JP2018168363A - Method for producing isoindoline dye - Google Patents

Abstract

To provide a method for producing an isoindoline dye capable of exhibiting high contrast.SOLUTION: The method for producing an isoindoline dye according to the present invention includes the steps of: bringing an isoindoline dye (A) into contact with a solvent (Z); and extracting the isoindoline dye (A) brought into contact with the solvent (Z) by solid-liquid separation. A distance Ra between the Hansen solubility parameter of the isoindoline dye (A) and the Hansen solubility parameter of the solvent (Z), which is calculated on the basis of a formula (E.1), is 0 to 10 MPa(inclusive). The amount of the solvent (Z) in the contact step is 0.1 to 10.0 mass times (inclusive) the amount of the isoindoline dye (A).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an isoindoline dye.

  Examples of yellow or orange pigments include C.I. I. A compound having an isoindoline skeleton such as CI Pigment Yellow 139 is known, and the pigment is used for color display by utilizing reflected light or transmitted light in the fields of printing ink, paint, and the like. (Non-Patent Document 1). Patent Document 1 discloses C.I. I. A technique is disclosed in which Pigment Yellow 139 is washed with a nonpolar organic solvent such as n-hexane to form a film containing a color paste having a small haze and few pinholes. Patent Document 2 discloses C.I. I. CI Pigment Yellow 185 is dissolved in a good solvent (DMSO), and the pigment solution is contacted with a poor solvent (hydrochloric acid). I. A method for refining CI Pigment Yellow 185 is disclosed.

JP 2007-39481 A JP 2010-174143 A

Journal of Color Material Association 1982, 55 (9), 677, Hidehiko Sakai et al., Color Material Association

  In producing a coloring composition containing a coloring matter, since there are few kinds of known yellow or orange pigments, the range of selection of the pigment according to the application is not sufficient. Moreover, when it was used as a color filter, the problem was that the contrast was low. Although Patent Document 2 discloses a technique for improving contrast, it is not economical because a large amount of good solvent is required to dissolve a low-solubility dye such as an isoindoline dye in a good solvent. Therefore, in the present invention, provision of a method for producing an isoindoline dye that can exhibit high contrast is listed as one of the problems.

［式中、
δ_Ｄ１：イソインドリン色素（Ａ）のハンセン溶解度パラメータの分散成分（ＭＰａ^0.5）、
δ_Ｄ２：溶剤（Ｚ）のハンセン溶解度パラメータの分散成分（ＭＰａ^0.5）、
δ_Ｐ１：イソインドリン色素（Ａ）のハンセン溶解度パラメータの極性成分（ＭＰａ^0.5）、
δ_Ｐ２：溶剤（Ｚ）のハンセン溶解度パラメータの極性成分（ＭＰａ^0.5）、
δ_Ｈ１：イソインドリン色素（Ａ）のハンセン溶解度パラメータの水素結合成分（ＭＰａ^0.5）、
δ_Ｈ２：溶剤（Ｚ）のハンセン溶解度パラメータの水素結合成分（ＭＰａ^0.5）である］
［２］ 溶剤（Ｚ）のハンセン溶解度パラメータにおける溶剤（Ｚ）の分散成分δ_Ｄ２が１６．０ＭＰａ^0.5以上１９．０ＭＰａ^0.5以下であり、溶剤（Ｚ）の極性成分δ_Ｐ２が９．０ＭＰａ^0.5以上１７．０ＭＰａ^0.5以下であり、溶剤（Ｚ）の水素結合成分δ_Ｈ２が６．５ＭＰａ^0.5以上１１．０ＭＰａ^0.5以下である、［１］記載の製造方法。
［３］ 溶剤（Ｚ）が、エステル溶剤、ケトン溶剤、アミド溶剤、スルホキシド溶剤及びスルホン溶剤からなる群から選ばれる少なくとも一種を含む［１］又は［２］記載の製造方法。
［４］ 溶剤（Ｚ）の量が、イソインドリン色素（Ａ）に対して０．５質量倍以上８．０質量倍以下である、［１］〜［３］のいずれか記載の製造方法。
［５］ イソインドリン色素（Ａ）が式（１）で表される化合物を含む、［１］〜［４］のいずれか記載の製造方法。

［式（１）中、
Ｒ¹は、置換基を有していてもよい炭素数１〜４０の炭化水素基、置換基を有していてもよい複素環基、又は水素原子を表し、該炭化水素基に含まれる−ＣＨ₂−及び該複素環基が環を構成しない−ＣＨ₂−を含むときの該−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−Ｓ（Ｏ）₂−、−ＮＲ^x1−に置き換わっていてもよい。ただし、−ＣＨ₂−が置き換わることで−ＣＯＯＨ及び−Ｓ（Ｏ）₂ＯＨを形成することはない。また該炭化水素基及び該複素環基は、−ＣＯ₂ ^-及び−Ｓ（Ｏ）₂Ｏ^-からなる群から選ばれる少なくとも一種を有していてもよい。
Ｒ²〜Ｒ⁹は、互いに独立に、置換基を有していてもよい炭素数１〜４０の炭化水素基、置換基を有していてもよい複素環基、水素原子、ハロゲン原子、シアノ基、ニトロ基、−ＣＯ₂ ^-又は−Ｓ（Ｏ）₂Ｏ^-を表し、該炭化水素基に含まれる−ＣＨ₂−及び該複素環基が環を構成しない−ＣＨ₂−を含むときの該−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−Ｓ（Ｏ）₂−、−ＮＲ^x1−に置き換わっていてもよい。ただし、−ＣＨ₂−が置き換わることで−ＣＯＯＨ及び−Ｓ（Ｏ）₂ＯＨを形成することはない。また該炭化水素基及び該複素環基は、−ＣＯ₂ ^-及び−Ｓ（Ｏ）₂Ｏ^-からなる群から選ばれる少なくとも一種を有していてもよい。
Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁶とＲ⁷、及び、Ｒ⁸とＲ⁹は、各々が結合する炭素原子と一緒になって置換基を有していてもよい環を形成してもよく、該環が環を構成しない−ＣＨ₂−を含むときの該−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−Ｓ（Ｏ）₂−、−ＮＲ^x1−に置き換わっていてもよい。ただし、−ＣＨ₂−が置き換わることで−ＣＯＯＨ及び−Ｓ（Ｏ）₂ＯＨを形成することはない。また、この環は−ＣＯ₂ ^-及び−Ｓ（Ｏ）₂Ｏ^-からなる群から選ばれる少なくとも一種を有していてもよい。
Ｒ^x1は、置換基を有していてもよい炭素数１〜４０の炭化水素基、置換基を有していてもよい複素環基又は水素原子を表し、該炭化水素基及び該複素環基は、−ＣＯ₂ ^-及び−Ｓ（Ｏ）₂Ｏ^-からなる群から選ばれる少なくとも一種を有していてもよい。Ｒ^x1が複数個存在する場合、これらは同一でも異なっていてもよい。
ａは、式（１）で表される化合物が有する−ＣＯ₂ ^-及び−Ｓ（Ｏ）₂Ｏ^-の合計数であり、０〜１０のいずれかの整数を表す。
Ｍ^b+は、ヒドロン又はｂ価の金属イオンを表す。Ｍ^b+が複数個存在する場合、これらは同一でも異なっていてもよい。Ｍ^ｂ+がヒドロンのとき、該ヒドロンは前記−ＣＯ₂ ^-又は−Ｓ（Ｏ）₂Ｏ^-と一緒になって−ＣＯ₂Ｈ及びＳ（Ｏ）₂ＯＨとして存在する。
ｂは、１〜６の整数を表す。
ｍは、ａが０の場合は０であり、aが１以上である場合はＭ^b+の個数を表す。
ｎは、ａ及びｍが０である場合は１であり、ａ及びｍが０でない場合はｎ＝ｂ×ｍ／ａの関係を満たす数である。］
［６］ 前記イソインドリン色素（Ａ）が式（１ａ）で表される化合物であり、
さらに、工程Ａ又は工程Ｂから選ばれる式（１ａ）で表される化合物の製造工程を含む、［５］記載の製造方法。
工程Ａ： 式（ｐｔ１）で表される化合物を式（ｐｔ２）で表される化合物と反応させた後、式（ｐｔ３）で表される化合物と式（ｐｔ４）で表される化合物とをさらに酸の存在下で反応させて式（１ａ）で表される化合物を製造する工程
工程Ｂ： 式（ｐｔ５）で表される化合物と式（ｐｔ３）で表される化合物と式（ｐｔ４）で表される化合物とを反応させて式（１ａ）で表される化合物を製造する工程

［式（ｐｔ１）〜式（ｐｔ５）及び式（１ａ）中、Ｒ²〜Ｒ⁹は、前記と同一の意味を表す。Ｒ⁴¹は、水素原子または炭素数１〜２０のアルキル基を表す。Ｍ¹は、アルカリ金属原子を表す。］
［７］ 前記イソインドリン色素（Ａ）が式（１ｂ）で表される化合物であり、
さらに、工程Ａ又は工程Ｂから選ばれる式（１ａ）の合成工程と、工程Ｃで表される式（１ｂ）で表される化合物の製造工程とを含む、［５］記載の製造方法。
工程Ａ： 式（ｐｔ１）で表される化合物を式（ｐｔ２）で表される化合物と反応させた後、式（ｐｔ３）で表される化合物と式（ｐｔ４）で表される化合物とをさらに酸の存在下で反応させて式（１ａ）で表される化合物を製造する工程
工程Ｂ： 式（ｐｔ５）で表される化合物と式（ｐｔ３）で表される化合物と式（ｐｔ４）で表される化合物とを反応させて式（１ａ）で表される化合物を製造する工程
工程Ｃ： 式（１ａ）で表される化合物と式（ｐｔ６）で表される化合物と反応させて式（１ｂ）で表される化合物を製造する工程

［式（ｐｔ１）〜式（ｐｔ６）及び式（１ｂ）中、Ｒ¹〜Ｒ⁹は、前記と同一の意味を表す。Ｒ⁴¹は、水素原子または炭素数１〜２０のアルキル基を表す。Ｍ¹は、アルカリ金属原子を表す。ＬＧ¹は、ハロゲン原子、メタンスルホニルオキシ基、クロロメチルスルホニルオキシ基、トルエンスルホニルオキシ基又はトリフルオロメタンスルホニルオキシ基を表す。ただしＲ¹は水素原子ではない。］ The method for producing an isoindoline dye according to the present invention is summarized as follows.
[1] A step of bringing the isoindoline dye (A) into contact with the solvent (Z), and a step of taking out the isoindoline dye (A) in contact with the solvent (Z) by solid-liquid separation,
The distance Ra between the Hansen solubility parameter of the isoindoline dye (A) and the Hansen solubility parameter of the solvent (Z) calculated based on the formula (E.1) is 0 MPa ^0.5 or more and 10 MPa ^0.5 or less, and The method for producing an isoindoline dye, wherein the amount of the solvent (Z) in the contacting step is 0.1 to 10.0 times the mass of the isoindoline dye (A).

[Where:
δ _D1 : disperse component of Hansen solubility parameter (MPa ^0.5 ) of isoindoline dye (A),
δ _D2 : dispersive component of Hansen solubility parameter of solvent (Z) (MPa ^0.5 ),
δ _P1 : polar component (MPa ^0.5 ) of Hansen solubility parameter of isoindoline dye (A),
δ _P2 : polar component (MPa ^0.5 ) of Hansen solubility parameter of solvent (Z),
δ _H1 : hydrogen bond component (MPa ^0.5 ) of Hansen solubility parameter of isoindoline dye (A),
δ _{H2 is} the hydrogen bonding component (MPa ^0.5 ) of the Hansen solubility parameter of the solvent (Z)]
[2] The dispersion component δ _D2 of the solvent (Z) in the Hansen solubility parameter of the solvent (Z) is 16.0 MPa ^0.5 or more and 19.0 MPa ^0.5 or less, and the polar component δ _P2 of the solvent (Z) is 9.0 MPa ^0.5 or more. [1] The production method according to [1], wherein the pressure is 17.0 MPa ^0.5 or less, and the hydrogen bonding component δ _H2 of the solvent (Z) is 6.5 MPa ^0.5 or more and 11.0 MPa ^0.5 or less.
[3] The production method according to [1] or [2], wherein the solvent (Z) contains at least one selected from the group consisting of an ester solvent, a ketone solvent, an amide solvent, a sulfoxide solvent, and a sulfone solvent.
[4] The production method according to any one of [1] to [3], wherein the amount of the solvent (Z) is 0.5 to 8.0 times by mass with respect to the isoindoline dye (A).
[5] The production method according to any one of [1] to [4], wherein the isoindoline dye (A) includes a compound represented by the formula (1).

[In Formula (1),
R ¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and is included in the hydrocarbon group − In the case where CH ₂ — and the heterocyclic group include —CH ₂ — that does not form a ring, —CH ₂ — is replaced by —O—, —CO—, —S (O) ₂ —, —NR ^x1 —. It may be. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— .
R ^{2 to} R ⁹ are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. group, a nitro group, -CO ₂ ^- or -S (O) ₂ O ^- represents, -CH ₂ - contained in the hydrocarbon group when including - and said heterocyclic group is -CH ₂ does not constitute a ring The —CH ₂ — may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— .
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁸ and R ⁹ have a substituent together with the carbon atom to which they are bonded. A ring may be formed, and when the ring contains —CH ₂ — that does not constitute a ring, —CH ₂ — represents —O—, —CO—, —S (O) ₂ —, — NR ^x1 − may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. Further, the ring -CO ₂ ^- and -S (O) ₂ O ^- may have at least one selected from the group consisting of.
R ^x1 represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, an optionally substituted heterocyclic group or a hydrogen atom, and the hydrocarbon group and the heterocyclic group May have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— . When a plurality of R ^x1 are present, these may be the same or different.
a is the total number of —CO ₂ ^— and —S (O) ₂ O ^— contained in the compound represented by the formula (1), and represents an integer of 0 to 10.
M ^{b +} represents hydron or a b-valent metal ion. When a plurality of M ^{b +} are present, these may be the same or different. When M ^{b +} is hydrone, the hydrone is present as —CO ₂ H and S (O) ₂ OH together with the —CO ₂ ^— or —S (O) ₂ O ^— .
b represents an integer of 1 to 6.
m represents 0 when a is 0, and represents the number of M ^{b +} when a is 1 or more.
n is 1 when a and m are 0, and is a number satisfying the relationship n = b × m / a when a and m are not 0. ]
[6] The isoindoline dye (A) is a compound represented by the formula (1a),
Furthermore, the manufacturing method of [5] description including the manufacturing process of the compound represented by Formula (1a) chosen from the process A or the process B.
Step A: After reacting the compound represented by the formula (pt1) with the compound represented by the formula (pt2), the compound represented by the formula (pt3) and the compound represented by the formula (pt4) are further added. Step of producing a compound represented by formula (1a) by reacting in the presence of an acid Step B: A compound represented by formula (pt5), a compound represented by formula (pt3) and a formula (pt4) For producing a compound represented by the formula (1a) by reacting with a compound to be produced

[In Formula (pt1) to Formula (pt5) and Formula (1a), R ^{2 to} R ⁹ represent the same meaning as described above. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. M ¹ represents an alkali metal atom. ]
[7] The isoindoline dye (A) is a compound represented by the formula (1b),
Furthermore, the manufacturing method of [5] description including the synthetic | combination process of the formula (1a) chosen from the process A or the process B, and the manufacturing process of the compound represented by the formula (1b) represented by the process C.
Step A: After reacting the compound represented by the formula (pt1) with the compound represented by the formula (pt2), the compound represented by the formula (pt3) and the compound represented by the formula (pt4) are further added. Step of producing a compound represented by formula (1a) by reacting in the presence of an acid Step B: A compound represented by formula (pt5), a compound represented by formula (pt3) and a formula (pt4) A step of producing a compound represented by the formula (1a) by reacting with a compound represented by the formula (1a) Step C: A compound represented by the formula (1a) and a compound represented by the formula (pt6) are reacted with the formula (1b). Step for producing a compound represented by

[In formula (pt1) to formula (pt6) and formula (1b), R ^{1 to} R ⁹ represent the same meaning as described above. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. M ¹ represents an alkali metal atom. LG ¹ represents a halogen atom, a methanesulfonyloxy group, a chloromethylsulfonyloxy group, a toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group. However, R ¹ is not a hydrogen atom. ]

  According to the present invention, a new method for producing an isoindoline dye is provided. According to the present invention, a color filter formed from a colored composition or a colored curable composition containing an isoindoline dye can have a high contrast.

The present invention includes a step of bringing the isoindoline dye (A) into contact with the solvent (Z), and a step of taking out the isoindoline dye (A) in contact with the solvent (Z) by solid-liquid separation,
The distance Ra between the Hansen solubility parameter of the isoindoline dye (A) and the Hansen solubility parameter of the solvent (Z) calculated based on the formula (E.1) is 0 MPa ^0.5 or more and 10 MPa ^0.5 or less, and The amount of the solvent (Z) in the contacting step relates to a method for producing an isoindoline dye that is 0.1 to 10.0 times by mass with respect to the isoindoline dye (A).
That is, the present invention
(I) A purified isoindoline dye (A) comprising a step of bringing the isoindoline dye (A) into contact with the solvent (Z) and a step of obtaining a purified isoindoline dye (A) by solid-liquid separation such as filtration. In the production method of A), in the solvent (Z), the distance Ra between the Hansen solubility parameter of the isoindoline dye (A) and the Hansen solubility parameter of the solvent (Z) is 0 MPa ^{0.5 to} 10 MPa ^0.5. The method for producing a purified isoindoline dye (A), which is a solvent and the amount of the solvent (Z) is 0.1 to 10.0 times by mass with respect to the isoindoline dye (A) About.

(0) Solvent (Z)
The Hansen solubility parameter is represented in a three-dimensional space by dividing the solubility parameter introduced by Hildebrand into three components: a dispersion term δ _D , a polar term δ _P , and a hydrogen bond term δ _H. Is. The dispersion term δ _D indicates the effect due to the dispersion force, the polar term δ _P indicates the effect due to the dipole force, and the hydrogen bond term δ _H indicates the effect due to the hydrogen bond force.

The definition and calculation of Hansen solubility parameters are described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007). Further, by using the computer software Hansen Solubility Parameters in Practice (HSPiP), the Hansen solubility parameter can be easily estimated from the chemical structure of a solvent whose literature values are not known.
In the present invention, using HSPiP version 3, the solvent is selected by using the value for the solvent registered in the database and the estimated value for the solvent not registered. In the present invention, a solvent satisfying the relationship of the isoindoline dye (A) and the formula (E.1) is referred to as a solvent (Z).

  The solvent (Z) may be either a single solvent composed of one kind of solvent or a solvent mixture containing two or more kinds of solvents. When the solvent (Z) is a solvent mixture, the Hansen solubility parameter of the solvent (Z) in formula (E.1) should be the average Hansen solubility parameter based on the mixing ratio (volume ratio) of each solvent contained in the solvent mixture. And

In general, the Hansen solubility parameter of a dye can be determined by conducting a test to measure the solubility of a sample of the dye in a number of different solvents for which the Hansen solubility parameter is established. Here, for example, when the Hansen solubility parameter of another solvent that was not used for the measurement of the Hansen solubility parameter of the dye is (δ _D2 , δ _P2 , and δ _H2 ), the point indicated by the coordinates is If encapsulated inside the Hansen solubility sphere of the dye, the solvent is considered to dissolve the dye. On the other hand, if the coordinate point is outside the Hansen solubility sphere of the dye, it is considered that the solvent cannot dissolve the dye.
In the present invention, among the solvents used in the solubility test, all the three-dimensional points of the solvent in which the dye is dissolved are encapsulated inside the sphere, and the non-dissolved solvent points are outside the sphere ( The Hansen Solubility Sphere) was found and the center coordinates of the sphere were taken as the Hansen Solubility parameter for the dye. A specific method for the solubility test will be described in detail in the Examples section.

［式中、δ_Ｄ１、δ_Ｐ１、及びδ_Ｈ１は式（Ｅ．１）に同じ。
ｘ_Ｉは、イソインドリン色素（Ａ）中のイソインドリン色素（ＡＩ）の体積分率、
ｘ_ＩＩは、イソインドリン色素（Ａ）中のイソインドリン色素（ＡＩＩ）の体積分率、
（δ_Ｄ１ ^Ｉ，δ_Ｐ１ ^Ｉ，δ_Ｈ１ ^Ｉ）は、イソインドリン色素（ＡＩ）のハンセン溶解度パラメータ、
（δ_Ｄ１ ^ＩＩ，δ_Ｐ１ ^ＩＩ，δ_Ｈ１ ^ＩＩ）は、イソインドリン色素（ＡＩＩ）のハンセン溶解度パラメータである。］ The isoindoline dye (A) may be either a single pigment composed of one kind of isoindoline dye or a mixture containing two or more kinds of isoindoline dyes. When the isoindoline dye (A) is a mixture of two kinds of dyes, the isoindoline dye (AI) and the isoindoline dye (AII), the Hansen solubility parameter of the isoindoline dye (A) based on the formula (E.2) Can be calculated. The volume fraction can be approximately changed to a weight fraction. When the isoindoline dye (A) is a mixture of three or more kinds, the Hansen solubility parameter of the isoindoline dye (A) can be calculated by the same calculation.

[Wherein δ _D1 , δ _P1 , and δ _H1 are the same as in formula (E.1).
x _I is the volume fraction of the isoindoline dye (AI) in the isoindoline dye (A),
x _II is the volume fraction of the isoindoline pigments (A) in isoindoline pigments (AII),
(Δ _D1 ^I , δ _P1 ^I , δ _H1 ^I ) is the Hansen solubility parameter of the isoindoline dye (AI),
(Δ _D1 ^II , δ _P1 ^II , δ _H1 ^II ) is a Hansen solubility parameter of the isoindoline dye (AII). ]

［式中、
δ_Ｄ１：イソインドリン色素（Ａ）のハンセン溶解度パラメータの分散成分（ＭＰａ^0.5）、
δ_Ｄ２：溶剤（Ｚ）のハンセン溶解度パラメータの分散成分（ＭＰａ^0.5）、
δ_Ｐ１：イソインドリン色素（Ａ）のハンセン溶解度パラメータの極性成分（ＭＰａ^0.5）、
δ_Ｐ２：溶剤（Ｚ）のハンセン溶解度パラメータの極性成分（ＭＰａ^0.5）、
δ_Ｈ１：イソインドリン色素（Ａ）のハンセン溶解度パラメータの水素結合成分（ＭＰａ^0.5）、
δ_Ｈ２：溶剤（Ｚ）のハンセン溶解度パラメータの水素結合成分（ＭＰａ^0.5）である］ The distance Ra between the Hansen solubility parameter of the isoindoline dye (A) and the Hansen solubility parameter of the solvent (Z) is defined by the equation (E.1). Distance Ra between the Hansen solubility parameters of the Hansen solubility parameters and solvents (Z) isoindoline pigment (A) is, 0 MPa ^0.5 or more, 10 MPa ^0.5 or less, preferably 9.0 MPa ^0.5 or less, more preferably 7.0 MPa ^0.5 or less, More preferably, it is 5.0 MPa ^0.5 or less. If Ra exceeds 10 MPa, the isoindoline dye may have a low contrast.

[Where:
δ _D1 : disperse component of Hansen solubility parameter (MPa ^0.5 ) of isoindoline dye (A),
δ _D2 : dispersive component of Hansen solubility parameter of solvent (Z) (MPa ^0.5 ),
δ _P1 : polar component (MPa ^0.5 ) of Hansen solubility parameter of isoindoline dye (A),
δ _P2 : polar component (MPa ^0.5 ) of Hansen solubility parameter of solvent (Z),
δ _H1 : hydrogen bond component (MPa ^0.5 ) of Hansen solubility parameter of isoindoline dye (A),
δ _{H2 is} the hydrogen bonding component (MPa ^0.5 ) of the Hansen solubility parameter of the solvent (Z)]

In the Hansen solubility parameter of the solvent (Z), the dispersion component δ _D2 of the solvent (Z) is preferably 16.0 MPa ^0.5 or more, more preferably 16.3 MPa ^0.5 or more, further preferably 16.5 MPa ^0.5 or more, preferably is 19.0 MPa ^0.5 or less, more preferably 18.7MPa ^0.5 or less, more preferably 18.5 MPa ^0.5 or less.
Polar component [delta] _P2 of the solvent (Z) is preferably from 9.0 MPa ^0.5 or more, more preferably 9.5 MPa ^0.5 or more, still more preferably 10.0 MPa ^0.5 or more, preferably 17.0MPa ^0.5 or less, more preferably 16.7 MPa ^0.5 or less, more preferably 16.4 MPa ^0.5 or less.
The hydrogen bond component [delta] _H2 of the solvent (Z), preferably 6.5 MPa ^0.5 or more, more preferably 6.8 MPa ^0.5 or more, more preferably 7.1 MPa ^0.5 or higher, preferably 11.0 MPa ^0.5 or less, more preferably 10 0.7 MPa ^0.5 or less, more preferably 10.4 MPa ^0.5 or less.

In the Hansen solubility parameter of the isoindoline dye (A), the dispersion component δ _D1 of the dye (A) is preferably 15.5 MPa ^0.5 or more, more preferably 16.0 MPa ^0.5 or more, and further preferably 16.5 MPa ^0.5 or more. There is preferably 18.5 MPa ^0.5 or less, more preferably 18.2MPa ^0.5 or less, more preferably 18.0 MPa ^0.5 or less.
Polar component [delta] _P1 of the dye (A) is preferably 9.0 MPa ^0.5 or more, more preferably 10.0 MPa ^0.5 or more, still more preferably 11.0 MPa ^0.5 or more, preferably 17.0MPa ^0.5 or less, more preferably Is 16.0 MPa ^0.5 or less, more preferably 15.0 MPa ^0.5 or less.
The hydrogen bonding component δ _H1 of the dye (A) is preferably 6.0 MPa ^0.5 or more, more preferably 7.5 MPa ^0.5 or more, still more preferably 9.0 MPa ^0.5 or more, preferably 14.0 MPa ^0.5 or less, more preferably 12.5 MPa ^0.5 or less, more preferably 11.0 MPa ^0.5 or less.

  As the solvent (Z), a solvent usually used in the art can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (in the molecule). Solvent containing -O- and not containing -COO-), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (containing -CO- in the molecule, -COO- Solvent), alcohol solvent (solvent containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvent, amide solvent, sulfoxide solvent, sulfone solvent. .

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

  As the amide solvent, formamide, N, N-dimethylformamide, acetamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethyl Acetoacetamide, N-methylpyrrolidone, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone Etc. The amide solvent is preferably N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylacetoacetamide, 1,3-dimethyl-2-imidazolidinone, more preferably N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylacetoacetamide, 1,3-dimethyl-2-imidazolidinone.

  Examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, and tetramethylene sulfoxide. The sulfoxide solvent is preferably dimethyl sulfoxide or diethyl sulfoxide, and more preferably dimethyl sulfoxide.

  Examples of the sulfone solvent include dimethyl sulfone, diethyl sulfone, dipropyl sulfone, isopropyl methyl sulfone, and sulfolane. The sulfone solvent is preferably dimethyl sulfone, diethyl sulfone or sulfolane, more preferably sulfolane.

  The solvent (Z) preferably contains at least one selected from the group consisting of ester solvents, ketone solvents, amide solvents, sulfoxide solvents and sulfone solvents, and at least selected from the group consisting of amide solvents, sulfone solvents, and sulfoxide solvents. More preferably, it contains at least one, and more preferably contains at least one selected from the group consisting of amide solvents and sulfoxide solvents. In 100% of the solvent (Z), the amide solvent, the sulfone solvent, and the sulfoxide solvent are preferably 40% or more, more preferably 50% or more, and still more preferably 60% or more by volume ratio.

  As a method of bringing the isoindoline dye (A) and the solvent (Z) into contact with each other, a method of mixing the isoindoline dye (A) and the solvent (Z) in a container is preferable. At the time of mixing, the liquid mixture containing the isoindoline dye (A) and the solvent (Z) may be stirred, and the stirring time is preferably 1 minute to 10 hours, more preferably 10 minutes to 5 hours. Agitation by ultrasonic vibration is also preferred.

The temperature at which the isoindoline dye (A) is brought into contact with the solvent (Z) is preferably −78 ° C. to the boiling point of the solvent (Z), more preferably −20 ° C. to the boiling point of the solvent (Z), and still more preferably. Is 10-50 ° C.
The contact time when the isoindoline dye (A) is contacted with the solvent (Z) is preferably 10 seconds or more, more preferably 10 minutes or more, still more preferably 1 hour or more, preferably 24 hours or less, more Preferably it is 12 hours or less, More preferably, it is 5 hours or less.

  The amount of the solvent (Z) in the contacting step is 0.1 mass times or more, more preferably 0.5 mass times or more, further preferably 2 mass times with respect to the isoindoline dye (A) from the viewpoint of yield. It is above, and is 10.0 mass times or less, More preferably, it is 8.0 mass times or less, More preferably, it is 6.0 mass times or less. The isoindoline dye (A) used in this step represents the isoindoline dye (A) before being brought into contact with the solvent (Z), and is not only a dried product of the isoindoline dye (A) but also a solid liquid from the reaction mixture. A residue containing the separated isoindoline dye (A) is also preferably used. In the latter case, the residue may contain a solvent used in the reaction or a solvent used in the subsequent washing, but the amount of the solvent (Z) in the contacting step includes these It shall be calculated including the amount of solvent (Z) contained in the solvent.

  The isoindoline dye (A) brought into contact with the solvent (Z) is separated from the solvent (Z) by solid-liquid separation and taken out as a solid. That is, the purified isoindoline dye (A) can be taken out by solid-liquid separation. Solid-liquid separation is preferably carried out by natural filtration, vacuum filtration, pressure filtration, centrifugal filtration, centrifugal separation, or the like. The isoindoline dye (A) from which the solvent (Z) has been removed may be further subjected to treatments such as washing, recrystallization and drying.

(1) Isoindoline dye The isoindoline dye (A) is preferably a compound represented by the formula (1) (hereinafter sometimes referred to as isoindoline dye (1)).

[In Formula (1),
R ¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and is included in the hydrocarbon group − In the case where CH ₂ — and the heterocyclic group include —CH ₂ — that does not form a ring, —CH ₂ — is replaced by —O—, —CO—, —S (O) ₂ —, —NR ^x1 —. It may be. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— .
R ^{2 to} R ⁹ are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. group, a nitro group, -CO ₂ ^- or -S (O) ₂ O ^- represents, -CH ₂ - contained in the hydrocarbon group when including - and said heterocyclic group is -CH ₂ does not constitute a ring The —CH ₂ — may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— .
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁸ and R ⁹ have a substituent together with the carbon atom to which they are bonded. A ring may be formed, and when the ring contains —CH ₂ — that does not constitute a ring, —CH ₂ — represents —O—, —CO—, —S (O) ₂ —, — NR ^x1 − may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. Further, the ring -CO ₂ ^- and -S (O) ₂ O ^- may have at least one selected from the group consisting of.
R ^x1 represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, an optionally substituted heterocyclic group or a hydrogen atom, and the hydrocarbon group and the heterocyclic group May have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— . When a plurality of R ^x1 are present, these may be the same or different.
a is the total number of —CO ₂ ^— and —S (O) ₂ O ^— contained in the compound represented by the formula (1), and represents an integer of 0 to 10.
M ^{b +} represents hydron or a b-valent metal ion. When a plurality of M ^{b +} are present, these may be the same or different. When M ^{b +} is hydrone, the hydrone is present as —CO ₂ H and S (O) ₂ OH together with the —CO ₂ ^— or —S (O) ₂ O ^— .
b represents an integer of 1 to 6.
m represents 0 when a is 0, and represents the number of M ^{b +} when a is 1 or more.
n is 1 when a and m are 0, and is a number satisfying the relationship n = b × m / a when a and m are not 0. ]
The number of carbon atoms of the group formed by replacing —CH ₂ — contained in the hydrocarbon group with —O—, —CO—, —S (O) ₂ —, —NR ^x1 — is: —O—, —CO It is counted as the number of carbons before being substituted with —, —S (O) ₂ —, —NR ^x1 — and the like.
In the present specification, the “substituent” does not include —COOH and —S (O) ₂ OH. The “substituent” does not include a group formed by replacing —CH ₂ — with —O—, —CO—, —S (O) ₂ —, —NR ^x1 — or —NR ^x3 —. A group formed by replacing —CH ₂ — with —O—, —CO—, —S (O) ₂ —, —NR ^x1 — may hereinafter be referred to as “group (Z1)”. A group formed by replacing —CH ₂ — with —O—, —CO—, —S (O) ₂ —, —NR ^x3 — may hereinafter be referred to as “group (Z2)”.

The compound represented by the formula (1) may be a compound represented by the formula (2) (hereinafter sometimes referred to as isoindoline dye (2)).

[In Formula (2),
R ¹¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and is included in the hydrocarbon group − When CH ₂ — and the heterocyclic group include —CH ₂ — that does not form a ring, —CH ₂ — is replaced with —O—, —CO—, —S (O) ₂ —, —NR ^x3 —. It may be. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
R ^{12 to} R ¹⁵ are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. represents a group or a nitro group, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, -O -, - CO- , -S (O) _2- , -NR ^x3- may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ may form a ring together with the carbon atoms to which they are bonded, and the ring does not constitute a ring —CH ₂ - is, -O - - the -CH ₂ when containing, - CO -, - S ( O) 2 -, - NR x3 - may be replaced with. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The ring may have a substituent.
R ¹⁶ is —CO—OR ⁿ³⁰ , —CO—NH ₂ , —CO—NH (R ⁿ³⁰ ), —CO—N (R ⁿ³¹ ) ₂ , —CO—H, —CO—R ⁿ³⁰ or —S (O ) ₂ ^-Rn30 is represented. However, when R ¹⁶ represents —CO—NH (R ⁿ³⁰ ), at least one of (a) and (b) is satisfied.
(A) At least one of R ^{12 to} R ¹⁵ may have a hydrocarbon group having 1 to 40 carbon atoms, a heterocyclic group optionally having a substituent, a halogen atom, a cyano group or a nitro group, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, -O -, - CO-, -S (O) _2- , ^-NRx3- may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
(B) At least one pair of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ is bonded to form a ring, and the ring includes —CH ₂ — that does not form a ring. The —CH ₂ — may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x3 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The ring may have a substituent. R ^{12 to} R ¹⁵ which do not form a ring are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, -O-, -CO-, -S (O) _2- , and ^-NRx3- may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
R ⁿ³⁰ is usually a monovalent group and represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent, and the hydrocarbon the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring - is, -O - -CH ₂ contained in the base, - CO -, - S ( O) 2 -, - NR ^x3 − may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. When a plurality of R ⁿ³⁰ are present, these may be the same or different.
R ⁿ³¹ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent, and —CH ₂ — contained in the hydrocarbon group. and heterocyclic group is -CH ₂ does not constitute a ring - the -CH ₂ when containing - is, -O -, - CO -, - S (O) 2 -, - NR x3 - be replaced in Good. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. When a plurality of R ⁿ³¹ are present, these may be the same or different.
X ¹ represents a group represented by the formula (1ax).

[In the formula (1ax), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, -O-, -CO-, -S (O) _2- , and ^-NRx3- may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
R ²¹ and R ²² may form a ring which may have a substituent together with the carbon atom to which each is bonded, and the ring contains —CH ₂ — that does not form a ring. The —CH ₂ — may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x3 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
* 1 represents a bond to the isoindoline ring.
R ^x3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. When a plurality of R ^x3 are present, these may be the same or different. ]]

The number of carbon atoms of the group formed by replacing —CH ₂ — contained in the hydrocarbon group with —O—, —CO—, —S (O) ₂ —, —NR ^x3 — is: —O—, —CO It is counted as the number of carbons before being substituted with —, —S (O) ₂ —, —NR ^x3 — or the like.
Isoindoline pigments (2), -CO ₂ ^- and -S (O) ₂ O ^- no. Hereinafter, —CO ₂ ^— and —S (O) ₂ O ^— may be referred to as a “hydrone-bonding group”.
The formula (1ax) includes the formula (2ax).

[In the formula (2ax), R ²³ and R ²⁴ are each independently a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or it represents a hydrogen atom, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, -O -, - CO-, -S (O) _2- , ^-NRx3- may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —.
* 2 represents a bond to the isoindoline ring.
R ^x3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. When a plurality of R ^x3 are present, these may be the same or different. ]

R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²² , R ^x1 , and R ^x3 represented by a hydrocarbon group having 1 to 40 carbon atoms, R ^{23 to} R ²⁴ and R ⁿ³⁰ The hydrocarbon group having 1 to 35 carbon atoms or the hydrocarbon group having 1 to 15 carbon atoms represented by R ⁿ³¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group The group may be saturated or unsaturated, and may be chain or alicyclic.

^Examples of the saturated or unsaturated chain hydrocarbon group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , and R ⁿ³¹ include methyl group, ethyl Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, linear alkyl group such as dodecyl group, etc .; isopropyl group, (2-methyl) propyl group , Isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl) butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl) pentyl group, (2-methyl) pentyl group, ( 1-ethyl) pentyl, (3-ethyl) pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl, and (3-ethyl) heptyl Etc .; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, (1-methyl) ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1 -(2-propenyl)) ethenyl group, (1,2-dimethyl) propenyl group and alkenyl group such as 2-pentenyl group; and the like. Examples of R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , and R ⁿ³⁰ include a heptadecyl group, an octadecyl group, and an icosyl group. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30 in the case of R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ . More preferably, it is 1-20, More preferably, it is 1-15, Even more preferably, it is 1-10, Even more preferably, it is 1-8, Most preferably, it is 1-5, R ^In the case of ⁿ³¹ , it is preferably 1-15, more preferably 1-10, and even more preferably 1-8.

The saturated or unsaturated alicyclic hydrocarbon group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , and R ⁿ³¹ is a cyclopropyl group. 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethyl Cyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethyl Cyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group and 3,3,3 A cycloalkyl group such as a 5,5-tetramethylcyclohexyl group, a 4-pentylcyclohexyl group, a 4-octylcyclohexyl group, a 4-cyclohexylcyclohexyl group; a cyclohexenyl group (for example, cyclohex-2-ene, cyclohex-3-ene), And cycloalkenyl groups such as cycloheptenyl and cyclooctenyl; norbornane, adamantyl, bicyclo [2.2.2] octane and the like. In the case of R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , the alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably Is from 3 to 20, more preferably from 4 to 20, even more preferably from 4 to 15, even more preferably from 5 to 15, particularly preferably from 5 to 10, among which a cyclopentyl group, A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are particularly preferable. In the case of R ⁿ³¹ , it is preferably 4 to 15, more preferably 5 to 15, and even more preferably 5 to 10, Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are particularly preferable.

The saturated or unsaturated hydrocarbon groups represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , and R ⁿ³⁰ , and R ⁿ³¹ are the chain structures listed above. The group may be a combination of a hydrocarbon group and an alicyclic hydrocarbon group, for example, cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group. , An alkyl group to which one or more alicyclic hydrocarbon groups such as a cyclohexylmethyl group and a cyclohexylethyl group are bonded. The number of carbon atoms ^{thereof, R 1 ~R 9, R 11} ~R 15, R 21 ~R 24, R x1, R x3, and if the R ^n30, is preferably 4 to 30, more preferably 4 to 20 ^Yes , more preferably 4-15, and in the case of ^Rn31 , 4-15 is preferred.

The aromatic hydrocarbon groups represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , and R ⁿ³¹ are a phenyl group, an o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, Mesityl group, 2,6-bis (2-propyl) phenyl group, 2,4,6-trimethylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group 5,6,7,8-tetrahydro-2-naphthyl group, a fluorenyl group, an aromatic hydrocarbon group such as a phenanthryl group and an anthryl group; and the like. In the case of R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , and R ⁿ³⁰ , the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, and more preferably Is 6 to 20, more preferably 6 to 15, and in the case of R ⁿ³¹ , it is preferably 6 to 15.

The aromatic hydrocarbon group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ and R ⁿ³¹ is a hydrocarbon group having an aromatic hydrocarbon ring. The chain hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group listed above are combined with the aromatic hydrocarbon group listed above. An aralkyl group such as benzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, phenylethyl group, phenylpropyl group, 1-methyl-1-phenylethyl group; An arylalkenyl group such as a phenylethenyl group (phenylvinyl group); an arylalkynyl group such as a phenylethynyl group; a phenyl group to which one or more phenyl groups such as a biphenylyl group or a terphenylyl group are bonded; cyclohexyl Butylphenyl group, benzyl phenyl group, (dimethyl (phenyl) methyl) phenyl group; and the like, the carbon ^{number, R 1 ~R 9, R 11} ~R 15, R 21 ~R 24, R x1, R x3 , And R ⁿ³⁰ , preferably ^7-30 , more preferably 7-20, still more preferably 7-15, and R ⁿ³¹ is preferably 7-15.

The hydrocarbon groups represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , and R ⁿ³¹ are monovalent substituents or divalent substituents. It may have a group. In the divalent substituent, two bonds are preferably bonded to the same carbon atom to form a double bond.

As the monovalent substituent,
An alkylsulfanyl group having 1 to 10 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group and a butylthio group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Nitro group; cyano group;
Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, A hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, in which all hydrogen atoms such as perfluorodecyl group, perfluorocyclohexyl group, and perfluorophenyl group are substituted by fluorine atoms;
* -CO-SH;
_{* -CO-S-CH 3,} * - CO-S-CH 2 CH 3, * - CO-S-CH 2 -CH 2 -CH 3, * - CO-S-CH 2 -CH 2 -CH 2 - A carbonyl group bonded to a sulfur atom bonded to an alkyl group such as CH ₃ (the alkyl group has 1 to 10 carbon atoms);
* —CO—S—C ₆ H _{5 and the} like, and a carbonyl group bonded to a sulfur atom bonded to an aryl group (the aryl group has 6 to 20 carbon atoms);

Examples of the divalent substituent include a thioxo group, an imino group, an imino group substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and an imino group substituted with an aryl group having 6 to 20 carbon atoms. Etc. Examples of the imino group substituted with an alkyl group include CH ₃ —N═, CH ₃ —CH ₂ —N═, CH ₃ — (CH ₂ ) ₂ —N═, CH ₃ — (CH ₂ ) ₃ —N =, and the like. Can be mentioned. Examples of the imino group substituted with an aryl group include C ₆ H ₅ —N═.

As the substituent, a halogen atom; a nitro group; a cyano group; a hydrocarbon group having 1 to 20 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms; a thiocarbonyl group;
More preferred are a fluorine atom, a chlorine atom, a bromine atom; a nitro group; a cyano group; a hydrocarbon group having 1 to 10 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms; a thiocarbonyl group, and the like.

The hydrocarbon group represented by R ^{1 to} R ⁹ is a group formed by replacing —CH ₂ — with —O—, —CO—, —S (O) ₂ —, —NR ^x1 — (that is, Group (Z1)).
In the hydrocarbon groups represented by R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ⁿ³⁰ , and R ⁿ³¹ , —CH ₂ — is —O—, —CO—, —S (O) ₂ —, or A group formed by replacing —NR ^x3 — (that is, group (Z2)) may be included.
As the group (Z1) and group (Z2),
Methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl) hexyloxy group, heptyloxy group, An oxy group in which a hydrocarbon group having 1 to 20 carbon atoms such as an octyloxy group, nonyloxy group, phenyloxy group, and o-tolyloxy group is bonded to one side;
Epoxy groups;
Formyl group;
An acetyl group, a propanoyl group, a butanoyl group, a tert-butanoyl group, a pentanoyl group, a hexanoyl group, a (2-ethyl) hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a benzoyl group, and the like, preferably 2-22 An acyl group having 2 to 12 carbon atoms (preferably an alkanoyl group);
Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, (2-ethyl) hexyloxycarbonyl group, heptyloxycarbonyl group and octyloxycarbonyl An oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a group, nonyloxycarbonyl group, phenyloxycarbonyl group, o-tolyloxycarbonyl group, etc. is bonded;
An amino group;
N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N-propylamino group, N, N-dipropylamino group, N-isopropylamino group, N, N-diisopropylamino group, N-butylamino group, N, N-dibutylamino group, N-isobutylamino group, N, N-diisobutylamino group, N-sec-butylamino group, N, N-disec-butyl Amino group, N-tert-butylamino group, N, N-ditert-butylamino group, N-pentylamino group, N, N-dipentylamino group, N- (1-ethylpropyl) amino group, N, N -Di (1-ethylpropyl) amino group, N-hexylamino group, N, N-dihexylamino group, N- (2-ethyl) hexylamino group, N, N-di (2-ethyl) Xylamino group, N-heptylamino group, N, N-diheptylamino group, N-octylamino group, N, N-dioctylamino group, N-nonylamino group, N, N-dinonylamino group, N-phenylamino group, N, N-diphenylamino group, N, N-ethylmethylamino group, N, N-propylmethylamino group, N, N-isopropylmethylamino group, N, N-butylmethylamino group, N, N-tert- An amino group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 20 carbon atoms, such as a butylmethylamino group and an N, N-phenylmethylamino group;
A sulfamoyl group;
N-methylsulfamoyl group, N, N-dimethylsulfamoyl group, N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N-propylsulfamoyl group, N, N-dipropyls Rufamoyl group, N-isopropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N-butylsulfamoyl group, N, N-dibutylsulfamoyl group, N-isobutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N-sec-butylsulfamoyl group, N, N-disec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N, N-ditert-butylsulfur Famoyl group, N-pentylsulfamoyl group, N, N-dipentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, , N-di (1-ethylpropyl) sulfamoyl group, N-hexylsulfamoyl group, N, N-dihexylsulfamoyl group, N- (2-ethyl) hexylsulfamoyl group, N, N-di ( 2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N, N-diheptylsulfamoyl group, N-octylsulfamoyl group, N, N-dioctylsulfamoyl group, N, N -Octylmethylsulfamoyl group, N-nonylsulfamoyl group, N, N-dinonylsulfamoyl group, N-phenylsulfamoyl group, N, N-diphenylsulfamoyl group, N, N-ethylmethyl Sulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-butylmethylsulfamoyl group , N, N-tert-butylmethylsulfamoyl group, N, N-phenylmethylsulfamoyl group and the like, substituted with 1 or 2 hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms A sulfamoyl group formed;
Formylamino group; acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (2-ethyl) hexanoylamino group, heptanoyl 1-22 carbon atoms such as amino group, octanoylamino group, nonanoylamino group, decanoylamino group, undecanoylamino group, dodecanoylamino group, heicosanoylamino group, benzoylamino group, preferably carbon The alkanoylamino group of the number 1-12;
A hydroxy group;
Formyloxy, acetoxy, propanoyloxy, butanoyloxy, 2,2-dimethylpropanoyloxy, pentanoyloxy, hexanoyloxy, (2-ethyl) hexanoyloxy, heptanoyloxy An alkanoyloxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a group, octanoyloxy group, nonanoyloxy group and benzoyloxy group;
Methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, (2-ethyl) hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, phenyl A sulfonyl group substituted with a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, such as a sulfonyl group and a p-tolylsulfonyl group;
A carbamoyl group;
N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-ethylcarbamoyl group, N, N-diethylcarbamoyl group, N-propylcarbamoyl group, N, N-dipropylcarbamoyl group, N-isopropylcarbamoyl group, N , N-diisopropylcarbamoyl group, N-butylcarbamoyl group, N, N-dibutylcarbamoyl group, N-isobutylcarbamoyl group, N, N-diisobutylcarbamoyl group, N-sec-butylcarbamoyl group, N, N-disec- Butylcarbamoyl group, N-tert-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group, N-pentylcarbamoyl group, N, N-dipentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N, N-di (1-ethylpropyl) carba Yl group, N-hexylcarbamoyl group, N, N-dihexylcarbamoyl group, N- (2-ethyl) hexylcarbamoyl group, N, N-di (2-ethyl) hexylcarbamoyl group, N-heptylcarbamoyl group, N, N-diheptylcarbamoyl group, N-octylcarbamoyl group, N, N-dioctylcarbamoyl group, N-nonylcarbamoyl group, N, N-dinonylcarbamoyl group, N-phenylcarbamoyl group, N, N-diphenylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-butylmethylcarbamoyl group, N, N-tert-butylmethylcarbamoyl group and N, N -1 or 2 carbon atoms such as phenylmethylcarbamoyl group 20, preferably a carbamoyl group substituted with a hydrocarbon group having 1 to 10 carbon atoms;
* -COCOR ^n2a ;
* -OCON (R ^n2a ) ₂ ;
* -N (R ^n2a ) COOR ^n2b ;
* -OP (O) (OR ^n2a ) ₂ ;
* -Si (R ^n2a ) (R ^n2b ) (R ^n2c );
In the above formula, R ^n2a , R ^n2b and R ^n2c may be the same or different and each represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or a substituent. a represents an even heterocyclic group optionally, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, -O -, - CO -, - S (O) 2 -, - NR x1 - may be replaced with. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group or heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— . R ^x1 is the same as described above. Specific examples and preferred ranges of R ^n2a , R ^n2b , and R ^n2c are the same as R ¹ , except that examples where the number of carbon atoms is 36 or more are not included.

The heterocyclic group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , and R ⁿ³¹ may be monocyclic or polycyclic. Preferably, it is a heterocyclic ring containing a hetero atom as a ring component. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

The carbon number of the heterocyclic group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , and R ⁿ³⁰ is preferably 2 to 30, more preferably. It is 3-22, More preferably, it is 3-20, Still more preferably, it is 3-18, More preferably, it is 3-15, Most preferably, it is 3-14. The number of carbon atoms in the heterocyclic ring represented by R ⁿ³¹ is preferably 2 to 15, more preferably 3 to 15, and even more preferably 3 to 14.

  Heterocycles containing only nitrogen atoms as heteroatoms include monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine, piperazine; pyrroles such as 2,5-dimethylpyrrole, 2-methylpyrazole, 3-methylpyrazole Pyrazoles such as pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole and the like; pyrimidines such as pyridine, pyridazine, 6-methylpyrimidine, pyrazine, 1,3, 6-membered unsaturated heterocycles such as 5-triazine; indazole, indoline, isoindoline, indole, indolizine, benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl) quinoxaline, 3 -Quinoxaline such as methylquinoxaline, quinazoline, cinnoline, Rajin, naphthyridine, purine, pteridine, benzopyrazole, fused bicyclic heterocyclic rings such as benzo piperidine; ring and the like represented by the following formula; carbazole, acridine, fused tricyclic heterocycle of phenazine and the like.

（式中、＊は結合手を表す）

(In the formula, * represents a bond)

  Heterocycles containing only oxygen atoms as heteroatoms include monocyclic saturated heterocycles such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1-cyclopentyldioxolane; 1,4 -Bicyclic saturated heterocycles such as dioxaspiro [4.5] decane and 1,4-dioxaspiro [4.5] nonane; α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, etc. Lactone type heterocycles; 5-membered unsaturated heterocycles such as 2,3-dimethylfuran and furan such as 2,5-dimethylfuran; 6-membered unsaturated heterocycles such as 2H-pyran and 4H-pyran; Benzopyran such as 1-benzofuran and 4-methylbenzopyran, condensed bicyclic heterocycles such as benzodioxole, chroman and isochroman; Ten, fused tricyclic heterocyclic ring such as dibenzofuran; and the like.

  Heterocycles containing only sulfur atoms as heteroatoms include 5-membered saturated heterocycles such as dithiolane; 6-membered saturated heterocycles such as thiane, 1,3-dithiane, 2-methyl-1,3-dithiane Thiophenes such as 3-methylthiophene and 2-carboxythiophene, 5-membered unsaturated heterocyclic rings such as benzothiopyran such as 4H-thiopyran and benzotetrahydrothiopyran; condensed bicyclic heterocyclic rings such as benzothiophene; And condensed tricyclic heterocycles such as dibenzothiophene;

  Heterocycles containing nitrogen and oxygen atoms as heteroatoms include monocyclic saturated heterocycles such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2-piperidone; 4 -Monocyclic unsaturated heterocycles such as oxazole such as methyloxazole, isoxazole such as 2-methylisoxazole, and 3-methylisoxazole; condensation such as benzoxazole, benzisoxazole, benzoxazine, benzodioxan, and benzimidazoline Bicyclic heterocycles; condensed tricyclic heterocycles such as phenoxazine; and the like.

  Heterocycles containing nitrogen and sulfur atoms as heteroatoms include monocyclic heterocycles such as 3-methylthiazole and 2,4-dimethylthiazole and the like; condensed bicyclic heterocycles such as benzothiazole; phenothiazine and the like And the like.

The heterocyclic group may be a group obtained by combining the hydrocarbon groups listed above, and examples thereof include a tetrahydrofurylmethyl group and a methyltetrahydrofuryl group.
In addition, the bonding position of the above heterocyclic ring is a portion from which any hydrogen atom contained in each ring is eliminated.

When the heterocyclic group represented by R ^{1 to} R ⁹ includes —CH ₂ — that does not constitute a ring, —CH ₂ — represents —O—, —CO—, —S (O) ₂ —, — It may be substituted with NR ^x1- . When —CH ₂ — is substituted, the heterocyclic group represented by R ^{1 to} R ⁹ includes the group (Z1).
When the heterocyclic group represented by R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ⁿ³⁰ , and R ⁿ³¹ includes —CH ₂ — that does not form a ring, —CH ₂ — is —O—, It may be substituted with —CO—, —S (O) ₂ —, or —NR ^x3 —. When —CH ₂ — is substituted, the heterocyclic group represented by R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ⁿ³⁰ , and R ⁿ³¹ includes the group (Z2).

Also, the heterocyclic ring, which may contain a nitrogen atom as its constituent elements, this nitrogen atom, R ¹ as described above may be bonded.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ^{When 21} and R ²² are bonded to form a ring, this ring may be a hydrocarbon ring or a heterocyclic ring. Examples of the hydrocarbon ring include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring.

  Aliphatic hydrocarbon rings include cyclopropane ring, methylcyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, methylcyclohexane ring, 1,1-dimethylcyclohexane ring, 1,2-dimethylcyclohexane ring 1,3-dimethylcyclohexane ring, 1,4-dimethylcyclohexane ring, cyclooctane ring, 1,3,5-trimethylcyclohexane ring, 1,1,3,3-tetramethylcyclohexane ring, pentylcyclohexane ring, octylcyclohexane Ring, cycloalkane ring such as cyclohexylcyclohexane ring; cycloalkene ring such as cyclohexene ring, cycloheptene ring, cyclooctene ring; norbornane, adamantane, bicyclo [2.2.2] octane and the like. The carbon number of the aliphatic hydrocarbon ring is, for example, 3 to 30, preferably 3 to 20, more preferably 4 to 20, still more preferably 4 to 15, and still more preferably 5 It is -15, Especially preferably, it is 5-10.

  Aromatic hydrocarbon rings include benzene, toluene, o-xylene, m-xylene, p-xylene, isopropylbenzene, tert-butylbenzene, mesitylene, 1,5-bis (2-propyl) benzene, naphthalene, 1, 2,3,4-tetrahydronaphthalene, fluorene, phenanthrene, anthracene; and the like. Carbon number of an aromatic hydrocarbon group is 6-30, for example, Preferably it is 6-20, More preferably, it is 6-15.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ^The ring formed by combining ²¹ and R ²² may have a substituent. The substituent may be a hydrocarbon group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ and R ^n31. The same thing as a group is mentioned.

When the ring formed by combining R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ contains —CH ₂ — that does not constitute a ring, The —CH ₂ — may be substituted with —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. When —CH ₂ — is substituted, the ring formed by combining R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ is Including group (Z1).

When the ring formed by combining R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ²¹ and R ²² includes —CH ₂ — that does not form a ring, the —CH ₂ — ^May be substituted with —O—, —CO—, —S (O) ₂ —, or —NR ^x3 —. When —CH ₂ — is substituted, the ring formed by combining R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ²¹ and R ²² represents the group (Z2). Including.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or When R ²¹ and R ²² are combined to form a heterocyclic ring, this heterocyclic ring is the above R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ , and R A heterocyclic ring similar to the heterocyclic group represented by ⁿ³¹ may be formed. When R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , or R ¹⁴ and R ¹⁵ are combined to form a heterocyclic ring, The ring group has ^two or more ring structures together with the benzene ring to which R ^{2 to} R ⁵ or R ^{12 to} R ¹⁵ are bonded. Examples of the heterocyclic ring having two or more ring structures include heterocyclic rings having the following structure.

  (The benzene ring in the formula corresponds to the benzene ring in the isoindoline structure of the isoindoline dye (1) or the isoindoline dye (2)).

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ^{When 21} and R ²² are combined to form a heterocyclic ring, the heterocyclic group may have a substituent. The substituent may be a hydrocarbon group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ and R ^n31. The same thing as a group is mentioned.

The heterocycle formed by combining R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁸ and R ⁹ includes —CH ₂ — that does not constitute a ring. In some cases, the —CH ₂ — may be substituted with —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. When —CH ₂ — is substituted, the ring formed by combining R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ is Including group (Z1).

When the heterocyclic ring formed by combining R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ²¹ and R ²² contains —CH ₂ — that does not form a ring, the —CH ₂ ^-May be substituted with -O-, -CO-, -S (O) _2- , or ^-NRx3- . When —CH ₂ — is substituted, the ring formed by combining R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , or R ²¹ and R ²² represents the group (Z2). Including.

Also, the heterocyclic ring, which may contain a nitrogen atom as its constituent elements, this nitrogen atom, R ¹ as described above may be bonded.

At least one of R ^{1 to} R ⁹ , preferably at least one of R ^{6 to} R ⁹ , more preferably one of R ⁶ and R ⁷ and one of R ⁸ and R ⁹ is a hydrocarbon group, It is preferable that —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. When one of R ⁶ and R ⁷ and one of R ⁸ and R ⁹ are a hydrocarbon group and —CH ₂ — contained in the hydrocarbon group is replaced, the other of R ⁶ and R ⁷ The other of R ⁸ and R ⁹ is preferably one selected from the group consisting of CN, COO ⁻ , S (O) ₂ O ^−, and more preferably CN.

Examples of the group in which —CH ₂ — is replaced include —CO—OR ⁿ¹⁰ (in this group, _two —CH ₂ —CH ₂ —R ⁿ¹⁰ —CH ₂ — is replaced by —CO— and —O—, respectively. was a group), - CO-NH ₂ (this group is the -CH ₂ -CH ₂ -H ₂ two -CH ₂ - is a radical is replaced with each -CO- and -NH-), - CO —NH (R ⁿ¹⁰ ) (this group is a group in which two —CH ₂ — of —CH ₂ —CH ₂ —R ⁿ¹⁰ is replaced by —CO— and —NH—, respectively)
^{, -CO-N (R n11)} 2 ( this group, two -CH ₂ -CH ₂ - -CH ₂ -R ⁿ¹¹ - is replaced by a group - each -CO- and -NR ^n11), - CO-H (this radical, -CH ₂ -H of -CH ₂ - is a group replaced by ^{-CO-), - CO-R n10} ( this radical, -CH ₂ of -CH ₂ -R ⁿ¹⁰ - it is a is) or -S (O) ₂ -R ⁿ¹⁰ (this group, -CH ₂ of -CH ₂ -R ⁿ¹⁰ - is -S (O) group substituted with a -CO- ₂ - replaced by a group For example).

In the formula, R ^{n10 represents} a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent, and is included in the hydrocarbon group— In the case where CH ₂ — and the heterocyclic group include —CH ₂ — that does not form a ring, —CH ₂ — is replaced by —O—, —CO—, —S (O) ₂ —, —NR ^x1 —. It may be. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group or heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— . R ^x1 is the same as described above. Specific examples and preferred ranges of R ⁿ¹⁰ are the same as those of R ¹ except that examples where the number of carbon atoms is 36 or more are not included.

R ⁿ¹⁰ may have a group (Z1). Preferred groups (Z1) that R ⁿ¹⁰ may have include a halogen atom such as a chlorine atom; a sulfamoyl group; a hydroxy group; an oxy group in which a hydrocarbon group having 1 to 10 carbon atoms such as a methoxy group is bonded to one side. An oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms such as a methoxycarbonyl group is bonded; —SO ₂ NH _{2 and the} like are preferable. R ⁿ¹⁰ may have —CO ₂ ⁻ , —S (O) ₂ O ^— or the like.

In the formula, R ⁿ¹¹ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent, and is included in the hydrocarbon group − In the case where CH ₂ — and the heterocyclic group include —CH ₂ — that does not form a ring, —CH ₂ — is replaced by —O—, —CO—, —S (O) ₂ —, —NR ^x1 —. It may be. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group or heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— . R ^x1 is the same as described above. Specific examples and preferred ranges of R ⁿ¹¹ are the same as those of R ¹ except that examples where the number of carbon atoms is 16 or more are not included.

R ⁿ¹¹ may have a group (Z1). The preferred group (Z1) that R ⁿ¹¹ may have is a halogen atom such as a chlorine atom; a sulfamoyl group; a hydroxy group; an oxy group in which a hydrocarbon group having 1 to 10 carbon atoms such as a methoxy group is bonded to one side. An oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms such as a methoxycarbonyl group is bonded; —SO ₂ NH _{2 and the} like are preferable. R ⁿ¹⁰ may have —CO ₂ ⁻ , —S (O) ₂ O ^— or the like.

When R ^{11 to} R ¹⁵ or R ^{21 to} R ²⁴ is a hydrocarbon group, —CH ₂ — contained in the hydrocarbon group is —O—, —CO—, —S (O) ₂ —, —NR. ^x3 − may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. Examples of the group in which —CH ₂ — is replaced include —CO—OR ⁿ³⁵ , —CO—NH ₂ , —CO—NH (R ⁿ³⁵ ), —CO—N (R ⁿ³⁶ ) ₂ , —CO—H, — CO- ^Rn35 or -S (O) _2- ^Rn35 is mentioned (in the formula, ^Rn35 has the same meaning as ^Rn30, and ^Rn36 has the same meaning as ^Rn31 ). In particular, as R ¹⁶ , —CO—OR ⁿ³⁰ , —CO—NH ₂ , —CO—NH (R ⁿ³⁰ ), —CO—N (R ⁿ³¹ ) ₂ , —CO—H, —CO—R ⁿ³⁰ or —S (O) ₂ —R ^{n30 and the} like are preferable (wherein R ⁿ³⁰ and R ⁿ³¹ are the same as above).

As —CO—OR ⁿ¹⁰ , —CO—OR ⁿ³⁰ , —CO—OR ⁿ³⁵ , methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl Group, (2-ethyl) hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group, dodecyloxycarbonyl group, phenyloxycarbonyl group and icosyl The oxycarbonyl group etc. which C1-C35 hydrocarbon groups, such as an oxycarbonyl group, couple | bonded are preferable, More preferably, the oxycarbonyl group etc. which C1-C10 hydrocarbon group couple | bonded are mentioned.

^{-CO-NH (R n10),} - CO-N (R n11) 2, -CO-NH (R n30), - CO-N (R n31) 2, -CO-NH (R n35), - CO- N (R ⁿ³⁶ ) ₂ includes N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butyl Rucarbamoyl group, N-tert-butylcarbamoyl group, N-pentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N-hexylcarbamoyl group, N- (2-ethyl) hexylcarbamoyl group, N-heptylcarbamoyl group N-octylcarbamoyl group, N-nonylcarbamoyl group, N-decylcarbamoyl group, N-undecylcarbamoyl group, N -Dodecylcarbamoyl group, N- Lee waist carbamoyl group and N-1 single carbamoyl group substituted with a hydrocarbon group having a carbon number of 1 to 35 phenylcarbamoyl group and the like;
N, N-dimethylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-dipropylcarbamoyl group, N, N-isopropylmethylcarbamoyl Group, N, N-diisopropylcarbamoyl group, N, N-tert-butylmethylcarbamoyl group, N, N-diisobutylcarbamoyl group, N, N-disec-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group N, N-butylmethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-butyloctylcarbamoyl group, N, N-dipentylcarbamoyl group, N, N-di (1-ethylpropyl) carbamoyl group, N , N-dihexylcarbamoyl group, N, N-di (2-ethyl) hexyl Rucarbamoyl group, N, N-diheptylcarbamoyl group, N, N-octylmethylcarbamoyl group, N, N-dioctylcarbamoyl group, N, N-dinonylcarbamoyl group, N, N-decylmethylcarbamoyl group, N, N A carbamoyl substituted with two hydrocarbon groups having 1 to 15 carbon atoms such as an undecylmethylcarbamoyl group, an N, N-dodecylmethylcarbamoyl group, an N, N-phenylmethylcarbamoyl group and an N, N-diphenylcarbamoyl group Group etc. are preferable, More preferably, the carbamoyl group substituted by the 1 or 2 C1-C10 hydrocarbon group is mentioned. In —CO—NH (R ⁿ¹⁰ ) and —CO—N (R ⁿ¹¹ ) ₂ , in the carbamoyl group substituted with the one or two hydrocarbon groups, the hydrocarbon group has —COO 2 ^—. Also good.

^{-CO-R n10, -CO-R} n30, as the -CO-R ^n35, acetyl group, propanoyl group, butanoyl group, 2,2-dimethylpropanoyl group, pentanoyl group, hexanoyl group, (2-ethyl) hexanoyl Group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group, heicosanoyl group, benzoyl group, phenylmethylcarbonyl group, phenylethylcarbonyl group, phenylpropylcarbonyl group, etc. Is preferably a carbonyl group to which a group of 1 to 35 is bonded, preferably a hydrocarbon group and a carbonyl group to which a group having 1 to 10 carbon atoms is bonded. In —CO—R ⁿ¹⁰ , —CO—R ⁿ³⁰ , and —CO—R ⁿ³⁵ , in the carbonyl group to which a hydrocarbon group is bonded, the hydrocarbon group is a halogen atom such as a chlorine atom; a sulfamoyl group; a hydroxy group; An oxy group having a C 1-10 hydrocarbon group bonded to one side; an oxycarbonyl group having a C 1-10 hydrocarbon group such as a methoxycarbonyl group bonded; and the like. In —CO—R ⁿ¹⁰ , in the carbonyl group to which a hydrocarbon group is bonded, the hydrocarbon group may have —COO ⁻ , S (O) ₂ O ^— or the like. Also ^{-CO-R n10, -CO-R} n30, as the -CO-R ^n35, a formyl group is also preferred.

—S (O) ₂ —R ⁿ¹⁰ , —S (O) ₂ —R ⁿ³⁰ , —S (O) ₂ —R ⁿ³⁵ are methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl. Group, hexylsulfonyl group, (2-ethyl) hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, undecylsulfonyl group, dodecylsulfonyl group, icosylsulfonyl group, phenylsulfonyl group, p -The sulfonyl group etc. which C1-C35 hydrocarbon groups, such as a tolylsulfonyl group couple | bonded, are preferable, More preferably, the sulfonyl group etc. which the C1-C10 hydrocarbon group couple | bonded are mentioned.

The ring formed by R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ is represented by formula (1) or formula (2 ) Of benzene with an isoindoline skeleton. As a condensed ring structure of a ring formed by R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁴ and R ¹⁵ and the benzene ring Are indene, naphthalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, acanthrylene, triphenylene, pyrene, chrysene, N-methylphthalimide, N- (1-phenylethyl) Hydrocarbon-based condensed ring structures such as phthalimide and tetracene and partially reduced forms thereof (for example, 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, etc.); indole, isoindole, indazole, quinoline, isoquinoline, Phthalazine, quinoxaline, quinazoline, cinnoline, carbazole Carboline, phenanthridine, acridine, perimidine, phenanthroline, nitrogen-containing condensed heterocyclic and partial reduction of phenazine and the like; 3- hydro oxygen-containing condensed heterocyclic benzofuran-2-one or their partially reduced products thereof.

Ring ring or R ⁸ and R ⁶ and R ⁷ form a and R ⁹ form is coupled with isoindoline skeleton of exomethylene (C = CH ₂₎ of formula (1), R ⁶ and R ^When the ring formed by ⁷ or the ring formed by R ⁸ and R ⁹ is exemplified as a structure containing this exomethylene (C═CH ₂ ), for example, a carbonyl group such as group A below, an exomethylene and a carbonyl group A structure in which these are arranged in this order can be illustrated. ** represents a bond to the isoindoline skeleton.

[Group A]

[Wherein, R ²⁵ and R ²⁶ are each independently a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. And —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. Further, the hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— as a substituent. Specific examples and preferred examples include examples in which R ¹ is an example in which the number of carbon atoms is 36 or more.

The ring formed by R ²¹ and R ²² is bonded to the isoindoline exomethylene (C═CH ₂ ) of formula (2), and the ring formed by R ²¹ and R ²² is the exomethylene ( As a structure including C═CH ₂ ), for example, a structure in which a carbonyl group, an exomethylene, and a carbonyl group are arranged in this order as shown in the following group B can be exemplified. ** represents a bond to the isoindoline skeleton.

[Group B]

[Wherein, R ²⁷ and R ²⁸ are each independently a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. And —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x3 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. Specific examples and preferred examples include the same examples as R ²³ ].

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , and R ^The ring formed by ²¹ and R ²² may have a substituent. The substituent may be a hydrocarbon group represented by R ^{1 to} R ⁹ , R ^{11 to} R ¹⁵ , R ^{21 to} R ²⁴ , R ^x1 , R ^x3 , R ⁿ³⁰ and R ^n31. The same thing as a group is mentioned.

Examples of the halogen represented by R ^{2 to} R ⁹ , R ^{12 to} R ¹⁵ , and R ^{21 to} R ²² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom or a bromine atom. is there.

As the isoindoline dye represented by formula (1) or formula (2), those in which R ^{1 to} R ⁹ , R ^{11 to} R ¹⁶ , and R ^{21 to} R ²⁴ are as follows are preferable.
R ¹ and R ¹¹ are preferably hydrogen atoms.
R ^{2 to} R ⁵ include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms such as a butyl group, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, and a C 1-10 carbon atom such as a trifluoromethyl group. Preferred are a fluoroalkyl group, a halogen atom such as a bromine atom, a nitro group, —CO ₂ ⁻ , —S (O) ₂ O ^{— and the} like.
R ^{12 to} R ¹⁵ include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms such as a butyl group, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, and a C 1-10 carbon atom such as a trifluoromethyl group. A fluoroalkyl group, a halogen atom such as a bromine atom, and a nitro group are preferred.

One group out of R ⁶ and R ⁷ (hereinafter referred to as R ^6a ) or one group out of R ⁸ and R ⁹ (hereinafter referred to as R ^8a ) is preferably a cyano group, and R ^6a out of R ⁶ and R ^7. Or a group other than R ^8a among R ⁸ and R ⁹ is —COO ⁻ , —CO—OR ⁿ¹⁵ , —CO—R ⁿ¹⁵ , —CO—NH ₂ , —CO—NH (R ⁿ¹⁵ ), — _{^{CO-N (R n16) 2}} , -CO-H, or -S (O) ₂ -R ⁿ¹⁵ is preferably (R ⁿ¹⁵ are the same as the R ^n10, R ⁿ¹⁶ are as defined above R ^n11).
As —CO—OR ⁿ¹⁵ , an alkoxycarbonyl group having 1 to 10 carbon atoms of an alkyl group such as a methoxycarbonyl group or an ethoxycarbonyl group is preferable.
As —CO—R ⁿ¹⁵ , a carbonyl group to which an aromatic ring having 6 to 10 carbon atoms such as a phenylcarbonyl group is bonded; an alkyl group having 1 to 10 carbon atoms such as an ethylcarbonyl group or a butylcarbonyl group is bonded. Carbonyl group; a carbonyl group to which a C 1-10 alkyl group to which a C 6-10 aromatic ring is bonded, such as a phenylmethyl group or a phenylethyl group, is preferable. The aromatic ring is bonded to a carbonyl group; the carbon atom of the carbonyl group in which the alkyl group in which an aromatic ring is bonded is bonded, a halogen atom such as chlorine atom; carbonyl group in which the alkyl group is bonded -CO ₂ ^{- _{; -S (O) 2 O -}} ; sulfamoyl group; hydroxy group; a hydrocarbon having 1 to 10 carbon atoms such as methoxycarbonyl group; group having a hydrocarbon group attached to one side of 1 to 10 carbon atoms such as a methoxy group An oxycarbonyl group to which a group is bonded; and the like may be bonded.
—CO—NH (R ⁿ¹⁵ ) includes an aminocarbonyl group to which an alkyl group having 1 to 10 carbon atoms such as a methylaminocarbonyl group is bonded, and an aromatic hydrocarbon ring having 6 to 10 carbon atoms such as a phenylaminocarbonyl group. A bonded aminocarbonyl group is preferred. Further, —CO ₂ ^— may be bonded to a carbon atom such as an aminocarbonyl group to which the alkyl group is bonded or an aminocarbonyl group to which an aromatic hydrocarbon ring is bonded.
As —CO—N (R ⁿ¹⁶ ) ₂ , an aminocarbonyl group in which two alkyl groups having 1 to 10 carbon atoms such as a dimethylaminocarbonyl group are bonded is preferable.

R ⁸ and R ⁹ also preferably form the group A structure.

One of R ²¹ and R ²² (hereinafter referred to as R ^21a ) is preferably a cyano group, and among R ²¹ and R ²² , groups other than R ^21a are preferably the same groups as R ¹⁶ .

As R ¹⁶ , —CO—OR ⁿ³⁰ , —CO—R ⁿ³⁰ , —CO—NH ₂ , —CO—NH (R ⁿ³⁰ ), —CO—N (R ⁿ³¹ ) ₂ , —CO—H, —S ( O) _2- ^{Rn30 and the} like are preferable.
As —CO—OR ⁿ³⁰ , an alkoxycarbonyl group having 1 to 10 carbon atoms of an alkyl group such as a methoxycarbonyl group and an ethoxycarbonyl group is preferable.
—CO—R ⁿ³⁰ includes a carbonyl group to which an aromatic ring having 6 to 10 carbon atoms such as a phenylcarbonyl group is bonded, a carbonyl group to which an alkyl group having 1 to 10 carbon atoms such as a butylcarbonyl group is bonded; A carbonyl group to which an alkyl group having 1 to 10 carbon atoms to which an aromatic ring having 6 to 10 carbon atoms such as a phenylethyl group is bonded is preferable. The carbon atom of the carbonyl group to which the aromatic ring is bonded, the carbonyl group to which the alkyl group is bonded, or the carbonyl group to which the alkyl group to which the aromatic ring is bonded is a halogen atom such as a chlorine atom; a sulfamoyl group; a hydroxy group An oxy group in which a hydrocarbon group having 1 to 10 carbon atoms such as a methoxy group is bonded to one side; an oxycarbonyl group in which a hydrocarbon group having 1 to 10 carbon atoms such as a methoxycarbonyl group is bonded; Good.
As —CO—NH (R ⁿ³⁰ ), an aromatic hydrocarbon ring having 6 to 10 carbon atoms such as an aminocarbonyl group or a phenylaminocarbonyl group to which an alkyl group having 1 to 10 carbon atoms such as a methylaminocarbonyl group is bonded. A bonded aminocarbonyl group is preferred.
-CO-N ( ^Rn31 ) ₂ is preferably an aminocarbonyl group in which two alkyl groups having 1 to 10 carbon atoms such as a dimethylaminocarbonyl group are bonded.

R ²¹ and R ²² preferably form the group B structure.

R ²³ and R ²⁴ are preferably a hydrogen atom.

M ^{b +} is preferably hydrogen or a monovalent metal ion such as Li ⁺ , Na ⁺ or K ⁺ , or a metal cation having a valence of 2 or more, more preferably hydrogen or a metal cation having a valence of 2 or more. Hydron is most preferred. Examples of the metal cation having a valence of 2 or more include cations of metals in groups 2 to 15 of the periodic table of elements, and preferably Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Cd Divalent metal cations such as ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , Hg ²⁺ , Fe ²⁺ , Co ²⁺ , Sn ²⁺ , Pb ²⁺ and Mn ²⁺ ; Al ³⁺ Trivalent metal cations such as Fe ³⁺ and Cr ³⁺ ; and tetravalent metal cations such as Sn ⁴⁺ , Mn ⁴⁺ and Ce ⁴⁺ , and more preferably Mg ²⁺ and Ca ^2+. , Sr ²⁺ , Ba ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Co ²⁺ , Sn ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Sn ⁴⁺ and Mn ⁴⁺ , more preferably Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Cr ³⁺ and Mn ⁴⁺ . When M ^{b +} is hydrone, the hydrone is bonded to —CO ₂ ^— or —S (O) ₂ O ^— and is present as —COOH or —S (O) ₂ OH.

  a is preferably 1 to 10, more preferably 1 to 5, and most preferably 2 to 4.

Specific examples of the isoindoline dye (1) or (2) include, for example, in the compound represented by the formula (Ia), R ³¹ , L ¹ , L ² , R ³² , B ¹ B ² , n, m and In the compound in which the combination of M ^{b +} is any one of Tables 1 to 4 and the compound represented by the formula (Ib), the combination of R ³³ , L ³ , B ¹ B ² , n, m and M ^{b +} is The compound which is either of Table 5-Table 6 is mentioned. R ³¹ , R ³² , and R ³³ represent any partial structure represented by formula (HH1) to formula (HH18). B ¹ B ² represents any partial structure represented by Formula (BB1) to Formula (BB9).

（式中、波線は、Ｅ体及びＺ体の両方を含むことを示す）

(Where, wavy lines indicate that both E and Z bodies are included.)

  Among the compounds shown in the table, compound numbers 28-31, 37-40, 46-49, 73-76, 82-85, 91-94, 136-139, 154-157, 190-193, 199-202, Compounds of 208 to 211, 244 to 247 and 298 to 301 are preferred.

The isoindoline dye (isoindoline dye (1)) represented by the formula (1) is represented by the formula (pt1) when R ¹ is a hydrogen atom (that is, an isoindoline dye represented by the formula (1a)). A compound represented by the formula (pt3) after reacting a compound represented by the following (hereinafter sometimes referred to as a phthalonitrile compound) with a compound represented by the formula (pt2) (hereinafter sometimes referred to as an alkoxide compound) (Hereinafter sometimes referred to as compound (pt3)) and a compound represented by formula (pt4) (hereinafter also referred to as compound (pt4)) may be further reacted in the presence of an acid. The isoindoline dye (1) is a compound represented by the formula (pt5) (hereinafter referred to as 1,3-) when R ¹ is a hydrogen atom (that is, an isoindoline dye represented by the formula (1a)). It may be produced by reacting a compound (pt3) and a compound (pt4). In addition, when R ¹ is other than a hydrogen atom (that is, an isoindoline dye represented by the formula (1b)), the isoindoline dye represented by the formula (1b) is further represented by the formula (1a). It can be produced by reacting a dye with a compound represented by the formula (pt6) (hereinafter sometimes referred to as a compound (pt6)). In Formula (1), when M ^{b +} is a metal ion (that is, an isoindoline dye represented by Formula (1c)), the isoindoline dye represented by Formula (1c) is further represented by Formula (1b). A compound represented by the formula (pt7) (hereinafter sometimes referred to as the compound (pt7)), a compound represented by the formula (pt8) (hereinafter sometimes referred to as the compound (pt8)), It can manufacture by making it react.

[In formula (pt1) to formula (pt8), formula (1a), formula (1b) and formula (1c), R ^{1 to} R ⁹ , M ^{b +} , a, m and n have the same meaning as described above. Represent. R ⁴¹ and R ⁴² each independently represent a hydrogen atom and / or an alkyl group having 1 to 20 carbon atoms. M ¹ and M ² each independently represent an alkali metal atom. LG ¹ and LG ² represent a halogen atom, a methanesulfonyloxy group, a chloromethylsulfonyloxy group, a toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴¹ and R ⁴² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Preferably, an alkyl group having 1 to 6 carbon atoms is used.
R ⁴¹ is preferably an alkyl group. R ⁴² is preferably a hydrogen atom.
Examples of the alkali metal atom represented by M ¹ and M ² include a lithium atom, a sodium atom, and a potassium atom.

  The amount of the alkoxide compound represented by the formula (pt2) is usually 0.1 to 10 mol, preferably 0.2 to 5 mol, more preferably 0, relative to 1 mol of the phthalonitrile compound. .3 to 3 mol, and more preferably 0.4 to 2 mol.

  The total amount of compound (pt3) and compound (pt4) used is usually 2 to 20 moles, preferably 2 to 10 moles per mole of phthalonitrile compound or 1,3-diiminoisoindoline compound. More preferably, it is 2-6 mol, More preferably, it is 2-4 mol. The compound (pt3) and the compound (pt4) may be the same.

Examples of acids include inorganic acids such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, fluorosulfonic acid and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; acetic acid , Carboxylic acids such as citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acid An acid is mentioned, More preferably, an acetic acid is mentioned.
The usage-amount of an acid is 1-500 mol normally with respect to 1 mol of phthalonitrile compounds, Preferably it is 5-200 mol, More preferably, it is 20-100 mol.

  The reaction of the phthalonitrile compound, alkoxide compound, compound (pt3) and compound (pt4) is usually carried out in the presence of a solvent. Solvents include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; Ester solvents such as ethyl; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; amides such as N, N-dimethylformaldehyde and N-methylpyrrolidone Solvent; sulfoxide solvents such as dimethyl sulfoxide are mentioned, preferably water, nitrile solvent, alcohol solvent, ether solvent, ketone solvent, ester solvent, aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, amide solvent and sulfoxide solvent. And More preferably, water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde, N -Dimethylacetaldehyde, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethyl sulfoxide; More preferably, water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformaldehyde, N-dimethylacetoa Dehydr, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N-methylpyrrolidone and dimethyl sulfoxide are particularly preferred. Include water, acetonitrile, methanol, ethanol, 2-propanol, N-methylpyrrolidone and dimethyl sulfoxide. The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of phthalonitrile compounds.

  The reaction temperature of the phthalonitrile compound, the alkoxide compound, the compound (pt3) and the compound (pt4) is usually 0 to 200 ° C, preferably 0 to 100 ° C, more preferably 0 to 50 ° C. The reaction time is usually 0.5 to 300 hours.

  The reaction of the 1,3-diiminoisoindoline compound, the compound (pt3) and the compound (pt4) is usually carried out in the presence of a solvent. Solvents include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; Ester solvents such as ethyl; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; amides such as N, N-dimethylformaldehyde and N-methylpyrrolidone Solvents: sulfoxide solvents such as dimethyl sulfoxide, preferably nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents and sulfoxide solvents. Than Preferably, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde, N, N -Dimethylacetaldehyde, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethyl sulfoxide; More preferably, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformaldehyde, N, N-dimethylacetaldehyde And N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethyl sulfoxide are particularly preferred. N, N-dimethylformamide, N, N-dimethylacetamide, 1-butanol, N-methylpyrrolidone, 3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro- 2 (1H) -pyrimidinone and dimethyl sulfoxide. The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of 1, 3- diimino isoindoline compounds.

  The reaction temperature of the 1,3-diiminoisoindoline compound, the compound (pt3) and the compound (pt4) is usually 0 to 200 ° C, preferably 0 to 100 ° C, more preferably 0 to 80 ° C. . The reaction time is usually 0.5 to 300 hours.

  The amount of compound (pt6) to be used is generally 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, per 1 mol of isoindoline dye represented by formula (1a). More preferably, it is 1-2 mol.

  Moreover, when making a compound (pt6) react, it is preferable that a base coexists. Bases include organic bases such as triethylamine, 4- (N, N-dimethylamino) pyridine, pyridine, piperidine, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, butyllithium Organic metal compounds such as tert-butyl lithium and phenyl lithium; inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide.

  The usage-amount of a base is 1-10 mol normally with respect to 1 mol of isoindoline dye represented by Formula (1a), Preferably it is 1-5 mol, More preferably, it is 1-3 mol, Furthermore, Preferably it is 1-2 mol.

  The reaction of the compound (pt6) is usually carried out in the presence of a solvent. A solvent can be selected from the range similar to the solvent used by reaction of a phthalonitrile compound, an alkoxide compound, a compound (pt3), and a compound (pt4).

  The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of isoindoline pigment | dye represented by Formula (1b). The reaction temperature of the compound (pt6) is usually -90 to 200 ° C, preferably -80 to 100 ° C, more preferably 0 to 50 ° C. The reaction time is usually 0.5 to 300 hours.

  When the isoindoline dye represented by the formula (1b) does not have a sulfo group, by reacting the isoindoline dye represented by the formula (1b) with a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid, A sulfo group can be introduced.

The amount of SO ₃ in the oleum, compared isoindoline dye 1 mole of the formula (1b), is usually 1 to 50 moles, preferably from 5 to 40 moles, more preferably from 5 to 30 Mol, more preferably 5 to 25 mol. The usage-amount of the sulfuric acid in fuming sulfuric acid is 1-200 mol normally with respect to 1 mol of isoindoline pigment | dyes represented by Formula (1b), Preferably it is 10-100 mol, More preferably, it is 10-75 mol. More preferably, it is 10-50 mol.

  The usage-amount of chlorosulfonic acid is 1-500 mol normally with respect to 1 mol of isoindoline dye represented by Formula (1b), Preferably it is 10-300 mol, More preferably, it is 10-200 mol. More preferably, it is 10 to 150 mol.

  The reaction temperature of the sulfonation is usually from -20 to 200 ° C, preferably from -10 to 100 ° C, more preferably from 0 to 50 ° C. The reaction time is usually 0.5 to 300 hours.

When the isoindoline dye represented by the formula (1b) has a carboxy group or a sulfo group, the compound (pt7) and the compound (pt8) are reacted to form an isoindo represented by the formula (1c) containing M ^{b +.} Indoline pigments may be produced.

  Compound (pt7) is a metal alkoxide such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, an organometallic compound such as butyllithium, tert-butyllithium and phenyllithium; lithium hydroxide, hydroxide Examples include inorganic bases such as sodium and potassium hydroxide. Lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable.

  The amount of compound (pt7) to be used is generally 0.1 to 10 mol, preferably 0.2 to 10 mol, more preferably, per 1 mol of isoindoline dye represented by formula (1b). Is 1 to 5 moles.

  The amount of compound (pt8) to be used is generally 0.1 to 10 mol, preferably 0.2 to 10 mol, more preferably relative to 1 mol of isoindoline dye represented by formula (1b). Is 1 to 5 moles.

The reaction of the isoindoline dye represented by formula (1b), the compound (pt7) and the compound (pt8) is usually carried out in the presence of a solvent. Solvents include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; Ester solvents such as ethyl; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; amides such as N, N-dimethylformaldehyde and N-methylpyrrolidone And sulfoxide solvents such as dimethyl sulfoxide, preferably water, nitrile solvent, alcohol solvent, ether solvent, ketone solvent, ester solvent, aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, amide solvent, and sulfoxide. Solvent More preferably, water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N, N-dimethyl Formaldehyde, N-methylpyrrolidone and dimethyl sulfoxide, and more preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformaldehyde, N-methylpyrrolidone and dimethylsulfoxide are mentioned, and water, acetonitrile, methanol, ethanol and 2-propanol are particularly preferable.
The usage-amount of a solvent is 1-1000 mass parts normally with respect to 1 mass part of isoindoline pigment | dye represented by Formula (1b).

  The reaction temperature of the isoindoline dye represented by the formula (1b), the compound (pt7), and the compound (pt8) is usually 0 to 200 ° C, preferably 0 to 100 ° C, more preferably 0 to 50 ° C. It is. The reaction time is usually 0.5 to 300 hours.

  The method for taking out the isoindoline dye (1) from the reaction mixture is not particularly limited, and it can be taken out by various known methods. For example, after completion of the reaction, the isoindoline dye (1) can be taken out by filtering the reaction mixture. Further, after filtration, the obtained residue may be washed with a solvent. Further, after filtration, column chromatography, recrystallization, or sublimation purification may be performed.

The isoindoline dye (A) obtained by the above method may be contained in the following composition.
(I) A composition (first composition) comprising an isoindoline dye (A) and a solvent (E).
(II) Composition (second composition) containing isoindoline dye (A), resin (B) and solvent (E) (hereinafter, the first composition and the second composition are referred to as colored compositions). Sometimes).
(III) Isoindoline dye (A), resin (B), polymerizable compound (C) and solvent (E)
A composition comprising (a third composition).
(IV) A composition (fourth composition) comprising an isoindoline dye (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). (Hereinafter, the third composition and the fourth composition may be referred to as a colored curable resin composition).

  In addition, in the coloring composition containing (I) isoindoline dye (A) and solvent (E), it is preferable that isoindoline dye (A) is dispersed in solvent (E). In addition, a colored composition containing the isoindoline dye (A) and the solvent (E) or a colored composition containing the resin (B) is further mixed with a polymerizable compound (C) or a polymerization initiator (D). A colored curable resin composition may be prepared.

(2) Colorant (A1)
The first to fourth compositions may contain a colorant other than the isoindoline dye (A) (hereinafter sometimes referred to as a colorant (A1)), and one or more colorants. (A1) may be included.

  The colorant (A1) may be a dye or a pigment. Examples of the dye include known dyes described in Color Index (published by The Society of Dyers and Colorists) and Dyeing Notes (Color Dye Co.). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. The colorant (A1) may be an isoindoline dye. Two or more of these dyes may be used in combination.

Specific examples include dyes having the following color index (CI) numbers. C. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Disperse Yellow 51, 54, 76;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Reactive Orange 16;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 34, 102;
C. I. Disperse violet 26, 27;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112;
C. I. Direct blue 40;
C. I. Disperse Blue 1, 14, 56, 60;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

As a pigment, a well-known pigment can be used, For example, the pigment classified into the pigment by the color index (The Society of Dyer's and Colorist publication) is mentioned. Two or more types may be combined.
Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, Red pigments such as 269, 273;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. And CI pigment green 7, 36, 58, 59.

  Examples of the colorant (A1) include yellow dyes and yellow pigments (hereinafter sometimes collectively referred to as “yellow colorants”), green dyes and green pigments (hereinafter collectively referred to as “green colorants”). May be preferred), yellow pigments and green pigments are more preferred, and green pigments are even more preferred.

  Examples of the yellow dye include dyes whose hue is classified as yellow among the dyes, and examples of the yellow pigment include pigments whose hue is classified as yellow among the pigments.

Examples of the green dye include dyes whose hue is classified as green among the dyes, and examples of the green pigment include pigments whose hue is classified as green among the pigments.
Among the green pigments, a phthalocyanine pigment is preferable, and at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment is more preferable. I. More preferred is at least one selected from the group consisting of CI Pigment Green 7, 36, 58 and 59.

  The amount of the colorant (A1) is 0 to 900 parts by mass, preferably 300 parts by mass or less, and more preferably 100 parts by mass or less with respect to 100 parts by mass of the isoindoline dye (A).

(3) Dispersant Isoindoline dye (A) or colorant (A1) (hereinafter referred to as colorant AX as a concept indicating both isoindoline dye (A) and colorant (A1). Colorant AX As an example, an isoindoline dye (A) is preferably a rosin treatment, a surface treatment using a colorant derivative in which an acidic group or a basic group is introduced, a colorant AX based on a polymer compound, or the like. Grafting to the surface, atomization by sulfuric acid atomization, etc., washing with an organic solvent or water to remove impurities, removal by ionic impurities, etc. may be performed. . The particle diameter of the colorant AX is preferably substantially uniform. The colorant AX can be made to be in a state where the colorant AX is uniformly dispersed in the dispersion by carrying out a dispersion treatment by containing a dispersant.

  Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. As the dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) (Manufactured by BASF), Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie), BYK (registered trademark) (manufactured by BYK Chemie) and the like.

  When the dispersant is used, the amount of the dispersant used is preferably 200 parts by mass or less, more preferably 5 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the colorant AX. When the usage-amount of a dispersing agent exists in the said range, there exists a tendency for the colorant AX containing liquid of a more uniform dispersion state to be obtained.

In the coloring composition, the content of the colorant AX is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, and more preferably 5% by mass in the total amount of solids. It is 75 mass% or less. In the coloring composition, the content of the isoindoline dye (A) is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably, in the total amount of solids. It is 5 mass% or more and 75 mass% or less.
In the colored curable resin composition, the content of the colorant AX is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, and more preferably, in the total amount of solids. It is 5 mass% or more and 75 mass% or less. In the colored curable resin composition, the content of the isoindoline dye (A) is usually 1% by mass or more and 90% by mass or less, and preferably 1% by mass or more and 80% by mass or less in the total amount of solids. More preferably, it is 5 mass% or more and 75 mass% or less.
In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored composition or colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

(4) Solvent (E)
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

Examples of the solvent (E) include ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone. (Solvent containing —COO— in the molecule and not —O—);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule and not -COO- );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (in the molecule -COO- And a solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone and cyclohexanone (solvents containing —CO— in the molecule and not —COO—);
Alcohol solvents such as butanol, cyclohexanol and propylene glycol (solvents containing OH in the molecule and not -O-, -CO- and -COO-);
Examples include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  As the solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, N-methylpyrrolidone and ethyl 3-ethoxypropionate are more preferable.

  When the solvent (E) is included, the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

(5) Resin (B)
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter referred to as “monomer ( A resin having a structural unit derived from “a)” may be more preferable. The resin (B) is further derived from a monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b)”). Structural unit, monomer (c) copolymerizable with monomer (a) (however, different from monomer (a) and monomer (b)) (hereinafter “monomer (c)” And at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the side chain.

  Specific examples of the monomer (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono [2 -(Meth) acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, and maleic anhydride.

The monomer (b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group. The body is preferred.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
Examples of the monomer (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth).
Acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1]. .0 ^2,6] decyl (meth) acrylate, 3-ethyl-3- (meth) acryloyloxy methyl oxetane.

Examples of the monomer (c) include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6. ] Decan-8-yl (meth) acrylate benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like are preferable. Are preferably styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like.

  The resin having a structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding the monomer (b) to the copolymer of the monomer (a) and the monomer (c) It can be produced by adding monomer (a) to a copolymer of (b) and monomer (c). The resin may be a resin obtained by adding the monomer (a) to the copolymer of the monomer (b) and the monomer (c) and further reacting with the carboxylic acid anhydride.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. .
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, still more preferably 70 to 135 mg-KOH / g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example. .

  The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content.

(6) Polymerizable compound (C)
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( And (meth) acrylate.
The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  When the polymerizable compound (C) is included, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, based on the total amount of the solid content. More preferably, it is 17-55 mass%.

(7) Polymerization initiator (D)
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of polymerization initiators that generate active radicals include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morpholino-1- ( 4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis (trichloromethyl) ) -6-Piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoy Diphenyl phosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole.

  When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 to 100 mass with respect to 100 mass parts of the total amount of the resin (B) and the polymerizable compound (C). Part, more preferably 20 to 70 parts by weight. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

(8) Polymerization initiation aid (D1)
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
As the polymerization initiation assistant (D1), 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone , N-phenylglycine and the like.

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

(9) Leveling agent (F)
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  When the leveling agent (F) is contained, the content thereof is usually 0.0005% by mass or more and 1% by mass or less, preferably 0.001 based on the total amount of the colored composition or the colored curable resin composition. % By mass or more and 0.5% by mass or less, more preferably 0.001% by mass or more and 0.2% by mass or less, still more preferably 0.002% by mass or more and 0.1% by mass or less, and particularly preferably. Is 0.005 mass% or more and 0.1 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

(10) Components other than the resin (B), the polymerizable compound (C), the polymerization initiator (D), the polymerization initiation assistant (D1), and the leveling agent (F) (hereinafter sometimes referred to as “other components”). is there)
The coloring composition of the present invention is a known component in the technical field such as a filler, a polymer compound other than the resin (B), an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, etc. May be included.

(11) Color filter A color filter can be formed from the colored curable resin composition of the present invention. Examples of the method for forming the colored pattern include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable.

  The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

  In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD6130 type).

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Analysis sample solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight obtained above in terms of polystyrene was defined as the dispersity.

The Hansen solubility parameter of the isoindoline dye includes all the three-dimensional points of the solvent in which the isoindoline dye used in the solubility test is dissolved in the sphere. A sphere that is outside the sphere (Hansen solubility sphere) was found and determined from the center coordinates of the sphere.
Solubility test; 1,4-dioxane, 1-butanol, 2-phenoxyethanol, acetone, acetonitrile, chloroform, cyclohexane, cyclohexanol, dibasic acid ester, diacetone alcohol, diethylene glycol, N, N-dimethylformamide, dimethyl sulfoxide, di Propylene glycol, ethanol, ethyl acetate, γ-butyrolactone, hexane, 2-butanone, methanol, 4-methyl-2-pentanone, dichloromethane, butyl acetate, N-methylpyrrolidone, 1-methoxy-2-propanol, propylene glycol 1- Monomethyl ether 2-acetate, propylene carbonate, tetrachloroethylene, tetrahydrofuran, toluene, 1,3-dimethyl-2-imidazolidinone, N, N′-dimethyl Le propylene urea, tetramethyl urea relative isoindoline pigments, under 23 ° C., with 200 times by weight, was examined visually whether isoindoline dye is soluble in the solvent.

Example 1
(1) Synthesis of 4-carboxy-1- (4-cyano-3-oxybutyl) benzene 30 parts of methyl 4-carboxy-1-benzenepropionate (synthesized according to the method described in WO2005 / 012220) in 900 parts of THF Dissolved. While maintaining the temperature of the obtained mixture at −50 ° C. or lower, 576 parts of a 1 mol / L hexane solution of lithium bis (trimethylsilyl) amide (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 120 minutes and stirred for 30 minutes. . While maintaining at −50 ° C. or lower, 36 parts of acetonitrile (manufactured by Kanto Chemical Co., Inc.) was dropped over 90 minutes, the temperature was raised to 25 ° C., and the mixture was stirred at 25 ° C. for 6 hours. The reaction solution was washed with water, the ethyl acetate extract was dried over anhydrous sodium sulfate, the solvent was distilled off after filtration, the residue was purified by reprecipitation with ethyl acetate / n-hexane (volume ratio 2/1), 4- 27 parts of carboxy-1- (4-cyano-3-oxybutyl) benzene were obtained (yield 85%).
(2) Synthesis of isoindoline dye 1 1.0 part of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts of methanol were mixed. While maintaining the temperature of the obtained mixture at 5 ° C. or lower, 0.9 part of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and 6 hours at 5 ° C. Stir. While maintaining the temperature of the obtained mixture at 5 ° C. or lower, 4.7 parts of acetic acid was added. To the obtained mixture, 4.1 parts of 4-carboxy-1- (4-cyano-3-oxybutyl) benzene was added and stirred at 45 ° C. for 26 hours. The obtained mixture was filtered, and the residue was washed with 100 parts of water, 100 parts of methanol, 5 parts of N, N-dimethylformamide and 20 parts of methanol in that order, and dried under reduced pressure at 60 ° C. 2.3 parts of a compound represented by 2.3 parts of the compound represented by the formula (I-1) thus obtained and 12 parts of N, N-dimethylacetamide were mixed and stirred at 20 ° C. for 3 hours. The obtained mixture was filtered, and the obtained residue was dried under reduced pressure at 60 ° C. to obtain 2.3 parts of isoindoline dye 1 (Compound No. 154) represented by the formula (I-1) (yield). Rate 55%).

<Identification of Isoindoline Dye 1>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 546
Exact Mass: 545

<Hansen solubility parameter of isoindoline dye 1>
The Hansen solubility parameter of isoindoline dye 1 was (δ _D1 , δ _P1 , δ _H1 ) = (17.3, 13.5, 10.0).

Example 2
The synthesis was performed in the same manner as in Example 1 except that 1.0 part of phthalonitrile of Example 1 was changed to 1.4 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.). 3.7 parts of isoindoline dye 2 (Compound No. 155) represented by the formula (I-2) was obtained (yield 63%).

<Identification of Isoindoline Dye 2>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 591
Exact Mass: 590

<Hansen solubility parameter of isoindoline dye 2>
The Hansen solubility parameter of isoindoline dye 2 was (δ _D1 , δ _P1 , δ _H1 ) = (17.0, 13.2, 9.9).

Example 3
4.1 parts of 4-carboxy-1- (4-cyano-3-oxybutyl) benzene of Example 1 was replaced with 3- (2-cyanoacetyl) benzoic acid (Bioorganic & Medicinal Chemistry Letters, 2010, 20 (3), 922. -Synthesis according to the method described in -926) The synthesis was performed in the same manner as in Example 1 except that the amount was 4.7 parts. 2.9 parts of isoindoline dye 3 (Compound No. 37) represented by the formula (I-3) was obtained (yield 76%).

<Identification of Isoindoline Dye 3>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 490
Exact Mass: 489

<Hansen solubility parameter of isoindoline dye 3>
The Hansen solubility parameter of the isoindoline dye 3 was (δ _D1 , δ _P1 , δ _H1 ) = (17.0, 12.5, 9.9).

Example 4
4.7 parts of 4-carboxy-1- (4-cyano-3-oxybutyl) benzene of Example 1 4- (2-cyanoacetyl) benzoic acid (synthesized according to the method described in US Pat. No. 2,680,731) The synthesis was performed in the same manner as in Example 1 except that. 2.9 parts of isoindoline dye 4 (Compound No. 46) represented by the formula (I-4) was obtained (76% yield).

<Identification of Isoindoline Dye 4>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 490
Exact Mass: 489

<Hansen solubility parameter of isoindoline dye 4>
The Hansen solubility parameter of the isoindoline dye 4 was (δ _D1 , δ _P1 , δ _H1 ) = (17.0, 12.5, 9.7).

Example 5
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide in Example 4 was changed to N, N-dimethylacetoacetamide. 2.6 parts of isoindoline dye 4 were obtained (yield 68%).

Example 6
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide in Example 4 was changed to dimethyl sulfoxide. 2.4 parts of isoindoline dye 4 were obtained (yield 65%).

Example 7
The synthesis was performed in the same manner as in Example 4 except that 1,3-dimethyl-2-imidazolidinone was used as the N, N-dimethylacetamide in Example 4. 2.4 parts of isoindoline dye 4 were obtained (yield 65%).

Example 8
The synthesis was performed in the same manner as in Example 4 except that N-N-dimethylacetamide in Example 4 was changed to N-methylpyrrolidone. 2.0 parts of isoindoline dye 4 was obtained (yield 53%).

Example 9
The same method as in Example 4 except that N, N-dimethylacetamide in Example 4 was changed to a mixed solvent of N, N-dimethylacetamide / γ-butyrolactone / N-methylpyrrolidone (volume ratio 66/16/18). Was synthesized. 2.4 parts of isoindoline dye 4 were obtained (yield 65%).

Example 10
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide of Example 4 was used as a mixed solvent of N, N-dimethylacetamide / sulfolane (volume ratio 49/51). 2.5 parts of isoindoline dye 4 were obtained (yield 66%).

Example 11
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide of Example 4 was used as a mixed solvent of N, N-dimethylacetamide / N-methylpyrrolidone (volume ratio 44/56). 2.6 parts of isoindoline dye 4 were obtained (yield 68%).

Example 12
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide of Example 4 was used as a mixed solvent of N, N-dimethylacetamide / dimethylsulfoxide (volume ratio 82/18). 2.3 parts of isoindoline dye 4 was obtained (yield 60%).

Example 13
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide in Example 4 was changed to N, N-dimethylacetamide / 2-butanone / propylene carbonate mixed solvent (volume ratio 66/26/8). went. 2.8 parts of isoindoline dye 4 were obtained (yield 73%).

Comparative Example 1
The synthesis was performed in the same manner as in Example 1 except that N-N-dimethylacetamide in Example 1 was changed to n-hexane. 3 parts of isoindoline dye 1 were obtained (yield 72%).

Comparative Example 2
Synthesis was performed in the same manner as in Example 2, except that n, N-dimethylacetamide in Example 2 was changed to n-hexane. 4.5 parts of isoindoline dye 2 were obtained (yield 77%).

Comparative Example 3
The synthesis was performed in the same manner as in Example 3 except that N, N-dimethylacetamide in Example 3 was changed to n-hexane. 3.2 parts of isoindoline dye 3 was obtained (yield 84%).

Comparative Example 4
The synthesis was performed in the same manner as in Example 4 except that N, N-dimethylacetamide in Example 4 was changed to n-hexane. 3.1 parts of isoindoline dye 4 was obtained (yield 81%).

Synthesis example 1
An appropriate amount of nitrogen was allowed to flow into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. Then 54 parts acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxy tricyclo [5.2.1.0 ^{2, 6} ] A solution dissolved in 225 parts of a mixture of decane-9-yl acrylate (trade name “E-DCPA”, manufactured by Daicel Corporation), 81 parts of vinyltoluene (isomer mixture), and 160 parts of propylene glycol monomethyl ether acetate. Was added dropwise over 5 hours. After completion of the dropwise addition of the initiator solution, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 37.5%. The obtained resin B1 had a weight average molecular weight of 10,600, a dispersity of 2.0, and a solid content acid value of 115 mg-KOH / g.

Example 14
(1) Preparation of coloring composition Coloring agent AX: Isoindoline dye 1 50 parts,
Dispersant (BYK-LPN6919; manufactured by Big Chemie Japan Co., Ltd.) 58 parts,
Resin (B): 93 parts of resin B1 solution,
And Solvent (E): 800 parts of propylene glycol monomethyl ether acetate was mixed, and the isoindoline dye 1 was dispersed using a bead mill to obtain a colored composition 1.
Then
Coloring composition 1: 400 parts;
Resin (B): Resin B1 solution 45 parts;
Polymerizable compound (C): 25 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation) 15 parts;
Solvent (E): 86 parts of propylene glycol monomethyl ether acetate;
And leveling agent: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts;
Were mixed to obtain a colored curable resin composition 1.

(2) Preparation of colored coating film A colored curable resin composition was applied on a 5 cm square glass substrate (Eagle XG; manufactured by Corning) by spin coating so that the film thickness after post-baking was 2 μm. After that, pre-baking was performed at 100 ° C. for 3 minutes to form a colored composition layer. After standing to cool, the colored composition layer formed on the substrate was exposed to light at an exposure amount of 80 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Irradiated. After light irradiation, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored coating film. The film thickness of the obtained colored pattern was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The film thickness of the colored pattern is shown in the “film thickness” column in Table 7.

(3) Contrast evaluation About the obtained colored coating film, a contrast meter (CT-1: Osaka Co., Ltd., color difference meter BM-5A: manufactured by Topcon Corporation, light source: F-10, polarizing film: Osaka Co., Ltd. Contrast was measured using this method. The blank value at the time of measurement is 30,000. The results are shown in Table 7.

Examples 15-26 and Comparative Examples 5-8
It replaced with the isoindoline dye 1 as a coloring agent (A), and it carried out similarly to Example 14 except using the isoindoline dye obtained by the Example and comparative example mentioned above. The results are shown in Table 7.

Claims (7)

The step of bringing the isoindoline dye (A) into contact with the solvent (Z), and the step of taking out the isoindoline dye (A) in contact with the solvent (Z) by solid-liquid separation,
The distance Ra between the Hansen solubility parameter of the isoindoline dye (A) and the Hansen solubility parameter of the solvent (Z) calculated based on the formula (E.1) is 0 MPa ^0.5 or more and 10 MPa ^0.5 or less, and The method for producing an isoindoline dye, wherein the amount of the solvent (Z) in the contacting step is 0.1 to 10.0 times the mass of the isoindoline dye (A).

[Where:
δ _D1 : disperse component of Hansen solubility parameter (MPa ^0.5 ) of isoindoline dye (A),
δ _D2 : dispersive component of Hansen solubility parameter of solvent (Z) (MPa ^0.5 ),
δ _P1 : polar component (MPa ^0.5 ) of Hansen solubility parameter of isoindoline dye (A),
δ _P2 : polar component (MPa ^0.5 ) of Hansen solubility parameter of solvent (Z),
δ _H1 : hydrogen bond component (MPa ^0.5 ) of Hansen solubility parameter of isoindoline dye (A),
δ _{H2 is} the hydrogen bonding component (MPa ^0.5 ) of the Hansen solubility parameter of the solvent (Z)] In the Hansen solubility parameter of the solvent (Z), the dispersion component δ _D2 of the solvent (Z) is 16.0 MPa ^0.5 or more and 19.0 MPa ^0.5 or less, and the polar component δ _P2 of the solvent (Z) is 9.0 MPa ^0.5 or more and 17.0 MPa. ^0.5 or less, and the hydrogen bond component [delta] _H2 of the solvent (Z) is 6.5 MPa ^0.5 or more 11.0 MPa ^{and 0.5} or less, the production method according to claim 1, wherein.   The production method according to claim 1 or 2, wherein the solvent (Z) contains at least one selected from the group consisting of an ester solvent, a ketone solvent, an amide solvent, a sulfoxide solvent, and a sulfone solvent.   The manufacturing method in any one of Claims 1-3 whose quantity of a solvent (Z) is 0.5 mass times or more and 8.0 mass times or less with respect to an isoindoline pigment | dye (A). The manufacturing method in any one of Claims 1-4 in which an isoindoline pigment | dye (A) contains the compound represented by Formula (1).

[In Formula (1),
R ¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and is included in the hydrocarbon group − In the case where CH ₂ — and the heterocyclic group include —CH ₂ — that does not form a ring, —CH ₂ — is replaced by —O—, —CO—, —S (O) ₂ —, —NR ^x1 —. It may be. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— .
R ^{2 to} R ⁹ are each independently a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, cyano. group, a nitro group, -CO ₂ ^- or -S (O) ₂ O ^- represents, -CH ₂ - contained in the hydrocarbon group when including - and said heterocyclic group is -CH ₂ does not constitute a ring The —CH ₂ — may be replaced by —O—, —CO—, —S (O) ₂ —, or —NR ^x1 —. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— .
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , and R ⁸ and R ⁹ have a substituent together with the carbon atom to which they are bonded. A ring may be formed, and when the ring contains —CH ₂ — that does not constitute a ring, —CH ₂ — represents —O—, —CO—, —S (O) ₂ —, — NR ^x1 − may be substituted. However, —COOH and —S (O) ₂ OH are not formed by replacing —CH ₂ —. Further, the ring -CO ₂ ^- and -S (O) ₂ O ^- may have at least one selected from the group consisting of.
R ^x1 represents an optionally substituted hydrocarbon group having 1 to 40 carbon atoms, an optionally substituted heterocyclic group or a hydrogen atom, and the hydrocarbon group and the heterocyclic group May have at least one selected from the group consisting of —CO ₂ ^— and —S (O) ₂ O ^— . When a plurality of R ^x1 are present, these may be the same or different.
a is the total number of —CO ₂ ^— and —S (O) ₂ O ^— contained in the compound represented by the formula (1), and represents an integer of 0 to 10.
M ^{b +} represents hydron or a b-valent metal ion. When a plurality of M ^{b +} are present, these may be the same or different. When M ^{b +} is hydrone, the hydrone is present as —CO ₂ H and S (O) ₂ OH together with the —CO ₂ ^— or —S (O) ₂ O ^— .
b represents an integer of 1 to 6.
m represents 0 when a is 0, and represents the number of M ^{b +} when a is 1 or more.
n is 1 when a and m are 0, and is a number satisfying the relationship n = b × m / a when a and m are not 0. ] The isoindoline dye (A) is a compound represented by the formula (1a),
Furthermore, the manufacturing method of Claim 5 including the manufacturing process of the compound represented by Formula (1a) chosen from the process A or the process B.
Step A: After reacting the compound represented by the formula (pt1) with the compound represented by the formula (pt2), the compound represented by the formula (pt3) and the compound represented by the formula (pt4) are further added. Step of producing a compound represented by formula (1a) by reacting in the presence of an acid Step B: A compound represented by formula (pt5), a compound represented by formula (pt3) and a formula (pt4) For producing a compound represented by the formula (1a) by reacting with a compound to be produced

[In Formula (pt1) to Formula (pt5) and Formula (1a), R ^{2 to} R ⁹ represent the same meaning as described above. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. M ¹ represents an alkali metal atom. ] The isoindoline dye (A) is a compound represented by the formula (1b),
Furthermore, the manufacturing method of Claim 5 including the synthetic | combination process of the formula (1a) chosen from the process A or the process B, and the manufacturing process of the compound represented by the formula (1b) represented by the process C.
Step A: After reacting the compound represented by the formula (pt1) with the compound represented by the formula (pt2), the compound represented by the formula (pt3) and the compound represented by the formula (pt4) are further added. Step of producing a compound represented by formula (1a) by reacting in the presence of an acid Step B: A compound represented by formula (pt5), a compound represented by formula (pt3) and a formula (pt4) A step of producing a compound represented by the formula (1a) by reacting with a compound represented by the formula (1a) Step C: A compound represented by the formula (1a) and a compound represented by the formula (pt6) are reacted with the formula (1b). Step for producing a compound represented by

[In formula (pt1) to formula (pt6) and formula (1b), R ^{1 to} R ⁹ represent the same meaning as described above. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. M ¹ represents an alkali metal atom. LG ¹ represents a halogen atom, a methanesulfonyloxy group, a chloromethylsulfonyloxy group, a toluenesulfonyloxy group, or a trifluoromethanesulfonyloxy group. However, R ¹ is not a hydrogen atom. ]