JP2022018965A - Colored curable resin composition, color filter, and display device - Google Patents

Abstract

To provide a colored curable resin composition capable of forming a color filter excellent in light fastness.SOLUTION: The colored curable resin composition contains a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant. The colorant includes at least one selected from compounds represented by formula (I) and compounds represented by formula (II).SELECTED DRAWING: None

Description

The present invention relates to a colored curable resin composition, a color filter and a display device.

The colored resin composition is used for manufacturing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. As a colored resin composition, a composition containing a quinophthalone compound represented by the following formula (x) is known (Patent Document 1).

Japanese Patent Application Laid-Open No. 2003-167112

However, the color filter formed from the conventionally known colored resin composition containing the quinophthalone compound may not be sufficiently satisfactory in light resistance. Therefore, it is an object of the present invention to provide a colored curable resin composition capable of forming a color filter having excellent light resistance.

［式中、
Ｒ¹～Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ、ＭＭ、炭素数１～４０の１価の炭化水素基又は炭素数１～４０の１価の複素環基を表し、
該１価の炭化水素基及び該１価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｒ¹及びＲ²、Ｒ²及びＲ³、Ｒ³及びＲ⁴、Ｒ⁴及びＲ⁶、及びＲ⁶及びＲ⁵は、それぞれ互いに結合して環を形成していてもよい。
Ｍは、水素原子、アルカリ金属原子、配位子を有していてもよい金属原子又はＮ（Ｚ¹）（Ｚ²）（Ｚ³）（Ｚ⁴）を表す。
ＭＭは、アルカリ金属原子、配位子を有していてもよい金属原子又はＮ（Ｚ¹）（Ｚ²）（Ｚ³）（Ｚ⁴）を表す。
Ｚ¹～Ｚ⁴は、それぞれ独立して、水素原子、炭素数１～４０の１価の炭化水素基又は炭素数１～４０の１価の複素環基を表し、
該１価の炭化水素基及び該１価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｑ¹及びＱ²は、それぞれ独立して、２価の炭化水素基又は２価の複素環基を表し、
該２価の炭化水素基及び該２価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｚ¹～Ｚ⁴、Ｍ及びＭＭがそれぞれ複数存在する場合、それらは互いに同一又は異なっていてよい。］
［２］ 前記酸化防止剤が、フェノール骨格を１個又は２個有するフェノール系酸化防止剤である［１］に記載の着色硬化性樹脂組成物。
［３］ さらに一重項酸素クエンチャーを含む［１］又は［２］に記載の着色硬化性樹脂組成物。
［４］ 前記一重項酸素クエンチャーが遷移金属錯体である［３］に記載の着色硬化性樹脂組成物。
［５］ 前記一重項酸素クエンチャーがニッケル錯体、銅錯体及びコバルト錯体から選ばれる少なくとも１種を含む遷移金属錯体である［４］に記載の着色硬化性樹脂組成物。
［６］ 前記式（Ｉ）又は式（ＩＩ）におけるＱ¹及びＱ²が、それぞれ独立して、式（ＱＱ１）又は式（ＱＱ２）で表される基である［１］～［５］のいずれかに記載の着色硬化性樹脂組成物。

［式中、
Ｒ^Q1～Ｒ^Q10は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ、ＭＭ、炭素数１～４０の１価の炭化水素基又は炭素数１～４０の１価の複素環基を表し、
該１価の炭化水素基及び該１価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、
－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｒ^Q1～Ｒ^Q4は、それぞれ互いにＲ^Q1～Ｒ^Q4から選ばれる１つ以上と結合して環を形成してもよく、
Ｒ^Q5～Ｒ^Q10は、それぞれ互いにＲ^Q5～Ｒ^Q10から選ばれる１つ以上と結合して環を形成してもよい。
Ｍ及びＭＭは、前記と同一の意味を表す。
※は、結合手を表す。］
［７］ 前記式（Ｉ）又は式（ＩＩ）におけるＱ¹及びＱ²の少なくとも一方が、式（ＱＱ１）で表される基である［６］に記載の着色硬化性樹脂組成物。
［８］ 前記着色剤が式（Ｉ）で表される化合物を含む［１］～［７］のいずれかに記載の着色硬化性樹脂組成物。
［９］ 前記式（Ｉ）におけるＱ¹又はＱ²が、少なくとも１つの－ＣＯ₂Ｈを有する［８］に記載の着色硬化性樹脂組成物。
［１０］ ［１］～［９］のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［１１］ ［１０］に記載のカラーフィルタを含む表示装置。 The gist of the present invention is as follows.
[1] A colorant, a resin, a polymerizable compound, a polymerization initiator and an antioxidant are contained, and the colorant is selected from a compound represented by the formula (I) and a compound represented by the formula (II). A colored curable resin composition containing at least one kind.

[During the ceremony,
R ¹ to R ⁶ are independently hydrogen atom, halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, MM, monovalent hydrocarbon group or carbon having 1 to 40 carbon atoms. Represents a monovalent heterocyclic group of the number 1-40.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
The monovalent hydrocarbon group and -CH _2- constituting the monovalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁶ , and R ⁶ and R ⁵ may be coupled to each other to form a ring, respectively.
M represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ).
MM represents an alkali metal atom, a metal atom which may have a ligand, or N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ).
Z ¹ to Z ⁴ independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent heterocyclic group having 1 to 40 carbon atoms.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
The monovalent hydrocarbon group and -CH _2- constituting the monovalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
Q ¹ and Q ² independently represent a divalent hydrocarbon group or a divalent heterocyclic group, respectively.
-C (-) (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -Si (-) (-)-.
-CH (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N (-)-.
-CH = constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N =.
The divalent hydrocarbon group and -CH _2- constituting the divalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
When there are a plurality of Z ¹ to Z ⁴ , M and MM, they may be the same or different from each other. ]
[2] The colored curable resin composition according to [1], wherein the antioxidant is a phenolic antioxidant having one or two phenol skeletons.
[3] The colored curable resin composition according to [1] or [2], which further comprises a singlet oxygen quencher.
[4] The colored curable resin composition according to [3], wherein the singlet oxygen quencher is a transition metal complex.
[5] The colored curable resin composition according to [4], wherein the single term oxygen quencher is a transition metal complex containing at least one selected from a nickel complex, a copper complex and a cobalt complex.
[6] ^Q1 and Q2 in the formula (I) or the formula ( ^II ) are the groups represented by the formula (QQ1) or the formula (QQ2) independently of [1] to [5]. The colored curable resin composition according to any one.

[During the ceremony,
R ^Q1 to R ^Q10 are independently hydrogen atom, halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, MM, monovalent hydrocarbon group or carbon with 1 to 40 carbon atoms. Represents a monovalent heterocyclic group of the number 1-40.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
-CH _2- , which constitutes the monovalent hydrocarbon group and the monovalent heterocyclic group, is -O-, -S-,
It may be replaced with -S (O) ₂ -or-CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
R ^Q1 to R ^Q4 may each be combined with one or more selected from R ^Q1 to R ^Q4 to form a ring.
R ^Q5 to R ^Q10 may each be bonded to one or more selected from R ^Q5 to R ^Q10 to form a ring.
M and MM have the same meanings as described above.
* Represents a bond. ]
[7] The colored curable resin composition according to [6], wherein at least one of Q ¹ and Q ² in the formula (I) or the formula (II) is a group represented by the formula (QQ1).
[8] The coloring curable resin composition according to any one of [1] to [7], wherein the coloring agent contains a compound represented by the formula (I).
[9] The colored curable resin composition according to [8], wherein Q ¹ or Q ² in the formula (I) has at least one −CO ₂ H.
[10] A color filter formed from the colored curable resin composition according to any one of [1] to [9].
[11] A display device including the color filter according to [10].

According to the present invention, it is possible to provide a colored curable resin composition that can be used for forming a color filter having excellent light resistance.

The color-curable resin composition of the present invention includes a colorant (hereinafter, may be referred to as a colorant (A)), a resin (hereinafter, may be referred to as a resin (B)), and a polymerizable compound (hereinafter, a polymerizable compound). (C)), a polymerization initiator (hereinafter, may be referred to as a polymerization initiator (D)) and an antioxidant (hereinafter, may be referred to as an antioxidant (G)).
The colored curable resin composition of the present invention may further contain a singlet oxygen quencher (hereinafter, may be referred to as a singlet oxygen quencher (H)).
The colored curable resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as a solvent (E)).
The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as a polymerization initiation aid (D1)).
The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as a leveling agent (F)).
In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of kinds unless otherwise specified.

<Colorant (A)>
The colorant (A) is a compound represented by the formula (I) (hereinafter, may be referred to as compound (I)) and a compound represented by the formula (II) (hereinafter, may be referred to as compound (II)). Includes at least one selected from.

［式中、
Ｒ¹～Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ、ＭＭ、炭素数１～４０の１価の炭化水素基又は炭素数１～４０の１価の複素環基を表し、
該１価の炭化水素基及び該１価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｒ¹及びＲ²、Ｒ²及びＲ³、Ｒ³及びＲ⁴、Ｒ⁴及びＲ⁶、及びＲ⁶及びＲ⁵は、それぞれ互いに結合して環を形成していてもよい。
Ｍは、水素原子、アルカリ金属原子、配位子を有していてもよい金属原子又はＮ（Ｚ¹）（Ｚ²）（Ｚ³）（Ｚ⁴）を表す。
ＭＭは、アルカリ金属原子、配位子を有していてもよい金属原子又はＮ（Ｚ¹）（Ｚ²）（Ｚ³）（Ｚ⁴）を表す。
Ｚ¹～Ｚ⁴は、それぞれ独立して、水素原子、炭素数１～４０の１価の炭化水素基又は炭素数１～４０の１価の複素環基を表し、
該１価の炭化水素基及び該１価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該１価の炭化水素基及び該１価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｑ¹及びＱ²は、それぞれ独立して、２価の炭化水素基又は２価の複素環基を表し、
該２価の炭化水素基及び該２価の複素環基を構成する－Ｃ（－）（－）－は、－Ｓｉ（－）（－）－に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する－ＣＨ（－）－は、－Ｎ（－）－に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する－ＣＨ＝は、－Ｎ＝に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する－ＣＨ₂－は、－Ｏ－、－Ｓ－、－Ｓ（Ｏ）₂－又は－ＣＯ－に置き換わっていてもよく、
該２価の炭化水素基及び該２価の複素環基を構成する水素原子は、ハロゲン原子、シアノ基、ニトロ基、－ＳＯ₃Ｍ、－ＣＯ₂Ｍ又はＭＭに置き換わっていてもよい。
Ｚ¹～Ｚ⁴、Ｍ及びＭＭがそれぞれ複数存在する場合、それらは互いに同一又は異なっていてよい。］ << Compound (I), Compound (II) >>

[During the ceremony,
R ¹ to R ⁶ are independently hydrogen atom, halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, MM, monovalent hydrocarbon group or carbon having 1 to 40 carbon atoms. Represents a monovalent heterocyclic group of the number 1-40.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
The monovalent hydrocarbon group and -CH _2- constituting the monovalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁶ , and R ⁶ and R ⁵ may be coupled to each other to form a ring, respectively.
M represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ).
MM represents an alkali metal atom, a metal atom which may have a ligand, or N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ).
Z ¹ to Z ⁴ independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent heterocyclic group having 1 to 40 carbon atoms.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
The monovalent hydrocarbon group and -CH _2- constituting the monovalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
Q ¹ and Q ² independently represent a divalent hydrocarbon group or a divalent heterocyclic group, respectively.
-C (-) (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -Si (-) (-)-.
-CH (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N (-)-.
-CH = constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N =.
The divalent hydrocarbon group and -CH _2- constituting the divalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
When there are a plurality of Z ¹ to Z ⁴ , M and MM, they may be the same or different from each other. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.

The monovalent hydrocarbon group represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ has 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and further. It is preferably 1 to 18, and even more preferably 1 to 12.
The monovalent hydrocarbon group having 1 to 40 carbon atoms represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be used. The hydrogen group may be saturated or unsaturated, and may be chain-shaped or cyclic (alicyclic hydrocarbon group).

Saturated or unsaturated chain hydrocarbon groups represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , Nonyl group, and linear alkyl group such as decyl group;
Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,1,3,3-tetramethylbutyl group, 1-methylbutyl group, 1-ethyl Branched chains such as propyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 2-methylpentyl group, 3-ethylpentyl group, 1,3-dimethylbutyl group, and 2-ethylhexyl group. Alkyl group;
Ethenyl group (vinyl group), propenyl group (eg, 1-propenyl group, 2-propenyl group (allyl group)), 1-methylethenyl group, butenyl group (eg, 1-butenyl group, 2-butenyl group, 3-butenyl) Group), 3-methyl-1-butenyl group, 1,3-butadienyl group, 1- (2-propenyl) ethenyl group, 1- (1-methylethenyl) ethenyl group, 1,2-dimethyl-1-propenyl group, Alkenyl groups such as a pentenyl group (eg, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group) and a hexenyl group (eg, 1-hexenyl group, 5-hexenyl group);
Ethynyl group, propynyl group (eg, 1-propynyl group, 2-propynyl group), octynyl group (eg, 1-octynyl group, 7-octynyl group), butynyl group, pentynyl group, alkynyl group such as hexynyl group; etc. Can be mentioned.

The saturated or unsaturated chain hydrocarbon group preferably has 1 to 30, more preferably 1 to 20, still more preferably 1 to 18, and even more preferably 1 to 12. Of these, a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferable.

Saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ include cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl. Cycloalkyl groups such as groups;
Cycloalkenyl groups such as cyclohexenyl groups (eg, cyclohex-1-en-1-yl group, cyclohex-2-en-1-yl group, cyclohex-3-en-1-yl group), cycloheptenyl group and cyclooctenyl group. ;
Saturated or unsaturated polycyclic hydrocarbon groups such as norbornyl group, norbornenyl group, adamantyl group and bicyclo [2.2.2] octyl group; and the like.

The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 30, more preferably 3 to 20, still more preferably 3 to 18, and even more preferably 3 to 12. .. Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group are particularly preferable.

The aromatic hydrocarbon groups represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-dimethylphenyl group and 2 , 6-Dimethylphenyl group, 2,4,6-trimethylphenyl group, o-propylphenyl group, m-propylphenyl group, p-propylphenyl group, 2,4-diisopropylphenyl group, 2,6-diisopropylphenyl group , 4-vinylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 3,5-di (tert-butyl) phenyl group, 1-naphthyl group, 2 Examples thereof include a naphthyl group, a 6-methyl-2-naphthyl group, a fluorenyl group, a phenanthryl group, an anthryl group, a perylene group and a pyrenyl group.

The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, still more preferably 6 to 18, and even more preferably 6 to 12.

The hydrocarbon groups represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ may be a group in which the above-mentioned hydrocarbon groups are combined. As the group in which the above-mentioned hydrocarbon groups are combined, for example, at least one selected from an aromatic hydrocarbon group, a chain hydrocarbon group, and an alicyclic hydrocarbon group is combined with an aromatic hydrocarbon group. Group; a group that combines a chain hydrocarbon group and an alicyclic hydrocarbon group; and the like.

Examples of the group in which at least one selected from the aromatic hydrocarbon group, the chain hydrocarbon group, and the alicyclic hydrocarbon group and the aromatic hydrocarbon group are combined include, for example, a benzyl group, (4-methylphenyl). Aralkyl groups such as methyl group and phenethyl group; 1-phenylethenyl group, 2-phenylethenyl group (phenylvinyl group), 2,2-diphenylethenyl group, 2-phenyl-2- (1-naphthyl) An arylalkenyl group such as an ethenyl group; an arylalkynyl group such as a phenylethynyl group; an aryl (preferably phenyl) group to which an arylalkynyl group such as a (phenylethynyl) phenyl group is bonded; Phenyl group to which a phenyl group is bonded; cyclohexylmethylphenyl group, benzylphenyl group, (dimethyl (phenyl) methyl) phenyl group and the like can be mentioned. These carbon atoms are preferably 7 to 30, more preferably 7 to 20, still more preferably 7 to 18, and even more preferably 7 to 15.

Examples of the group combining the chain hydrocarbon group and the alicyclic hydrocarbon group include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, and a cyclopentylethyl group. , Cyclohexylmethyl group, (2-methylcyclohexyl) methyl group, cyclohexylethyl group, adamantylmethyl group and the like may be an alkyl group to which one or more alicyclic hydrocarbon groups are bonded. These carbon atoms are preferably 4 to 30, more preferably 4 to 20, still more preferably 4 to 18, and particularly preferably 4 to 12.

The monovalent heterocyclic group having 1 to 40 carbon atoms represented by R ¹ to R ⁶ and Z ¹ to Z ⁴ represents a group containing a hetero atom as a component of the ring. The monovalent heterocyclic group means a group obtained by removing one hydrogen atom directly bonded to a carbon atom or a hetero atom constituting the ring from the heterocycle. The monovalent heterocyclic group having 1 to 40 carbon atoms may be a monocyclic ring or a polycyclic ring. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom and the like.

The number of carbon atoms of the heterocyclic group is preferably 3 to 30, more preferably 3 to 20, still more preferably 3 to 18, and even more preferably 3 to 12.

Examples of the heterocycle containing a nitrogen atom include monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine and piperazine; pyrazole, pyrazole, imidazole, 1,2,3-triazole and 1,2,4-triazole and the like. 5-membered ring-based unsaturated heterocycles; 6-membered ring-based unsaturated heterocycles such as pyridine, pyridazine, pyridimine, pyrazine and 1,3,5-triazole; indazole, indolin, isoindrin, indol, indolidine, benzoimidazole, Kinoxalin such as quinoline, isoquinoline, 3-methylquinoxalin, quinazoline, cinnoline, phthalazine, naphthylidine, purine, pteridine, benzopyrazole, benzopiperidin and the like fused bicyclic heterocycle; Ring; etc.

Examples of the heterocycle containing an oxygen atom include monocyclic saturated heterocycles such as oxylane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, and 1,4-dioxane; 1,4-dioxaspiro [4.5] decane, Bicyclic saturated heterocycles such as 1,4-dioxaspiro [4.5] nonane and 1,4-dioxaspiro [4.4] nonane; α-acetlactone, β-propiolactone, γ-butyrolactone, γ-valero Lactone-based heterocycles such as lactone and δ-valerolactone; 5-membered ring-based unsaturated heterocycles such as furan, 2,3-dimethylfuran, 2,5-dimethylfuran and the like; 2H-pyran, 4H-pyran and the like. 6-membered ring-based unsaturated heterocycle; fused bicyclic heterocycles such as benzofuran, benzopyran, benzodioxol, 1,3-benzodioxol, benzodioxane, chroman and isochroman; fused three of xanthene, dibenzofuran and the like. Heterocyclic ring system; etc.

Examples of the heterocycle containing a sulfur atom include a 5-membered ring-based saturated heterocycle such as dithiolane; a 6-membered ring-based saturated heterocycle such as thiane, 1,3-dithiane, and 2-methyl-1,3-dithiane; thiophene and thiopyran. , 5-membered ring-based unsaturated heterocycles such as benzothiopyran and 6-membered ring-based unsaturated heterocycles; fused bicyclic heterocycles such as benzothiopyran and benzothiophene; Can be mentioned.

Examples of the heterocycle containing a nitrogen atom and an oxygen atom include morpholin, 2-pyrrolidone, 1-methyl-2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 1-methyl-2-piperidone and 2-methyl-. Monocyclic saturated heterocycles such as 2-piperidone; monocyclic unsaturated heterocycles such as oxazole and isooxazole; fused bicyclic heterocycles such as benzoxazole, benzoisoxazole, benzoxazine, benzodioxane and benzoimidazolin; Condensed tricyclic heterocycles such as phenoxazine; and the like.

Examples of the heterocycle containing a nitrogen atom and a sulfur atom include a monocyclic heterocycle such as thiazole; a fused bicyclic heterocycle such as benzothiazole; a condensed tricyclic heterocycle such as phenothiazine; and the like.

The -C (-) (-)-constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -Si (-) (-)-, and the monovalent hydrocarbon may be replaced. The -CH (-)-that constitutes the hydrogen group and the monovalent heterocyclic group may be replaced with -N (-)-, and the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with the -N (-)-. The constituent -CH = may be replaced with -N =, and the monovalent hydrocarbon group and the -CH _2- constituting the monovalent heterocyclic group are -O-, -S-,-. It may be replaced with S (O) ₂ -or-CO-. As such a basis,

-SiH ₃ ;
A silyl group having 1 to 3 hydrocarbon groups such as -Si (CH ₃ ) ₃ , -Si (CH ₂ CH ₃ ) ₃ , -Si (CH ₃ ) ₂ (CH ₂ CH ₃ );
-Si (OH) ₃ , -Si (OCH ₃ ) ₃ , -Si (OCH ₂ CH ₃ ) ₃ , -Si (O (CH ₂ ) ₂ CH ₃ ) ₃ , -SiH ₂ (OH), -Si (CH) ₃ ) A silyl group having 1 to 3 at least one selected from a hydroxy group such as ₂ (OCH ₃ ), an alkoxy group, and an aryloxy group;
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-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-butylmethylamino group and N, N-phenylmethylamino group and other amino groups having one or two hydrocarbon groups;
Methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl) hexyloxy group, phenyloxy An oxy group (alkoxy group and aryloxy group) to which a hydrocarbon group such as a group, m-tolyloxy group, and 3,4-kisilyloxy group is bonded;
Oxylanyl group;
Holmil group;
An alkanoyl group such as an acetyl group, a propanoyl group, a butanoyl group, a tert-butanoyl group, a pentanoyl group, a hexanoyl group, a (2-ethyl) hexanoyl group, and a benzoyl group;
Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, (2-ethyl) hexyloxycarbonyl group, phenyloxycarbonyl group, o-tolyl An oxycarbonyl group to which a hydrocarbon group such as an oxycarbonyl group is bonded;
Mercapto group;
A mercapto group to which a hydrocarbon group such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a (2-ethylhexyl) thio group, a phenylthio group or an o-tolylthio group is bonded;
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-butylsul Famoyl group, N-phenylsulfamoyl group, N, N-diphenylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethyl One or two hydrocarbon groups such as a sulfamoyl group, an N, N-butylmethylsulfamoyl group, an N, N-tert-butylmethylsulfamoyl group and an N, N-phenylmethylsulfamoyl group. Sulfamoyl group with;
N-formylamino group;
N-acetylamino group, N-propanolamino group, N-butanoylamino group, N-2,2-dimethylpropanolamino group, N-pentanoylamino group, N-hexanoylamino group, N- (2) -Ethyl) N-alkanoylamino groups such as hexanoylamino group and N-benzoylamino group;
Hydroxy group;
Formyloxy group, acetoxy group, propanoyloxy group, butanoyloxy group, 2,2-dimethylpropanoyloxy group, pentanoyloxy group, hexanoyloxy group, (2-ethyl) hexanoyloxy group, benzoyloxy group Alcanoyloxy groups such as;
Hydrocarbon groups such as methyl sulfonyl group, ethyl sulfonyl group, propyl sulfonyl group, butyl sulfonyl group, pentyl sulfonyl group, hexyl sulfonyl group, (2-ethyl) hexyl sulfonyl group, phenyl sulfonyl group and p-tolyl sulfonyl group were substituted. Sulfonyl group;
Carbamic 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-phenylcarbamoyl group, N, N-diphenylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N- One or two charcoal groups such as propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-butylmethylcarbamoyl group, N, N-tert-butylmethylcarbamoyl group and N, N-phenylmethylcarbamoyl group. Carbamoyl group having a hydrogen group; and the like.

Further, the hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M or MM. ..

Examples of the alkali metal atom represented by M and MM include an alkali metal atom such as a lithium atom, a sodium atom and a potassium atom.

Examples of the metal atom of the metal atom which may have a ligand represented by M and MM include a metal atom belonging to groups 2 to 15 of the periodic table of elements. The metal atoms are more preferably Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Rh, Ir, Pd, Ti. Zr, Hf, Si, Ge, more preferably Mg, Ca, Sr, Ba, Ni, Zn, Cu, Fe, Co, Sn, Mn, Al, Cr, and particularly preferably Mg, Ca, Sr, Ba, Ni, Zn, Cu, Fe, Co, Mn, Al, Cr.

The ligand of the metal atom which may have a ligand is not particularly limited, and may be, for example, a halogen atom, NO, NO ₃ , SO ₄ , CH ₃ CO ₂ , OH, or the like.
The ligand coordinated to the metal atom and the carbon atom, nitrogen atom, oxygen atom, sulfur atom, etc. contained in the same ligand may be coordinated to the same metal atom.
A plurality of different ligands may be coordinated to the same metal atom on the metal atom.
It may form an oligomer or a polymer.
When the ligand contains a metal atom in which the compound (I) or the compound (II) may have a ligand, the compound excluding the metal atom which may have a ligand ( I) or compound (II) is also included.
Compound (I) and compound (II) also contain such oligomers or polymers.
However, the charges of compound (I) and compound (II) are 0.

Z ¹ to Z ⁴ may be the same or different, and are preferably the same.
For Z ¹ to Z ⁴ ,
Independently, each is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 40 carbon atoms.
It is more preferable that each of them is a hydrogen atom, or a linear alkyl group or a branched-chain alkyl group (hereinafter, may be simply referred to as “alkyl group”).
It is more preferable that each of them is independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
It is particularly preferable that it is a hydrogen atom.

Examples of N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ) represented by M and MM include NH ₄ ; NH ₃ (CH ₂ CH ₃ ) and NH ₃ ((CH ₂ ) ₇ CH. ₃ ), etc., 3 of Z ¹ to Z ⁴ are hydrogen atoms and 1 is an alkyl group; NH ₂ (CH ₃ ) ₂ , NH ₂ (CH ₂ CH ₃ ) ₂ , etc. Z ¹ to Z ⁴ Two of them are hydrogen atoms and two are alkyl groups; one of Z ¹ to Z ⁴ such as NH (CH ₃ ) ₃ and NH (CH ₂ CH ₃ ) ₃ is a hydrogen atom and three are Groups that are alkyl groups; groups in which all of Z ¹ to Z ⁴ such as N (CH ₃ ) ₄ , N (CH ₂ CH ₃ ) ₄ are alkyl groups; and the like; among them, NH ₄ is preferable.

As M, a hydrogen atom and an alkali metal atom are preferable, and a hydrogen atom, a sodium atom or a potassium atom is more preferable.

The MM has an alkali metal atom, Mg which may have a ligand, Ca which may have a ligand, Sr which may have a ligand, and a ligand. Ba which may have, Ni which may have a ligand, Zn which may have a ligand, Cu which may have a ligand, and has a ligand. Fe may have Fe, Co which may have a ligand, Sn which may have a ligand, Mn which may have a ligand, and may have a ligand. Al or Cr, which may have a ligand, is preferable.

R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^4. and R ⁶ , and R ⁶ and R ⁵ , respectively, may be coupled to each other to form a ring.

As R ¹ to R ⁶ ,
Independently, each is preferably a hydrogen atom, a halogen atom, and a monovalent hydrocarbon group having 1 to 40 carbon atoms.
It is more preferable that each of them is independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms.
It is particularly preferable that it is a hydrogen atom.

Q ¹ and Q ² independently represent a divalent hydrocarbon group or a divalent heterocyclic group, respectively. The divalent hydrocarbon group includes a group excluding one hydrogen atom directly bonded to a carbon atom constituting the monovalent hydrocarbon group, and a preferred embodiment thereof is the number of carbon atoms described above. A group obtained by removing one hydrogen atom from a preferred embodiment of a monovalent hydrocarbon group of 1 to 40, and the divalent heterocyclic group is a carbon atom or a hetero atom constituting the monovalent heterocyclic group. Examples thereof include a group excluding one directly bonded hydrogen atom, and a preferred embodiment thereof is a group excluding one hydrogen atom from the preferred embodiment of the monovalent heterocyclic group having 1 to 40 carbon atoms described above. be.

-C (-) (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -Si (-) (-)-.
-CH (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N (-)-.
-CH = constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N =.
The divalent hydrocarbon group and -CH _2- constituting the divalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.

The group that replaces the hydrogen atom constituting the divalent hydrocarbon group and the divalent heterocyclic group is preferably a halogen atom, a cyano group, a nitro group, -SO ₃ H, or -CO ₂ M. It is more preferably a halogen atom, a nitro group, —CO ₂ M, still more preferably a nitro group, —CO ₂ M, even more preferably a nitro group, —CO ₂ H, and particularly preferably −CO ₂ H. Is.

Q ¹ or Q ² in compound (I) preferably has at least one -CO ₂ M by replacing at least one hydrogen atom with -CO ₂ M, with at least one hydrogen atom. It is more preferred to have at least one —CO ₂ H by being replaced by —CO ₂ H.

Q ¹ and Q ² may be the same or different, and are preferably the same.

It is preferable that Q ¹ and Q ² are independently one of the groups represented by the formulas (QQ1) to (QQ19).

[During the ceremony,
R ^Q1 to R ^Q94 are independently hydrogen atom, halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, MM, monovalent hydrocarbon group or carbon with 1 to 40 carbon atoms. Represents a monovalent heterocyclic group of the number 1-40.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
-CH _2- , which constitutes the monovalent hydrocarbon group and the monovalent heterocyclic group, is -O-, -S-,
It may be replaced with -S (O) ₂ -or-CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
R ^Q1 to R ^Q94 may be bonded to one or more selected from R ^Q1 to R ^Q94 to form a ring.
M and MM have the same meanings as described above.
* Represents a bond. ]

Examples of the halogen atom include atoms similar to the halogen atom described above, and the preferred embodiment thereof is also the same.

The monovalent hydrocarbon group having 1 to 40 carbon atoms and the monovalent heterocyclic group having 1 to 40 carbon atoms represented by R ^Q1 to R ^Q94 are the monovalent hydrocarbon groups having 1 to 40 carbon atoms described above. Examples thereof include a group similar to a hydrocarbon group and a monovalent heterocyclic group having 1 to 40 carbon atoms, and the preferred embodiment thereof is also the same.

M and MM have the same meanings as described above, and the preferred embodiments are also the same.

As R ^Q1 to R ^Q94 in compound (I),
Independently, each is preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO ₂ M, and a monovalent hydrocarbon group having 1 to 40 carbon atoms.
It is more preferable that each of them is independently a hydrogen atom, a nitro group, -CO 2M, an alkyl group having ₁ to 40 carbon atoms, and an arylalkynyl group having 8 to 40 carbon atoms.
It is more preferable that each of them is independently a hydrogen atom, a nitro group, -CO 2M, and an arylalkynyl group having ₈ to 18 carbon atoms.
It is even more preferable that each of them is independently a hydrogen atom, a nitro group, -CO 2M, and an arylalkynyl group having ₈ to 12 carbon atoms.
It is particularly preferable that each of them is a hydrogen atom, a nitro group, -CO 2M, or a phenylethynyl group, _respectively .
It is even more preferable to have a hydrogen atom, a nitro group, and -CO 2M independently of _each other.
It is particularly preferable that each of them is a hydrogen atom, a nitro group, and -CO ₂ H independently.
Most preferably, they are hydrogen atoms and −CO ₂ H, respectively.

As R ^Q1 to R ^Q94 in compound (II),
Independently, each is preferably a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO ₂ M, and a monovalent hydrocarbon group having 1 to 40 carbon atoms.
It is more preferable that each of them is independently a hydrogen atom, a nitro group, -CO 2M, an alkyl group having ₁ to 40 carbon atoms, and an arylalkynyl group having 8 to 40 carbon atoms.
It is more preferable that each of them is independently a hydrogen atom, a nitro group, -CO 2M, and an arylalkynyl group having ₈ to 18 carbon atoms.
It is even more preferable that each of them is independently a hydrogen atom, a nitro group, -CO 2M, and an arylalkynyl group having ₈ to 12 carbon atoms.
It is particularly preferable that each of them is a hydrogen atom, a nitro group, -CO _2H , and a phenylethynyl group, respectively.
It is more preferable that they are each independently a hydrogen atom and a phenylethynyl group.

As for Q ¹ and Q ² ,
It is more preferable that the groups are independently represented by the formulas (QQ1) to (QQ12).
It is more preferable that the groups are independently represented by the formulas (QQ1) to (QQ5).
It is more preferable that the groups are independently represented by the formula (QQ1) or the formula (QQ2).
Further, as Q ¹ and Q ² , it is preferable that at least one of Q ¹ and Q ² is a group represented by the formula (QQ 1), and Q ² is a group represented by the formula (QQ 1). It is preferable that both Q ¹ and Q ² are groups represented by the formula (QQ1).

The group represented by the formula (QQ1) in the compound (I) is
It is preferable that any one of R ^Q1 to R ^Q4 is a halogen atom, a cyano group, a nitro group, -CO 2M, or a monovalent hydrocarbon group having ₁ to 40 carbon atoms, and the rest are all hydrogen atoms. ,
It is more preferable that any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or an arylalkynyl group having 8 to 40 carbon atoms, and the rest are all hydrogen atoms.
It is more preferable that any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or an arylalkynyl group having 8 to 18 carbon atoms, and the rest are all hydrogen atoms.
It is even more preferable that any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or an arylalkynyl group having 8 to 12 carbon atoms, and the rest are all hydrogen atoms.
A group in which any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or a phenylethynyl group and all the rest are hydrogen atoms is particularly preferable.
A group in which any one of R ^Q1 to R ^Q4 is a nitro group or -CO ₂ M and all the rest are hydrogen atoms is more preferable.
A group in which any one of R ^Q1 to R ^Q4 is a nitro group or -CO ₂ H and all the rest are hydrogen atoms is particularly preferable.
Most preferred is a group in which any one of R ^Q1 to R ^Q4 is -CO ₂ H and the rest are all hydrogen atoms.

As a group represented by the formula (QQ1) in the compound (II),
It is preferable that any one of R ^Q1 to R ^Q4 is a halogen atom, a cyano group, a nitro group, -CO 2M, or a monovalent hydrocarbon group having ₁ to 40 carbon atoms, and the rest are all hydrogen atoms. ,
It is more preferable that any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or an arylalkynyl group having 8 to 40 carbon atoms, and the rest are all hydrogen atoms.
It is more preferable that any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or an arylalkynyl group having 8 to 18 carbon atoms, and the rest are all hydrogen atoms.
It is even more preferable that any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ M, or an arylalkynyl group having 8 to 12 carbon atoms, and the rest are all hydrogen atoms.
A group in which any one of R ^Q1 to R ^Q4 is a nitro group, -CO ₂ H, or a phenylethynyl group and all the rest are hydrogen atoms is particularly preferable.
It is more preferable that any one of R ^Q1 to R ^Q4 is a phenylethynyl group and the rest are all hydrogen atoms.

The group represented by the formula (QQ2) is
A group in which all of R ^Q5 to R ^Q10 are hydrogen atoms; a group in which any one of R ^Q5 to R ^Q10 is a halogen atom, a cyano group, a nitro group, or -CO ₂ M, and the rest are all hydrogen atoms; Preferably
Groups in which R ^Q5 to R ^Q10 are all hydrogen atoms are particularly preferable.

The group represented by the formula (QQ3) is
A group in which all of R ^Q11 to R ^Q16 are hydrogen atoms; a group in which any one of R ^Q11 to R ^Q16 is a halogen atom, a cyano group, a nitro group, or -CO ₂ M, and the rest are all hydrogen atoms; Preferably
Groups in which all of R ^Q11 to R ^Q16 are hydrogen atoms are particularly preferable.

The group represented by the formula (QQ4) is
A group in which all of R ^Q17 to R ^Q24 are hydrogen atoms; a group in which any one of R ^Q17 to R ^Q24 is a halogen atom, a cyano group, a nitro group, or -CO ₂ M, and the rest are all hydrogen atoms; Preferably
Groups in which all of R ^Q17 to R ^Q24 are hydrogen atoms are particularly preferable.

The group represented by the formula (QQ5) is
A group in which all of R ^Q25 to R ^Q30 are hydrogen atoms; a group in which any one of R ^Q25 to R ^Q30 is a halogen atom, a cyano group, a nitro group, or -CO ₂ M, and the rest are all hydrogen atoms; Preferably
Groups in which R ^Q25 to R ^Q30 are all hydrogen atoms are particularly preferable.

The compound (I) or the compound (II) is at least one selected from a halogen atom, a cyano group, a nitro group, -CO ₂ M, and an arylalkynyl group, preferably a nitro group, -CO ₂ M, and a carbon number of carbon atoms. A compound having at least one selected from 8 to 12 arylalkynyl groups (hereinafter, may be referred to as a modified compound (I) or a modified compound (II)) is preferable. According to the colored curable resin composition containing the modified compound (I) or the modified compound (II) as the colorant (A), the light resistance of the obtained color filter can be further improved.

The halogen atom, cyano group, nitro group, -CO ₂ M, and aryl alkynyl group can be introduced into the modified compounds (I) and (II) as any of R ¹ to R ⁶ and R ^Q1 to R ^Q94 . It is preferable that the compound is introduced into the modified compounds (I) and (II) as any of R ^Q1 to R ^Q94 .

Examples of the compound (I) include compounds (Ia1) to compounds (Ia144) represented by the formulas (Ia) shown in Tables 1 and 2 below.

Examples of the compound (II) include compounds (IIa1) to compounds (IIa144) represented by the formulas (IIa) shown in Tables 3 to 4 below.

In Tables 1 to 4, Qa1 to Qa12 mean groups represented by the following formulas (Qa1) to (Qa12), respectively.

［式中、※は結合手を表す。］

[In the formula, * represents a bond. ]

As compound (I),
Compound (Ia1) to compound (Ia12), compound (Ia90) to compound (Ia100), and compound (Ia123) to compound (Ia144) are preferable.
Compound (Ia1) to compound (Ia12), compound (Ia91) to compound (Ia94), compound (Ia96), compound (Ia98) to compound (Ia100), compound (Ia124) to compound (Ia127), compound (Ia129), Compound (Ia130), compound (Ia132), and compound (Ia133) are more preferable.
Compound (Ia7), compound (Ia8), compound (Ia10), compound (Ia11), compound (Ia12), compound (Ia91), compound (Ia99), compound (Ia124), compound (Ia130) are more preferable.
Compound (Ia7), compound (Ia11), and compound (Ia124) are even more preferred.
Compound (Ia11) is particularly preferred.

As compound (II),
Compound (IIa1) to compound (IIa12), compound (IIa90) to compound (IIa100), and compound (IIa123) to compound (IIa133) are preferable.
Compound (IIa1) to compound (IIa12), compound (IIa91) to compound (IIa94), compound (IIa96), compound (IIa98) to compound (IIa100), compound (IIa124) to compound (IIa127), compound (IIa129), More preferably, compound (IIa130), compound (IIa132), compound (IIa133), compound (IIa135) to compound (IIa138), compound (IIa140), compound (IIa141), compound (IIa143), compound (IIa144).
Compound (IIa7), compound (IIa8), compound (IIa10), compound (IIa11), compound (IIa12), compound (IIa91), compound (IIa99), compound (IIa124), compound (IIa130), compound (IIa99), Compound (IIa124), compound (IIa130), compound (IIa135), compound (IIa141), compound (IIa144) are more preferred.
Compound (IIa12) is even more preferred.

The method for producing the compound (I) is not particularly limited, but for example, it is produced by reacting a compound represented by the formula (pt1) with a compound represented by the formula (pt2) and a compound represented by the formula (pt3). can do. Hereinafter, this manufacturing method may be referred to as manufacturing method 1.

［式中、Ｒ¹～Ｒ⁵、Ｑ¹及びＱ²は、前記と同一の意味を表す。］

[In the formula, R ¹ to R ⁵ , Q ¹ and Q ² have the same meanings as described above. ]

The amount of the compound represented by the formula (pt2) used in the reaction of the production method 1 is usually 0.1 to 30 mol, preferably 1 mol, with respect to 1 mol of the compound represented by the formula (pt1). It is -20 mol, more preferably 1-16 mol, still more preferably 1-10 mol.

The amount of the compound represented by the formula (pt3) used in the reaction of the production method 1 is usually 0.1 to 30 mol, preferably 1 mol, with respect to 1 mol of the compound represented by the formula (pt1). It is -20 mol, more preferably 1-16 mol, still more preferably 1-10 mol.

The reaction temperature is usually −100 to 300 ° C., preferably 0 to 280 ° C., more preferably 50 to 250 ° C., still more preferably 100 to 230 ° C., still more preferably 150 to 200 ° C. Is.

The reaction time is usually 0.5 to 500 hours.

The reaction of Production Method 1 is usually carried out in the presence of a solvent.

As the solvent, water; a nitrile solvent such as acetonitrile; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-ethyl-1-hexanol, 1 -Alcohol solvents such as octanol and phenol; amine solvents; ether solvents such as diethyl ether, tetrahydrofuran and diphenyl ether; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and methyl benzoate; aliphatic carbonization such as hexane Hydrogen solvent; Aromatic hydrocarbon solvents such as toluene, trimethylbenzene (eg 1,3,5-trimethylbenzene), decalin, tetralin; methylene chloride, chloroform, 1,2-dichlorobenzene, trichlorobenzene (eg 1,1) 2,5-Trichlorobenzene), 1-chloronaphthalene, 2-chloronaphthalene and other halogenated hydrocarbon solvents; nitrobenzene and other nitrated hydrocarbon solvents; N, N-dimethylformamide, N, N-dimethylacetamide, N- An amide solvent such as methylpyrrolidone; a sulfoxide solvent such as dimethylsulfoxide is mentioned, and methyl benzoate is preferable.

The amount of the solvent used is the compound represented by the formula (pt1) in the reaction between the compound represented by the formula (pt1), the compound represented by the formula (pt2) and the compound represented by the formula (pt3). It is usually 1 to 1000 parts by mass with respect to 1 part by mass.

It is preferable that an acid coexists in the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2) and the compound represented by the formula (pt3).

Examples of the acid 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. , Trifluoroacetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, benzoic acid, tartrate and other carboxylic acids; etc., preferably hydrogen chloride, hydrogen bromide, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid. Acids, p-toluene sulfonic acids and carboxylic acids can be mentioned, more preferably carboxylic acids and even more preferably benzoic acids.

The amount of the acid used in the reaction of the production method 1 is usually 1 to 90 mol, preferably 1 to 70 mol, and more preferably 1 to 50 mol with respect to 1 mol of the compound represented by the formula (pt1). It is mol, more preferably 1 to 30 mol.

When the compound (I) has a carboxylic acid and / or an ester in the structure, and an alcohol, an ether, an ester or the like is present as a solvent or the like in the manufacturing process of the compound (I), the compound (I) The carboxylic acid and / or ester possessed by I) may be produced as a mixture of the esterified and / or ester-exchanged compound together with the target compound (I). For example, when methyl benzoate is used as a solvent in the step of producing the following compound (Ia11), the compound represented by the formula (Ia11-a), the compound represented by the formula (Ia11-b), and the formula The compound represented by (Ia11-c) may be contained together with the compound (Ia11).

The method for extracting compound (I) from the reaction mixture is not particularly limited, and it can be extracted by various known methods.
For example, after completion of the reaction, the compound (I) in the reaction mixture may be difficult to dissolve, but after the reaction mixture is well mixed with a solvent such as methanol in which the compound other than the compound (I) is easily dissolved. , The compound (I) can be taken out by filtering. Further, an amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, a sulfoxide solvent such as dimethyl sulfoxide or a mixed solvent thereof, an alkaline aqueous solution such as sodium hydroxide aqueous solution, and / Alternatively, the obtained residue may be washed with an acidic aqueous solution such as hydrochloric acid and then washed with water, a low boiling alcohol such as methanol or a mixed solvent thereof, and the compound (I) may be taken out. Further, it may be purified by column chromatography and / or recrystallization.
Alternatively, after completion of the reaction, the solvent of the reaction mixture may be distilled off, and the obtained residue may be purified by column chromatography and / or recrystallization or the like.
After completion of the reaction, the reaction mixture may be purified by column chromatography and / or recrystallization or the like.

Further, the compound represented by the formula (I) is a compound represented by the formula (I') by the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2) (hereinafter referred to as a compound represented by the formula (I'). , Sometimes referred to as compound (I')), followed by
The compound (I') is hydrolyzed in the presence of a base to produce a compound represented by the formula (IM1) (hereinafter, may be referred to as a compound (IM1)), and further.
It can be produced by reacting the compound (IM1) with the compound represented by the formula (pt3).

［式中、Ｒ¹～Ｒ⁵、Ｑ¹、Ｑ²は、前記と同一の意味を表す。］

[In the formula, R ¹ to R ⁵ , Q ¹ and Q ² have the same meanings as described above. ]

The amount of the compound represented by the formula (pt2) used in the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is 1 mol of the compound represented by the formula (pt1). On the other hand, it is usually 0.1 to 60 mol, preferably 1 to 40 mol, more preferably 1 to 32 mol, and further preferably 2 to 20 mol.

The amount of the compound represented by the formula (pt3) used in the reaction between the compound represented by the formula (IM1) and the compound represented by the formula (pt3) is 1 mol of the compound represented by the formula (IM1). On the other hand, it is usually 0.1 to 30 mol, preferably 1 to 20 mol, more preferably 1 to 16 mol, and further preferably 1 to 10 mol.

The reaction temperature and reaction time in the reaction of the compound represented by the formula (pt1) and the compound represented by the formula (pt2), the compound represented by the formula (IM1), and the compound represented by the formula (pt3). The reaction temperature and reaction time in the reaction with the compound are the same as those in the production method 1, and the preferred embodiments thereof are also the same.

The reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2), and the reaction between the compound represented by the formula (IM1) and the compound represented by the formula (pt3) are usually carried out. , Performed in the presence of a solvent. Examples of the solvent include the solvent exemplified in the production method 1, and the preferred embodiment is also the same.

The amount of the solvent used in the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is usually 1 to 1000 mass by mass with respect to 1 part by mass of the compound represented by the formula (pt1). It is a department.

The amount of the solvent used in the reaction between the compound represented by the formula (IM1) and the compound represented by the formula (pt3) is usually 1 to 1000 with respect to 1 part by mass of the compound represented by the formula (IM1). It is a mass part.

In the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2), and the reaction between the compound represented by the formula (IM1) and the compound represented by the formula (pt3), the acid is used. It is preferable that Examples of the acid include the acid exemplified in the production method 1, and the preferred embodiment is also the same.

The amount of acid used in the reaction between the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is usually 1 to 90 mol with respect to 1 mol of the compound represented by the formula (pt1). It is preferably 1 to 70 mol, more preferably 1 to 50 mol, still more preferably 1 to 30 mol.

The amount of acid used in the reaction between the compound represented by the formula (IM1) and the compound represented by the formula (pt3) is usually 1 to 90 mol with respect to 1 mol of the compound represented by the formula (IM1). It is preferably 1 to 70 mol, more preferably 1 to 50 mol, still more preferably 1 to 30 mol.

As in the production method 1, when the compound (I) has a carboxylic acid and / or an ester in the structure, the carboxylic acid and / or the ester of the compound (I) is esterified and / or ester-exchanged. Ester may be produced as a mixture together with the compound (I) of interest.

A method for extracting the compound represented by the formula (I') from the reaction mixture in the reaction of the compound represented by the formula (pt1) and the compound represented by the formula (pt2), and the formula (IM1). The method for extracting the compound represented by the formula (I) from the reaction mixture in the reaction between the compound represented by the formula (pt3) and the compound represented by the formula (pt3) is not particularly limited, and can be extracted by various known methods. For example, the method exemplified in the production method 1 can be mentioned.

Examples of the base in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base include triethylamine, 4- (N, N-dimethylamino) pyridine, pyridine, piperidine, and 1,8-diazabicyclo [5. 4.0] Organic bases such as undec-7-ene and 1,5-diazabicyclo [4.3.0] nona-5-ene, sodium methoxydo, sodium ethoxydo, sodium tert-butoxide, potassium tert-butoxide, etc. Metal alkoxides, organic metal compounds such as methyllithium, butyllithium, tert-butyllithium and phenyllithium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Inorganic bases and the like are mentioned, and inorganic bases are preferable, and potassium hydroxide is more preferable.

The amount of the base used in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base is usually 0.1 to 100 mol with respect to 1 mol of the compound represented by the formula (I'). It is preferably 1 to 70 mol, more preferably 2 to 40 mol.

The amount of water used in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base is usually 1 to 1000 parts by mass with respect to 1 part by mass of the compound represented by the formula (I'). It is preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, and further preferably 1 to 50 parts by mass.

The reaction temperature in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base is usually 0 to 100 ° C, preferably 5 to 100 ° C, and more preferably 20 to 100 ° C. , More preferably 40 to 100 ° C, and even more preferably 60 to 100 ° C.

The reaction time in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base is preferably continued until the disappearance of the compound represented by the formula (I') is confirmed, and is usually 0. It is 5 to 120 hours, preferably 1 to 72 hours, and more preferably 1 to 24 hours.

The method for extracting the compound represented by the formula (IM1) from the reaction mixture in the hydrolysis reaction of the compound represented by the formula (I') in the presence of a base is not particularly limited, and can be extracted by various known methods. For example, the method exemplified in the production method 1 can be mentioned.

The method for producing the compound (II) is not particularly limited, but the compound represented by the formula (pt1) is replaced with the compound represented by the following formula (pt1') with reference to the above-mentioned method for producing the compound (I). Can be manufactured.

［式中、Ｒ²～Ｒ⁶は、前記と同一の意味を表す。］

[In the formula, R ² to R ⁶ have the same meanings as described above. ]

When the colorant (A) contains the compound (I), the content of the compound (I) may be 100% by mass with respect to the total amount of the colorant (A), and the lower limit is, for example, 0. It may be 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, still more preferably 50% by mass or more.

When the colorant (A) contains the compound (II), the content of the compound (II) may be 100% by mass with respect to the total amount of the colorant (A), and the lower limit is, for example, 0. It may be 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, still more preferably 50% by mass or more.

The colorant (A) preferably contains the compound (I), and may contain both the compound (I) and the compound (II).

When one or more of the compound (I) and the compound (II) are contained as the colorant (A), the total content of the compound (I) and the compound (II) is based on the total amount of the colorant (A). The lower limit may be, for example, 0.1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more. , 30% by mass or more is more preferable, and 50% by mass or more is even more preferable.

When one or more of the compound (I) and the compound (II) are contained as the colorant (A), the content ratio of the compound (I) to the compound (II) (compound (II) / compound (I)) is , 0.01 or more and 100 or less, more preferably 0.05 or more and 50 or less on a molar basis.

<< Colorant (A1) >>
In the color curable resin composition of the present invention, as the colorant (A), a dye other than the compound (I) and the compound (II) (hereinafter, may be referred to as a dye (A1-1)) and / or a pigment (hereinafter, a pigment) (hereinafter, may be referred to as a dye (A1-1)). , May be referred to as a pigment (A1-2)) (hereinafter, the dye (A1-1) and the pigment (A1-2) may be collectively referred to as a colorant (A1)). These may be used alone or in combination of two or more.

As the dye (A1-1), known dyes can be used as long as the compound (I) and the compound (II) are not included, and examples thereof include solvent dyes, acid dyes, direct dyes, and medium dyes. Examples of the dye include compounds classified as dyes in the Color Index (The Society of Dyers and Colorists Publishing) and known dyes described in Dyeing Note (Color Dyeing Co., Ltd.). According to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridin dyes, styryl dyes, coumarin dyes, quinoline. Examples thereof include dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinophthalone dyes, and isoindrin dyes.

Specific examples thereof include dyes having the following color index (CI) numbers.
C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;
C. I. Solvent Red 24, 45, 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. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; etc. I. Solvent dye,
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. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270, 274,277,280,281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
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. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1,3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41,42,43,45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, 104, 105, 106, 109; etc. I. Acid dye,
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. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241 and 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; etc. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 6; 0 etc. C.I. I. Disperse dye,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. Basic Red 9;
C. I. Basic Green 1; etc. C.I. I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive orange 16;
C. I. Reactive Red 36; etc. I. Reactive dye,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modant Blue 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; etc. I. Mordant dye,
C. I. Bat Green 1; etc. I. Vat dye, etc.

Further, BASF's product, Lumogen (registered trademark), is mentioned, Lumogen (registered trademark) F Yellow 083 (BASF), Lumogen (registered trademark) F Yellow 170 (BASF), Lumogen (registered trademark). Examples thereof include F Orange 240 (manufactured by BASF) and Lumogen (registered trademark) F Red 305 (manufactured by BASF).

As the pigment (A1-2), known pigments can be used as long as they do not include compound (I) and compound (II), and are classified into pigments by, for example, Color Index (The Society of Dyers and Colorists Publishing). Examples include pigments that have been used.

Specific examples of the pigments classified as pigments include 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, 231;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, Red pigments such as 265, 266, 268, 269, 273;
C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 32, 36, 38 and other violet pigments;
C. I. Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Pigment Black 1, 7, 31, 32 and other black pigments; and the like.

The colorant (A1) includes a yellow dye and a yellow pigment (hereinafter, these may be collectively referred to as "yellow colorant"), an orange dye and an orange pigment (hereinafter, these are collectively referred to as "orange colorant"). (In some cases), red dyes and red pigments (hereinafter, these may be collectively referred to as "red colorants"), green dyes and green pigments (hereinafter, these may be collectively referred to as "green colorants"). ) Is preferable, yellow colorants and green colorants are more preferable, yellow pigments and green pigments are even more preferable, and green pigments are even more preferable.

Examples of the yellow dye include dyes whose hue is classified as yellow among the above dyes, and examples of yellow pigments include pigments whose hue is classified as yellow among the above pigments.
As the yellow colorant, a yellow dye and a yellow pigment are preferable, a yellow pigment is more preferable, a quinophthalone pigment, a metal-containing pigment, and an isoindoline pigment are further preferable, and C.I. I. Pigment Yellow 129, 138, 139, 150, 185, 231 are even more preferred, and C.I. I. Pigment Yellow 138, 139, 150, 185, 231 are particularly preferred.

Examples of the orange dye include dyes whose hue is classified as orange among the above dyes, and examples of the orange pigment include pigments whose hue is classified as orange among the above pigments.
As the orange colorant, an orange dye and an orange pigment are preferable, an orange pigment is more preferable, and C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 are even more preferred.

Examples of the red dye include dyes whose hue is classified as red among the above dyes, and examples of the red pigment include pigments whose hue is classified as red among the above pigments.
As the red colorant, red dyes and red pigments are preferable, and azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, perylene dyes, azo pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, triphenylmethane pigments and xanthene pigments. , Perylene pigments are more preferred, C.I. I. Acid Red 52, C.I. I. Pigment Red 144, 177, 179, 242, 254, 269 are even more preferred.

Further, as the yellow colorant, the orange colorant or the red colorant, the xanthene compound described in JP2013-235257A may be used.

Examples of the green dye include dyes whose hue is classified as green among the above dyes, and examples of the green pigment include pigments whose hue is classified as green among the above pigments.
As the green colorant, green dyes and green pigments are preferable, green pigments are more preferable, phthalocyanine pigments are further preferable, copper halide phthalocyanine pigments, zinc halide phthalocyanine pigments, and aluminum zinc halide phthalocyanine pigments are even more preferable. .. I. Pigment Greens 7, 36, 58, 59, 62 and 63 are particularly preferred.

When the colorant (A) further contains the colorant (A1), the lower limit of the total content of the compound (I) and the compound (II) in the colorant (A) is the lower limit of the total content of the colorant (A). For example, it is 1% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. On the other hand, when the colorant (A) further contains the colorant (A1), the upper limit of the total content of the compound (I) and the compound (II) in the colorant (A) is the total amount of the colorant (A). On the other hand, for example, it is less than 100% by mass.

When the color-curable resin composition contains a solvent (E), after preparing a color composition containing the colorant (A) and the solvent (E) in advance (hereinafter, may be referred to as a colorant-containing liquid). The coloring composition may be used to prepare a coloring curable resin composition. When the colorant (A) is insoluble in the solvent (E), for example, when the colorant (A) contains the pigment (A1-2), the coloring composition uses the colorant (A) as the solvent (E). It can be prepared by dispersing and mixing in (the coloring composition in this case may be hereinafter referred to as a coloring dispersion liquid). The coloring composition may contain a part or all of the solvent (E) contained in the coloring curable resin composition.

The content of the solid content in the coloring composition is less than 100% by mass, preferably 0.01% by mass or more and 99.99% by mass or less, more preferably 0.% by mass, based on the total amount of the coloring composition. It is 1% by mass or more and 99.9% by mass or less, more preferably 0.1% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 90% by mass or less, and particularly preferably 1% by mass. It is 80% by mass or less, more preferably 1% by mass or more and 70% by mass or less, particularly preferably 1% by mass or more and 60% by mass or less, and most preferably 1% by mass or more and 50% by mass or less.

The content of the colorant (A) in the coloring composition is 100% by mass or less, preferably 0.0001% by mass or more and 99.9999% by mass or less, based on the total amount of solids in the coloring composition. It is more preferably 0.001% by mass or more and 99% by mass or less, further preferably 1% by mass or more and 95% by mass or less, still more preferably 3% by mass or more and 90% by mass or less, and particularly preferably. It is 5% by mass or more and 90% by mass or less.

The colorant (A) may be treated with a rosin, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the colorant (A) with a polymer compound or the like, and sulfuric acid, if necessary. A micronization treatment by an atomization method, a salt milling method or the like, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities or the like may be performed.
Further, the colorant (A) is subjected to crystal structure conversion, particle shaping and / or substantially uniform particle size treatment, if necessary;
The colorant (A) is mixed with water and / or an organic solvent and stirred while stirring and / or heating to obtain a suspension, and then the suspension is filtered to change the crystal structure. Processing to obtain the colorant (A);
Treatment that changes the crystal structure of the colorant (A) by recrystallization;
The colorant (A) is mixed with water, sulfuric acid or an organic solvent and stirred while stirring and / or heating to obtain a solution or suspension, and then the solution or suspension is used as a colorant. After mixing with the poor solvent of (A) to obtain a suspension, the suspension is filtered to obtain a colorant (A) having a changed crystal structure;
The colorant (A), the derivative, water and / or an organic solvent are mixed and stirred while stirring and / or heating to obtain a suspension, and then the suspension is filtered to crystallize. A treatment for obtaining a mixture containing the colorant (A) having a changed structure and / or a treatment for mixing the colorant (A) and the derivative;
A treatment for obtaining a mixture containing the colorant (A) having a changed crystal structure by recrystallizing the mixture of the colorant (A) and the derivative and / or a treatment for mixing the colorant (A) and the derivative;
The colorant (A), the derivative, water, sulfuric acid or an organic solvent are mixed and stirred while stirring and / or heating to obtain a solution or suspension, and then the solution or suspension is prepared. , Mixing with the poor solvent of the colorant (A) to obtain a suspension, and then filtering the suspension to obtain a mixture containing the colorant (A) having a changed crystal structure and / or coloring. Treatment of mixing agent (A) and derivative;
Etc. may be applied.
When a plurality of types of the colorant (A) or the derivative are used, these treatments may be performed individually, or a plurality of types may be mixed and treated.
The particle size of the colorant (A) is preferably substantially uniform.

When the coloring composition contains a derivative, the content of the derivative is 0.01 part by mass or more and 100 parts by mass or less, and 0.01 part by mass or more and 70 parts by mass with respect to 100 parts by mass of the colorant (A). It is preferably 0.1 parts by mass or more, more preferably 50 parts by mass or less, further preferably 0.1 parts by mass or more and 30 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 20 parts by mass or less.

The colorant (A) can be uniformly dispersed in the solution by containing the dispersant and performing the dispersion treatment. When two or more kinds of colorants (A) are used in combination, each of them may be dispersed alone or a plurality of kinds may be mixed and dispersed.

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

When a dispersant is used, the amount of the dispersant (solid content) used is usually 1 part by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the colorant (A) in the coloring composition, preferably 5. It is 5 parts by mass or more and 5000 parts by mass or less, more preferably 10 parts by mass or more and 3000 parts by mass or less, further preferably 15 parts by mass or more and 1000 parts by mass or less, and further preferably 18 parts by mass or more and 500 parts by mass or less. It is particularly preferably 20 parts by mass or more and 350 parts by mass or less. When the amount of the dispersant used is in the above range, a colored composition in a more uniform dispersed state tends to be obtained.

When a coloring composition containing a coloring agent (A) and a solvent (E) is prepared in advance and then a coloring curable resin composition is prepared using the coloring composition, the coloring composition is a coloring curable resin. A part or all, preferably a part of the resin (B) contained in the composition may be contained in advance. By including the resin (B) in advance, the dispersion stability of the coloring composition can be further improved.

When the coloring composition contains the resin (B), the content of the resin (B) is, for example, 0.01 part by mass or more and 10,000 parts by mass with respect to 100 parts by mass of the coloring agent (A) in the coloring composition. It is preferably 0.01 parts by mass or more and 5000 parts by mass or less, more preferably 0.01 parts by mass or more and 1000 parts by mass or less, further preferably 0.1 parts by mass or more and 500 parts by mass or less, and 0.1 parts by mass. More than 300 parts by mass is more preferable.

The content of the colorant (A) is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.5% by mass or more and 40% by mass, based on the total solid content of the coloring curable resin composition. It is more preferably 0.8% by mass or more and 30% by mass or less, still more preferably 1% by mass or more and 20% by mass or less. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the required amount of the resin (B) can be contained in the composition, so that it is mechanical. It is preferable because it can form a pattern having sufficient strength.
Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid content and the content of each component relative to the total amount of solid content can be measured by a known analytical means such as, for example, liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin, and is at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, "monomer (a)"). It is more preferable that the polymer has a structural unit derived from (may be said to be).
The resin (B) is a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (b)”), and a structural unit. It is preferably a copolymer having other structural units.
The other structural unit is a monomer copolymerizable with the monomer (a) (however, it is different from the monomer (a) and the monomer (b). Hereinafter, “monomer (c)) A structural unit derived from), a structural unit having an ethylenically unsaturated bond, and the like can be mentioned.

As used herein, the term "(meth) acrylic acid" refers to 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 (a) include acrylic acid, methacrylic acid, crotonic acid and unsaturated monocarboxylic acids such as o-, m- and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] A bicyclounsaturated compound containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, Citraconic acid anhydride, Itaconic acid anhydride, 3-Vinylphthalic acid anhydride, 4-Vinylphthalic acid anhydride, 3,4,5,6-Tetrahydrophthalic acid anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydrate;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinic acid mono [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. ;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, o-, m-, p-vinylbenzoic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerizability and solubility of the obtained resin in an alkaline aqueous solution.

The monomer (b) has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring (oxolan ring)) and an ethylenically unsaturated bond. A polymerizable compound having.
The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

The monomer (b) may be, for example, a monomer having an oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (b1)”), or an oxetanyl group and an ethylenically unsaturated bond. Monomer having (hereinafter, may be referred to as "monomer (b2)"), monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, referred to as "monomer (b3)"). In some cases), etc.

As the monomer (b1), for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, “monomer (b1-1)””. ), A monomer having an epoxidized structure of an unsaturated alicyclic hydrocarbon (hereinafter, may be referred to as “monomer (b1-2)”).

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable.
Examples of the monomer (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2, Examples thereof include 4,6-tris (glycidyloxymethyl) styrene and the like.

Examples of the monomer (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide® 2000; manufactured by Daicel Corporation), 3,4-epoxy. Cyclohexenemethyl (meth) acrylate (eg, Cyclomer® A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexenemethyl (meth) acrylate (eg, Cyclomer® M100; Daicel Co., Ltd.) Manufactured by), a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

［式（ＢＩ）及び式（ＢＩＩ）中、Ｒ^a及びＲ^bは、互いに独立に、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^a及びＸ^bは、互いに独立に、単結合、＊－Ｒ^c－、＊－Ｒ^c－Ｏ－、＊－Ｒ^c－Ｓ－又は＊－Ｒ^c－ＮＨ－を表す。
Ｒ^cは、炭素数１～６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］

[In the formula (BI) and the formula (BII ^{), Ra and R b independently} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be replaced with.
X ^a and X ^b independently represent a single bond, * -R ^{c-, * -R c-O-, * -R c-S- or * -R c - NH- .}
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and 1 -Hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.

Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and the like. Examples thereof include a hexane-1,6-diyl group.

Examples of X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O-, and * -CH ₂ CH ₂ -O-, and more preferably a single bond, * -CH ₂ CH ₂ -O-can be mentioned (* represents a bond with O).

Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15). Among them, the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI-9) and the formula (BI-11) to the formula (BI-15). The compound represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) and the compound represented by the formula (BI-15) are more preferable.

Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15), and among them, the formula (BII-1) and the formula are preferable. (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and compounds represented by formulas (BII-11) to formula (BII-15) can be mentioned. Preferred examples thereof include compounds represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) and the formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination of two or more. A compound represented by the formula (BI) and a compound represented by the formula (BII) may be used in combination. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used in combination, the content ratio thereof [the compound represented by the formula (BI): the compound represented by the formula (BII)] is On a molar basis, it is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20.

As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable.
Examples of the monomer (b2) include 3-methyl-3- (meth) acrylic loyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and 3-methyl-3- (meth) acryloyl. Examples thereof include oxyethyl oxetane and 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.
Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

The monomer (b) is preferably the monomer (b1) in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further improved. Further, the monomer (b1-2) is more preferable in that the storage stability of the coloring composition is excellent.

Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl. (Meta) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2. 1.0 ^2,6 ] Decane-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate" and "tricyclodecyl (meth) acrylate". ”), Tricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth). ) Acrylate (in the art, commonly referred to as "dicyclopentenyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decene-9-yl (meth) acrylate, di. Cyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) (Meta) acrylic acid esters such as acrylates;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
2,2,3,3,4,4,5-Halogen atom-containing (meth) acrylic acid ester such as octafluoropentyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyl) Oxycarbonyl) bicyclounsaturated compounds such as bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 9-vinylcarbazole and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; chloride. Halogenated hydrocarbons such as vinyl and vinylidene chloride; vinyl group-containing amides such as (meth) acrylamide; esters such as vinyl acetate; diene such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene. ; Etc. can be mentioned.
Of these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, tricyclo [5.2.1. .0 ^2,6 ] Decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decene-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene, phenyl (meth) acrylate, 2,2 , 3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 9-vinylcarbazole, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. preferable.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6 . ] Decyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / benzyl (meth) acrylate / (meth) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / 9-vinylcarbazole / (meth) acrylic acid copolymer, 3,4-epoxy Tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / phenyl (meth) acrylate / o-vinyl benzoic acid copolymer, 3,4-epoxytricyclo [5.2.1.0] ^2,6 ] Decyl (meth) acrylate / phenyl (meth) acrylate / m-vinyl benzoic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / Phenyl (meth) acrylate / p-vinyl benzoic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / phenyl (meth) acrylate / (meth) acrylic Acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / 2,2,3,3,4,5,5-octafluoropentyl ( Meta) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer , 3,4-Epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5. 2.1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (Meta) Acrylic Acid / 2-Ethylhexyl (Meta) Acrylate Copolymerization Body, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2.1.0 ^2,6 ] decenyl (meth) acrylate / (meth) acrylic Acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, benzyl (meth) acrylate / (meth) acrylic acid copolymer , Styrene / (meth) acrylic acid copolymer, and the resins described in JP-A-9-106071, JP-A-2004-29518 and JP-A-2004-361455.
Among them, as the resin (B), a copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b) is preferable.

The resin (B) may be a combination of two or more kinds, and in this case, the resin (B) is at least
It is preferable to contain at least one copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b).
It is more preferable to contain at least one copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b1).
It is more preferable to contain at least one copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b1-2).
3,4-Epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.2.10 ² ] ^{, 6} ] Decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] ] Decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / It is even more preferable to contain one or more selected from 2-ethylhexyl (meth) acrylate copolymers.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and further preferably 3,000 or more. It is 30,000 or less, and more preferably 5,000 or more and 30,000 or less. When the weight average molecular weight is in the above range, the unexposed portion tends to have high solubility in a developing solution, and the residual film ratio and hardness of the obtained pattern tend to be high.

The dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and further preferably 1 or more and 4 or less. Is.

The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH / g or more and 300 mg-KOH / g or less, and more preferably 20 mg-KOH / g or more and 250 mg-KOH / g or less. It is more preferably 25 mg-KOH / g or more and 200 mg-KOH / g or less, still more preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, and particularly preferably 40 mg-KOH / g or more and 150 mg-KOH /. It is less than or equal to g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 13 with respect to 100% by mass of the solid content of the colored curable resin composition. It is about 70% by mass, and more preferably 15 to 60% by mass. When the content of the resin (B) is in the above range, the unexposed portion tends to have high solubility in the developing solution.

<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 compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Etc., as well as the above-mentioned monomers (a), monomer (b) and monomer (c).

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di. Examples thereof include (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

Above all, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (dipentaerythritol hexa (). Meta) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl ) Isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, Examples thereof include caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4000 or less, more preferably 70 or more and 3500 or less, still more preferably 100 or more and 3000 or less, and further preferably 150 or more and 2900 or less. Yes, and particularly preferably 250 or more and 1500 or less.

The content of the polymerizable compound (C) may be, for example, 1% by mass or more and 99% by mass or less, preferably 5% by mass or more and 90% by mass, based on the total solid content of the colored curable resin composition. It is more preferably 10% by mass or more and 80% by mass or less, and further preferably 15% by mass or more and 70% by mass or less.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an oxime compound (for example, an O-acyloxime compound, etc.), an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound, and the like.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine, N-acetyloxy-1- (4-phenylsulfanylphenyl) -3-Cyclopentylpropane-1-on-2-imine, N-acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-on-2-imine, N-acetyloxy-1-[ 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- {2-methyl-4- (3) , 3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetyloxy-1- [9-ethyl-6- (2) -Methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Il] -3-cyclopentylpropane-1-on-2-imine and the like. Further, as the O-acyloxime compound, commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF) and N-1919 (manufactured by ADEKA Corporation) may be used. Among them, the O-acyloxym compounds include N-acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine and N-acetyloxy-1- (4-phenylsulfanyl). Phenyl) -3-cyclohexylpropane-1-on-2-imine, N-acetyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine , N-Acetyloxy-1- {9-ethyl-6- [2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl] -9H-carbazole-3- Il} Etan-1-imine and N-acetyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1-imine At least one selected is preferable, and N-acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine is more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-. Examples thereof include on and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one. As the alkylphenone compound, a commercially available product such as Irgacure (registered trademark) 369, 907, 379 (all manufactured by BASF) may be used.
Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, and Also included are 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomers, α, α-diethoxyacetophenone and benzyldimethylketal.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2' -Bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) and 4 , 4', 5,5'-position phenyl group is substituted with a carboalkoxy group, and examples thereof include a biimidazole compound (see, for example, JP-A-7-10913).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. ..

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoyl compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinon compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methylphenylglycoxylate and titanosen compounds.
These are preferably used in combination with the polymerization initiation aid (D1) described later, particularly amines.

The polymerization initiator (D) is a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound and a biimidazole compound, and more preferably an oxime compound. It is a polymerization initiator containing, and more preferably a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.01 part by mass or more with respect to 100 parts by mass of the total amount of the total resin (B) and the polymerizable compound (C) contained in the colored curable resin composition. It is 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Antioxidant (G)>
The antioxidant (G) is not particularly limited as long as it is an antioxidant that is generally used industrially, and examples thereof include a radical chain inhibitor, a peroxide decomposing agent, and a metal inactivating agent, which are preferable. Is a radical chain inhibitor or peroxide degrading agent, more preferably a radical chain inhibitor. It is assumed that the antioxidant (G) does not contain the singlet oxygen quencher (H) described later. Examples of these antioxidants (G) include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. The color curable resin composition of the present invention can form a color filter having excellent light resistance by containing the antioxidant (G).

The phenolic antioxidant is an antioxidant having a phenolic hydroxy group in the molecule, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl. -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 3,3', 3'', 5,5', 5''-hex-tert-butyl-a, a', a ''-(Mesitylen-2,4,6-toluyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3,5-di -Tert-Butyl-4-hydroxy-hydrocarcinate, 4,6-bis (octylthiomethyl) -o-cresol, 1,3,5-tris {2- [3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) propanoyloxy] ethyl} hexahydro-1,3,5-triazine-2,4,6-trione, 2,4-bis (n-octylthio) -6- (4-hydroxy 3') , 5'-di-tert-butylanilino) -1,3,5-triazine, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]- 1,1-Dimethylethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, vitamin E and the like can be mentioned.

Commercially available products may be used as the phenolic antioxidant, and specifically, Irganox (registered trademark) 565, 1010, 1035, 1076, 1135, 1330, 1520L, 3114, and 3114. 3125, 3790 (above, BASF), ADEKA STAB (registered trademark) AO-80 (registered trademark), ADEKA (registered trademark) BHT, GA-80, GS (registered trademark), Sumitomo Chemical Co., Ltd. ), Cyax (registered trademark) 1790 (manufactured by Cytec Co., Ltd.) and the like.

From the viewpoint of improving the light resistance of the obtained color filter, the phenolic antioxidant is preferably a compound having 1 or more and 10 or less phenolic skeletons, more preferably a compound having 1 or more and 5 or less phenolic skeletons, and phenol. A compound having one or two skeletons is more preferable, and a compound having two phenolic skeletons is even more preferable. The phenolic antioxidant is preferably a compound having at least one phenolic skeleton in which the ortho position of the phenolic hydroxy group is an alkyl group, and one of the two ortho positions of the phenolic hydroxy group has 3 to 5 carbon atoms. A compound having at least one phenolic skeleton, which is a branched alkyl group and the other is a linear alkyl group having 1 to 3 carbon atoms, is more preferable, and one of the two ortho positions of the phenolic hydroxy group is carbon. A compound having two phenolic skeletons, which are branched alkyl groups having the number 3 to 5 and the other being a linear alkyl group having 1 to 3 carbon atoms, is more preferable.

The molecular weight of the phenolic antioxidant is preferably 400 or more and 1200 or less, more preferably 500 or more and 1000 or less, and further preferably 600 or more and 900 or less.

Phenolic antioxidants include 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4. , 8,10-Tetraoxaspiro (5,5) undecane is particularly preferred.

The amine-based antioxidant is an antioxidant having an amino group in the molecule, and examples thereof include a hindered amine-based agent and an aromatic amine-based agent. The amine-based antioxidant is preferably a hindered amine-based agent.

Examples of the hindered amine antioxidant include sebacic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, and poly {[. 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] -1,6-hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} and the like can be mentioned.

Commercially available products may be used as the hindered amine-based antioxidant, and specific examples thereof include ADEKA STAB (registered trademark) LA series (manufactured by ADEKA Corporation) and chinubin (registered trademark) series (manufactured by BASF). ..

From the viewpoint of improving the light resistance of the obtained color filter, the hindered amine-based antioxidant is preferably a compound having an acryloyl group or a methacryloyl group in the molecule, and 2,2,6,6-tetramethyl-4-piperidyl methacrylate is preferable. Is particularly preferable.

Examples of the aromatic amine-based antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, N, N'-diisopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine and N-. 1,3-Dimethylbutyl-N'-Phenyl-p-Phenylrangeamine, Diphenylamine, N-Phenyl-p-Truidine, N, Bis-p-Truylamine, p, p'-Dioctyldiphenylamine, Phenyl-α-naphthylamine, Examples include phenothiazine.

The phosphorus-based antioxidant is an antioxidant having a phosphorus atom in the molecule, and examples thereof include phosphite-based and phosphine-based, and the phosphorus-based antioxidant is preferably phosphine-based.

Examples of the phosphite-based antioxidant include triphenylphosphite, diphenylnonylphosphite, diphenyl (2-ethylhexyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and trisnonylphenylphos. Phenyl, diphenylisooctylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, diphenylisodecylphosphite, diphenylmono (tridecyl) phosphite, phenyldiisodecylphosphite, phenyldi (Tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, dibutylhydrogen phosphite, trilauryltrithiophosphite, tetrakis (2,4-di-tert) -Butylphenyl) -4,4'-biphenylenediphosphonite, 4,4'-isopropyridendiphenol dodecylphosphite, 4,4'-isopropyridendiphenol tridecylphosphite, 4,4'-isopropyridenge Phenoltetradecylphosphite, 4,4'-isopropyridenediphenol pentadecylphosphite, 4,4'-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecylphosphite, 1,1,3-tris (2-Methyl-4-tridecylphosphite-5-tert-butylphenyl) butane, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3,4,5,6-dibenzo- Examples thereof include 1,2-oxaphosphan-2-oxide.

Examples of the phosphine-based antioxidant include triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris (p-tolyl) phosphine, tris (p-nonylphenyl) phosphine, tris (naphthyl) phosphine, and diphenyl (hydroxymethyl). Phosphine, diphenyl (acetoxymethyl) phosphine, diphenyl (β-ethylcarboxyethyl) phosphine, tris (p-chlorophenyl) phosphine, tris (p-fluorophenyl) phosphine, diphenylbenzyl phosphine, diphenyl-β-cyanoethyl phosphine, diphenyl (p) -Hydroxyphenyl) Phosphine, diphenyl-1,4-dihydroxyphenyl-2-phosphine, phenylnaphthylbenzylphosphine and the like can be mentioned.

From the viewpoint of improving the light resistance of the obtained color filter, the phosphine-based antioxidant includes a compound in which three phenyl groups, which may have substituents, are bonded to a phosphorus atom (having three substituents). The phenyl group may be the same or different, and examples of the substituent include a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and the like). Preferred, triphenylphosphine is particularly preferred.

The sulfur-based antioxidant is an antioxidant having a sulfur atom in the molecule, and is, for example, a dialkylthiodipropionate compound such as dilauryl thiodipropionate, dimyristyl, or distearyl; tetrakis [methylene (3-dodecylthio) propionate. ] Β-alkyl mercaptopropionic acid ester compound of polyol such as methane; and the like.

The antioxidant (G) is preferably an antioxidant containing at least one selected from the group consisting of a phenol-based antioxidant, an amine-based antioxidant and a phosphorus-based antioxidant, and more preferably a phenol-based antioxidant. It is an antioxidant containing at least one of an agent or a phosphorus-based antioxidant, and more preferably an antioxidant containing a phenol-based antioxidant.

The content of the antioxidant (G) is preferably 1 part by mass or more and 500 parts by mass or less, more preferably 100 parts by mass, based on 100 parts by mass of the total polymerization initiator (D) contained in the colored curable resin composition. It is 10 parts by mass or more and 400 parts by mass or less, more preferably 15 parts by mass or more and 300 parts by mass or less, and further preferably 20 parts by mass or more and 250 parts by mass or less. When the content of the antioxidant (G) is within the above range, the light resistance of the obtained color filter is further improved.
The content of the antioxidant (G) is preferably 0.05% by mass or more and 25% by mass or less, more preferably 0.10% by mass, based on the total solid content of the colored curable resin composition. It is 20% by mass or less, more preferably 0.50% by mass or more and 15% by mass or less, and even more preferably 1.0% by mass or more and 10% by mass or less. When the content of the antioxidant (G) is within the above range, the light resistance of the obtained color filter is further improved.

<Singlet oxygen citric acid (H)>
The singlet oxygen quencher (H) is not particularly limited as long as it is a compound capable of inactivating singlet oxygen by energy transfer from oxygen in the singlet state, and a known singlet oxygen quencher is used. be able to.

The single-term oxygen quencher (H) includes a transition metal complex, an azide such as sodium azide, an antioxidant such as ascorbic acid, a transition metal containing a heme such as isobenzofuran, dihydroquinone, and hemoglobin, 4-oxo-. Examples thereof include 2,2,6,6-tetramethylpiperidin1-oxyl. The transition metal complex as the singlet oxygen quencher (H) does not include those having the structures of the above-mentioned compound (I) and / or compound (II).

As the singlet oxygen quencher (H), a transition metal complex is particularly preferable. According to the colored curable resin composition containing the transition metal complex as a singlet oxygen (H) quencher, the light resistance of the formed color filter is further improved. In particular, the transition metal complex as the singlet oxygen quencher (H) is formed by combining the modified compound (I) as the compound (I) or the compound (II) or the modified compound (II). It is most preferable because the light resistance of the color filter is further improved.

Examples of the central metal atom of the transition metal complex include various metal atoms belonging to groups 3 to 11 of the periodic table of elements, and a metal atom which is a first transition element or a third transition element is preferable. Metal atoms, which are transition elements, are more preferred, Co, Ni or Cu are even more preferred, Co or Ni is even more preferred, and Co is particularly preferred.

The transition metal complex includes a transition metal complex in which the central metal atom is Co (hereinafter, may be referred to as a cobalt complex), a transition metal complex in which the central metal atom is Ni (hereinafter, may be referred to as a nickel complex), and a central metal atom. It is preferable to contain at least one selected from Cu transition metal complexes (hereinafter, may be referred to as copper complexes).

The ligand of the transition metal complex is a neutral or anionic monodentate ligand that forms at least one bond selected from the group consisting of coordination bonds and covalent bonds with the central metal atom. , Or a neutral or anionic polydentate ligand, preferably a neutral or anionic monodentate ligand, or a neutral or anionic bidentate ligand. Examples of the bond between the central metal atom and the ligand include a metal-nitrogen bond, a metal-carbon bond, a metal-oxygen bond, a metal-phosphorus bond, a metal-sulfur bond and a metal-halogen bond. Preferably, it is a metal-carbon bond, a metal-oxygen bond, a metal-sulfur bond or a metal-halogen bond.

As the cobalt complex, 2,4-pentandionato group, 2,2,6,6-tetramethyl-3,5-heptandionat, benzoylacetonato group, 1,3-butandionato group, 1,1,1-tri A complex having a β-diketonato group such as a fluoro-2,4-pentandionato group as a ligand is preferable, and a complex represented by the following formula (Co-x) is more preferable.

［式中、
Ｒ^Co1及びＲ^Co3は、それぞれ独立して、ハロゲン原子又は炭素数１～１５の１価の炭化水素基を表し、
該１価の炭化水素基を構成する－ＣＨ₂－は、－Ｏ－又は－Ｓ－に置き換わっていてもよい。
Ｒ^Co2は、水素原子又は炭素数１～１５の１価の炭化水素基を表し、
該１価の炭化水素基を構成する－ＣＨ₂－は、－Ｏ－又は－Ｓ－に置き換わっていてもよい。］

[During the ceremony,
R ^Co1 and R ^Co3 independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms.
-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-.
R ^Co2 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms.
-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The monovalent hydrocarbon group having 1 to 15 carbon atoms represented by R ^Co1 to R ^Co3 is the above-mentioned hydrocarbon represented by R ¹ to R ⁶ except that the example in which the number of carbon atoms is 16 or more is not included. The same example as the hydrogen group can be mentioned.

-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-.

The R ^Co1 and R ^Co3 are preferably monovalent hydrocarbon groups having 1 to 15 carbon atoms, more preferably monovalent hydrocarbon groups having 1 to 10 carbon atoms, and having 1 to 5 carbon atoms. Is more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group having 1 to 3 carbon atoms.

R ^Co2 is preferably a hydrogen atom.

As the cobalt complex, bis (2,4-pentanedionato) cobalt (II) is particularly preferable.

Nickel complexes include bis (dithiobenzyl) nickel (II), bis (tetrabutylammonium) bis (maleonitrile dithiolat) nickel (II), and bis [4,4'-dimethoxy (dithiobenzyl)] nickel (II). , Bis (4-dimethylaminodithiobenzyl) Nickel (II), Tetrabutylammonium bis (1,3-dithiol-2-thion-4,5-dithiorat) Nickel (III), Tetrabutylammonium bis (maleonitrile dithiorat) ) Nickel (III), Tetrabutylammonium bis (3,6-dichloro-1,2-benzenedithiolate) Nickel (III), Tetramethylammonium bis (3,4,6-trichloro-1,2-benzenedithiolate) ) Nickel (III), Tetrabutylammonium bis (4-methyl-1,2-benzenedithiolate) Nickel (III) includes tetramethylammonium bis (3,4,6-trichloro-1,2-benzenedithiolate). ) A dithiolene complex such as nickel (III) is preferable, a complex having a benzenedithiorat ligand is more preferable, and a complex represented by the following formula (Ni—x) is further preferable.

［式中、
Ｒ^Ni1～Ｒ^Ni8は、それぞれ独立して、水素原子、ハロゲン原子又は炭素数１～１５の１価の炭化水素基を表し、
該１価の炭化水素基を構成する－ＣＨ₂－は、－Ｏ－又は－Ｓ－に置き換わっていてもよい。
Ｒ^Ni1～Ｒ^Ni4は、それぞれ互いにＲ^Ni1～Ｒ^Ni4から選ばれる１つ以上と結合して環を形成してもよく、
Ｒ^Ni5～Ｒ^Ni8は、それぞれ互いにＲ^Ni5～Ｒ^Ni8から選ばれる１つ以上と結合して環を形成してもよい。
Ｙ⁺はカチオンを表す。］

[During the ceremony,
R ^Ni1 to R ^Ni8 independently represent a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 15 carbon atoms.
-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-.
R ^Ni1 to R ^Ni4 may be bonded to one or more selected from R ^Ni1 to R ^Ni4 to form a ring, respectively.
R ^Ni5 to R ^Ni8 may each bond with one or more selected from R ^Ni5 to R ^Ni8 to form a ring.
Y ⁺ represents a cation. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

The monovalent hydrocarbon group having 1 to 15 carbon atoms represented by R ^Ni1 to R ^Ni8 is the above-mentioned hydrocarbon represented by R ¹ to R ⁶ except that the example in which the number of carbon atoms is 16 or more is not included. The same example as the hydrogen group can be mentioned.

-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-.

R ^Ni1 to R ^Ni4 may be bonded to one or more selected from R ^Ni1 to R ^Ni4 to form a ring, respectively.
R ^Ni5 to R ^Ni8 may each bond with one or more selected from R ^Ni5 to R ^Ni8 to form a ring.

R ^Ni1 to R ^Ni8 are preferably a hydrogen atom, a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and are a hydrogen atom, a halogen atom or a linear or branched chain having 1 to 5 carbon atoms. It is more preferably a state alkyl group, further preferably a hydrogen atom or a halogen atom, and even more preferably a hydrogen atom or a chlorine atom.

As for R ^Ni1 to R ^Ni8 , it is preferable that 2 to 8 of R ^Ni1 to R ^Ni8 are halogen atoms and all the rest are hydrogen atoms, and 4 to 8 of R ^Ni1 to R ^Ni8 are halogen atoms. It is more preferable that all the rest are hydrogen atoms, 2 to 4 of R ^Ni1 to R ^Ni4 are halogen atoms, and 2 to 4 of R ^Ni5 to R ^Ni8 are halogen atoms, and the rest are all hydrogen. It is more preferably an atom, in which 2 to 4 of R ^Ni1 to R ^Ni4 are chlorine atoms, 2 to 4 of R ^Ni5 to R ^Ni8 are chlorine atoms, and all the rest are hydrogen atoms. Even more preferable.

Examples of the cation represented by Y ⁺ include ammonium cation and phosphonium cation, and ammonium cation is preferable.

Examples of the ammonium cation include pyridinium ion, N, N-dimethylaminopyridinium ion, triethylammonium ion, tetramethylammonium ion, tetraethylammonium cation, piperidinium ion, N-methylpiperidinium ion, morpholinium ion and the like. Therefore, tetramethylammonium ion is preferable.

Examples of the phosphonium cation include tetraethylphosphonium ion, tetrabutylphosphonium ion, tetraphenylphosphonium ion and the like.

As the nickel complex, tetramethylammonium bis (3,4,6-trichloro-1,2-benzenedithiolate) nickel (III) is particularly preferable.

As the copper complex, a complex having a carben compound containing a hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom as a ligand is preferable, and the carben having a structure in which the hetero atom is bonded adjacent to both sides of the carben carbon atom is preferable. A complex having a compound as a ligand is more preferable, and a complex having a carben compound having a structure in which a heterocycle is formed including a carben carbon atom and heteroatoms on both sides thereof as a ligand is further preferable, and a nitrogen atom is used. A complex having an N-heterocyclic carben compound contained as a hetero atom as a ligand is even more preferable, and a complex represented by the following formula (Cu-x) is particularly preferable.

［式中、
Ｒ^Cu1～Ｒ^Cu4は、それぞれ独立して、水素原子、ハロゲン原子又は炭素数１～２０の１価の炭化水素基を表し、
該１価の炭化水素基を構成する－ＣＨ₂－は、－Ｏ－又は－Ｓ－に置き換わっていてもよい。
Ｒ^Cu1～Ｒ^Cu4は、それぞれ互いにＲ^Cu1～Ｒ^Cu4から選ばれる１つ以上と結合して環を形成してもよい。
Ｘ^Cuはハロゲン原子を表す。］

[During the ceremony,
R ^Cu1 to R ^Cu4 independently represent a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-.
R ^Cu1 to R ^Cu4 may each be bonded to one or more selected from R ^Cu1 to R ^Cu4 to form a ring.
X ^Cu represents a halogen atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

The monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ^Cu1 to R ^Cu4 is the above-mentioned hydrocarbon group represented by R ¹ to R ⁶ except that the example having 21 or more carbon atoms is not included. The same example as the hydrogen group can be mentioned.

-CH _2- constituting the monovalent hydrocarbon group may be replaced with -O- or -S-.

R ^Cu1 to R ^Cu4 may each be bonded to one or more selected from R ^Cu1 to R ^Cu4 to form a ring.

R ^Cu1 and R ^Cu4 are preferably monovalent hydrocarbon groups having 6 to 20 carbon atoms, and are phenyl groups to which at least one linear or branched alkyl group having 1 to 10 carbon atoms is bonded. It is more preferably a phenyl group in which two or more linear or branched alkyl groups having 1 to 10 carbon atoms are bonded, and a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable. It is more preferably a phenyl group in which two or more groups are bonded, and a 2,4,6-trimethylphenyl group or a 2,6-diisopropylphenyl group is particularly preferable.

The R ^Cu2 and R ^Cu3 are preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

The X ^Cu is preferably a chlorine atom.

As the copper complex, chloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-iriden] copper (I) is particularly preferable.

By further containing the singlet oxygen quencher (H) in addition to the antioxidant (G), the colored curable resin composition of the present invention can form a color filter having more excellent light resistance.

When the single-term oxygen quencher (H) is contained, the content of the single-term oxygen quencher (H) is preferably 100 parts by mass with respect to 100 parts by mass of the total polymerization initiator (D) contained in the colored curable resin composition. It is 1 part by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 400 parts by mass or less, further preferably 20 parts by mass or more and 300 parts by mass or less, and further preferably 25 parts by mass or more and 250 parts by mass or less. It is as follows.
When the single term oxygen quencher (H) is contained, the content of the single term oxygen quencher (H) is preferably 100 parts by mass with respect to 100 parts by mass of the total antioxidant (G) contained in the colored curable resin composition. 1 part by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 400 parts by mass or less, further preferably 20 parts by mass or more and 300 parts by mass or less, still more preferably 30 parts by mass or more and 250 parts by mass or less. It is less than or equal to, and particularly preferably 40 parts by mass or more and 200 parts by mass or less.
When the single term oxygen quencher (H) is contained, the content of the single term oxygen quencher (H) is preferably 0.05% by mass or more with respect to the total solid content of the colored curable resin composition 25. It is 0% by mass or less, more preferably 0.10% by mass or more and 20% by mass or less, further preferably 0.50% by mass or more and 15% by mass or less, still more preferably 1.0% by mass or more and 12% by mass. % Or less.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound (C) whose polymerization has been started by the polymerization initiator (D). When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4'-bis ( Ethylmethylamino) benzophenone and the like, preferably 4,4'-bis (diethylamino) benzophenone and the like. Further, as the amine compound, a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 100 parts by mass based on the total amount of the resin (B) and the polymerizable compound (C) contained in the colored curable resin composition. It is 0.01 part by mass or more and 30 parts by mass or less, more preferably 0.1 part by mass or more and 20 parts by mass or less.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used.
The solvent (E) includes, for example, an ester solvent (a solvent containing -CO-O- in the molecule and not containing -O-) and an ether solvent (a solvent containing -O- in the molecule and containing -CO-O-). No solvent), ether ester solvent (solvent containing -CO-O- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not -CO-O-), alcohol Examples thereof include a solvent (solvent containing OH in the molecule and not containing -O-, -CO- and -CO-O-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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, γ-butyrolactone and the like.

Examples of the ether solvent 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, and 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, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol, methyl anisol and the like.

Examples of the ether ester solvent 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 Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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. And so on.

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

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

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Two or more of these solvents may be used in combination.

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone , Cyclohexanone and N, N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone and cyclohexanone are more preferred.

When the solvent (E) is contained, the content of the solvent (E) is usually less than 100% by mass, preferably 99.99% by mass or less, more preferably 99.99% by mass or less, based on the total amount of the colored curable resin composition. Is 1% by mass or more and 99.9% by mass or less, more preferably 10% by mass or more and 99% by mass or less, still more preferably 20% by mass or more and 97% by mass or less, and particularly preferably 30% by mass or more. It is 95% by mass or less, more preferably 40% by mass or more and 95% by mass or less, and particularly preferably 50% by mass or more and 95% by mass or less. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good. ..

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: 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, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Denshikase Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by 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. Specific examples thereof include Megafuck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.00001% by mass or more and 3% by mass or less, more preferably 3% by mass or less, based on the total amount of the colored curable resin composition. It is 0.0001% by mass or more and 1% by mass or less, and more preferably 0.0005% by mass or more and 0.5% by mass or less. The content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
If necessary, the color-curable resin composition may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents.

<Manufacturing method of colored curable resin composition>
The color-curable resin composition comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and an antioxidant (G), and a polymerization initiation aid used as necessary. It can be prepared by mixing the agent (D1), the solvent (E), the leveling agent (F), the single-term oxygen quencher (H) and / or other components. Mixing can be carried out by known or conventional equipment and conditions.
The colorant (A) may be mixed with a part or all of the solvent (E) in advance and dispersed in a bead mill or the like until the average particle size becomes about 0.2 μm or less. At this time, if necessary, a part or all of the dispersant and the resin (B) may be blended. The diameter of the beads using the bead mill is preferably 0.05 mm or more and 0.5 mm or less, and the material of the beads includes glass, ceramic, metal and the like.
The colorant (A) may be used in the state of a solution (coloring composition) previously dissolved in a part or all of the solvent (E).
The desired coloring curable resin composition can be prepared by mixing the remaining components with the coloring composition obtained as described above so as to have a predetermined concentration.

<Color filter>
Examples of the method for forming a coloring pattern from the coloring curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the composition layer can be formed by not using a photomask at the time of exposure and / or not developing the photomask. The colored pattern and the colored coating film thus formed are the color filters of the present invention.

The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose, application and the like. For example, it is preferably 30 μm or less, more preferably 20 μm or less, and 6 μm or less. It is more preferably 3 μm or less, and the lower limit is not particularly limited, but it is usually 0.1 μm or more.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit and the like may be formed on these substrates. Further, a substrate obtained by subjecting the silicon substrate to HMDS (1,1,1,3,3,3-hexamethyldisilazane) treatment may be used.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.
First, the colored curable resin composition is applied onto a substrate and dried by heating and drying (pre-baking) and / or under reduced pressure to remove volatile components such as a solvent to obtain a smooth composition layer.
Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.
The temperature at the time of heat drying is preferably 30 ° C. or higher and 120 ° C. or lower, and more preferably 50 ° C. or higher and 110 ° C. or lower. The heating time is preferably 10 seconds or more and 60 minutes or less, and more preferably 30 seconds or more and 30 minutes or less.
When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 Pa or more and 150 Pa or less in a temperature range of 20 ° C. or more and 25 ° C. or less.
The film thickness of the composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The composition layer is then exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. As the light source used for exposure, a light source that generates light having a wavelength of 250 nm or more and 450 nm or less is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like. In addition, since it is possible to uniformly irradiate the entire exposed surface with parallel light rays and accurately align the photomask with the substrate on which the composition layer is formed, a stepper (reduced projection exposure machine) and proximity. It is preferable to use an exposure device (mask aligner) such as an exposure machine.

A colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution for development. By development, the unexposed portion of the composition layer is dissolved in a developer and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.03% by mass or more and 5% by mass or less. Further, the developer may contain a surfactant.
The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
The developed substrate is preferably washed with water.

Further, it is preferable to post-bake the obtained coloring pattern. The post-bake temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 250 ° C. or lower, and more preferably 245 ° C. or lower. The post-baking time is preferably 1 minute or more, more preferably 2 minutes or more, preferably 120 minutes or less, more preferably 60 minutes or less, still more preferably 30 minutes or less.
The colored pattern and the color filter which is the colored coating film thus obtained may be further subjected to a surface coating treatment in order to impart various characteristics.

<Display device>
The color filter is a color filter used for a display device (for example, a liquid crystal display device, an organic EL display device, etc.), an electronic paper, a solid-state image pickup element, etc., and is a high color gamut standard such as a DCI (Digital Cinema Initiatives) standard. It is useful as a color filter used in a display device compliant with the above.

According to the colored curable resin composition of the present invention, it is possible to form a color filter having excellent light resistance. In the present invention, the excellent light resistance of the color filter means that the change in color before and after the light irradiation test is small, and the change in absorbance before and after the light irradiation test is small (that is, the maintenance rate of absorbance is high). Satisfying at least one of them.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can meet the purposes of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

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

(Synthesis Example 1)
[Preparation of compound represented by formula (Ia11)]
4-Amino-2-methylquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.04 parts, trimellitic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 15.6 parts and methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) 92.3 parts were mixed.
The mixture was stirred for 5 hours while keeping at 167 ° C.
To this mixture was added 40.2 parts of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.).
The mixture was stirred for 9 hours while keeping at 167 ° C.
To this mixture was added 28.0 parts of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.).
The mixture was stirred for 11 hours while keeping at 170 ° C.
The mixture was cooled to room temperature and 2000 parts of methanol was added to the mixture.
The mixture was stirred at room temperature.
173 parts of methanol was added to the resulting mixture.
The mixture was filtered and the resulting residue was washed once with 124 parts of methanol, once with 160 parts and once with 400 parts.
The obtained residue was dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (Ia11) (dry weight 9.91 parts; hereinafter, may be referred to as a colorant (Ia11)).

<Identification of the compound represented by the formula (Ia11)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 507
(Mass spectrometry) Ionization mode = ESI-: m / z = [MH ^] -505
Exact Mass: 506

(Synthesis Example 2)
[Preparation of compound represented by formula (Ia7)]
4-Amino-2-methylquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.23 parts, 3-nitrophthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.2 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) ) And 119 parts of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed.
The mixture was stirred for 12 hours while keeping at 168 ° C.
In this mixture, 7.12 parts of 3-nitrophthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.3 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) (Manufactured) 16.0 parts were added.
The mixture was stirred for 26 hours while keeping at 170 ° C.
The mixture was cooled to room temperature and 2400 parts of methanol was added to the mixture.
The resulting mixture was stirred at room temperature and then filtered.
The obtained residue was washed 5 times with 400 parts of methanol.
The obtained residue was dried under reduced pressure at 60 ° C. to obtain 13.0 parts of the compound represented by the formula (Ia7) (hereinafter, may be referred to as a colorant (Ia7)).

<Identification of the compound represented by the formula (Ia7)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 509
(Mass spectrometry) Ionization mode = ESI-: m / z = [MH ^] -507
Exact Mass: 508

(Synthesis Example 3)
[Preparation of compound represented by formula (Ia124)]
4-Amino-2-methylquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.02 parts, 2,3-naphthalenedicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.33 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 11.7 parts (manufactured by Kogyo Co., Ltd.) and 66.7 parts of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed.
The mixture was stirred for 9 hours while keeping at 170 ° C.
In this mixture, 13.6 parts of 2,3-naphthalenedicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.9 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) 66.4 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) were added.
The mixture was stirred for 49 hours while keeping at 170 ° C.
This mixture contains 8.32 parts of 2,3-naphthalenedicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.7 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.). (Manufactured by Co., Ltd.) 43.5 parts were added.
The mixture was stirred for 28 hours while keeping at 170 ° C.
The mixture was cooled to room temperature and 1300 parts of methanol was added to the mixture.
The mixture was stirred at room temperature and then filtered and the resulting residue was washed 7 times with 400 parts of methanol.
The obtained residue was dried under reduced pressure at 60 ° C.
To this residue was added 875 parts of N, N-dimethylformamide.
The mixture was stirred at room temperature and then filtered and the resulting residue was washed 3 times with the same volume of N, N-dimethylformamide as the resulting residue.
The residue was washed 3 times with 200 parts of methanol.
The obtained residue was dried under reduced pressure at 60 ° C. to obtain 7.25 parts of the compound represented by the formula (Ia2).

<Identification of the compound represented by the formula (Ia2)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 519
(Mass spectrometry) Ionization mode = ESI-: m / z = [MH ^] -517
Exact Mass: 518

A mixture of 1 mol of the compound represented by the formula (Ia2) and 20 mol of potassium hydroxide and water having a weight of 10 times the weight of 1 mol of the compound represented by the formula (Ia2) was mixed.
The mixture was stirred while keeping the temperature at 90 ° C. until the compound represented by the formula (Ia2) disappeared.
This mixture was mixed with 36% hydrochloric acid and neutralized.
The mixture was filtered.
The obtained residue was washed with water.
This residue was purified by column chromatography to obtain a compound represented by the formula (IM1-1).

<Identification of the compound represented by the formula (IM1-1)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 339
(Mass spectrometry) Ionization mode = ESI-: m / z = [MH ^] -337
Exact Mass: 338

1 mol of the compound represented by the formula (IM1-1), 8 mol of trimellitic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 21 mol of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and the formula (IM1-1). ) Was mixed with a weight of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) 73 times the weight of 1 mol of the compound.
The mixture was stirred for 120 hours while keeping at 170 ° C.
The mixture was cooled to room temperature and 13 times the weight of the mixture was added to the mixture.
The resulting mixture was stirred at room temperature and then filtered.
The obtained residue was washed with methanol.
The obtained residue was purified by column chromatography to obtain a compound represented by the formula (Ia124) (hereinafter, may be referred to as a colorant (Ia124)).

<Identification of the compound represented by the formula (Ia124)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 513
(Mass spectrometry) Ionization mode = ESI-: m / z = [MH ^] -511
Exact Mass: 512

(Synthesis Example 4)
[Preparation of compound represented by formula (IIa12)]
8-Amino-2-methylquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.01 parts, 4-phenylethynylphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.49 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.95 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) and 28.7 parts of methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed.
The mixture was stirred for 20 hours while keeping at 170 ° C.
To this mixture, 0.476 parts of 4-phenylethynyl phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.32 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) Made by Tokyo Chemical Industry Co., Ltd.) 3.3 parts were added.
The mixture was stirred for 10 hours while keeping at 170 ° C.
To this mixture, 0.801 parts of 4-phenylethynyl phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.90 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and methyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) Made by Tokyo Chemical Industry Co., Ltd.) 9.13 parts were added.
The mixture was stirred for 29 hours while keeping at 170 ° C.
The mixture was cooled to room temperature, 400 parts of methanol was added to the mixture, and the mixture was stirred for 1 hour.
The mixture was filtered and the resulting residue was washed 6 times with 140 parts of methanol.
The obtained residue was dried under reduced pressure at 60 ° C. to obtain 3.12 parts of the compound represented by the formula (IIa12) (hereinafter, may be referred to as a colorant (IIa12)).

<Identification of the compound represented by the formula (IIa12)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 619
(Mass spectrometry) Ionization mode = ESI-: m / z = [MH ^] -617
Exact Mass: 618

(Synthesis Example 5)
[Preparation of resin B-1]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.10 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decane-9-ylacrylate (content ratio: 1: 1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropping is completed, the solution is kept at 80 ° C. for 4 hours, cooled to room temperature, and has a solid content of 35.1% and a copolymer (resin B-1) solution having a viscosity of 125 mPas measured with a B-type viscometer (23 ° C.). Got The weight average molecular weight (Mw) of the obtained copolymer was 9.2 × 103 ^, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. Resin B-1 has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

(Synthesis Example 6)
[Preparation of Colored Dispersion Liquid (CD-1)]
Each component was mixed at the following ratios, 300 parts of zirconia beads having a diameter of 0.2 mm were added and shaken, and then the zirconia beads were removed by filtration to prepare a colored dispersion liquid (CD-1).
Colorant (A): Colorant (Ia11) 4 parts;
Dispersant: DISPERBYK-161 (manufactured by BYK; solid content equivalent) 7.5 parts;
Resin (B): Resin B-1 (solid content equivalent) 4 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 84.5 parts;

(Synthesis Example 7)
[Preparation of colored dispersion (CD-2)]
Each component was mixed at the following ratios, 300 parts of zirconia beads having a diameter of 0.2 mm were added and shaken, and then the zirconia beads were removed by filtration to prepare a colored dispersion liquid (CD-2).
Colorant (A): Colorant (Ia7) 4 parts;
Dispersant: BYK-LP N 21324 (manufactured by BYK; solid content equivalent) 7.5 parts;
Resin (B): Resin B-1 (solid content equivalent) 4 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 84.5 parts;

(Synthesis Example 8)
[Preparation of Colored Dispersion Liquid (CD-3)]
Each component was mixed at the following ratios, 300 parts of zirconia beads having a diameter of 0.1 mm were added, and the mixture was shaken, and then the zirconia beads were removed by filtration to prepare a colored dispersion liquid (CD-3).
Colorant (A): Colorant (Ia124) 4 parts;
Dispersant: BYK-LP N 6919 (manufactured by BYK; solid content equivalent) 7.5 parts;
Resin (B): Resin B-1 (solid content equivalent) 4 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 84.5 parts;

(Synthesis Example 9)
[Preparation of Colored Dispersion Liquid (CD-4)]
Each component was mixed at the following ratios, 300 parts of zirconia beads having a diameter of 0.2 mm were added, and the mixture was shaken, and then the zirconia beads were removed by filtration to prepare a colored dispersion liquid (CD-4).
Colorant (A): Colorant (IIa12) 4 parts;
Dispersant: DISPERBYK-161 (manufactured by BYK; solid content equivalent) 7.5 parts;
Resin (B): Resin B-1 (solid content equivalent) 4 parts;
Solvent (E): Propylene glycol monomethyl ether acetate 84.5 parts;

(Synthesis Example 10)
[Preparation of resin B-2]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 85 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.10 ^{2, 6} ] A mixed solution of 25 parts of a mixture of decane-9-ylacrylate (content ratio is 1: 1 in molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethylmethacrylate, and 338 parts of propylene glycol monomethyl ether acetate. It was dropped over 5 hours. On the other hand, a solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the solution was held at 85 ° C. for 4 hours, cooled to room temperature, and measured with a B-type viscometer (23 ° C.) to have a viscosity of 23 mPas and a solid content of 25.6% in a copolymer (resin B-2) solution. Got The weight average molecular weight (Mw) of the obtained copolymer was 8.0 × 103 ^, the dispersity was 2.1, and the acid value in terms of solid content was 109 mg-KOH / g. Resin B-2 has the following structural units.

(Examples 1 to 9, comparative examples 1 to 4)
[Preparation of Colored Curable Resin Composition]
Each component was mixed so as to have the composition shown in Table 5, and each colored curable resin composition was obtained.

In Table 5, each component represents the following compound.
Antioxidant (Ph-1): 3,9-Bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) proportionyloxy] -1,1-dimethyl} -2,4,8 , 10-tertraoxaspiro [5.5] undecane (GA-80: manufactured by Sumitomo Chemical Co., Ltd.)
Antioxidant (Am-1): 2,2,6,6-ttramethyl-4-piperidyl methyllate (LA-87: manufactured by ADEKA Corporation)
Antioxidant (P-1): Triphenylphosphine Singlet Oxygen Quencher (Cu-1): Chloro [1,3-bis (2,6-diisopropylphenyl) imidazol-2-iriden] Copper (I)
Resin (B-2): Resin B-2 (solid content conversion)
Polymerizable compound (C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization Initiator (D-1): N-Acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-on-2-imine (PBG-327; oxime compound; Changzhou strong electron new material ( Made by Co., Ltd.)
Solvent (E-1): Propylene glycol monomethyl ether acetate Solvent (E-2): Diacetone alcohol Solvent (E-3): Cyclohexanone leveling agent (F-1): Polyether-modified silicone oil (Toray Dow Corning Co., Ltd.) ) Made "Torre Silicone SH8400")

[Making a color filter (colored coating film)]
A color curable resin composition is applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method so that the film thickness after post-baking is 2.0 μm, and then the temperature is 100 ° C. for 3 minutes. Prebaked to form a composition layer. After allowing to cool, the composition layer formed on the substrate was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 100 mJ / cm ² (365 nm standard) under an atmospheric atmosphere. did. After light irradiation, post-baking was performed at 230 ° C. for 30 minutes in an oven to obtain a colored coating film. The film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was confirmed that the film thickness was 2.0 μm.

[Measurement of chromaticity]
The chromaticity of the colored coating film is determined by the spectroscopy measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) and the characteristic function of the C light source, and the xy chromaticity in the XYZ color system of CIE. It was obtained as the coordinates (x, y) and the stimulus value Y.

[Light resistance evaluation]
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya; cuts light of 380 nm or less) is placed on the obtained colored coating film, and a xenon lamp is used in a light resistance tester (SUNTEST CPS +: manufactured by Toyo Seiki Co., Ltd.). The light was irradiated for 48 hours.
The chromaticity was measured before and after the light resistance test, and the color difference ΔEab ^* was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The smaller the color difference ΔEab ^* , the smaller the color change, and the higher the light resistance. The results are shown in Table 6.
Further, the maximum absorbance was obtained from the spectroscopy measured by a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) before and after the light resistance test, and the maintenance rate of the maximum absorbance was calculated according to the following formula.
Absorbance maintenance rate (ΔAbs.Max) = maximum absorbance after light resistance test / maximum absorbance before light resistance test × 100 (%)
The higher the absorbance retention rate, the higher the light resistance. The results are shown in Table 7.

According to the colored curable resin composition of the present invention, it is possible to form a color filter having excellent light resistance.

Claims (11)

At least one selected from a compound represented by the formula (I) and a compound represented by the formula (II), which contains a colorant, a resin, a polymerizable compound, a polymerization initiator and an antioxidant. Color curable resin composition containing.

[During the ceremony,
R ¹ to R ⁶ are independently hydrogen atom, halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, MM, monovalent hydrocarbon group or carbon having 1 to 40 carbon atoms. Represents a monovalent heterocyclic group of the number 1-40.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
The monovalent hydrocarbon group and -CH _2- constituting the monovalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁶ , and R ⁶ and R ⁵ may be coupled to each other to form a ring, respectively.
M represents a hydrogen atom, an alkali metal atom, a metal atom which may have a ligand, or N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ).
MM represents an alkali metal atom, a metal atom which may have a ligand, or N (Z ¹ ) (Z ² ) (Z ³ ) (Z ⁴ ).
Z ¹ to Z ⁴ independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent heterocyclic group having 1 to 40 carbon atoms.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
The monovalent hydrocarbon group and -CH _2- constituting the monovalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
Q ¹ and Q ² independently represent a divalent hydrocarbon group or a divalent heterocyclic group, respectively.
-C (-) (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -Si (-) (-)-.
-CH (-)-that constitutes the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N (-)-.
-CH = constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with -N =.
The divalent hydrocarbon group and -CH _2- constituting the divalent heterocyclic group may be replaced with -O-, -S-, -S (O) _2- or -CO-.
The hydrogen atom constituting the divalent hydrocarbon group and the divalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
When there are a plurality of Z ¹ to Z ⁴ , M and MM, they may be the same or different from each other. ] The colored curable resin composition according to claim 1, wherein the antioxidant is a phenolic antioxidant having one or two phenol skeletons. The colored curable resin composition according to claim 1 or 2, further comprising a singlet oxygen quencher. The colored curable resin composition according to claim 3, wherein the singlet oxygen quencher is a transition metal complex. The colored curable resin composition according to claim 4, wherein the single-term oxygen quencher is a transition metal complex containing at least one selected from a nickel complex, a copper complex and a cobalt complex. The invention according to any one of claims 1 to 5, wherein Q ¹ and Q ² in the formula (I) or the formula (II) are independently represented by the formula (QQ1) or the formula (QQ2). Color curable resin composition.

[During the ceremony,
R ^Q1 to R ^Q10 are independently hydrogen atom, halogen atom, cyano group, nitro group, -SO ₃ M, -CO ₂ M, MM, monovalent hydrocarbon group or carbon with 1 to 40 carbon atoms. Represents a monovalent heterocyclic group of the number 1-40.
The —C (−) (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with −Si (−) (−) −.
The —CH (−) − constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with —N (−) −.
-CH = constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with -N =.
-CH _2- , which constitutes the monovalent hydrocarbon group and the monovalent heterocyclic group, is -O-, -S-,
It may be replaced with -S (O) ₂ -or-CO-.
The hydrogen atom constituting the monovalent hydrocarbon group and the monovalent heterocyclic group may be replaced with a halogen atom, a cyano group, a nitro group, —SO ₃ M, —CO ₂ M or MM.
R ^Q1 to R ^Q4 may each be combined with one or more selected from R ^Q1 to R ^Q4 to form a ring.
R ^Q5 to R ^Q10 may each be bonded to one or more selected from R ^Q5 to R ^Q10 to form a ring.
M and MM have the same meanings as described above.
* Represents a bond. ] The colored curable resin composition according to claim 6, wherein at least one of Q ¹ and Q ² in the formula (I) or the formula (II) is a group represented by the formula (QQ1). The color-curable resin composition according to any one of claims 1 to 7, wherein the colorant contains a compound represented by the formula (I). The colored curable resin composition according to claim 8, wherein Q ¹ or Q ² in the formula (I) has at least one -CO ₂ H. A color filter formed from the colored curable resin composition according to any one of claims 1 to 9. A display device including the color filter according to claim 10.