevent foaming during the production of water-based pigment dispersions. The type of antifoaming agent is not particularly limited, and any commercially available one can be used. For example, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol ＰＳＡ－３３６（いずれも日信化学工業株式会社製）、ＡＤＤＩＴＯＬ ＶＸＷ ６２１１、ＡＤＤＩＴＯＬ ＶＸＷ４９７３、ＡＤＤＩＴＯＬ ＶＸＷ６２３５、ＡＤＤＩＴＯＬ ＸＷ３７５、ＡＤＤＩＴＯＬ ＸＷ３７６、ＡＤＤＩＴＯＬ ＶＸＷ６３８１、ＡＤＤＩＴＯＬ ＶＸＷ６３８６、ＡＤＤＩＴＯＬ ＶＸＷ６３９２、ＡＤＤＩＴＯＬ ＶＸＷ６３９３、ＡＤＤＩＴＯＬ ＶＸＷ６３９９、ＡＤＤＩＴＯＬ ＸＷ６５４４等（ Both are manufactured by Allnex).

Wetting agents are used to facilitate wetting of pigments in water-based pigment dispersions. The type of wetting agent is not particularly limited, and any commercially available one can be used.例えば、ＡＤＤＩＴＯＬ ＶＸＬ６２３７Ｎ、ＡＤＤＩＴＯＬ ＸＬ２６０Ｎ、ＡＤＤＩＴＯＬ ＶＸＬ６２１２、ＡＤＤＩＴＯＬ ＵＶＸ７３０１/６５、ＡＤＤＩＴＯＬ ＸＷ３３０、ＡＤＤＩＴＯＬ ＶＸＷ６２００、ＡＤＤＩＴＯＬ ＶＸＷ６２０５、ＡＤＤＩＴＯＬ ＶＸＷ６３９４、ＡＤＤＩＴＯＬ ＶＸＷ６２０８、ＡＤＤＩＴＯＬ ＶＸＷ６２０８/６０、ＡＤＤＩＴＯＬ ＶＸＷ６３７４（いずれもＡｌｌｎｅｘ社製）が挙げられる。

A dispersing machine used for preparing an aqueous pigment dispersion is not particularly limited. Examples include horizontal sand mills, vertical sand mills, annular bead mills, attritors, microfluidizers, high-speed mixers, homomixers, homogenizers, ball mills, paint shakers, roll mills, stone mills, and ultrasonic dispersers. In addition, dispersers and mixers commonly used in the art for preparing various dispersions can be appropriately selected and used.

In addition, before dispersing with various dispersers, pre-dispersion using a kneader, a kneading mixer such as a three-roll mill, or solid dispersion with a two-roll mill or the like may be performed. In addition, after dispersing with various dispersers, a post-treatment of storing in a heated state of 30 to 80 ° C. for several hours to a week, or a post-treatment using an ultrasonic disperser or a collision type beadless disperser. is effective for imparting dispersion stability to the pigment dispersion.

(water-based inkjet ink)
One embodiment relates to a water-based inkjet ink using the water-based pigment dispersion. A water-based inkjet ink can be produced by adding water and, if necessary, a water-soluble solvent, a resin, an additive, etc. to the water-based pigment dispersion to form an ink.

The content of the pigment containing the isoindoline compound (1) in the water-based inkjet ink is not particularly limited. For example, the content of the pigment is preferably 0.5 to 30% by mass, more preferably 1 to 15% by mass, based on the total mass of the water-based inkjet ink.

The water used for producing the water-based inkjet ink is not particularly limited, but it is preferable to use ion-exchanged water from which metal ions and the like have been removed, or distilled water. The water content is not particularly limited, but is preferably 60 to 99% by mass based on the total mass of the aqueous pigment dispersion.

A water-soluble solvent can be used as necessary in order to prevent drying and solidification at the nozzle portion of the printer head of the water-based inkjet ink and to achieve stable ink ejection. Examples of water-soluble solvents include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, ketone alcohol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene. Glycol monoethyl ether, 1,2-hexanediol, N-methyl-2-pyrrolidone, substituted pyrrolidone, 2,4,6-hexanetriol, tetrafurfuryl alcohol, 4-methoxy-4methylpentanone and the like. One of these may be used alone, or two or more may be used in combination. When using these water-soluble solvents, the content of the water-soluble solvent is preferably in the range of 1 to 50% by weight based on the total weight of the water-based inkjet ink.

In the preparation of water-based inkjet inks, resins can be used to impart fixability of the ink to the substrate to be printed. The resin that can be used is not particularly limited, and may be a resin that is water-soluble or has excellent dispersibility in an aqueous medium. One of these can be used alone, or two or more can be used in combination.

Specific examples of the resin include water-soluble resins such as acrylic resins, styrene-acrylic resins, polyester resins, polyamide resins, polyurethane resins, and oil-in-water emulsions thereof. Among them, an oil-in-water emulsion is preferable. The use of an oil-in-water emulsion is preferable because a low-viscosity water-based inkjet ink and recorded matter with excellent water resistance can be easily obtained.

The content of the resin is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total mass of the water-based inkjet ink. When the content of the resin is 0.5% by mass or more, a sufficient effect in fixing the film components can be easily obtained. On the other hand, when the content of the resin is 15% by mass or less, it is possible to suppress deterioration in ejection stability of the water-based inkjet ink. These resins can be used after neutralizing the acidic functional groups with a pH adjusting agent such as ammonia, various amines, various inorganic alkalis, etc., if necessary.

Other additives such as drying accelerators, penetrating agents, preservatives, chelating agents, and pH adjusters may be used in the production of water-based inkjet inks.

Alcohols such as methanol, ethanol, and isopropyl alcohol can be used to speed up the drying of the water-based inkjet ink after printing. One type of these alcohols may be used alone, or two or more types may be used in combination. The content of these alcohols is preferably 1 to 50% by mass based on the total mass of the water-based inkjet ink.

When the substrate to be printed is a permeable substrate such as paper, various penetrants can be used to accelerate the penetration of the ink into the substrate and quicken the apparent drying property. Penetrants include glycol ethers such as diethylene glycol monobutyl ether, alkylene glycols, and the like, and polyethylene glycol monolauryl ether, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium dioctylsulfosuccinate, and the like, which are exemplified as water-soluble solvents. can be used. A sufficient effect can be obtained with an amount of 5% by mass or less based on the total mass of the water-based inkjet ink. By adjusting the amount to be used to 5% by mass or less, it is possible to suppress the occurrence of defects such as bleeding of print and paper dropout.

Preservatives can be used to prevent the development of mold and bacteria in water-based inkjet inks. The type of antiseptic is not particularly limited, but for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazolin-3-one, 1 -benzisothiazolin-3-one amine salts and the like. These are preferably used within the range of 0.05 to 1.0% by weight based on the total weight of the water-based inkjet ink.

A chelating agent can be used to capture metal ions contained in the water-based inkjet ink and prevent precipitation of insoluble matter in the nozzle or in the ink. The type of chelating agent is not particularly limited, but examples thereof include ethylenediaminetetraacetic acid, sodium salt of ethylenediaminetetraacetic acid, diammonium salt of ethylenediaminetetraacetic acid, and tetraammonium salt of ethylenediaminetetraacetic acid. be done. The chelating agent is preferably used within the range of 0.005 to 0.5% by weight based on the total weight of the water-based inkjet ink.

Various pH adjusters can be used to adjust the pH of the water-based inkjet ink to a desired value. The type of pH adjuster is not particularly limited, and for example, various amines, inorganic salts, ammonia, various buffers and the like can be used.

In the preparation of the inkjet ink, the method of mixing the raw materials is not particularly limited, and the mixing can be carried out using a conventional stirrer using a blade, a high-speed disperser, an emulsifier, or the like. At that time, the order of adding the raw materials, the mixing method, and the like are not particularly limited.

<Production of isoindoline compound>
(Example 1-1)
1400 parts of water, 50 parts of 1,3-diiminobenzo[f]isoindoline and 200 parts of 28% aqueous ammonia were sequentially added to a 5 L four-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer, followed by stirring. A solution prepared by dissolving 26.38 parts of 2-cyano-N-methylacetamide in 200 parts of water was added dropwise thereto over 30 minutes using a dropping funnel. The mixture was heated and stirred at 30° C. until the raw material, 1,3-diiminobenzo[f]isoindoline, disappeared. Disappearance of raw materials was confirmed by UPLC (ultra-high resolution liquid chromatography). This reaction slurry was filtered using a Buchner funnel to obtain a solid content. The entire amount of this solid content was used in the following reactions.
Into a 5 L four-necked flask equipped with a reflux condenser, a dropping funnel, and a stirrer, 2400 parts of water and 800 parts of 80% acetic acid were added and stirred as the raw materials. 37.73 parts of barbituric acid was added thereto and stirred at 85°C. The heating and stirring was continued until the solid content used as the raw material disappeared. Disappearance of raw materials was confirmed by UPLC.
Then, after cooling to room temperature, it was washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80° C. to obtain 62.43 parts of isoindoline compound 1-1 (yield 65%).

(Example 1-2)
50 parts of 6-fluoro-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-fluoro-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -Cyano-N-ethylacetamide (27.61 parts) and barbituric acid (37.73 parts) were changed to 35.54 parts. -2 was obtained 60.92 parts (yield 62%).

(Example 1-3)
50 parts of 6,7-dibromo-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide was changed to 14.59 parts, and 37.73 parts of barbituric acid was changed to 20.86 parts. part (yield 60%).

(Example 1-4)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-tertbutyl-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide Except for changing 29.28 parts of 2-cyano-N-butylacetamide and 37.73 parts of barbituric acid to 29.30 parts, the reaction was carried out in the same manner as in Example 1-1 to obtain an isoindoline compound. 63.68 parts of 1-4 were obtained (yield 66%).

(Example 1-5)
50 parts of 5-nitro-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 5-nitro-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide, Except for changing .44 parts and 37.73 parts of barbituric acid to 30.66 parts, the reaction operation was performed in the same manner as in Example 1-1, and 38.65 parts of isoindoline compound 1-5 ( Yield 43%).

(Example 1-6)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1 was added to 50 parts of 2-(1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-6-ylthio)ethanamine , 26.38 parts of 2-cyano-N-methylacetamide was changed to 19.05 parts, and 37.73 parts of barbituric acid was changed to 27.24 parts. to obtain 35.03 parts of isoindoline compound 1-6 (yield 41%).

(Example 1-7)
50 parts of 6,7-diphenoxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide was changed to 13.57 parts, and 37.73 parts of barbituric acid was changed to 19.41 parts. part (yield 55%).

(Example 1-8)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of N-ethyl-6-sulfonamido-1,3-diiminobenzo[f]isoindoline, 26 parts of 2-cyano-N-methylacetamide Except for changing .38 parts to 14.21 parts and barbituric acid 37.73 parts to 20.33 parts, the reaction operation was performed in the same manner as in Example 1-1, and isoindoline compound 1-8 was obtained. 28.63 parts (yield 42%) were obtained.

(Example 1-9)
Except for changing 26.38 parts of 2-cyano-N-methylacetamide in Example 1-1 to 26.65 parts of methyl 2-cyanoacetate, the reaction was carried out in the same manner as in Example 1-1 to give isoindoline. 40.74 parts of compound 1-9 were obtained (yield 41%).

(Example 1-10)
50 parts of 4,9-dihydroxy-5-nitro-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 4,9-diiminobenzo[f]isoindoline, 2-cyano-N-methylacetamide Except for changing 26.38 parts of ethyl 2-cyanoacetate to 21.83 parts and 37.73 parts of barbituric acid to 27.07 parts, the reaction was carried out in the same manner as in Example 1-1, iso 33.45 parts of indoline compound 1-10 (yield 38%) were obtained.

(Example 1-11)
50 parts of 6-carboxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-carboxy-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -Ethyl cyanoacetate 24.82 parts and barbituric acid 37.73 parts were changed to 30.79 parts, the reaction operation was performed in the same manner as in Example 1-1, and isoindoline compound 1-11 was obtained. 28.90 parts (yield 31%) were obtained.

(Example 1-12)
26.38 parts of 2-cyano-N-methylacetamide of Example 1-1 was mixed with 37.70 parts of 2-cyano-N-butylacetamide, and 37.73 parts of barbituric acid was mixed with 41.5 parts of 1-methylbarbituric acid. Except for changing the amount to 86 parts, the same reaction operation as in Example 1-1 was carried out to obtain 70.35 parts of isoindoline compound 1-12 (yield 62%).

(Example 1-13)
50 parts of 5-bromo-1,3-diiminobenzo[f]isoindoline of Example 1-1 and 26.38 parts of 2-cyano-N-methylacetamide to 18 .79 parts and 37.73 parts of barbituric acid were changed to 32.75 parts of 1-ethylbarbituric acid. 47.76 parts (53% yield) were obtained.

(Example 1-14)
26.38 parts of 2-cyano-N-methylacetamide of Example 1-1 to 26.65 parts of methyl 2-cyanoacetate and 37.73 parts of barbituric acid to 41.86 parts of 1-methylbarbituric acid Except for the changes, the reaction was carried out in the same manner as in Example 1-1 to obtain 49.70 parts of isoindoline compound 1-14 (yield: 42%).

(Example 1-15)
50 parts of 5-carboxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 5-carboxy-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -Ethyl cyanoacetate 24.82 parts and barbituric acid 37.73 parts were changed to 1-ethylbarbituric acid 37.53 parts. 28.73 parts of indoline compound 1-15 (yield 29%) were obtained.

(Example 1-16)
Except for changing 37.73 parts of barbituric acid in Example 1-1 to 45.99 parts of 1,3-dimethylbarbituric acid, the reaction was carried out in the same manner as in Example 1-1 to give isoindoline compound 1 -16 was obtained in 72.28 parts (yield 68%).

(Example 1-17)
26.38 parts of 2-cyano-N-methylacetamide of Example 1-1 was added to 30.15 parts of 2-cyano-N-ethylacetamide, and 37.73 parts of barbituric acid to 1,3-diethylbarbituric acid. Except for changing the amount to 54.25 parts, the same reaction operation as in Example 1-1 was carried out to obtain 80.76 parts of isoindoline compound 1-17 (yield 69%).

(Example 1-18)
Except for changing 37.73 parts of barbituric acid in Example 1-1 to 50.12 parts of 1-ethyl-3-methylbarbituric acid, the reaction was carried out in the same manner as in Example 1-1 to give isoindoline. 76.91 parts of compound 1-18 were obtained (yield 70%).

(Example 1-19)
Except for changing 37.73 parts of barbituric acid in Example 1-1 to 70.78 parts of 1,3-dibutylbarbituric acid, the reaction was carried out in the same manner as in Example 1-1 to give isoindoline compound 1 -19 was obtained in 89.46 parts (yield 70%).

(Example 1-20)
50 parts of 5-bromo-1,3-diiminobenzo[f]isoindoline of Example 1-1 and 26.38 parts of 2-cyano-N-methylacetamide to 18 .76 parts and 37.73 parts of barbituric acid were changed to 32.75 parts of 1,3-dimethylbarbituric acid. -20 was obtained in 59.35 parts (yield 66%).

(Example 1-21)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1 was added to 50 parts of 6-fluoro-1,3-diiminobenzo[f]isoindoline, and 26.38 parts of 2-cyano-N-methylacetamide was added to 24 .16 parts and 37.73 parts of barbituric acid were changed to 42.11 parts of 1,3-dimethylbarbituric acid. -21 was obtained in 63.97 parts (yield 66%).

(Example 1-22)
50 parts of 6,7-dibromo-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide and 37.73 parts of barbituric acid were changed to 47.62 parts of 1,3-dicyclohexylbarbituric acid. 41.17 parts of compound 1-22 were obtained (yield 41%).

(Example 1-23)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-tertbutyl-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide 29.28 parts of 2-cyano-N-butylacetamide and 37.73 parts of barbituric acid were changed to 35.72 parts of 1,3-dimethylbarbituric acid in the same manner as in Example 1-1. Reaction operation was carried out to obtain 60.21 parts of isoindoline compound 1-23 (yield 59%).

(Example 1-24)
50 parts of 5-nitro-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 5-nitro-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide, .44 parts and 37.73 parts of barbituric acid were changed to 44.09 parts of 1,3-diethylbarbituric acid. -24 was obtained in 40.63 parts (yield 40%).

(Example 1-25)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1 was added to 50 parts of 2-(1,3-diimino-2,3-dihydro-1H-benzo[f]isoindol-6-ylthio)ethanamine , 26.38 parts of 2-cyano-N-methylacetamide was changed to 19.05 parts, and 37.73 parts of barbituric acid was changed to 33.21 parts of 1,3-dimethylbarbituric acid. The same reaction operation as in 1-1 was carried out to obtain 36.25 parts of isoindoline compound 1-25 (yield 40%).

(Example 1-26)
50 parts of 6,7-diphenoxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide 13.71 parts of methyl 2-cyanoacetate, and 37.73 parts of barbituric acid were changed to 23.66 parts of 1,3-dimethylbarbituric acid. was carried out to obtain 30.83 parts of isoindoline compound 1-26 (yield 39%).

(Example 1-27)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of N-ethyl-6-sulfonamido-1,3-diiminobenzo[f]isoindoline, 26 parts of 2-cyano-N-methylacetamide All the same as in Example 1-1 except that .38 parts were changed to 16.39 parts of ethyl 2-cyanoacetate and 37.73 parts of barbituric acid were changed to 24.78 parts of 1,3-dimethylbarbituric acid. 20.01 parts of isoindoline compound 1-27 (yield 27%) was obtained.

(Example 1-28)
50 parts of 5-methoxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 5-methoxy-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -Butyl cyanoacetate 32.90 parts and 37.73 parts of barbituric acid were changed to 43.44 parts of 1-ethyl-3-methylbarbituric acid. to obtain 44.57 parts of isoindoline compound 1-28 (yield 40%).

(Example 1-29)
50 parts of 4,9-dihydroxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide 22.90 parts of methyl 2-cyanoacetate, and 37.73 parts of barbituric acid were changed to 39.51 parts of 1,3-dimethylbarbituric acid. to obtain 32.53 parts of isoindoline compound 1-29 (yield 33%).

(Comparative compound 1)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 1,3-diiminoisoindoline, 35.48 parts of 26.38 parts of 2-cyano-N-methylacetamide, and barbi Except for changing 37.73 parts of turic acid to 50.74 parts, the reaction was carried out in the same manner as in Example 1-1. I. Pigment Yellow 185 was obtained in an amount of 102.16 parts (88% yield).

Table 4 summarizes the structures of the isoindoline compounds obtained in Examples 1-1 to 1-29. For example, when the relationships between R ₁ and R ₆ , R ₂ and R ₅ , R ₃ and R ₄ , and R ₇ and R ₈ are asymmetric as seen in the compound of Example 1-2, , the compound is obtained as a mixture of isomers.
The isoindoline compound was identified by comparing the mass spectrum molecular ion peak with the calculated mass number (theoretical value). Measurement of the molecular ion peak of the mass spectrum was performed using Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm×50 mm)/Ms TAP XEVO TQD. Table 4 shows the theoretical molecular weights of the isoindoline compounds (Examples 1-1 to 1-29) and the measured values obtained by mass spectrometry. Due to the nature of the measurement, the H (proton) of the compound is eliminated from the measured value, so if the value is the theoretical molecular weight mass number-(minus) 1, the compound will match.

Comparative compound 1 C.I. I. Pigment Yellow 185 had a theoretical molecular weight of 337 and a measured value of 336.

(Example 2-1)
1600 parts of water and 1600 parts of 80% acetic acid were added to a 5 L four-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer and stirred. 68.90 parts of barbituric acid was added thereto and stirred at 85° C. to dissolve the barbituric acid. 50 parts of 1,3-diiminobenzo[f]isoindoline was added thereto and stirred at 85°C. The mixture was stirred until the starting material, 1,3-diiminobenzo[f]isoindoline, disappeared. Disappearance of raw materials was confirmed by UPLC. After cooling to room temperature, it was washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80° C. to obtain 98.26 parts of isoindoline compound 2-1 (yield 92%).

(Example 2-2)
55.98 parts of 68.90 parts of barbituric acid of Example 2-1 and 50 parts of 6-nitro-1,3-diiminobenzo[f]isoindoline of 50 parts of 1,3-diiminobenzo[f]isoindoline 72.12 parts of the isoindoline compound 2-2 (yield 75%) was obtained in the same manner as in Example 2-1, except for changing to .

(Example 2-3)
38.1 parts of 68.90 parts of barbituric acid of Example 2-1 and 50 parts of 1,3-diiminobenzo[f]isoindoline of 6,7-dibromo-1,3-diiminobenzo[f]isoindoline Except for changing the amount to 50 parts, the same reaction operation as in Example 2-1 was carried out to obtain 70.85 parts of isoindoline compound 2-3 (yield 87%).

(Example 2-4)
59.70 parts of 68.90 parts of barbituric acid of Example 2-1 and 50 parts of 6-methoxy-1,3-diiminobenzo[f]isoindoline of 50 parts of 1,3-diiminobenzo[f]isoindoline 93.27 parts of the isoindoline compound 2-4 (yield 94%) was obtained by carrying out the reaction operation in the same manner as in Example 2-1, except for changing to .

(Example 2-5)
1550 parts of water and 50 parts of 80% acetic acid were added to a 3 L four-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer and stirred. 41.99 parts of 1-ethylbarbituric acid was added thereto and stirred at 25°C. 50 parts of 1,3-diiminobenzo[f]isoindoline was added thereto and stirred at 25°C. The mixture was stirred until the starting material, 1,3-diiminobenzo[f]isoindoline, disappeared. Disappearance of raw materials was confirmed by UPLC. This reaction slurry was filtered using a Buchner funnel to obtain a solid content. The entire amount of this solid content was used in the following reactions.
1600 parts of water and 1600 parts of 80% acetic acid were added to a 5 L four-necked flask equipped with a reflux condenser, a dropping funnel and a stirrer and stirred. 34.45 parts of barbituric acid was added thereto and stirred at 85° C. to dissolve the barbituric acid. To this, the whole amount of the solid content obtained in the previous adjustment was added as a raw material, and the mixture was stirred at 85°C. The heating and stirring was continued until the solid content used as the raw material disappeared. Disappearance of raw materials was confirmed by UPLC.
Then, after cooling to room temperature, it was washed three times with 2000 parts of water to obtain a solid content. This solid content was dried in a hot air dryer at 80° C. to obtain 66.10 parts of isoindoline compound 2-5 (yield 58%).

(Example 2-6)
The reaction was carried out in the same manner as in Example 2-5 except that 41.99 parts of 1-ethylbarbituric acid in Example 2-5 was changed to 41.99 parts of 1,3-dimethylbarbituric acid, and iso 75.22 parts of indoline compound 2-6 (yield 66%) were obtained.

(Example 2-7)
41.99 parts of 1-ethylbarbituric acid of Example 2-5 was 41.99 parts of 1,3-dimethylbarbituric acid, and 34.45 parts of barbituric acid was 41.99 parts of 1-ethylbarbituric acid. 71.48 parts of the isoindoline compound 2-7 (yield 59%) was obtained in the same manner as in Example 2-5, except for changing to .

(Example 2-8)
Except for changing 68.90 parts of barbituric acid in Example 2-1 to 83.98 parts of 1,3-dimethylbarbituric acid, the reaction was carried out in the same manner as in Example 2-1 to give isoindoline compound 2. -8 was obtained in 113.88 parts (yield 94%).

(Example 2-9)
41.99 parts of 1-ethylbarbituric acid of Example 2-5 was mixed with 41.99 parts of 1,3-dimethylbarbituric acid, and 34.45 parts of barbituric acid was mixed with 49.9 parts of 1,3-diethylbarbituric acid. Except for changing the amount to 53 parts, the reaction was carried out in the same manner as in Example 2-5 to obtain 85.97 parts of isoindoline compound 2-9 (yield 67%).

(Example 2-10)
68.90 parts of barbituric acid of Example 2-1 was added to 65.24 parts of 1,3-dimethylbarbituric acid, and 50 parts of 1,3-diiminobenzo[f]isoindoline was added to 6-tertbutyl-1,3- Except for changing to 50 parts of diiminobenzo[f]isoindoline, the reaction was carried out in the same manner as in Example 2-1 to obtain 96.82 parts of isoindoline compound 2-10 (yield 92%).

(Example 2-11)
41.99 parts of 1-ethylbarbituric acid of Example 2-5 was added to 32.49 parts of 1,3-dimethylbarbituric acid, and 50 parts of 1,3-diiminobenzo[f]isoindoline was added to N-methyl-6-carbamide. -1,3-diiminobenzo[f]isoindoline 50 parts and barbituric acid 34.45 parts were changed to 1,3-diethylbarbituric acid 38.33 parts, all in the same manner as in Example 2-5 Reaction operation was carried out to obtain 72.99 parts of isoindoline compound 2-11 (yield 66%).

(Example 2-12)
68.90 parts of barbituric acid of Example 2-1 was added to 76.90 parts of 1,3-dimethylbarbituric acid, and 50 parts of 1,3-diiminobenzo[f]isoindoline was added to 5-fluoro-1,3-diiminobenzo [f] 105.93 parts of isoindoline compound 2-12 (yield 92%) was obtained by carrying out the reaction operation in the same manner as in Example 2-1, except that 50 parts of isoindoline was used.

(Example 2-13)
41.99 parts of 1-ethylbarbituric acid of Example 2-5 was added to 30.13 parts of 1,3-dimethylbarbituric acid, and 50 parts of 1,3-diiminobenzo[f]isoindoline was added to 4,9-dihydroxy-5. -Nitro-1,3-diiminobenzo[f]isoindoline 50 parts, and 34.45 parts of barbituric acid were changed to 40.96 parts of 1-ethyl-3-butylbarbituric acid, except for Example 2- 47.89 parts of isoindoline compound 2-13 (yield 43%) was obtained by the same reaction operation as in 5.

(Example 2-14)
68.90 parts of barbituric acid of Example 2-1 was added to 43.90 parts of 1,3-dimethylbarbituric acid, and 50 parts of 1,3-diiminobenzo[f]isoindoline was added to N-(2-(diethylamino)ethyl )-1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-6-sulfonamide was used in 50 parts. 71.47 parts of indoline compound 2-14 (yield 82%) were obtained.

(Comparative compound 2)
All except that 68.90 parts of barbituric acid in Example 2-1 were changed to 92.66 parts and 50 parts of 1,3-diiminobenzo[f]isoindoline were changed to 50 parts of 1,3-diiminoisoindoline The reaction was carried out in the same manner as in Example 2-1, and C.I. I. Pigment Yellow 139 was obtained in an amount of 111.25 parts (88% yield).

Table 5 summarizes the structures of the isoindoline compounds obtained in Examples 2-1 to 2-14. For example, as seen in Example 2-2, R ₁ and R ₆ , R ₂ and R ₅ , R ₃ and R ₄ , R ₇ and R ₈ , and R ₁₀ and R When the relationship with ₁₁ becomes asymmetric, the final product is obtained as a mixture of isomers.
The isoindoline compound was identified by comparing the mass spectrum molecular ion peak with the calculated mass number (theoretical value). Measurement of the molecular ion peak of the mass spectrum was performed using Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm×50 mm)/Ms TAP XEVO TQD. Table 5 shows the theoretical molecular weights of the isoindoline compounds (Examples 2-1 to 2-14) and the values measured by mass spectrometry. Due to the nature of the measurement, the H (proton) of the compound is eliminated from the measured value, so if the value is the theoretical molecular weight mass number-(minus) 1, the compound will match.

Comparative compound 2 C.I. I. Pigment Yellow 139 had a theoretical molecular weight of 367 and a measured value of 366.

(Example 3-1)
All except that 26.38 parts of 2-cyano-N-methylacetamide in Example 1-1 was changed to 49.80 parts of 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile The reaction was carried out in the same manner as in Example 1-1 to obtain 74.05 parts of isoindoline compound 3-1 (yield 61%).

(Example 3-2)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1 was added to 2,2′-(1,3-diimino-2,3-dihydro-1H-benzo[f]isoindole-6,7- diyl)bis(sulfanidiyl)diethylamine 50 parts, 2-cyano-N-methylacetamide 26.38 parts 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile 28.14 parts, and barbiturates Except for changing the acid from 37.73 parts to 21.32 parts, the reaction was carried out in the same manner as in Example 1-1 to obtain 59.60 parts of isoindoline compound 3-2 (yield: 66%).

(Example 3-3)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of N-ethyl-6-sulfonamido-1,3-diiminobenzo[f]isoindoline, 26 parts of 2-cyano-N-methylacetamide .38 parts were changed to 28.86 parts of 2-(3-methyl-4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile, and 37.73 parts of barbituric acid were changed to 20.33 parts 48.44 parts of the isoindoline compound 3-3 (yield 59%) was obtained by carrying out the same reaction operation as in Example 1-1.

(Example 3-4)
26.38 parts of 2-cyano-N-methylacetamide of Example 1-1 was added with 49.80 parts of 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile and 37.73 parts of barbituric acid. Except for changing the part to 45.99 parts of 1-ethylbarbituric acid, the reaction operation was carried out in the same manner as in Example 1-1 to obtain 55.29 parts of isoindoline compound 3-4 (yield 43%). rice field.

(Example 3-5)
50 parts of 4,9-dihydroxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide 2-(4-oxo-3,4-dihydroquinazolin-2-yl) 42.79 parts of acetonitrile, and 37.73 parts of barbituric acid were changed to 39.51 parts of 1-ethylbarbituric acid, All reaction operations were carried out in the same manner as in Example 1-1 to obtain 52.88 parts of isoindoline compound 3-5 (yield 45%).

(Example 3-6)
26.38 parts of 2-cyano-N-methylacetamide of Example 1-1 was added with 49.80 parts of 2-(4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile and 37.73 parts of barbituric acid. Except for changing the part to 45.99 parts of 1,3-dimethylbarbituric acid, the reaction operation was carried out in the same manner as in Example 1-1, and 79.72 parts of isoindoline compound 3-6 (yield 62% )Obtained.

(Example 3-7)
50 parts of 6,7-dibromo-1,3-diiminobenzo[f]isoindoline of Example 1-1, 26.38 parts of 2-cyano-N-methylacetamide 2-(3-methyl-4-oxo-3,4-dihydroquinazolin-2-yl) acetonitrile 29.63 parts, and barbituric acid 37.73 parts 1,3-dimethylbarbituric acid 25.43 parts 59.19 parts of the isoindoline compound 3-7 (yield 62%) was obtained in the same manner as in Example 1-1, except for changing to .

(Example 3-8)
50 parts of 5-fluoro-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 5-fluoro-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -(6-fluoro-4-oxo-3,4-dihydroquinazolin-2-yl) 50.03 parts of acetonitrile and 37.73 parts of barbituric acid changed to 42.11 parts of 1,3-dimethylbarbituric acid The reaction was carried out in the same manner as in Example 1-1, except for the above, to obtain 80.75 parts of isoindoline compound 3-8 (yield 64%).

(Example 3-9)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-tertbutyl-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide 2-(4-oxo-3,4-dihydroquinazolin-2-yl) 38.68 parts of acetonitrile and 37.73 parts of barbituric acid were changed to 38.93 parts of 1-ethyl-3-methylbarbituric acid Except for this, the reaction was carried out in the same manner as in Example 1-1 to obtain 59.17 parts of isoindoline compound 3-9 (yield: 52%).

(Example 3-10)
50 parts of 5-thioethyl-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 5-thioethyl-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -(4-oxo-3,4-dihydroquinazolin-2-yl) 38.07 parts of acetonitrile and 37.73 parts of barbituric acid were changed to 35.16 parts of 1,3-dimethylbarbituric acid, All reaction operations were carried out in the same manner as in Example 1-1 to obtain 73.73 parts of isoindoline compound 3-10 (yield 67%).

(Example 3-11)
50 parts of 6,7-dichloro-1,3-diiminobenzo[f]isoindoline and 26.38 parts of 2-cyano-N-methylacetamide were added to 50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1. 2-(3-butyl-4-oxo-3,4-dihydroquinazolin-2-yl)acetonitrile 47.96 parts, and barbituric acid 37.73 parts 1,3-dimethylbarbituric acid 33.99 parts 60.54 parts of the isoindoline compound 3-11 (yield 51%) was obtained in the same manner as in Example 1-1, except for changing to .

(Example 3-12)
50 parts of 6-methoxy-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-methoxy-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -(4-oxo-3,4-dihydroquinazolin-2-yl) 43.16 parts of acetonitrile and 37.73 parts of barbituric acid were changed to 47.02 parts of 1,3-diethylbarbituric acid, All reaction operations were carried out in the same manner as in Example 1-1 to obtain 84.53 parts of isoindoline compound 3-12 (yield 68%).

(Example 3-13)
50 parts of 6-thiophenyl-1,3-diiminobenzo[f]isoindoline of Example 1-1, 50 parts of 6-thiophenyl-1,3-diiminobenzo[f]isoindoline, 26.38 parts of 2-cyano-N-methylacetamide -(6-chloro-4-oxo-3,4-dihydroquinazolin-2-yl) 40.43 parts of acetonitrile and 37.73 parts of barbituric acid changed to 29.59 parts of 1,3-dimethylbarbituric acid 64.08 parts of the isoindoline compound 3-13 (yield 59%) was obtained by carrying out the reaction operation in the same manner as in Example 1-1, except for the above.
(Comparative compound 3)
50 parts of 1,3-diiminobenzo[f]isoindoline of Example 1-1 was added to 50 parts of 1,3-diiminoisoindoline, and 26.38 parts of 2-cyano-N-methylacetamide was added to 2-(4-oxo- 3,4-dihydroquinazolin-2-yl)acetonitrile 66.98 parts, and barbituric acid 37.73 parts were changed to 50.74, the reaction operation was carried out in the same manner as in Example 1-1, C . I. Pigment Red 260 was obtained in 109.54 parts (yield 75%).

Table 6 summarizes the structures of the isoindoline compounds obtained in Examples 3-1 to 3-13. For example, when the relationships between R ₁ and R ₆ , R ₂ and R ₅ , R ₃ and R ₄ , and R ₇ and R ₈ are asymmetrical as seen in the compound of Example 3-3, , the compound is obtained as a mixture of isomers.
The isoindoline compound was identified by comparing the mass spectrum molecular ion peak with the calculated mass number (theoretical value). Measurement of the molecular ion peak of the mass spectrum was performed using Waters ACQUITY UPLS H-Class (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm×50 mm)/Ms TAP XEVO TQD. Table 6 shows the theoretical molecular weights of the isoindoline compounds (Examples 3-1 to 3-13) and the measured values obtained by mass spectrometry. Due to the nature of the measurement, the H (proton) of the compound is eliminated from the measured value, so if the value is the theoretical molecular weight mass number-(minus) 1, the compound will match.

Comparative compound 3 C.I. I. Pigment Red 260 had a theoretical molecular weight of 424 and a measured value of 423.

<Coloring composition and its property evaluation>
Using each of the previously synthesized isoindoline compounds, colored compositions for various uses were prepared, and various properties were evaluated.

<1> Coloring Composition for Plastics and Evaluation Thereof The following relates to a coloring composition for plastics prepared using each of the previously prepared isoindoline compounds.

(Examples A-1 to A-56, Comparative Examples A-1 to A-3)
The heat resistance test method referred to German Industrial Standard DIN12877-1.
First, each of the previously synthesized isoindoline compounds and resins was used to prepare a colored plate as a sample to be used in the test, the coloring strength being adjusted to a concentration of SD1/3. Table 7 shows the isoindoline compounds used in each example and each comparative example. High-density polyethylene (product name: Hizex 2208J, manufactured by Prime Polymer Co., Ltd.) was used as the resin constituting the test sample. The molding of the colored plates was carried out at 200° C. under the conditions that the residence time in the barrel was as short as possible to obtain 11 colored plates. In order to detect the average color difference, the 6th to 11th colored plates were measured using a colorimeter capable of measuring the total luminous flux (Konica Minolta CM-700d). colored. 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. Six of the obtained colored plates (6th to 11th) were each subjected to colorimetry, and the average value of the colorimetry values was calculated. The color difference (ΔE*) between the above reference value and the measured value of the plate molded at 300° C. was determined and evaluated according to the following criteria. Table 7 shows the results. If it is "△" or more in the following evaluation criteria, it is a practical level.

(Evaluation criteria)
A: ΔE* is less than 5.0.
○: ΔE* is 5.0 or more and less than 10.
Δ: ΔE* is 10.0 or more and less than 15.0.
x: ΔE* is 15.0 or more.

(Example A-57)
As an example of a coloring composition for plastics, a coloring composition containing an isoindoline compound (1) and polypropylene as a resin was examined. First, 2 parts of an isoindoline compound (Example 1-1) and 1000 parts of a polypropylene resin (product name: Prime Polypro J105, manufactured by Prime Polymer Co., Ltd.) were mixed to obtain a coloring composition for plastics. Next, the colored composition obtained as described above was injection molded using an injection molding machine in which the injection conditions were set to a molding temperature of 220°C and a mold temperature of 40°C to obtain a molded product (plate). . As a result of visual observation of the molded product, no warpage or deformation was observed, and it was a highly colored yellow plate.

(Example A-58)
As an example of a coloring composition for plastics, a coloring composition containing an isoindoline compound (1) and polyethylene terephthalate as a resin was examined.
First, 2 parts of an isoindoline compound (Examples 1-16) and 1000 parts of a polyethylene terephthalate resin (product name: Vylopet EMChaihun 307, manufactured by Toyobo Co., Ltd.) were mixed to obtain a coloring composition for plastics. Next, the colored composition obtained as described above was injection molded using an injection molding machine in which the injection conditions were set to a molding temperature of 275°C and a mold temperature of 85°C to obtain a molded product (plate). As a result of visual observation of the molded product, no warpage or deformation was observed, and it was a highly colored yellow plate.

<2> Preparation and Evaluation of Coloring Composition for Toner.
The following relates to preparation examples of toner coloring compositions (negative charging toners) that can be used to make toners.
(Example A-59)
2500 g of the isoindoline compound (Examples 1-16) and 2500 g of thermoplastic polyester resin were mixed and kneaded in a pressure kneader. Mixing and kneading were performed at a set temperature of 120° C. for 15 minutes. Next, the resulting kneaded product was taken out from the pressure kneader and further kneaded using three rolls with a roll temperature of 95°C. After cooling the resulting kneaded product, it was coarsely pulverized to 10 mm or less to obtain a colored resin composition.
500 g of the colored resin composition obtained as described above, 4375 g of thermoplastic polyester resin, 50 g of calcium salt compound of 3,5-di-tert-butylsalicylic acid (charge control agent), and ethylene homopolymer (release agent, molecular weight 850, Mw/Mn=1.08, melting point 107° C.) 75 g are mixed using a Henschel mixer having a volume of 20 L (3000 rpm, 3 minutes), and further using a twin-screw kneading extruder, the discharge temperature is 120° C. Melt kneading was performed at. Then, the kneaded product was cooled and solidified, and then coarsely pulverized with a hammer mill. Next, the obtained coarsely pulverized product was finely pulverized using an I-type jet mill (IDS-2 type), and then classified to obtain toner base particles.
Next, 2500 g of the toner base particles obtained above and 12.5 g of hydrophobic titanium oxide (STT-30A manufactured by Titan Kogyo Co., Ltd.) were mixed in a 10 L Henschel mixer to obtain a negatively charged toner 1 .

On the other hand, as a comparative control, negatively charged toner 2 was obtained in the same manner as in Example A-59, except that the isoindoline compound (Example 1-16) of Example A-59 was changed to Comparative Compound 1. .
The obtained negatively charged toner 1 and negatively charged toner 2 were each sliced to a thickness of 0.9 μm using a microtome to form a sample. Next, the dispersion state of the pigment was observed for each sample using a transmission electron microscope. As a result, it was found that the negatively charged toner 1 using the compound of Example 1-16 had higher dispersibility than the negatively charged toner 2 using the comparative compound 1 because the pigment was uniformly distributed. did.

<3> Solid Base Paint and Evaluation Thereof The following relates to solid base paint prepared using each of the previously prepared isoindoline compounds and evaluation of weather resistance of the solid base painted plate prepared using the solid base paint.

<3-1> Preparation of Solid Base Paint 1. Preparation of base paint (Example B-1) Preparation method of base paint 1 First, the following raw materials and 230 parts of steel beads were placed in a 225 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil. to obtain a mixture.
・Isoindoline compound (Example 1-1): 19 parts ・Acrylic resin (manufactured by DIC, Acrydic 47-712): 7.7 parts ・Dispersion solvent (toluene: xylene: butyl acetate: Solvesso manufactured by Tonen General Sekiyu Co., Ltd. 150 mass ratio is 3:3:2:2 mixed solvent): 40.7 parts Next, to the above mixture, 75.4 parts of Acrydic 47-712, melamine resin (DIC Amidia L-117-60 ) 17.2 parts were added and dispersed for an additional 10 minutes to obtain a dispersion liquid.
Then, the steel beads were removed from the above dispersion to obtain a base paint 1 of an isoindoline compound (Example 1-1).

(Examples B-2 to B-56, Comparative Examples B-1 to B-3) Preparation of base paints 2 to 59 In the method for preparing base paint 1 described in Example B-1, the isoindoline compound (Example 1-1) was changed to Examples 1-2 to 1-29, 2-1 to 2-14, 3-1 to 3-13 and Comparative Compounds 1 to 3, respectively, except for Example B-1 Base paints 2 to 59 were obtained in the same manner.

2. White Paint Preparation The following relates to an example of white paint preparation for use in solid base paints.
First, the following raw materials and 900 parts of steel beads were placed in a 900 ml glass bottle and dispersed for 60 minutes using a paint shaker manufactured by Red Devil to obtain a dispersion.
・ Titanium oxide (titanium oxide Typaque CR90 manufactured by Ishihara Sangyo Co., Ltd.): 66.6 parts ・ Acrylic resin (manufactured by DIC, Acrydic 47-712): 101.7 parts ・ Melamine resin (manufactured by DIC, Amidia L-117 -60): 21.3 parts Dispersion solvent (toluene: xylene: butyl acetate: mixed solvent with a mass ratio of Solvesso 150 manufactured by Tonen General Sekiyu Co., Ltd. of 3: 3: 2: 2): 20.9 parts Then, the dispersion A white paint was obtained by removing the steel beads from the liquor.

3. Preparation of Solid Base Paint (Example C-1) Preparation of Solid Base Paint 1 A solid base paint 1 was obtained by stirring the following components using a high-speed stirrer.
・ Base paint 1: 10 parts prepared in Example B-1 ・ White paint: 31.9 parts

(Examples C-2 to C-56, Comparative Examples C-1 to C-3) Preparation of solid base paints 2 to 59 The base paint 1 of Example C-1 was changed to base paints 2 to 59, respectively. Solid base paints 2 to 59 were obtained in the same manner as in Example C-1, except for
Table 8 shows the isoindoline compounds of the base paints used in the solid base paints prepared in each example and each comparative example.

4. Preparation of Topcoat Clear Paint Using a high-speed stirrer, the following raw materials were stirred to obtain a topcoat clear paint.
・Acrylic resin (manufactured by DIC, Acrydic 44-179): 120 parts ・Melamine resin (manufactured by DIC, Amidia L117-60): 30 parts ・Dilution solvent (toluene, xylene, Solvesso 150, 3 manufactured by TonenGeneral Sekiyu K.K.) -mixed solvent in which the mass ratio of ethyl ethoxypropionate and ethyl acetate is 3:2:2:1:2): 50 parts

<3-2> Preparation of solid base painted board and evaluation of weather resistance The following examples and comparative examples are used to prepare and paint a solid base painted board using the previously prepared solid base paint and topcoat clear paint. Regarding board evaluation.

(Example D-1) Production of Solid Base Coated Plate 1 A steel plate was coated with the solid base coating 1 by spraying with a spray gun. In order to adjust the viscosity to be easy to spray, dilute solvent (toluene, xylene, Solvesso 150 manufactured by Tonen General Sekiyu Co., Ltd., ethyl 3-ethoxypropionate, ethyl acetate with a mass ratio of 3: 2:2:1:2 mixed solvent) were mixed appropriately.
The coating was carried out in 9 batches, and then the clear topcoat paint was sprayed in 6 batches. Then, after drying at 25° C. for 8 hours, it was dried at 140° C. for 30 minutes to obtain a solid base coated panel 1 .

(Examples D-2 to D-56, Comparative Examples D-1 to D-3) Production of Solid Base Coated Plates 2 to 59 The solid base paint 1 in Example D-1 was changed to solid base paints 2 to 59, respectively. Solid base coated boards 2 to 59 were obtained in the same manner as in Example D-1, except that

A weather resistance test was carried out in the following manner using the solid base coated boards 1 to 59 produced in each example and comparative example.
(Evaluation method for weather resistance test)
The weather resistance test was performed using a super-accelerated weather resistance tester (Iwasaki Electric Co., Ltd., Eye Super Xenon Tester SUV-W151) under the conditions of 90 mW/cm ² and 48 hours (2 cycles of 12 hours day and night). . The coated plate before and after the weather resistance test was visually observed, and the weather resistance was evaluated according to the following criteria. Table 9 shows the results. If it is "△" or more in the following evaluation criteria, it is a practical level.

(Evaluation criteria)
O: No change in color.
Δ: The color is fading to white.
x: The color is discolored to black.

<4> Aqueous pigment dispersion and evaluation of its dispersion stability The following examples and comparative examples are aqueous pigment dispersions (hereinafter referred to as aqueous dispersions) prepared using the respective isoindoline compounds prepared above. and the evaluation of its dispersion stability.

<4-1> Preparation of aqueous dispersion (Example E-1) Preparation of aqueous dispersion 1 The following raw materials and 70 parts of zirconia beads with a diameter of 1.25 mm were charged in a 70 ml glass bottle, and a paint shaker manufactured by Red Devil Co., Ltd. for 60 minutes to obtain a dispersion.
Isoindoline compound (Example 1-1): 3.15 parts Polyester-modified acrylic acid polymer (ADDITOL XW 6528, manufactured by Allnex): 5.25 parts Wetting agent (ADDITOL XW 6374, manufactured by Allnex): 0.95 parts Antifoaming agent (ADDITOL XW 6211 manufactured by Allnex): 0.63 parts Ion-exchanged water: 21.52 parts rice field.

(Examples E-2 to E-56, Comparative Examples E-1 to E-3) Preparation of aqueous dispersions 2 to 59 As shown in Table 10, the isoindoline pigment of Example E-1 (Example 1- 1) to Examples 1-2 to 1-29, Comparative Compound 1, Examples 2-1 to 2-14, Comparative Compound 2, and Examples 3-1 to 3-13, Comparative Compound 3, sequentially Aqueous dispersions 2 to 59 were obtained in the same manner as in Example E-1, except for the changes.

2. Evaluation of Dispersion Stability The aqueous dispersions obtained in Examples E-1 to E-56 and Comparative Examples E-1 to E-3 were evaluated for dispersion stability according to the following method.
(Evaluation method for initial viscosity and viscosity stability)
The initial viscosity at 25° C. of the resulting aqueous dispersion was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity was measured after aging at 25° C. for 1 week and after aging at 50° C. for 1 week. Based on the obtained measured values, the rate of increase in viscosity relative to the initial viscosity was calculated and used as an index of viscosity stability, and evaluated according to the following evaluation criteria. Table 10 shows the results. If it is "△" or more in the following evaluation criteria, it is a practical level.

(Evaluation criteria for initial viscosity)
A: The initial viscosity is less than 6.0 mPa·s.
Good: The initial viscosity is 6.0 mPa·s or more and less than 8.0.
Δ: The initial viscosity is 8.0 mPa·s or more and less than 10.0.
x: The initial viscosity is 10.0 mPa·s or more.

(Evaluation criteria for viscosity stability)
A: The viscosity increase rate is less than 10%.
○: The viscosity increase rate is 10% or more and less than 20%.
Δ: The viscosity increase rate is 20% or more and less than 40%.
x: Viscosity increase rate is 40% or more.

<5> Evaluation of water-based paints and their painted products The following are water-based paints using the water-based dispersions prepared in the previous examples and comparative examples, and hue stability of pet film coatings prepared using the water-based paints. about the evaluation of The aqueous dispersions obtained in Examples E-1 to E-56 above are shown as aqueous dispersions E-1 to E-56, and the aqueous dispersions obtained in Comparative Examples E-1 to E-3 are , as Comparative Aqueous Dispersions E-1 to E-3.

<5-1> Preparation of water-based paint (Example F-1)
(1) Preparation of water-based paint 1-1 Using a high-speed stirrer, the following raw materials were stirred to obtain water-based paint 1-1 (stored at 25°C for 1 week).
Aqueous dispersion E-1 (stored at 25 ° C. for 1 week): 1.4 parts Acrylic resin (oxidation 65.0, OH value 50, Mw = 15000, solid content 35%): 13.6 parts Melamine resin ( Allnex, Cymel 325): 3.4 parts

(2) Preparation of water-based paint 1-2 Using a high-speed stirrer, the following raw materials were stirred to obtain water-based paint 1-2 (stored at 50°C for 1 week).
Aqueous dispersion E-1 (stored at 50 ° C. for 1 week): 1.4 parts Acrylic resin (oxidation 65.0, OH value 50, Mw = 15000, solid content 35%): 13.6 parts Melamine resin ( Allnex, Cymel 325): 3.4 parts

(Examples F-2 to F-56, Comparative Examples F-1 to F-3) Preparation of water-based paints 2 to 59 Water-based dispersion E-1 of Example F-1 (stored at 25 ° C. for 1 week) Dispersion E-2 to 29, Comparative Aqueous Dispersion E-1, Aqueous Dispersion E-30 to 43, Comparative Aqueous Dispersion E-2, Aqueous Dispersion E44 to 56, and Comparative Aqueous Dispersion E-3 (each Water-based paints 2-1 to 59-1 were obtained in the same manner as in Example F-1, except that they were stored at 25° C. for 1 week).
Further, aqueous dispersion E-1 of Example F-1 (stored at 50 ° C. for 1 week), aqueous dispersion E-2 to 29, comparative aqueous dispersion E-1, aqueous dispersion E-30 to 43, Everything was the same as in Example F-1, except that the comparative aqueous dispersion E-2, the aqueous dispersions E44 to 56, and the comparative aqueous dispersion E-3 (each stored at 50 ° C. for 1 week) were sequentially changed. to obtain water-based paints 2-2 to 59-2.

<5-2> Preparation of pet film coating (Example G-1) Preparation of pet film coating 1 Water-based paint 1-1 and water-based paint 1-2 were applied to a pet film using an applicator of 0.007 INCH. rice field. After the coating, the PET film was allowed to dry for 18 hours at room temperature. Then, it was dried at 60° C. for 5 minutes and at 140° C. for 20 minutes to obtain a PET film coating 1.

(Examples G-2 to G-56, Comparative Examples G-1 to G-3) Preparation of pet film coatings 2 to 59 Water-based paint 1-1 and water-based paint 1-2 of Example G-1 PET film coatings 2 to 59 were obtained in the same manner as in Example G-1, except for changing to 59-1 and 2-2 to 59-2.

<5-3> Evaluation of pet film coating For each pet film coating obtained in Examples G-1 to G-56 and Comparative Examples G-1 to G-3, hue stability was evaluated according to the following method. .

(Evaluation method for hue stability)
Using a colorimeter (manufactured by Konica Minolta, CM-700d), measure the color of a pet film painted with an aqueous dispersion paint stored at 25 ° C. for 1 week and an aqueous dispersion paint stored at 50 ° C. for 1 week. Then, the color difference (ΔE*) was determined and judged according to the following criteria. Table 11 shows the results. If it is "△" or more in the following evaluation criteria, it is a practical level.
(Evaluation criteria)
○: ΔE* is less than 1.5.
Δ: ΔE* is 1.5 or more and less than 3.0.
x: ΔE* is 3.0 or more.

<6> Aqueous inkjet ink and evaluation thereof The following relates to a dispersion for aqueous inkjet ink prepared using the previously prepared isoindoline compound, an aqueous inkjet ink using the dispersion, and evaluation thereof.

<6-1> Preparation of aqueous inkjet ink dispersion (Example H-1) Preparation of aqueous IJ dispersion 1 Isoindoline compound (Example 1-1): 19.0 parts Styrene-acrylic acid copolymer Combined (manufactured by BASF Japan Co., Ltd., Joncryl 61J): 16.4 parts Surfactant (manufactured by Kao Corporation, Emulgen 420): 5.0 parts Ion-exchanged water: 59.6 parts and a diameter of 1.25 mm 200 parts of zirconia beads were placed in a 200 ml glass bottle and dispersed in a paint shaker manufactured by Red Devil for 6 hours. Next, the zirconia beads were removed from the above dispersion to obtain dispersion 1 for aqueous inkjet ink (aqueous IJ dispersion 1).

(Examples H-2 to H-56, Comparative Examples H-1 to H-3) Preparation of Aqueous IJ Dispersions 2 to 59 Examples 1-2 to 1-29, 2-1 to 2-14, 3-1 to 3-13, and comparative compounds 1 to 3 as shown in Example H-1 and Water-based inkjet ink dispersions 2 to 59 (water-based IJ dispersions 2 to 59) were obtained in the same manner.

<6-2> Preparation of Water-Based Inkjet Inks The following relates to the preparation of water-based inkjet inks using the previously prepared water-based IJ Dispersions 1 to 59.
(Example I-1) Aqueous inkjet ink 1
Using a high speed mixer, the following raw materials were stirred and mixed for 30 minutes to obtain a mixture.
Aqueous IJ Dispersion 1 (Example H-1): 12.5 parts Styrene-acrylic acid copolymer (manufactured by Gifu Shellac Co., Ltd., Emapoly TYN-40, solid content 44.8%):2. 5 parts Surfactant (manufactured by Kao Corporation, Emulgen 420): 2.0 parts Ion-exchanged water: 64.9 parts Next, diethylene glycol monobutyl ether was added to the above mixture as appropriate, and the viscosity at 25 ° C. was 2.5 mPa. · s (25 ° C.), the surface tension was adjusted to 40 mN / m, then filtered using a 1.0 μm membrane filter, and further filtered using a 0.45 μm membrane filter to obtain aqueous inkjet ink 1. Obtained.

(Examples I-2 to I-56, Comparative Examples I-1 to I-3) Aqueous inkjet inks 2 to 59
Aqueous inkjet inks 2 to 59 were obtained in the same manner as in Example I-1, except that the aqueous IJ dispersion 1 in Example I-1 was changed to the aqueous IJ dispersions 2 to 59, respectively.

<6-3> Evaluation of Water-Based Inkjet Inks The viscosity stability of the water-based inkjet inks 1 to 59 prepared in Examples and Comparative Examples was evaluated as follows.
(Method for evaluating viscosity stability)
For each water-based inkjet ink, the initial viscosity at 25° C. was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.). Similarly, the viscosity was measured after aging at 25° C. for 4 weeks and after aging at 50° C. for 4 weeks. Using each measured value, the rate of increase in viscosity relative to the initial viscosity was calculated and used as an index of viscosity stability, and evaluated according to the following criteria. Table 12 shows the results. If it is "△" or more in the following evaluation criteria, it is a practical level.

(Evaluation criteria for viscosity stability)
A: The viscosity increase rate is less than 10%.
○: The viscosity increase rate is 10% or more and less than 20%.
Δ: The viscosity increase rate is 20% or more and less than 40%.
x: Viscosity increase rate is 40% or more.

In addition, each of the water-based inkjet inks 1 to 59 prepared in each example and each comparative example was filled in a cartridge of a printer HG5130 manufactured by Seiko Epson Corporation, and printed. When the water-based inkjet inks of Comparative Examples I-1 to I-3 were used, nozzle clogging occurred and printing could not be performed. On the other hand, when the water-based inkjet inks of Examples I-1 to I-56 were used, no nozzle clogging occurred and clear printing was possible.

From the above results, it can be seen that the use of the isoindoline compound (1) according to the present invention can provide a colored composition that is excellent in various properties and can be suitably used in various applications. For example, in the form of colorants for plastics and plastic molding compounds, colorants with excellent heat resistance can be provided. And, because of its high heat resistance, it is possible to efficiently provide a plastic molded product. In the form of a toner, it is possible to provide a toner with excellent pigment dispersibility. In addition, in the form of a paint, it is possible to provide a film having excellent weather resistance, and both can suppress discoloration. On the other hand, in the form of an aqueous pigment dispersion, it is possible to improve initial viscosity and storage stability. Furthermore, in the form of water-based inkjet ink, it is possible to provide an ink that has good storage stability, is less susceptible to nozzle clogging, and enables high-quality printing.

Claims (10)

An isoindoline compound represented by the following formula (1).

[wherein R ₁ to R ₆ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, a thioaryl group, represents an amide group or a sulfonamide group,
R ₇ and R ₈ each independently represent a hydrogen atom or an alkyl group,
A represents a group represented by the following formula (2), (3), or (4),

In the formula, X represents -O- or -NH-, R ₉ represents an alkyl group or an aryl group,
R ₁₀ and R ₁₁ each independently represent a hydrogen atom or an alkyl group,
R ₁₂ to R ₁₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group. ] A coloring composition comprising a pigment comprising the isoindoline compound of claim 1 and a dispersing medium. 3. The coloring composition of claim 2, wherein said dispersion medium comprises a resin. A coloring agent for plastics comprising the coloring composition according to claim 2 or 3. A plastic molded article containing the colorant for plastics according to claim 4 . A toner comprising the coloring composition according to claim 2 or 3. 3. The coloring composition of Claim 2, wherein the dispersing medium comprises a resin and a solvent. 8. The coloring composition of Claim 7, wherein the solvent comprises water. A paint or printing ink comprising the coloring composition according to claim 7 or 8. An inkjet ink comprising the coloring composition according to claim 7 or 8.