JP2020026513A - Coloring curable resin composition - Google Patents

Abstract

To solve the problem in which: the conventionally known coloring curable resin composition does not have satisfactory solubility in a developer in color filter production.SOLUTION: A coloring curable resin composition has a colorant, a resin, a polymerizable compound, a polymerization initiator and a compound containing cobalt (III); the colorant has triarylmethane lake; and a maximum of molar extinction coefficients of the compound containing cobalt (III) in a visible light region is smaller than that of the colorant in the visible light region.SELECTED DRAWING: None

Description

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

  A color filter used for a liquid crystal display, an electroluminescence display, a display such as a plasma display, or a solid-state imaging device such as a CCD or a CMOS sensor is manufactured from a colored curable resin composition. As such a colored curable resin composition, a composition containing a compound containing cobalt (II) for the purpose of containing a dye as a colorant and improving its light resistance is known (Patent Document 1). ). Patent Document 1 describes that the above composition has excellent resistance to a developer and a high residual film ratio of development.

JP 2004-295116 A

  The above-described conventionally known colored curable resin compositions have not been sufficiently satisfactory in solubility in a developing solution at the time of producing a color filter.

［式（Ｉ）中、
Ｒ¹¹〜Ｒ¹⁴は、それぞれ独立して、水素原子、炭素数１〜２０の飽和炭化水素基、置換基を有していてもよい炭素数６〜２０の芳香族炭化水素基又は置換基を有していてもよい炭素数７〜３０のアラルキル基を表し、該炭素数１〜２０の飽和炭化水素基において、該飽和炭化水素基に含まれる水素原子は、置換若しくは非置換のアミノ基又はハロゲン原子に置換されていてもよく、該飽和炭化水素基の炭素数が２〜２０である場合、該飽和炭化水素基に含まれるメチレン基は酸素原子又は−ＣＯ−に置換されていてもよい。ただし、該炭素数２〜２０の飽和炭化水素基において、隣接するメチレン基が同時に酸素原子に置換されることはない。Ｒ¹¹とＲ¹²とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ¹³とＲ¹⁴とが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ｒ¹⁷〜Ｒ²⁴は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、炭素数１〜８のアルキル基を表し、該アルキル基を構成するメチレン基は酸素原子又は−ＣＯ−に置換されていてもよい。Ｒ¹⁸とＲ²²とが互いに結合して、−ＮＨ−、−Ｏ−、−Ｓ−又は−ＳＯ₂−を形成していてもよい。
環Ｔ¹は、置換基を有していてもよい炭素数３〜１０の芳香族複素環又は置換基を有していてもよい炭素数６〜１０の芳香族炭化水素環を表す。
［Ｙ］^m-は、タングステン、モリブデン、ケイ素、及びリンからなる群より選ばれる少なくとも１つの元素と、酸素とを含有する任意のｍ価のアニオンを表す。
ｍは任意の自然数を表す。
なお、１分子中に下記式で表される構造が複数含まれる場合、それらは同じ構造であっても異なる構造であってもよい。

［式中、環Ｔ¹、Ｒ¹¹〜Ｒ¹⁴及びＲ¹⁷〜Ｒ²⁴は、それぞれ、上記と同義である。］］

［式（ＩＩ）中、
Ｒ⁴¹〜Ｒ⁴⁴は、それぞれ独立して、水素原子、炭素数１〜２０の飽和炭化水素基、置換基を有していてもよい炭素数６〜２０の芳香族炭化水素基、又は、置換基を有していてもよい炭素数７〜３０のアラルキル基を表し、該芳香族炭化水素基及び該アラルキル基が有していてもよい置換基は、−ＳＯ₃ ^-又は−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ^fであってもよく、該飽和炭化水素基に含まれる水素原子は、置換若しくは非置換のアミノ基又はハロゲン原子に置換されていてもよく、該飽和炭化水素基の炭素数が２〜２０である場合、該飽和炭化水素基に含まれるメチレン基は、酸素原子又は−ＣＯ−に置き換わっていてもよい。ただし、該炭素数２〜２０の飽和炭化水素基において、隣接するメチレン基が同時に酸素原子に置き換わることはない。Ｒ⁴¹とＲ⁴²とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ⁴³とＲ⁴⁴とが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ｒ⁴⁷〜Ｒ⁵⁴は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシ基、−ＳＯ₃ ^-、−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ^f、又は炭素数１〜８のアルキル基を表し、該アルキル基を構成するメチレン基は、酸素原子又は−ＣＯ−に置き換わっていてもよく、Ｒ⁴⁸とＲ⁵²とが互いに結合して、−ＮＨ−、−Ｓ−、又は−ＳＯ₂−を形成していてもよい。ただし、該アルキル基において、隣接するメチレン基が同時に酸素原子に置換されることはない。
環Ｔ²は、炭素数３〜１０の芳香族複素環又は炭素数６〜１０の芳香族炭化水素環を表し、該芳香族複素環及び該芳香族炭化水素環は、炭素数１〜２０の飽和炭化水素基、置換若しくは非置換のアミノ基又は置換基を有していてもよい炭素数６〜２０の芳香族炭化水素基を有していてもよい。該芳香族炭化水素基が有していてもよい置換基は、−ＳＯ₃ ^-又は−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ^fであってもよい。
Ｍ^r+は、ｒ価の金属イオンを表す。
ｋは、Ｒ⁴¹〜Ｒ⁴⁴、Ｒ⁴⁷〜Ｒ⁵⁴及び環Ｔ²が有する−ＳＯ₃ ^-の個数及び−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ^fの個数の和を表す。
ｒは、１以上の整数を表す。
Ｒ^fは、炭素数１〜１２のフルオロアルキル基を表す。
ただし、Ｒ⁴¹〜Ｒ⁴⁴、Ｒ⁴⁷〜Ｒ⁵⁴及び環Ｔ²は、−ＳＯ₃ ^-又は−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ^fを少なくとも１つ有する。
なお、１分子中に下記式で表される構造が複数含まれる場合、それらは同じ構造であっても異なる構造であってもよい。

［式中、環Ｔ²、Ｒ⁴¹〜Ｒ⁴⁴及びＲ⁴⁷〜Ｒ⁵⁴は、それぞれ、上記と同義である。］］
[３] トリアリールメタンレーキとは異なる色素をさらに含む[１]又は[２]記載の着色硬化性樹脂組成物。
[４] [１]〜[３]のいずれか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。
[５] [４]記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A colorant, a resin, a polymerizable compound, a polymerization initiator, and a compound containing cobalt (III), wherein the colorant contains a triarylmethane lake, and a mole of a compound containing cobalt (III) in a visible light region. A colored curable resin composition in which the maximum value of the extinction coefficient is smaller than the maximum value of the molar extinction coefficient in the visible light region of the colorant.
[2] The colored curable resin composition according to [1], wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). .

[In the formula (I),
R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group is a substituted or unsubstituted amino group or It may be substituted by a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted by an oxygen atom or -CO- . However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms. R ¹¹ and R ¹² may be bonded to form a ring together with the nitrogen atom to which they are bonded, or R ¹³ and R ¹⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ¹⁷ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, an alkyl group having 1 to 8 carbon atoms, a methylene group constituting the alkyl group is an oxygen atom or -CO- May be substituted. R ¹⁸ and R ²² may combine with each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen.
m represents an arbitrary natural number.
When one molecule includes a plurality of structures represented by the following formulas, they may have the same structure or different structures.

Wherein ring T ¹ , R ^{11 to} R ¹⁴ and R ^{17 to} R ²⁴ are as defined above. ]]

[In the formula (II),
R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or Represents an aralkyl group having 7 to 30 carbon atoms which may have a group, wherein the aromatic hydrocarbon group and a substituent which the aralkyl group may have are -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^f, hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group, or a halogen atom, the carbon of the saturated hydrocarbon group When the number is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they bind, or R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they bind.
R ⁴⁷ to R ⁵⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or alkyl of 1 to 8 carbon atoms A methylene group constituting the alkyl group may be replaced by an oxygen atom or —CO—, and R ⁴⁸ and R ⁵² are bonded to each other to form —NH—, —S—, or —SO— _2- may be formed. However, in the alkyl group, adjacent methylene groups are not simultaneously substituted with oxygen atoms.
Ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocyclic ring and the aromatic hydrocarbon ring have 1 to 20 carbon atoms. It may have a saturated hydrocarbon group, a substituted or unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^{f.
Mr +} represents an r-valent metal ion.
k represents the sum of the number of —SO ₃ ^{— and} the number of —SO ₂ —N ^—— SO ₂ —R ^f of R ^{41 to} R ⁴⁴ , R ^{47 to} R ⁵⁴ and ring T ² .
r represents an integer of 1 or more.
R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.
^{However, R 41 ~R 44, R 47} ~R 54 and ring T ² are, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f.
When one molecule includes a plurality of structures represented by the following formulas, they may have the same structure or different structures.

Wherein ring T ² , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ are as defined above. ]]
[3] The colored curable resin composition according to [1] or [2], further comprising a dye different from the triarylmethane lake.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

  ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, when forming a color filter, it is excellent in solubility to a developing solution, and also the peeling piece derived from a colored curable resin composition hardly remains in a developing solution.

The colored curable resin composition of the present invention includes a colorant (hereinafter sometimes referred to as a colorant (A)), a resin (hereinafter sometimes referred to as a resin (B)), a polymerizable compound (hereinafter referred to as a polymerizable compound). (Hereinafter sometimes referred to as (C)), a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)), and a compound containing cobalt (III) (hereinafter sometimes referred to as a compound (G)).
The colorant (A) contains a triarylmethane lake (hereinafter also referred to as a colorant (A1)).
The colored curable resin composition of the present invention preferably further contains a solvent.
The colored curable resin composition of the present invention may contain a leveling agent.
In the present specification, compounds exemplified as each component can be used alone or in combination of two or more, unless otherwise specified.

<Colorant (A)>
The triarylmethane lake refers to a dye having a triarylmethane skeleton and being insoluble or hardly soluble in an organic solvent (preferably a solvent contained in the colored curable resin composition of the present invention).
The triarylmethane skeleton is a skeleton in which three aromatic rings are bonded to one carbon, of which two are aromatic hydrocarbon rings and one is an aromatic heterocycle. A skeleton is preferred.

  The triarylmethane lake is at least selected from the group consisting of a compound represented by formula (I) (hereinafter also referred to as compound (I)) and a compound represented by formula (II) (hereinafter also referred to as compound (II)). It is preferable to use one type.

<Compound represented by Formula (I)>

[In the formula (I),
R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group is a substituted or unsubstituted amino group or It may be substituted by a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted by an oxygen atom or -CO- . However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms. R ¹¹ and R ¹² may be bonded to form a ring together with the nitrogen atom to which they are bonded, or R ¹³ and R ¹⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ¹⁷ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, an alkyl group having 1 to 8 carbon atoms, a methylene group constituting the alkyl group is an oxygen atom or -CO- May be substituted. R ¹⁸ and R ²² may combine with each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen.
m represents an arbitrary natural number.
When one molecule includes a plurality of structures represented by the following formulas, they may have the same structure or different structures.

Wherein ring T ¹ , R ^{11 to} R ¹⁴ and R ^{17 to} R ²⁴ are as defined above. ]]

The aromatic heterocyclic ring of the ring T ¹ may be a single ring or a condensed ring.
Examples of the substituent which the aromatic heterocyclic ring of the ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent. And an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and an amino group which may have a substituent. Ring T ¹ preferably has an amino group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.
Above all, the aromatic heterocyclic ring of the ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

Further, the ring T ¹ is particularly preferably a ring represented by the formula (Ab2-y1).

[R ²⁶ represents a hydrogen atom, a saturated hydrocarbon group, or optionally substituted aromatic hydrocarbon group having 1 to 20 carbon atoms.
X1 represents an oxygen atom, -NR ²⁷ - represents a or sulfur atom.
R ²⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ¹⁵ and R ¹⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms which may have a substituent, and methylene contained in the alkyl group; The group represents a group which may be substituted with an oxygen atom, an aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent or a hydrogen atom. R ¹⁵ and R ¹⁶ may combine to form a ring together with the nitrogen atom to which they are attached.
However, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and methylene groups bonded to N are not substituted with oxygen atoms.
* Represents a bond to a carbocation. ]

The aromatic hydrocarbon ring in T ^1, a benzene ring, a naphthalene ring and the like.
Examples of the substituent which the aromatic hydrocarbon ring of the ring T ¹ may have include a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent. And an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and an amino group which may have a substituent.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{11 to} R ¹⁶ and R ²⁶ may be linear, branched or cyclic. Examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group. Linear alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and still more preferably has 1 to 6 carbon atoms.

Saturated cyclic hydrocarbon group represented by R ¹¹ to R ^16, and R ²⁶ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably has 6 to 10 carbon atoms.

The saturated hydrocarbon group of R ^{11 to} R ¹⁶ and R ²⁶ may be substituted with a halogen atom or an amino group which may be substituted. Examples of the amino group which may be substituted include, for example, an amino group; an alkylamino group such as a methylamino group, a dimethylamino group, and a diethylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When the halogen atom is a fluorine atom, the halogen atom is preferably substituted so as to form a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit, and a heptafluoropropyl unit.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{17 to} R ²⁴ include a straight-chain or branched-chain saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^11. To 8 groups.
Further, as the alkyl group having 1 to 10 carbon atoms represented by R ²⁷ , a linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ¹¹ has 1 to 1 carbon atoms. Ten groups are included.

When the number of carbon atoms of the saturated hydrocarbon groups represented by R ¹¹ to R ¹⁶ (preferably an alkyl group) is 2 or more, a methylene group contained in the saturated hydrocarbon group (preferably an alkyl group) is an oxygen atom or a - It may be substituted by CO-, preferably by an oxygen atom. The preferred carbon number of the saturated hydrocarbon group (preferably an alkyl group) is 2 to 10, more preferably 2 to 8. When the methylene group is substituted with an oxygen atom or -CO-, the number of carbon atoms between the terminal and the oxygen atom or -CO- or between the oxygen atom or -CO- and the oxygen atom or -CO- is For example, it is 1 to 5, preferably 2 to 3, and more preferably 2. However, adjacent methylene groups are not simultaneously substituted with oxygen atoms.

Further, the aromatic hydrocarbon group which may have a substituent represented by R ^{11 to} R ¹⁶ and R ²⁶ preferably has 6 to 20 carbon atoms, more preferably 6 to 20 carbon atoms. 15, more preferably 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, an aryl group such as a terphenyl group, preferably a phenyl group, a naphthyl group, They are a tolyl group and a xylyl group, particularly preferably a phenyl group. The aromatic hydrocarbon group may have one or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; a methoxy group and an ethoxy group. A C1-6 alkoxy group such as a group; a hydroxy group; a sulfamoyl group; a C1-6 alkylsulfonyl group such as a methylsulfonyl group; a C1-6 alkoxycarbonyl such as a methoxycarbonyl group and an ethoxycarbonyl group. Groups; and the like.

As the aralkyl group which may have a substituent represented by R ^{11 to} R ¹⁶ , a group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, etc. And a group to which an alkanediyl group is bonded.

A ring formed by R ¹¹ and R ¹² with the nitrogen atom to which they are bonded, a ring formed by R ¹³ and R ¹⁴ with the nitrogen atom to which they are bonded, and R ¹⁵ and R ¹⁶ Examples of the ring that is formed together with the nitrogen atom to which they are bonded include a nitrogen-containing non-aromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring. And a 4- to 7-membered ring having only one nitrogen atom as the hetero atom.

Among them, as R ^{11 to} R ¹⁴ and R ²⁶ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable. And more preferably a saturated hydrocarbon group of 1 to 8 or a group represented by the following formula. In the following formula, * represents a bond to a nitrogen atom.

R ^{15 to} R ¹⁶ each independently have a saturated hydrocarbon group having 1 to 20 carbon atoms, a group having an oxygen atom inserted between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or a substituent. It is preferable that R ¹⁵ and R ¹⁶ be an aromatic hydrocarbon group which may be bonded to each other, or form a ring together with the nitrogen atom to which they are bonded. In a more preferred embodiment, R ^{15 to} R ¹⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ¹⁵ and R ¹⁶ Is bonded to form a 4- to 7-membered ring having only one nitrogen atom as a hetero atom. In the following formula, * represents a bond to a nitrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{17 to} R ²⁴ and the group in which the methylene group of the alkyl group having 2 to 8 carbon atoms is substituted with an oxygen atom or —CO— include the above-described R. ¹¹ corresponding groups selected from those having 8 or less carbon atoms from the group to R ¹⁶ can be exemplified.

R ^{17 to} R ²⁴ are each independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms from the viewpoint of ease of synthesis, and are each independently a hydrogen atom or a methyl group. , A fluorine atom or a chlorine atom is more preferable.

  X1 is preferably a sulfur atom.

  Examples of the cation moiety of the formula (I) include cations 1 to 14 represented by the formula (Ia) as shown in Table 1 below.

  In Table 1, Ph1 to Ph9 shall mean a group represented by the following formula. In the formula, * represents a bond.

  Among them, the cation moiety of the formula (I) is preferably cation 1 to cation 6, cation 11 to cation 14, particularly preferably cation 1, cation 2, or cation 12 to cation 14, and most preferably cation 12.

[Y] ^m- is preferably an arbitrary m-valent anion containing oxygen and at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus. Compounds containing such anions tend to have good heat resistance and solvent resistance.
m is more preferably 1 to 20, further preferably 1 to 10, and still more preferably 2 to 6.
The anion is preferably an anion of a heteropoly acid and an isopoly acid containing tungsten, an anion of a phosphotungstic acid, a silicotungstic acid and a tungsten-based isopoly acid.

Examples of the anion of the heteropolyacid or isopolyacid containing tungsten include Keggin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ and Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^{6. -} , Β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type silicotungstate ions α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ- [SiW ₁₂ O _{40] ^{] 4-, [P 2 W 17}} O 61] 10-, [P 2 W 15 O 56] 12-, [H 2 P 2 W 12 O 48] 12-, [NaP 5 W 30 O 110] 14-, α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^{_{2-, [W 10 O 32]}} 4-, WO 4 2- and mixtures thereof.

The anion is also preferably an anion comprising oxygen and at least one element selected from the group consisting of silicon and phosphorus.
And at least one element selected from the group consisting of silicon and phosphorus, as the anion consisting of oxygen, SiO ₃ ^2-, PO ₄ ^3- and the like.

Ease of synthesis and post-Keggin-type phosphotungstic acid ion, phosphotungstic acid, such as Dawson-type phosphotungstic acid ion anion; Keggin silicotungstic acid anions such as silicotungstic acid ion, [W ₁₀ O _32] ^4- And the like are preferred. Among them, a phosphotungstate anion and a tungsten isopolyacid anion are particularly preferred.

  Examples of the compound (I) include a compound represented by the following formula.

  Compound (I) is preferably a compound represented by any one of formulas (I-41) to (I-44), and more preferably a compound represented by formula (I-41).

  The compound represented by the formula (I) can be produced according to the method described in JP-A-2015-28121.

<Compound represented by Formula (II)>

［式中、環Ｔ²、Ｒ⁴¹〜Ｒ⁴⁴及びＲ⁴⁷〜Ｒ⁵⁴は、それぞれ、上記と同義である。］］ [In the formula (II),
R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or Represents an aralkyl group having 7 to 30 carbon atoms which may have a group, wherein the aromatic hydrocarbon group and a substituent which the aralkyl group may have are -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^f, hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group, or a halogen atom, the carbon of the saturated hydrocarbon group When the number is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they bind, or R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they bind.
R ⁴⁷ to R ⁵⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or alkyl of 1 to 8 carbon atoms A methylene group constituting the alkyl group may be replaced by an oxygen atom or —CO—, and R ⁴⁸ and R ⁵² are bonded to each other to form —NH—, —S—, or —SO— _2- may be formed.
However, in the alkyl group, an adjacent methylene group-is not simultaneously substituted with an oxygen atom.
Ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocyclic ring and the aromatic hydrocarbon ring have 1 to 20 carbon atoms. It may have a saturated hydrocarbon group, a substituted or unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^{f.
Mr +} represents an r-valent metal ion.
k represents the sum of the number of —SO ₃ ^{— and} the number of —SO ₂ —N ^—— SO ₂ —R ^f of R ^{41 to} R ⁴⁴ , R ^{47 to} R ⁵⁴ and ring T ² .
r represents an integer of 1 or more.
R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.
^{However, R 41 ~R 44, R 47} ~R 54 and ring T ² are, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f. ]
When one molecule includes a plurality of structures represented by the following formulas, they may have the same structure or different structures.

Wherein ring T ² , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ are as defined above. ]]

Aromatic heterocyclic ring represented by Ring T ² are, may be a condensed ring with a single ring. The number of carbon atoms of the aromatic heterocyclic ring represented by Ring T ² are, preferably 3-10, more preferably 3-8. The aromatic heterocycle is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocycle include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; a 5-membered ring containing no nitrogen atom such as a furan ring and a thiophene ring. And a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring; and the like; Condensed rings containing nitrogen atoms such as rings; condensed rings containing no nitrogen atoms such as benzofuran rings; and the like.
As the substituent which the aromatic heterocyclic ring of the ring T ² may have, a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, substituted or unsubstituted An amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the like, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is exemplified. Ring T ² preferably has an amino group which may have a substituent, and the substituent which the amino group may have is a saturated hydrocarbon group having 1 to 20 carbon atoms. And an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and an aralkyl group having 7 to 30 carbon atoms which may have a substituent.
Among them, as the aromatic heterocyclic ring T ^2, aromatic heterocyclic ring is preferred containing a nitrogen atom, an aromatic heterocyclic 5-membered ring containing a nitrogen atom is more preferable.
The ring T ² is preferably a ring represented by the formula (t1).

[In the equation (t1),
R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
X2 represents -O-, -N ( ^R57 )-or -S-.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ⁴⁵ and R ⁴⁶ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 carbon atoms which may have a substituent. Represents an aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and is included in the saturated hydrocarbon group when the saturated hydrocarbon group has 2 to 20 carbon atoms. The methylene group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms. R ⁴⁵ and R ⁴⁶ may combine to form a ring together with the nitrogen atom to which they are attached.
* Represents a bond to a carbocation. ]

Ring T ² is more preferably a ring represented by formula (t2-1).

[In the formula (t2-1),
R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.
R ⁶¹ represents a hydrogen atom, —SO ₃ ⁻ , or —SO ₂ —N ^—— SO ₂ —R ^f .
R ⁵⁹ is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have
* Represents a bond to a carbocation. ]

The aromatic hydrocarbon ring represented by ring T ^2, a benzene ring, a naphthalene ring and the like.
The aromatic hydrocarbon ring substituent which may be possessed for ring T ^2, aromatic heterocycles described above substituent group which may have.

A saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , and a carbon number which may be contained in an amino group which may be substituted on ring T ^2. The saturated hydrocarbon group of 1 to 20 may be linear, branched or cyclic. Examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a hexadecyl group. And a straight-chain alkyl group such as an icosyl group; and a branched-chain alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6.

Cyclic saturated hydrocarbon groups represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , and cyclic saturated hydrocarbon groups which may be possessed by an amino group which ring T ² may have May be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.
The saturated hydrocarbon groups represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ and the saturated hydrocarbon groups which the amino group which the ring T ² optionally has may have may be a methyl group , Ethyl, isopropyl, propyl, butyl, pentyl, hexyl, isobutyl, 2-ethylhexyl, cyclohexyl, adamantyl and the like.

The saturated hydrocarbon group represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ and the saturated hydrocarbon group which the amino group which ring T ² optionally has may have a substituent or It may have an unsubstituted amino group or a halogen atom as a substituent. Examples of the substituted amino group include an alkylamino group such as a methylamino group, a dimethylamino group, and a diethylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as a trifluoromethyl group, a perethyl group, and a perfluoropropyl group.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ include a linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ and having 1 carbon atom. To 8 groups.
The alkyl group having 1 to 10 carbon atoms represented by R ^57, the carbon number of the exemplified straight chain or branched chain saturated hydrocarbon groups as a saturated hydrocarbon group represented by R ^41. 1 to Ten groups are included.

When the saturated hydrocarbon group represented by R ^{41 to} R ⁴⁶ has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or —CO—. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms. In this case, the saturated hydrocarbon group is preferably a straight-chain or branched-chain saturated hydrocarbon group (ie, a straight-chain or branched-chain alkyl group), and is preferably a straight-chain saturated hydrocarbon group (ie, a straight-chain saturated hydrocarbon group). Alkyl group) is more preferred. The preferred carbon number of the saturated hydrocarbon group in which the methylene group may be replaced by an oxygen atom or -CO- is 2 to 10, more preferably 2 to 8. When the methylene group is replaced with an oxygen atom or -CO-, the number of carbon atoms between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is preferably Is 1 to 5, more preferably 2 to 3, and still more preferably 2.

Further, an aromatic hydrocarbon group which may have a substituent represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , and an amino group which may have a ring T ² have The aromatic hydrocarbon group which may be substituted (however, the aromatic hydrocarbon group may have a substituent) has preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. And more preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a terphenyl group, and preferably, a phenyl group, a naphthyl group, a tolyl group, It is a xylyl group, particularly preferably a phenyl group. Further, the aromatic hydrocarbon group may have one or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; number 1-6 alkylsulfonyl group; a methoxycarbonyl group, an alkoxycarbonyl group having 1 to 6 carbon atoms such as an ethoxycarbonyl _{^{group; -SO 3 -; -SO 2 -N}} - -SO 2 -R f; and the like , -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^f. However, -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -R ^f are directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, bonded to the aromatic hydrocarbon ring. It is preferable that a hydrogen atom is substituted.
Specific examples of the aromatic hydrocarbon group which may have a substituent include, for example, a group represented by the following formula. In the following formula, * represents a bond to a nitrogen atom.

R ^{41 to} R ⁴⁶ , an aralkyl group which may have a substituent represented by R ⁵⁹ and an aralkyl group which may be possessed by an amino group which ring T ² may have (however, the aralkyl group May have a substituent.) As the aromatic hydrocarbon group described above as a group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group). )), And the like. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and still more preferably 7 to 17 carbon atoms.

A ring formed by R ⁴¹ and R ⁴² with the nitrogen atom to which they are bonded, a ring formed by R ⁴³ and R ⁴⁴ with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ Examples of the ring formed together with the nitrogen atom to which they are bonded include a nitrogen-containing non-aromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring, and preferably a pyrrolidine ring and a piperidine ring. And a 4- to 7-membered ring having only one nitrogen atom as the hetero atom.

As R ⁵⁸ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent is preferable.
Among them, as R ^{41 to} R ⁴⁴ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable. And more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. R ⁵⁶ and R ^{58 to} R ⁶⁰ are more preferably groups represented by the following formula. In the following formula, * represents a bond to a nitrogen atom.

R ^{45 to} R ⁴⁶ each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, a group in which a methylene group constituting an alkyl group having 2 to 20 carbon atoms is replaced with an oxygen atom or —CO—, or It is preferably an aromatic hydrocarbon group which may have a group, or R ⁴⁵ and R ⁴⁶ are bonded to form a ring together with the nitrogen atom to which they are bonded. R ^{45 to} R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or a combination of R ⁴⁵ and R ⁴⁶ It is more preferable to form a 4- to 7-membered ring having only one nitrogen atom as a hetero atom, and each is independently represented by a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or the following formula: More preferably, it is a group. In the following formula, * represents a bond to a nitrogen atom.

A group in which the methylene group constituting the alkyl group having 2 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ is replaced with an oxygen atom or a group represented by —CO— ) Is a group in which the methylene group constituting the alkyl group having 2 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ is an oxygen atom or a group having 8 carbon atoms, The following groups are mentioned.

R ^{47 to} R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and are each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom. Is more preferable.
As the R ^57, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms are preferred.
The R ^61, a hydrogen atom is preferable.

^Examples of the r-valent metal ion represented by ^{Mr +} include alkali metal ions such as lithium ion, sodium ion, and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion; Transition metal ions such as titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion; zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion, etc. And the like. r is, for example, 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less.
As M ^{r +} , alkaline earth metal ions, typical metal ions and the like are more preferable, alkaline earth metal ions and zinc ions are more preferable, and alkaline earth metal ions are even more preferable.

In the formula (II), the number of ^{Mr +} is (k-1) / r. At this time, the compound (II) has a valence of 0, that is, an electrically neutral compound.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by ^Rf include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, Perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluorobutyl, trifluorobutyl , A tetrafluorobutyl group, a pentafluorobutyl group, a hexafluorobutyl group, a heptafluorobutyl group, an octafluorobutyl group, a perfluorobutyl group, and the like. Among them, the fluoroalkyl group represented by R ^f is preferably a perfluoroalkyl group. Further, the number of carbon atoms of the fluoroalkyl group represented by R ^f is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

In the formula (II), R ^{41 to} R ⁴⁴ , R ^{47 to} R ⁵⁴ and the ring T ² have at least one of —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f . The sum (k) of the number of —SO ₃ ^— and —SO ₂ —N ^—— SO ₂ —R ^f contained in R ^{41 to} R ⁴⁴ , R ^{47 to} R ⁵⁴ and ring T ¹ is preferably 1 to 7. , More preferably 2 to 7, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.

—SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f preferably satisfies at least one or more conditions selected from the following (Ia) to (Id). It is more preferable to satisfy at least one or more selected conditions.
(Ia) contained in any of the above R ^{47 to} R ⁵⁴ (Ib) any of C 6 to C 20 aromatic hydrocarbon groups which may have a substituent represented by R ^{41 to} R ⁴⁴ (Ic) bonded to any of the aralkyl groups having 7 to 30 carbon atoms which may have a substituent represented by R ^{41 to} R ^44. (Id) represented by T ² To any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which replace the hydrogen atoms of the aromatic heterocycle

However, when -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or an aralkyl group, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is preferably directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group or an aralkyl group. That is, it is preferable that —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f replaces a hydrogen atom bonded to the aromatic hydrocarbon ring.
—SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represented by R ^{41 to} R ⁴⁴ or R ⁴¹ to R ⁴⁴ . in the aromatic hydrocarbon ring in the aralkyl group of carbon atoms which may 7-30 have a substituent group representing R ⁴⁴ (e.g., benzene ring), it is attached at the para position relative to the bonding site to the nitrogen atom Is preferred.
When the compound (II) contains a plurality of —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f , the plurality of —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f are Although they may be bonded to the same aromatic hydrocarbon ring, they are preferably bonded to different aromatic hydrocarbon rings.

  Compound (II) preferably has no ethylenically unsaturated bond.

  The compound (II) is preferably a compound represented by the following formula (II-1) (hereinafter sometimes referred to as “compound (II-1)”).

[In the formula (II-1),
R ^{81 to} R ⁹⁰ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f .
k1 represents the sum of the number of —SO ₃ ^{— and} the number of —SO ₂ —N ^—— SO ₂ —R ^f of R ⁴¹ , R ⁴³ , R ^{47 to} R ⁵⁴ , R ^{81 to} R ⁹⁰ and the ring T ^2. Represent.
R ⁴¹ , R ⁴³ , R ^{47 to} R ⁵⁴ , T ² , M ^{r +} , r and R ^f are as defined above.
^{However, R 41, R 43, R} 47 ~R 54, R 81 ~R 90 and ring T ² are, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f. ]

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{81 to} R ⁹⁰ include the same groups as the groups exemplified as the saturated hydrocarbon group represented by R ⁴¹ . As R ^{81 to} R ⁹⁰ , a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f is preferable, and a hydrogen atom, —SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f is more preferred.

—SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f preferably satisfies at least one condition selected from (Ie) to (Ig), and is selected from (If) and (Ig). More preferably, at least one condition is satisfied, and more preferably the condition (If) is satisfied.
(Ie) Included in any of R ^{47 to} R ⁵⁴ (If) Included in any of R ^{81 to} R ⁹⁰ (Ig) C6 having 6 carbon atoms which replaces a hydrogen atom of the aromatic heterocyclic ring represented by T ² Bound to ~ 20 aromatic hydrocarbon groups

—SO ₃ ^— or —SO ₂ —N ^—— SO ₂ —R ^f more preferably satisfies the condition (If ′).
Included in either or both of (If ') R ⁸⁶ and R ⁸⁹

In formula ^{(II-1), R 41} , R 43, R 47 ~R 54, R 81 ~R 90 and ring T -SO ₃ ² has ^- the number of -SO ₂ -R ^{f -} and -SO ₂ -N (K1) is preferably 1 to 7, more preferably 1 to 4, and still more preferably 1 or 2.

  Examples of the compound (II) include the following compounds (compounds represented by formulas (AI-1) to (AI-13)).

なかでも、式（Ａ−Ｉ−７）が特に好ましい。

Among them, the formula (AI-7) is particularly preferred.

Colored Dispersion In producing the colored curable resin composition of the present invention, it is preferable that the colorant (A1) is dispersed in a solvent to prepare a colored dispersion. The colored dispersion may contain a colorant (A1), a solvent, a dispersant, and, if necessary, a resin. The colored dispersion, a resin (B), a polymerizable compound (C), and a polymerization initiator (D) and the like can be mixed to prepare a colored curable resin composition.

As the solvent, any solvent can be used as long as it can be used as the solvent (E) for the colored curable resin composition. Examples of the solvent include an ether ester solvent described below.
The content of the solvent in the colored dispersion is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 12 parts by mass with respect to 1 part by mass of the coloring agent (A1).

  In dispersing the colorant (A1) in a solvent to prepare a color dispersion, it is preferable to use a dispersant. As the dispersant, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acryl can be used. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by BASF), Ajispar (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (by Big Chemie), BYK (by Big Chemie) and the like.

  The content of the dispersant in the colored dispersion is, for example, 1 to 1000 parts by mass, preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the colorant (A1). Particularly preferably, it is 10 to 80 parts by mass.

  When preparing a colored dispersion by dispersing the coloring agent (A1) in a solvent, the colored dispersion is prepared by preliminarily or partially prescribing part or all, preferably part of the resin (B) contained in the curable resin composition. May be included. By including the resin (B) in advance, the dispersion stability of the colored curable resin composition can be further improved. The content of the resin (B) in the coloring dispersion is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the coloring agent (A1). It is.

  The content of the coloring agent (A1) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, based on the total amount of the coloring agent (A). Preferably it is 90 mass% or more.

The content of the coloring agent (A1) is preferably from 2 to 60% by mass, more preferably from 4 to 55% by mass, and still more preferably from 6 to 50% by mass, based on the total solid content of the colored curable resin composition. .
In addition, in this specification, the "total amount of solid content" means the total amount of components excluding the solvent from the colored curable resin composition of the present invention. The total amount of the solid content and the content of each component with respect to the solid content can be measured by known analytical means such as liquid chromatography and gas chromatography.

  It is preferable that the coloring agent (A) further contains a coloring matter (hereinafter, also referred to as a coloring agent (A2)) different from the coloring agent (A1).

The colorant (A2) may be either a dye or a pigment.
Examples of the dye include compounds classified as those having a hue other than pigment in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in Dyeing Note (Syokusensha). Can be Xanthene dyes are particularly preferred.

  A xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. Xanthene dyes include, for example, C.I. I. Acid Red 51 (hereinafter, CI Acid Red is omitted, and only the number is described. Others are the same), 52, 87, 92, 94, 289, 388, C.I. I. Acid violet 9, 30, 102, C.I. I. Basic Red 1 (rhodamine 6G), 2, 3, 4, 8, 10, 11, C.I. I. Basic violet 10 (rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Modern Red 27, C.I. I. Reactive Red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in JP-A-4492760. Those that dissolve in an organic solvent are preferred.

  Among these, as the xanthene dye, a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When using the compound (1a), the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye.

[In the formula (1a), R ^{a1 to} R ^a4 each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a substituent. It represents a monovalent aromatic hydrocarbon group carbon atoms which may 6-10, methylene group contained in the saturated hydrocarbon group, -O -, - CO- or -NR ^a11 - may be replaced by . R ^a1 and R ^a2 may together form a ring containing a nitrogen atom, and R ^a3 and R ^a4 may together form a ring containing a nitrogen atom.
R ^{a5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R a8, -SO 3 R a8 or -SO ₂ NR ^a9 represents R ^a10 .
R ^a6 and R ^a7 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, a plurality of R ^a5 may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ^a11 ) ₄ , Na ⁺ or K ⁺ , and the four R ^a11 may be the same or different.
R ^a8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ^a9 and R ^a10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and methylene contained in the saturated aliphatic hydrocarbon group; groups, -O -, - CO -, - NH- or -NR ^a8 - a tower may have I conversion, R ^a9 and R ^a10 are 3-10 membered rings containing nitrogen atoms bonded to each other It may form a heterocyclic ring.
^Ra11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (1a), when —SO ₃ ^— is present, the number thereof is preferably one.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{a1 to} R ^a4 include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R a8, -OH, -OR a8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - ^{_{CO 2 H, -CO 2 R a8}} , -SR a8, -SO 2 R a8, -SO 3 R a8 or -SO ₂ NR ^a9 R ^a10 and the like. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - preferably Z ⁺ and _{^{-SO 2 NR a9 R a10, -SO}} 3 - Z + and -SO ₂ NR ^a9 R ^a10 Is more preferred. The _{^{Z +, -SO 3 - - -SO}} 3 in this case + N (R ^a11) ₄ is preferred. When R ^{a1 to} R ^a4 are these groups, a color filter having less heat generation and having less heat generation can be formed from the colored curable resin composition of the present invention containing the compound (1a).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{a1 to} R ^a4 and R ^{a8 to} R ^a11 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. Linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; Examples thereof include an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.
The hydrogen atom contained in the saturated hydrocarbon group in R ^{a1 to} R ^a4 may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
The hydrogen atom contained in the saturated hydrocarbon group in R ^a9 and R ^a10 may be substituted with, for example, a hydroxy group or a halogen atom.

Examples of the ring formed by R ^a1 and R ^a2 together and the ring formed by R ^a3 and R ^a4 together include the following. In the formula, * represents a bond.

Examples of -OR ^a8 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

Examples of —CO ₂ R ^a8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of -SR ^a8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ^a8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
The -SO ₃ R ^a8, for example, methoxy sulfonyl group, ethoxysulfonyl group, propoxy sulfonyl group, tert- butoxysulfonyl group, and hexyloxy sulfonyl group and icosyl oxysulfonyl group.

As —SO ₂ NR ^a9 R ^a10 , for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl , N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2 An N-1-substituted sulfamoyl group such as, 2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl, N, N-ethylmethylsulfamoyl, N, N-diethylsulfamoyl, N, N-propylmethylsulfamoyl, N, N-isopropylmethylsulfamo Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.

R ^{a5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R a8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ^a9 are preferred, -SO _{3 ^{-, -SO 3 - Z +,}} -SO 3 H or -SO ₂ NHR ^a9 is more preferable.
m is preferably 1 to 4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in ^Ra6 and ^Ra7 include those having 1 to 6 carbon atoms among the above-described alkyl groups.

^Examples of the aralkyl group having 7 to 10 carbon atoms in Ra11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ^a11 ) ₄ , Na ⁺ or K ⁺ , and is preferably ⁺ N (R ^a11 ) ₄ .
As ⁺ N (R ^a11 ) ₄ , at least two of the four R ^a11 are preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ^a11 is preferably 20 to 80, 20 to 60 is more preferable. In the case where ⁺ N (R ^a11 ) ₄ is present in the compound (1a), when R ^a11 is any of these groups, a color filter containing few foreign substances is obtained from the colored curable resin composition of the present invention containing the compound (1a). Can be formed.

  Further, as the compound (1a), a compound represented by the formula (3a) (hereinafter, may be referred to as “compound (3a)”) is preferable. Compound (3a) may be a tautomer thereof.

[In the formula (3a), R ^a31 and R ^a32 independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group has 6 to 10 carbon atoms. And a hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms. a methylene group contained in the hydrogen group, -O -, - CO- or -NR ^a11 - may be replaced by.
R ^a33 and R ^a34 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ^a31 and R ^a33 may together form a ring containing a nitrogen atom, and R ^a32 and R ^a34 may together form a ring containing a nitrogen atom.
p and q each independently represent an integer of 0 to 5. When p is 2 or more, a plurality of ^Ra33 may be the same or different, and when q is 2 or more, a plurality of ^Ra34 may be the same or different.
^Ra11 has the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in ^Ra31 and ^Ra32 include groups having 1 to 10 carbon atoms among those in ^Ra8 .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent include the same groups as those described for R ^a1 .
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.
Preferably, R ^a31 and R ^a32 are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

^Examples of the alkyl group having 1 to 4 carbon atoms in ^Ra33 and ^Ra34 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
^Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for ^Ra33 and ^Ra34 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
^Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for ^Ra33 and ^Ra34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
^Ra33 and ^Ra34 are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

  p and q are preferably integers of 0 to 2, and preferably 0 or 1.

  Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-13).

  Further, a compound represented by any one of formulas (1-1) to (1-10) is also preferable in terms of excellent solubility in an organic solvent.

  As the xanthene dye, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink R-H / C” manufactured by Chugai Chemical Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. Further, it can be synthesized by using a commercially available xanthene dye as a starting material with reference to JP-A-2010-32999.

As other dyes, azo dye, cyanine dye, triphenylmethane dye, thiazole dye, oxazine dye, phthalocyanine dye, quinophthalone dye, anthraquinone dye, naphthoquinone dye, quinone imine dye, methine dye, azomethine dye, squarylium dye, acridine dye, A styryl dye, a coumarin dye, a quinoline dye, a nitro dye, or the like may be used, and each known dye is used.
Specific examples of such dyes include C.I. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 , 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
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, 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, 57, 66, 73, 76, 80, 88, 91, 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, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 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, 169, 173;
C. I. Acid Violet 6B, 7, 15, 16, 17, 19, 21, 23, 24, 25, 34, 38, 49, 72;
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, 29,234,236,242,243,256,259,267,269,278,280,285,290,296,315,324: 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, C. 104, 105, 106, 109, etc. I. Acid dyes,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 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, 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, 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, 77, 79, 82, etc. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27;
C. I. C. Disperse Blue 1, 14, 56, 60 and the like. I. Disperse dye,
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; I. Basic dyes,
C. I. Reactive yellow 2, 76, 116;
C. I. Reactive orange 16;
C. I. C. Reactive Red 36; I. Reactive dyes,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 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. Modern 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. A modant dye, C.I. I. Bat green 1 etc. I. Vat dyes and the like.

  Examples of the pigment include pigments classified into pigments according to the Color Index (published by The Society of Dyers and Colorists) (however, different from the compounds (I) and (II)). Can be illustrated.

Green pigment: C.I. I. Pigment Green 7, 36, 58, etc. Yellow pigment: 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, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc. Orange pigment: C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. Red pigment: C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Blue pigment: C . I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, etc. Purple pigment: C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. As these pigments, one kind or plural kinds of pigments may be used for each color, or pigments of each color may be combined.

  Among them, the pigment is preferably a blue pigment or a violet pigment, and more preferably C.I. I. Pigment Blue 15: 3, 15: 6 or C.I. I. Pigment Violet 23.

  If necessary, the pigment may be treated with rosin, a surface treatment using a pigment derivative having an acidic or basic group introduced, a grafting treatment on the pigment surface with a polymer compound, etc. A treatment, a washing treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed. The particle size of the pigment is preferably substantially uniform. The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by performing a dispersion treatment by including the pigment dispersant. Each of the pigments may be subjected to a dispersion treatment alone, or a mixture of a plurality of pigments may be subjected to a dispersion treatment.

  Examples of the pigment dispersant include the same as described above.

  When a pigment dispersant is used, its amount is preferably from 10 parts by mass to 200 parts by mass, more preferably from 15 parts by mass to 180 parts by mass, and still more preferably 20 parts by mass, per 100 parts by mass of the pigment. To 160 parts by mass. When the amount of the pigment dispersant is within the above range, a pigment dispersion having a more uniform dispersion state tends to be obtained when two or more pigments are used.

  When the coloring agent (A) includes the coloring agent (A2), the content of the coloring agent (A2) is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, based on the total amount of the coloring agent (A). , More preferably 1 to 10% by mass.

  The content of the coloring agent (A) in the colored curable resin composition is usually from 1% by mass to 70% by mass, and preferably from 7% by mass to 65% by mass, based on the total amount of solids. , More preferably 10% by mass or more and 60% by mass or less, particularly preferably 12% by mass or more and 57% by mass or less. When the content of the compound is within the above range, desired spectral and color densities are more easily obtained.

  The colorant (A) is preferably a compound represented by the formula (I) or a compound represented by the formula (II), preferably a compound represented by the formula (I), and a blue pigment or a xanthene dye. And preferably a combination of the compound represented by the formula (II) and a blue pigment or a xanthene dye.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; a structural unit derived from at least one type (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, A copolymer having a structural unit derived from a monomer (b) having a cyclic ether structure of (1) to (4) and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2]; a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (however, (a) and (b) A copolymer having a structural unit derived from the same (hereinafter sometimes referred to as “(c)”);
Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4]; a copolymer having a structural unit derived from (a) with (b) added thereto and a structural unit derived from (c);
Resin [K5]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);
Resin [K6]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic anhydride and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 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-cyclohexene dicarboxylic 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] Bicyclo unsaturated compounds containing a carboxy group such as hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate Kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
In this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”) and a monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”) and the like. No.

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

  (B1-1) includes glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl 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, 2,4,6- Tris (glycidyloxymethyl) styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), 3,4-epoxytricyclo [5.2.1. 0 ^2,6 ] decyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyloxyethyl (meth) acrylate, and the like.

  As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane And 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

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

  (B) is preferably (b1) in that the reliability of the obtained color filter, such as heat resistance and chemical resistance, can be further improved. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). 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, this is commonly used as "dicyclopentanyl (meth) acrylate". In the case of "tricyclodecyl (meth) acrylate" There is.), Bird Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylates;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 Dicarbonylimide derivatives such as -maleimidopropionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural units derived from each of the resins [K1] is as follows:
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
Is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (b); 50 to 90 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter are excellent. Tend.

  The resin [K1] can be obtained, for example, by the method described in the document "Experimental Method for Polymer Synthesis" (published by Takayuki Otsu, published by Kagaku Dojin, 1st Edition, 1st edition, March 1, 1972) and the literature. And can be produced with reference to the references described in the above.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by replacing oxygen with nitrogen to form a deoxygenated atmosphere, and while stirring, A method of heating and keeping the temperature is included. The polymerization initiator and the solvent used here are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like) Any solvent may be used as long as it can dissolve each monomer, and examples of the solvent (E) for the colored curable resin composition of the present invention include the solvents described below.

  The obtained copolymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. A thing may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the production process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the resins [K2] is defined as:
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
Is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K2] is in the above range, storage stability of the colored curable resin composition, developability when forming a colored pattern, and solvent resistance of the obtained color filter, It tends to have excellent heat resistance and mechanical strength.

  The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units derived from each of the resin [K3] is as follows:
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
Is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (c); 50 to 90 mol%
Is more preferable.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has a cyclic ether having 2 to 4 carbon atoms and (a) has a carboxylic acid and / or carboxylic anhydride. Can be produced by adding
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that of the resin [K3].

Next, the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is partially reacted with a cyclic ether having 2 to 4 carbon atoms of (b).
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b), a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, Tris ( A resin [K4] can be produced by putting a dimethylaminomethyl) phenol or the like) and a polymerization inhibitor (for example, hydroquinone) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours. it can.
(B) is preferably used in an amount of 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting the content in this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are well balanced. Tend. Since the reactivity of the cyclic ether is high and the unreacted (b) hardly remains, (b1) is preferably used as (b) used in the resin [K4], and more preferably (b1-1).
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

As the resin [K5], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing the resin [K1] described above. In the same manner as above, the obtained copolymer may be used as it is after the reaction, as a concentrated or diluted solution, or as a solid (powder) by reprecipitation or the like. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is, based on the total number of moles of all the structural units constituting the copolymer, respectively:
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
Is preferably
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (c); 10 to 90 mol%
Is more preferable.

Further, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). By reacting the product, resin [K5] can be obtained.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol per 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferably used as (b) used in the resin [K5], and more preferably (b1-1).

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. A carboxylic anhydride is reacted with a hydroxy group generated by a reaction between a cyclic ether and a carboxylic acid or a carboxylic anhydride.
Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol per 1 mol of the (a) used.

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 ] Resin [K1] such as decyl 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 acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^{2, 6]} decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleimide / 2-hydroxyethyl (meth) acrylate Resin [K2] such as copolymers of 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene and copolymers of benzyl (meth) acrylate / (meth) acrylic acid Resin [K3] such as styrene / (meth) acrylic acid copolymer; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer; tricyclodecyl (meth) A) acrylate / styrene / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate is added; tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer to glycidyl ( Resin [K4] such as resin to which meth) acrylate is added; tricyclodecyl (meth) acrylate A resin in which (meth) acrylic acid is reacted with a copolymer of / glycidyl (meth) acrylate, and a resin in which tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate is reacted with (meth) acrylic acid [K5], such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further reacting tetrahydrophthalic anhydride Resin [K6].
Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K2] is particularly preferable.

  The weight average molecular weight in terms of polystyrene of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.

  The degree of dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, and more preferably from 1.2 to 4.

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

  The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film ratio of the colored pattern tend to be improved.

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) 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, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.
Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

  The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of solids. is there. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound.

The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

  Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-dioxacyclopentanylmethyloxy) benzoyl {-9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01 and OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, O-acyl oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferable, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octan-1-one-2-imine is more preferred. With these O-acyl oxime compounds, a color filter with high brightness tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

  Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one And the like. Commercial products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyldimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  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-methoxy (Styryl) -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- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheni ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

  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 (for example, see JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-Tetraphenylbiimidazole, 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 (trial (Xyphenyl) biimidazole (for example, see JP-B-48-38403 and JP-A-62-174204), wherein the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group. And biimidazole compounds (for example, see JP-A-7-10913).

  Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone; Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with the later-described polymerization initiator (D1) (particularly amines).

  Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and 4-acetoxy Onium salts such as phenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound and a biimidazole compound is preferable. Polymerization initiators containing a polymer compound are more preferred.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts by weight. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

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

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like, among which 4,4′-bis (diethylamino) benzophenone is preferable. A commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry 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-di. Butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

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

  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, Examples include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

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

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), and an ether ester solvent (a solvent containing -COO- in the molecule) , A solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (containing OH in the molecule, -O-,- Solvents that do not contain CO— and —COO—), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

  Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

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

  Examples of the ketone solvent 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 the like.

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

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

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

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

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

<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 a molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK). .

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

  Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

  The content of the leveling agent (F) is preferably from 0.001% by mass to 0.2% by mass, more preferably from 0.002% by mass to 0.2% by mass, based on the total amount of the colored curable resin composition. It is at most 1 mass%, more preferably at least 0.01 mass% and at most 0.05 mass%. The content does not include the content of the pigment dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Compound (G)>
The colored curable resin composition of the present invention contains a compound containing cobalt (III). Compound (G) contains a carbon atom, and the maximum value of the molar extinction coefficient in the visible light region of the compound containing cobalt (III) is smaller than the maximum value of the molar extinction coefficient of the colorant in the visible light region. By containing the compound containing cobalt (III), it is possible to improve the solubility in a developer and to improve the persistence of the peeled pieces.
The compound containing cobalt (III) may be a metal complex, a metal salt, or the like, or may be a compound that dissolves in an organic solvent.
It is preferable that the colored curable resin composition of the present invention does not contain a compound containing cobalt (II). It may contain an agent.

  The maximum value of the molar extinction coefficient ε in the visible light region (wavelength 400 nm to 780 nm) is obtained by diluting 0.1 g of a compound containing cobalt (III) to 0.100 L with propylene glycol monomethyl ether acetate to prepare a solution. Is measured by measuring the absorption spectrum in the visible light region with an ultraviolet-visible spectrophotometer and calculating using Lambert-Beer's law.

The maximum value of the molar extinction coefficient ε in the visible light region of the compound containing cobalt (III) is smaller than the maximum value of the molar extinction coefficient ε in the visible light region of the coloring agent contained in the colored curable resin composition of the present invention, Preferably it is 0 or more and 1000 or less, more preferably 0 or more and 500 or less.
When the maximum value of the molar extinction coefficient ε in the visible light region is 1000 or less, the brightness of the color filter tends to increase, which is preferable.
The maximum value of the molar extinction coefficient ε in the visible light region of the colorant is determined by diluting 0.01 g of the colorant to 0.100 L with propylene glycol monomethyl ether acetate to prepare a solution, and then visualizing the solution with an ultraviolet-visible spectrophotometer. It is determined by measuring the absorption spectrum in the light region and calculating using Lambert-Beer's law.
The maximum value of the molar extinction coefficient ε in the visible light region of a coloring agent (preferably a triarylmethane lake, more preferably a compound represented by the formula (I) or a compound represented by the formula (II)) exceeds 1000, for example. It is 500,000 or less, preferably 5,000 to 300,000, more preferably 7000 to 200,000, further preferably 9000 to 150,000.

  The compound containing cobalt (III) is preferably a compound represented by Formulas (F1) to (F3) from the viewpoint of improving solubility.

[In the formulas (F1) to (F3), X ¹ and X ² independently represent an oxygen atom and a sulfur atom, and Z ¹ represents a carbon atom or a sulfur atom.
R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a halogen atom or an amino group optionally having a monovalent substituent.
R ² and R ³ independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
X ³ and X ⁴ independently represent an oxygen atom, a nitrogen atom or a carbonyl-containing group.
R ^{4 to} R ⁷ independently represent a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms. In addition, adjacent substituents of R ⁴ and R ⁵ , or R ⁵ and R ⁶ , or R ⁶ and R ⁷ may be closed to form a ring.
M ^{1 to} M ³ represent cobalt (III).
a, b and d represent an integer of 3, and when a is an integer of 3, a plurality of R ¹ may be the same or different from each other; and when b is an integer of 3, a plurality of R 1 ² and R ³ may be the same or different from each other, and when d is an integer of 3, a plurality of R ^{4 to} R ⁷ may be the same or different from each other. c represents an integer of 0 to 6. ]

The aliphatic hydrocarbon group for R ¹ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Examples of the halogen atom for R ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R ¹ is preferably an alkyl group having 1 to 20 carbon atoms.
Examples of the amino group represented by R ¹ include a monoalkylamino group and a dialkylamino group. Examples of the alkyl group in the monoalkylamino group and the dialkylamino group include an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, and a butyl group).
The aliphatic hydrocarbon group for R ² and R ³ is preferably an alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
The aromatic hydrocarbon group for R ² and R ³ is preferably a phenyl group or a naphthyl group.
R ² and R ³ are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. Is still more preferable, and an alkyl group having 1 to 6 carbon atoms is still more preferable. R ² and R ³ may be the same or different.
c is preferably from 0 to 1, and more preferably 0.
Examples of the carbonyl-containing group represented by X ³ and _{^{X 4, - (CO) m1}} - (O) m2 - (CH 2) m3 - [m1 and m2 represents 0 or 1, m3 is 0 to 4 integer Represents Here, the sum of m1, m2 and m3 represents an integer of 1 to 6, and-(CO) _m1 -is bonded to the benzene ring. _{], - (O) m4 -} (CO) m5 - (CH 2) m6 - [m4 and m5 each represent 0 or 1, m6 is an integer of 0-4. Here, the sum of m4, m5 and m6 represents an integer of 1 to 6, and-(O) _m4 -is bonded to the benzene ring. And the like.
X ³ and X ⁴ are preferably each independently —CO—O— or —O—.
Examples of the ring formed by bonding two adjacent substituents among R ^{4 to} R ⁷ include a benzene ring, a naphthalene ring, and a cycloalkane ring.
Examples of the aliphatic hydrocarbon group represented by R ^{4 to} R ⁷ include an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
Among them, the compound containing cobalt (III) is particularly preferably a compound represented by the formula (F2).

The maximum value of the molar extinction coefficient ε has a correlation with the structure (eg, molecular weight) of the compound, and as the molecular weight increases, the molar extinction coefficient tends to increase.
The molecular weight of the compound containing cobalt (III) is preferably 260 or more, more preferably 270 or more, and further preferably 295 or more. The upper limit of the molecular weight is not particularly limited, and is, for example, about 5000 or less, about 3000 or less, or about 1000 or less.

  The other compound containing cobalt (III) may be a complex in which an amino group (preferably ammonia) is coordinated with cobalt (III), or a chloride thereof.

  The compound containing cobalt (III) preferably has a monodentate ligand or a bidentate ligand from the viewpoint of improving the light resistance of the obtained cured film.

Examples of the compound containing cobalt (III) having the ligand include hexaammine cobalt (III) chloride, tris (2,4-pentanedionato) cobalt (III), and the like.
As the compound containing cobalt (III), only one kind may be used, or two or more kinds may be used in combination.

The content of the compound containing cobalt (III) is preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the colored curable resin composition. Yes, more preferably 0.5 to 15% by mass, particularly preferably 1 to 10% by mass. When the content of the compound containing cobalt (III) is within the above range, the solubility in the developer and the suppression of the generation of peeled pieces can be significantly improved.
The content of the compound containing cobalt (III) is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 17 parts by mass, when the total amount of the coloring agent is 100 parts by mass. And more preferably 0.5 to 15 parts by mass.

<Other ingredients>
The colored curable resin composition of the present invention, if necessary, fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention is used, for example, as a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a compound (G), and if necessary. It can be prepared by mixing the solvent (E), the leveling agent (F), the polymerization initiator (D1) and other components.
The colorant (A) is preferably prepared using the above-described colored dispersion or pigment dispersion. The desired colored curable resin composition can be prepared by mixing the remaining components into a colored dispersion or pigment dispersion so as to have a predetermined concentration.
When the dye is contained, the solution may be prepared by dissolving the dye in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<Production method of color filter>
Examples of a method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, exposed to light through a photomask, and developed. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or the colored coating film thus formed is the color filter of the present invention.
The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted depending on the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 20 μm. ６6 μm.

  Examples of the substrate include quartz glass, borosilicate glass, alumina silicate glass, a glass plate such as soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and the like. Formed with a thin film of aluminum, silver, silver / copper / palladium alloy, or the like. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used device or condition. For example, it can be manufactured as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and dried to obtain a smooth colored 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 in the case of performing heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.
When performing drying under reduced pressure, it is preferable to perform drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.
The thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, and light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like can be mentioned.
Use of an exposure device such as a mask aligner and a stepper can uniformly irradiate a parallel light beam on the entire exposed surface or perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer by contacting it with a developer. By the development, the unexposed portions of the colored composition layer are dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. 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 inclined at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Further, it is preferable to perform post-baking on the obtained colored pattern. The postbake temperature is preferably from 150 to 250C, more preferably from 160 to 235C. The post-bake time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

  According to the colored curable resin composition of the present invention, the color filter is excellent in solubility in a developing solution in particular, and a peeled piece is less likely to remain. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging device.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the examples, percentages and parts representing contents or amounts used are based on mass unless otherwise specified.
In the following, the structure of the compound was confirmed by mass spectrometry (LC; 1200 type from Agilent, MASS; LC / MSD type from Agilent).

[Synthesis Example 1]
The following reactions were performed under a nitrogen atmosphere. 50 parts of the compound represented by the formula (C-I-2) and 188 parts of N, N-dimethylformamide were charged into a flask equipped with a condenser and a stirrer, and the mixture was stirred for 30 minutes while cooling in an ice bath. 40 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into the flask, and the mixture was further stirred for 1 hour while cooling in an ice bath. While the reaction solution was ice-cooled, 55.6 parts of iodoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. The reaction solution was heated to 35 ° C. using an oil bath, stirred for 5 hours, and allowed to cool to room temperature. 1000 parts of a 10% aqueous solution of sodium chloride was charged into another flask equipped with a stirrer, and the reaction solution was added dropwise with stirring. After stirring for 30 minutes, the mixture was filtered to obtain a solid. The obtained solid was washed three times with 500 parts of ion-exchanged water and dried under reduced pressure at 60 ° C. to obtain 53.0 parts of a compound represented by the formula (BP-2) (yield 93.5%). ).

  The following reactions were performed under a nitrogen atmosphere. 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were charged into a flask equipped with a condenser and a stirrer, and then stirred at room temperature for 30 minutes. After 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. After 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 30 minutes, the mixture was stirred at room temperature for 1 hour. An aqueous solution in which 79.2 parts of sodium monochloroacetate was dissolved in 120 parts of ion-exchanged water was charged into the flask, and 60.4 parts of a 30% aqueous sodium hydroxide solution was charged, followed by stirring at room temperature for 18 hours. After further adding 600 parts of ion-exchanged water to the flask, the mixture was stirred for 1 hour, and the precipitated yellow-white solid was collected by filtration. The obtained yellow-white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. A yellow-white solid after washing, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene were charged into a flask equipped with a stirrer, and the mixture was added at room temperature for 2 hours. Stirred. To this, 80.8 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. After 156 parts of ion-exchanged water was added to the obtained organic layer for liquid-separation washing, 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid-separation washing. The obtained organic layer was concentrated using an evaporator, and then dried under reduced pressure at 35 ° C. to obtain a compound represented by the formula (BI-2) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

  The following reactions were performed under a nitrogen atmosphere. 13.2 parts of the compound represented by the formula (BP-2), 19.0 parts of the compound represented by the formula (BI-2) and 38 parts of toluene are charged into a flask equipped with a condenser and a stirring device. Then, 9.2 parts of phosphorus oxychloride was added, and the mixture was stirred at 100 ° C for 7 hours. Then, the reaction mixture was cooled to room temperature and diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of a 35% hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. After evaporating the solvent of the obtained organic layer with an evaporator, the compound was dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (X0) as a blue-violet solid. The yield of blue-violet solid was 39.4 parts.

  The following reactions were performed under a nitrogen atmosphere. A flask equipped with a condenser and a stirring device was charged with 38.4 parts of the compound represented by the formula (X0) and 112 parts of methylene chloride, and stirred for 30 minutes. After adding 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) while cooling the reaction solution on ice and keeping the internal temperature at 10 ° C., the reaction solution was heated to room temperature and stirred for 9 hours. Next, the reaction solution was ice-cooled and diluted with a mixed solution of 64 parts of N, N-dimethylformamide and 4.9 parts of ion-exchanged water while keeping the internal temperature at 10 ° C. After pouring the diluted reaction solution into 1120 parts of toluene, the mixture was stirred for 30 minutes to precipitate a viscous solid. After discharging the oil layer by decantation, 320 parts of toluene was added to the obtained viscous solid, followed by stirring for 30 minutes. The oil layer was discharged by decantation, and 832 parts of 20% saline was added to the obtained viscous solid, followed by stirring for 1 hour. Then, a blue solid was collected by filtration. The obtained blue solid was washed with 576 parts of 20% saline and dried at 35 ° C. under reduced pressure. The obtained solid and 128 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, filtered, and separated into a solid and a filtrate. This filtrate is referred to as filtrate A3. The collected solid was washed with 192 parts of methanol, and separated into a solid and a filtrate by filtration. This filtrate is referred to as filtrate B3. After the filtrate A3 and the filtrate B3 were mixed and the solvent was removed with an evaporator, the mixture was dried under reduced pressure at 40 ° C. to obtain a compound represented by the formula (X1) as a blue-violet solid. The yield of blue-violet solid was 38.3 parts.

  28.0 parts of the compound represented by the formula (X1), 43.2 parts of barium chloride dihydrate and 356 parts of ion-exchanged water are added to a flask equipped with a condenser and a stirring device, and the mixture is stirred at 40 ° C. for 2 hours. After that, the reaction suspension was filtered. The filtered solid and 350 parts of ion-exchanged water were charged into a flask equipped with a stirrer, stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water, and then dried under reduced pressure at 60 ° C. to obtain a compound represented by the formula (a2) as a blue-violet solid. The yield was 24.5 parts and the yield was 81.7%.

Identification of Compound Represented by Formula (a2) (Mass Spectrometry) Ionization Mode = ESI−: m / z = 949.5 [M−Ba + 2H] ⁻
Exact Mass [M-Ba]: 947.28

[Synthesis Example 2]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and heated to 85 ° C. with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] dec-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 25 parts of a mixture of deca-9-yl acrylate (content is 1: 1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate is dropped over 5 hours. did. On the other hand, a mixed solution in which 5 parts of 2,2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH / g. Resin (B-1) has the following structural units.

[Synthesis Example 3]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to form a nitrogen atmosphere. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate and 3,4-epoxytricyclo [5.2. A solution prepared by dissolving 289 parts of a mixture of 1.0 ^2,6 ] decane-9-yl acrylate (content ratio: 1: 1) in 125 parts of propylene glycol monomethyl ether acetate was dropped using a dropping pump over about 5 hours. . On the other hand, a solution prepared by dissolving 33 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over about 6 hours using another dropping pump. did. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. Resin (B-2) 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.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Tosoh Corporation)
The ratio of the polystyrene-equivalent weight average molecular weight and number average molecular weight (Mw / Mn) obtained above was defined as the degree of dispersion.

[Preparation of colored dispersion liquid 1]
21. 51.2 parts of a compound represented by the formula (a1) (synthesized according to the method described in JP-A-2015-38201) and 21. a dispersant (BYKLPN-6919, a 60% solution of propylene glycol monomethyl ether acetate manufactured by BYK). 4 parts, 20.5 parts of resin (B-2) (in terms of solid content), 334 parts of propylene glycol monomethyl ether acetate are mixed, 600 parts of 0.4 μm zirconia beads are added, and a paint conditioner (manufactured by LAU) is used. And shaken for 1 hour. Thereafter, the zirconia beads were removed by filtration to obtain a colored dispersion 1.

[Preparation of colored dispersion liquid 2]
21.3 parts of the compound represented by the formula (a2), 26.7 parts of a dispersant (BYKLPN-6919, manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate), and resin (B-2) (in terms of solid content). 5.3 parts, diacetone alcohol 26.7 parts and propylene glycol monomethyl ether acetate 187 parts were mixed, 600 μm of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). did. Thereafter, the zirconia beads were removed by filtration to obtain a colored dispersion 2.

[Preparation of pigment dispersion 3]
C. I. 26.2 parts of CI Pigment Blue 15: 6 (pigment), 9.2 parts of an acrylic pigment dispersant (in terms of solid content), 197 parts of propylene glycol monomethyl ether acetate, and 20 parts of ethyl lactate. Thus, the pigment was sufficiently dispersed to obtain a pigment dispersion 3.

[Examples 1 to 6, Comparative Example 1]
(Preparation of colored curable resin composition)
The components shown in Table 4 were mixed to obtain each colored curable resin composition.

-Colorant (A-4): a compound represented by the formula (3-44) (compound synthesized according to the method described in JP 2013-68941 A)

-Resin (B): Resin (B-1) (in terms of solid content)
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; oxime compound)
-Solvent (E):
Solvent (E-1): Ethyl lactate Solvent (E-2): Propylene glycol monomethyl ether acetate / leveling agent (F): Polyether-modified silicone oil (solid content)
(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
-Compound (G):
Compound (G-1): Tris (2,4-pentanedionato) cobalt (III); manufactured by Tokyo Chemical Industry Co., Ltd.)
Compound (g-1): bis (2,4-pentanedionato) cobalt (II); manufactured by Tokyo Chemical Industry Co., Ltd.)

[Calculation of molar extinction coefficient]
In a volumetric flask, 0.1 g of each of the compounds (G-1) shown in Table 4 was weighed, and then diluted with propylene glycol monomethyl ether acetate to 0.10 L. Similarly, 0.01 g of each of the compounds represented by the formulas (a1) and (a2) was weighed, and then diluted with diacetone alcohol to 0.10 L. The absorption spectra of these solutions were measured with an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), and the visible light region was determined using Lambert-Beer's law. (400 nm to 780 nm), the maximum value of the molar extinction coefficient ε was calculated. Table 5 shows the results.

<Evaluation of developer solubility>
A colored curable resin composition is applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating so that the film thickness after post-baking is 2.0 μm, and then is applied at 100 ° C. for 3 minutes. By pre-baking, a composition layer was formed.
The substrate on which the composition layer was formed was immersed and developed in a Petri dish containing 50 ml of an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. The time at which the portion 20 mm from the end of dissolution was completed was defined as the development time.
Further, the developer after immersion was visually observed, and was evaluated as “O” when no peeled pieces derived from the colored curable resin composition were observed in the developer, and as “Poor” when peeled pieces were observed. It is not preferable that peeled pieces derived from the colored curable resin composition are observed in the developer, as foreign matters adhering to the pattern and causing defects. Table 4 shows the results.

Claims (5)

  It contains a colorant, a resin, a polymerizable compound, a polymerization initiator and a compound containing cobalt (III), wherein the colorant contains a triarylmethane lake, and the molar extinction coefficient of the compound containing cobalt (III) in the visible light region. A colored curable resin composition having a maximum value smaller than the maximum value of the molar extinction coefficient in the visible light region of the colorant. The colored curable resin composition according to claim 1, wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II).

[In the formula (I),
R ^{11 to} R ¹⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent or a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group is a substituted or unsubstituted amino group or It may be substituted by a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted by an oxygen atom or -CO- . However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms.
R ¹¹ and R ¹² may be bonded to form a ring together with the nitrogen atom to which they are bonded, or R ¹³ and R ¹⁴ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ¹⁷ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy group, an alkyl group having 1 to 8 carbon atoms, a methylene group constituting the alkyl group is an oxygen atom or -CO- May be substituted. R ¹⁸ and R ²² may combine with each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon ring having 6 to 10 carbon atoms which may have a substituent.
[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen.
m represents an arbitrary natural number.
When one molecule includes a plurality of structures represented by the following formulas, they may have the same structure or different structures.

Wherein ring T ¹ , R ^{11 to} R ¹⁴ and R ^{17 to} R ²⁴ are as defined above. ]]

[In the formula (II),
R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or Represents an aralkyl group having 7 to 30 carbon atoms which may have a group, wherein the aromatic hydrocarbon group and a substituent which the aralkyl group may have are -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^f, hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group, or a halogen atom, the carbon of the saturated hydrocarbon group When the number is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms. R ⁴¹ and R ⁴² may combine to form a ring together with the nitrogen atom to which they bind, or R ⁴³ and R ⁴⁴ may combine to form a ring together with the nitrogen atom to which they bind.
R ⁴⁷ to R ⁵⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, hydroxy _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or alkyl of 1 to 8 carbon atoms A methylene group constituting the alkyl group may be replaced by an oxygen atom or —CO—, and R ⁴⁸ and R ⁵² are bonded to each other to form —NH—, —S—, or —SO— _2- may be formed.
However, in the alkyl group, adjacent methylene groups are not simultaneously substituted with oxygen atoms.
Ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms or an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and the aromatic heterocyclic ring and the aromatic hydrocarbon ring have 1 to 20 carbon atoms. It may have a saturated hydrocarbon group, a substituted or unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^{f.
Mr +} represents an r-valent metal ion.
k represents the sum of the number of —SO ₃ ^{— and} the number of —SO ₂ —N ^—— SO ₂ —R ^f of R ^{41 to} R ⁴⁴ , R ^{47 to} R ⁵⁴ and ring T ² .
r represents an integer of 1 or more.
R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.
^{However, R 41 ~R 44, R 47} ~R 54 and ring T ² are, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f.
When one molecule includes a plurality of structures represented by the following formulas, they may have the same structure or different structures.

Wherein ring T ² , R ^{41 to} R ⁴⁴ and R ^{47 to} R ⁵⁴ are as defined above. ]]   3. The colored curable resin composition according to claim 1, further comprising a dye different from the triarylmethane lake.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 4.