JP2018131490A - Colored resin composition - Google Patents

Abstract

Provided is a colored resin composition capable of forming a color filter having excellent light resistance. A resin composition containing a colorant represented by the formula (AI) [R41 to R44 is H, hydrocarbon group, etc .; R45 to R52 are H, halogen, hydroxy, etc .; An unsubstituted aromatic hydrocarbon ring or a substituted / unsubstituted aromatic heterocycle; when it has a pre-substituent, the aromatic hydrocarbon ring and the aromatic heterocycle have two or more halogen atoms; [Y] m -Is an arbitrary m-valent anion containing at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen] [Selection] None

Description

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

  Color filters used in liquid crystal display devices, electroluminescence display devices, plasma display devices and other solid-state imaging devices such as CCDs and CMOS sensors are manufactured from colored resin compositions. As such a colored resin composition, a colored resin composition containing a compound represented by the following formula as a colorant is known (Patent Document 1: Examples 29 to 32, Formula (AI-18). ).

Japanese Patent Laid-Open No. 2006-88894

  The present invention provides a colored resin composition capable of forming a color filter having excellent light resistance.

［式（Ａ−Ｉ）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く、末端のメチレン基が酸素原子又は−ＣＯ−に置換されることはない。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。
Ｒ⁴⁵〜Ｒ⁵²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、該アルキル基の炭素数が２〜８である場合、該アルキル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１〜８の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く、末端のメチレン基が酸素原子又は−ＣＯ−に置換されることはない。Ｒ⁴⁶とＲ⁵⁰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芳香族炭化水素環又は置換基を有していてもよい芳香族複素環を表し、該置換基を有していてもよい芳香族炭化水素環及び該置換基を有していてもよい芳香族複素環は、ハロゲン原子を２個以上有する。
［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カチオン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、Ｒ⁴¹〜Ｒ⁴⁴及びＲ⁴⁵〜Ｒ⁵²は、それぞれ、上記と同義である。］］
［２］ 環Ｔ¹が、式（Ａｂ２−ｘ１）で表される環である［１］記載の着色樹脂組成物。

［式（Ａｂ２−ｘ１）中、Ｒ⁵⁵は、置換基を有していてもよい芳香族炭化水素基を表し、該芳香族炭化水素基は、ハロゲン原子を２個以上有する。
Ｒ⁵³及びＲ⁵⁴は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数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。Ｒ⁵³とＲ⁵⁴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。
環Ｔ²は、芳香族炭化水素環又は芳香族複素環を表す。
＊は、式（Ａ−Ｉ）における環Ｔ¹が結合する炭素との結合手を表す。］
［３］ さらに、重合性化合物及び重合開始剤を含む［１］又は［２］記載の着色樹脂組成物。
［４］ ［１］〜［３］のいずれか記載の着色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 colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the formula (AI).

[In the formula (AI),
R ^{41 to} R ⁴⁴ each independently represents 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 optionally substituted aralkyl group having 7 to 30 carbon atoms, 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 with 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 with 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, and terminal methylene groups are not substituted with oxygen atoms or —CO—. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and when the alkyl group has 2 to 8 carbon atoms, The methylene group contained in the alkyl group may be substituted with an oxygen atom or —CO—. However, in the alkyl group having 1 to 8 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and the terminal methylene group is not substituted with oxygen atoms or —CO—. R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent, and the aromatic hydrocarbon which may have this substituent The aromatic heterocyclic ring which may have a ring and the substituent has two or more halogen atoms.
[Y] ^m− represents an arbitrary 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 a plurality of cations represented by the following formula are contained in one molecule, they may be the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{45 to} R ⁵² have the same meanings as described above, respectively. ]]
[2] The colored resin composition according to [1], wherein the ring T ¹ is a ring represented by the formula (Ab2-x1).

[In the formula (Ab2-x1), R ⁵⁵ represents an aromatic hydrocarbon group which may have a substituent, and the aromatic hydrocarbon group has two or more halogen atoms.
R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a C 6 to 20 carbon atom which may have a substituent. An aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, included in the saturated hydrocarbon group The methylene group may be substituted with an oxygen atom or -CO-. R ⁵³ and R ⁵⁴ may combine to form a ring together with the nitrogen atom to which they are bonded.
Ring T ² represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
* Represents a bond to the carbon to which the ring T ¹ in Formula (AI) is bonded. ]
[3] The colored resin composition according to [1] or [2], further comprising a polymerizable compound and a polymerization initiator.
[4] A color filter formed from the colored 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 this invention, the colored resin composition which can form the color filter which has favorable light resistance is provided.

<Colored resin composition>
The colored resin composition of the present invention includes a colorant (A) and a resin (B), and includes a compound represented by the formula (AI) as the colorant (A).
The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).
The colored resin composition of the present invention may further contain a polymerization initiation assistant (D1), a solvent (E), and a leveling agent (F).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colored resin composition of the present invention contains a compound represented by the formula (AI) (hereinafter may be referred to as compound (AI)) as the colorant (A).

［式中、環Ｔ¹、Ｒ⁴¹〜Ｒ⁴⁴及びＲ⁴⁵〜Ｒ⁵²は、それぞれ、上記と同義である。］］ [In the formula (AI),
R ^{41 to} R ⁴⁴ each independently represents 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 optionally substituted aralkyl group having 7 to 30 carbon atoms, 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 with 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 with 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, and terminal methylene groups are not substituted with oxygen atoms or —CO—. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and when the alkyl group has 2 to 8 carbon atoms, The methylene group contained in the alkyl group may be substituted with an oxygen atom or —CO—. However, in the alkyl group having 1 to 8 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and the terminal methylene group is not substituted with oxygen atoms or —CO—. R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent, and the aromatic hydrocarbon which may have this substituent The aromatic heterocyclic ring which may have a ring and the substituent has two or more halogen atoms.
[Y] ^m− represents an arbitrary 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 a plurality of cations represented by the following formula are contained in one molecule, they may be the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{45 to} R ⁵² have the same meanings as described above, respectively. ]]

The aromatic hydrocarbon ring represented by ring T ¹ may be either a single ring or a condensed ring, and has 6 to 6 carbon atoms such as benzene, toluene, xylene, naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, and the like. There are 20 aromatic hydrocarbon groups.
Examples of the substituent that the aromatic hydrocarbon ring may have include a halogen atom, a cyano group, and a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent (preferably 1 to 1 carbon atoms). 20 alkyl groups), or an amino group which may have a substituent.

The aromatic heterocyclic ring represented by the ring T ¹ may be either a monocyclic ring or a condensed ring, and is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. The aromatic heterocyclic ring represented by ring T ¹ has 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms.
As the monocyclic aromatic heterocycle, a 5-membered ring having a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring;
A 5-membered ring having an oxygen atom or sulfur atom, such as a furan ring or a thiophene ring;
A 6-membered ring having a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring;
As the condensed aromatic heterocyclic ring, a condensed ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, a quinoline ring;
And a ring having an oxygen atom or a sulfur atom such as a benzofuran ring.
Examples of the substituent that the aromatic heterocyclic ring may have include a halogen atom, a cyano group, and a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent (preferably having 1 to 20 carbon atoms). Alkyl group), an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an amino group which may have a substituent.

The aromatic hydrocarbon ring which may have a substituent in the ring T ¹ and the aromatic heterocyclic ring which may have a substituent preferably have two or more halogen atoms. It means that the hydrogen atom contained in the aromatic hydrocarbon ring which may be substituted and the aromatic heterocyclic ring which may have a substituent is substituted with two or more halogen atoms, more preferably the above aromatic It means that the aromatic hydrocarbon ring and the aromatic heterocyclic ring have a substituent, and the hydrogen atom contained in the substituent is substituted with two or more halogen atoms. The halogen atom included in the ring T ¹ is preferably a fluorine atom, a chlorine atom, and a bromine atom, and more preferably a fluorine atom. The number of halogen atoms is preferably 5 or less, more preferably 3 or less, and even more preferably 2.

Ring T ¹ is more preferably a ring represented by the formula (Ab2-x1).

[In the formula (Ab2-x1), R ⁵⁵ represents an aromatic hydrocarbon group which may have a substituent, and the aromatic hydrocarbon group has two or more halogen atoms.
R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a C 6 to 20 carbon atom which may have a substituent. An aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, included in the saturated hydrocarbon group The methylene group may be substituted with an oxygen atom or -CO-. R ⁵³ and R ⁵⁴ may combine to form a ring together with the nitrogen atom to which they are bonded.
Ring T ² represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
* Represents a bond to the carbon to which the ring T ¹ in Formula (AI) is bonded. ]

The aromatic hydrocarbon group which may have a substituent for R ⁵⁵ has two or more halogen atoms, preferably that the hydrogen atom contained in the aromatic hydrocarbon group which may have a substituent is It means that it is substituted with 2 or more halogen atoms. Halogen atom R ⁵⁵ has is preferably a fluorine atom, a chlorine atom, and bromine atom, more preferably a fluorine atom. The number of halogen atoms is preferably 5 or less, more preferably 3 or less, and even more preferably 2.

The aromatic hydrocarbon ring and aromatic heterocycle represented by the ring T ² are the same as the ring exemplified for the ring T ¹ . Among them, the ring T ² is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

Ring T ¹ is more preferably a ring represented by the formula (Ab2-y1).

[In the formula (Ab2-y1), R ^{53 to} R ⁵⁵ and * are as defined above. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁴ and R ^{53 to} R ⁵⁴ may be linear, branched or cyclic. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. is there.
Examples of the linear or branched saturated hydrocarbon group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. A branched alkyl group such as an isopropyl group, an isobutyl group, and a 2-ethylhexyl group; The carbon number of the linear or branched saturated hydrocarbon is preferably 1-8, more preferably 1-6, and still more preferably 1-4.
The cyclic saturated hydrocarbon group 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. Carbon number of a cyclic saturated hydrocarbon group becomes like this. Preferably it is 3-10, More preferably, it is 6-10.

The alkyl group having 1 to 8 carbon atoms represented by R ^{45 to} R ⁵² is an alkyl group having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon group having 1 to 20 carbon atoms of R ^{41 to} R ^44. The group can be mentioned.

  In the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom. Examples of the substituted amino group include a dialkylamino group such as a dimethylamino group, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the saturated hydrocarbon group in which a hydrogen atom is substituted with a substituted or unsubstituted amino group or a halogen atom include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

The case where the carbon number of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁴ and R ^{53 to} R ⁵⁴ is 2 to 20 and the carbon number of 1 to 8 represented by R ^{45 to} R ⁵² When the alkyl group has 2 to 8 carbon atoms, the saturated hydrocarbon group and the methylene group contained in the alkyl group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms and the alkyl group having 1 to 8 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and the terminal methylene group is an oxygen atom or- It is not replaced by CO-. In this case, the saturated hydrocarbon group and the alkyl group are preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and a linear saturated hydrocarbon group. (That is, a linear alkyl group) is more preferable. 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 1-5, Preferably it is 2-3, More preferably, it is 2.

The number of carbon atoms of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^{41 to} R ⁴⁴ , R ^{53 to} R ⁵⁴ and R ⁵⁵ is more preferably 6 to 15, and further preferably 6 to 12. is there. 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, a terphenyl group, and the like, preferably a phenyl group, a naphthyl group, a tolyl group, A xylyl group, particularly preferably a phenyl group.
The aromatic hydrocarbon group may have one or more substituents, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; A haloalkyl group having 1 to 6 carbon atoms such as a fluoromethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; A C 1-6 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;

The aralkyl group having 7 to 30 carbon atoms represented by R ^{41 to} R ⁴⁴ and R ^{53 to} R ⁵⁴ has 1 to 3 carbon atoms such as a methylene group, an ethylene group, and a propylene group in addition to the group described as the aromatic hydrocarbon group. And a group to which 5 alkanediyl groups are bonded. The number of carbon atoms of the aralkyl group is more preferably 7-20, and still more preferably 7-10. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, and a naphthylethyl group.
The aralkyl group may have one or more substituents, and the substituents are the same as the groups described as the substituents of the aromatic hydrocarbon group.

A ring formed by combining R ⁴¹ and R ⁴² together with the nitrogen atom to which they are bonded, a ring formed by combining R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded, and R ⁵³ and R ⁵⁴ Examples of the ring formed together with the nitrogen atom to which they are bonded include a 5-membered ring such as a pyrrolidine ring; a 6-membered ring such as a morpholine ring, piperidine ring and piperazine ring;

R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —NH—, —O—, —S—, or —SO ₂ —.

Among these, as R ⁴¹ to R ^44, preferably an aromatic hydrocarbon group, saturated hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a 1 to 20 carbon atoms, each independently, a carbon A saturated hydrocarbon group of 1 to 8 or a group represented by the following formula (hereinafter sometimes referred to as group A) is more preferable. In the following formula, * represents a bond with a nitrogen atom.
One of R ⁴¹ and R ⁴² , or one of R ⁴³ and R ⁴⁴ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and the other has 6 to 20 carbon atoms that may have a substituent. The aromatic hydrocarbon group is preferable.

R ^{45 to} R ⁵² are each independently preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, and independently of each other, a hydrogen atom or a methyl group. More preferably, they are a fluorine atom or a chlorine atom.

R ⁵⁵ is preferably a group represented by the following formula (hereinafter sometimes referred to as group B). In the following formula, * represents a bond to ring T ² .

R ^{53 to} R ⁵⁴ are preferably each independently 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, and more Preferably, each independently, a saturated hydrocarbon group having 1 to 8 carbon atoms, a group represented by the group A, or a group represented by the group B (in the groups A and B, * represents a nitrogen atom) More preferably, one of R ⁵³ and R ⁵⁴ is a saturated hydrocarbon group having 1 to 8 carbon atoms, and the other is a group represented by the following formula (hereinafter referred to as group C). May be).

  Examples of the cation moiety of the formula (AI) include a Cation No. represented by the formula (AI-1) shown in Tables 1 to 3 below. 1-220 etc., and Cation No. 1-6, Cation No. 21-26, Cation No. 41-46 are preferable, and Cation No. 1-6, Cation No. 41 to 46 are more preferable. In the table, No. Is no. Is the meaning.

  In Tables 1 to 3, Ph1 to Ph14 mean groups represented by the following formulae.

  In Tables 1 to 3, Me represents a methyl group, and Et represents an ethyl group.

  When a plurality of cations represented by the following formula are contained in one molecule, they may be the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{45 to} R ⁵² have the same meanings as described above, respectively. ]

[Y] ^m− represents an arbitrary m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen. ^Examples of the anion represented by [Y] ^m- include a heteropolyacid anion containing tungsten, molybdenum, silicon and phosphorus, and an isopolyacid anion containing tungsten, molybdenum, silicon and phosphorus.

More preferably, the heteropolyacid anion containing tungsten and the isopolyacid anion containing tungsten include a phosphotungstic anion, a silicotungstate anion and a tungsten isopolyacid anion. Examples of the anion include Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ³⁻ , Dawson type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstate ion 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.

Examples of the anion containing at least one element selected from the group consisting of silicon and phosphorus and oxygen include SiO ₃ ²⁻ and PO ₄ ³⁻ .

m represents an arbitrary natural number, and is a number equal to the negative charge of [Y] ^m− . The m on the cation side is determined so that the charge of the cation is equal to [Y] ^m− . m is preferably a natural number of 1 to 10.

[Y] ^m− is preferably [PW ₁₂ O ₄₀ ] ³⁻ , [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ , [SiW ₁₂ O ₄₀ ] ⁴⁻ or [W ₁₀ O ₃₂ ] ⁴⁻ . more preferably [PW ₁₂ O _40] ^3- or [P ₂ W ₁₈ O _62] is ^6, and more preferably from ^3- [PW ₁₂ O _40].

  As the compound (AI), compounds represented by the formula (Aa-I-1) to the formula (Aa-I-32) shown in Table 4 below are preferable, and the formula (Aa-I-1) to the formula A compound represented by (Aa-I-6), a compound represented by formula (Aa-I-21) to formula (Aa-I-32) is more preferred, and formula (Aa-I-1) to formula ( More preferred are compounds represented by Aa-I-6) and compounds represented by formula (Aa-I-27) to (Aa-I-32). Note that the Cation No. Is synonymous with Table 1.

  Compound (AI) can be produced according to the method described in JP-A-2015-28121.

  The content of the compound (AI) is preferably 0.1 to 150 parts by mass, more preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the resin (B), and 5 to 80 More preferably, it is part by mass.

  The colored resin composition of the present invention may contain a dye (A1) and a pigment (A2) as the colorant (A) in addition to the compound (AI).

  The dye (A1) is not particularly limited, and a known dye can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. 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 notes (color dyeing company). It is done. Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin And dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

The content of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and further preferably 1 to 50% by mass with respect to the total amount of the solid content. %.
The content of the compound (AI) is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more in the total amount of the colorant (A). preferable.
Here, the “total amount of solids” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter “(a)”. More preferred is a resin having a structural unit derived from The resin (B) is a structural unit derived from a monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), A structural unit derived from the monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”), and the side It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

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

(B) is preferably a monomer having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group. .
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl-3- (Meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like can be mentioned. Glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( (Meth) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

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

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

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

  The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 150 mg-KOH / g, and still more preferably 40 to 135 mg-KOH / g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example. .

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

  The colored resin composition of the present invention may contain a polymerizable compound (C) and a polymerization initiator (D). Hereinafter, the colored resin composition containing the polymerizable compound (C) and the polymerization initiator (D) may be referred to as “colored curable resin composition”.

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

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( And (meth) acrylate.

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

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

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

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

  The colored resin composition of the present invention may contain a polymerization initiation assistant (D1).

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

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

  The colored resin composition of the present invention may contain a solvent (E).

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

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

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

  The colored resin composition of the present invention may contain a leveling agent (F).

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

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

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

  When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to the total amount of the colored resin composition. 0.1% by mass. This 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.

<Other ingredients>
The colored resin composition of the present invention contains additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as necessary. But you can.

<Method for producing colored resin composition>
The colored resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation assistant (D1), a solvent used as necessary. It can be prepared by mixing (E), the leveling agent (F) and other components.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable.

  When the colored resin composition contains the compound (AI) as a colorant, a color filter particularly excellent in light resistance can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  Hereinafter, the colored resin composition of the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

[Synthesis Example 1]
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, and then stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When the water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

[Synthesis Example 2]
The following reaction was performed in a nitrogen atmosphere. After putting 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile into a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. After dropping 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 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 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 added, and 60.4 parts of a 30% aqueous sodium hydroxide solution was added, followed by stirring at room temperature for 18 hours. After adding 600 parts of ion-exchanged water, the mixture was stirred for 1 hour, and the precipitated yellowish white solid was collected by filtration. The obtained solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. 156 parts of solid and ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts of toluene were added to a flask equipped with a stirrer and stirred at room temperature for 2 hours. . 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. To the obtained organic layer, 156 parts of ion exchanged water was added and subjected to liquid separation washing, and then 156 parts of ion exchanged water and 0.1 part of 35% hydrochloric acid were added to carry out liquid separation washing. The obtained organic layer was concentrated with an evaporator and then dried under reduced pressure at 35 ° C. to obtain a compound represented by the formula (BI-1) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

[Synthesis Example 3]
The following reaction was performed in a nitrogen atmosphere. After charging 10 parts of the compound represented by the formula (BI-1), 10 parts of the compound represented by the formula (CI-18) and 20 parts of toluene into a flask equipped with a condenser and a stirrer. Then, 5 parts of phosphorus oxychloride was added and stirred at 100 ° C. for 7 hours. The reaction mixture was then cooled to room temperature and diluted with 15 parts of methyl ethyl ketone. Next, a mixed solution of 60 parts of ion-exchanged water and 5 parts of 35% hydrochloric acid aqueous solution was poured into the diluted reaction solution, and the aqueous layer was discarded by a liquid separation operation. The obtained organic layer was evaporated with an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (A-II-1) as a blue-violet solid. The amount of blue-violet solid obtained was 16 parts.

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 8 parts of the compound represented by the formula (A-II-1) and 400 parts of methanol, and then stirred at room temperature for 30 minutes to prepare a blue solution. Next, 400 parts of water was added to the blue solution, and further stirred at room temperature for 30 minutes to obtain a reaction solution. 50 parts of water was put into a beaker, and 12 parts of Keggin type phosphotungstic acid (manufactured by Aldrich) and 50 parts of methanol were put into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. .
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 18 parts of a compound represented by the formula (Aa-I-1).

[Synthesis Example 4]
A compound represented by the formula (CI-19) was obtained in the same manner as in [Synthesis Example 1] except that N-methylaniline was changed to N-ethylaniline.

[Synthesis Example 5]
The following reaction was performed in a nitrogen atmosphere. After charging 10 parts of the compound represented by the formula (BI-1), 10 parts of the compound represented by the formula (CI-19) and 20 parts of toluene into a flask equipped with a condenser and a stirrer. Then, 5 parts of phosphorus oxychloride was added and stirred at 100 ° C. for 7 hours. The reaction mixture was then cooled to room temperature and diluted with 15 parts of methyl ethyl ketone. Next, a mixed solution of 60 parts of ion-exchanged water and 5 parts of 35% hydrochloric acid aqueous solution was poured into the diluted reaction solution, and the aqueous layer was discarded by a liquid separation operation. The obtained organic layer was evaporated using an evaporator and then dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (A-II-2) as a blue-violet solid. The yield of blue-violet solid was 15.5 parts.

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 8 parts of the compound represented by the formula (A-II-2) and 400 parts of methanol, and then stirred at room temperature for 30 minutes to prepare a blue solution. Next, 400 parts of water was added to the blue solution, and further stirred at room temperature for 30 minutes to obtain a reaction solution.
50 parts of water was put into a beaker, and 12 parts of Keggin type phosphotungstic acid (manufactured by Aldrich) and 50 parts of methanol were put into the water and mixed at room temperature in an air atmosphere to prepare a phosphotungstic acid solution. .
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 16.5 parts of a compound represented by the formula (Aa-I-2).

[Synthesis Example 6]
A compound represented by the formula (AI-18) was obtained in the same manner as in [Synthesis Example 6] described in JP-A-2006-27149.

[Synthesis Example 7]
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution obtained by dissolving 26 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in the flask over another 5 hours using another dropping pump. It was dripped. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8,000, a dispersity of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g. Resin (B-1) has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight obtained above in terms of polystyrene was defined as the dispersity.

[Example 1]
<Dispersion preparation>
10 parts of a compound represented by the formula (Aa-I-1), 2 parts of a dispersant (BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan)) (solid content conversion), resin (B-1) (solid 4 parts and 84 parts of propylene glycol monomethyl ether acetate were mixed, and the dispersion 1 was obtained by fully dispersing the compound represented by the formula (Aa-I-1) using a bead mill.

<Preparation of colored resin composition>
Dispersion 1 400 parts;
Alkali-soluble resin (B): Resin (B-1) (solid content conversion) 33.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25.7 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.6 parts;
Solvent (E): 189 parts of propylene glycol monomethyl ether acetate;
And leveling agent (H): polyether-modified silicone oil (solid content conversion) (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.04 parts;
Were mixed to obtain a colored resin composition.

[Example 2]
A dispersion 2 was obtained in the same manner as in Example 1 except that the compound (Aa-I-2) was used instead of the compound (Aa-I-1). Moreover, the colored resin composition was obtained by the method similar to Example 1 by using the dispersion liquid 2 instead of the dispersion liquid 1. FIG.

[Comparative Example 1]
A dispersion 3 was obtained in the same manner as in Example 1 except that the compound (AI-18) was used instead of the compound (Aa-I-1). Further, a colored resin composition was obtained in the same manner as in Example 1 by using Dispersion 3 instead of Dispersion 1.

<Preparation of colored coating film>
On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the colored resin composition was applied by spin coating so that the film thickness after post-baking was 2 μm, and then pre-baked at 100 ° C. for 3 minutes. After standing to cool, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), it was irradiated with light at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. After light irradiation, post-baking was performed at 220 ° C. for 20 minutes in an oven to obtain a colored coating film.

<Light resistance test>
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is disposed on the obtained colored coating film, and is placed on a light resistance tester (Suntest CPS +: manufactured by Toyo Seiki Co., Ltd.). Then, xenon lamp light was irradiated for 48 hours.
The xy chromaticity coordinates (x, y) and the stimulus value Y are measured before and after the irradiation, and the color difference ΔEab * is calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). The results are shown in Table 5. ΔEab * means that the smaller the color change, the smaller the color change. If the light resistance of the colored coating film is good, it can be said that the light resistance of a colored pattern prepared from the same colored resin composition is also good.

  According to the colored resin composition of the present invention, a color filter having excellent light resistance can be produced.

Claims (5)

Including colorants and resins,
The coloring resin composition in which a coloring agent contains the compound represented by a formula (AI).

[In the formula (AI),
R ^{41 to} R ⁴⁴ each independently represents 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 optionally substituted aralkyl group having 7 to 30 carbon atoms, 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 with 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 with 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, and terminal methylene groups are not substituted with oxygen atoms or —CO—. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{45 to} R ⁵² each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and when the alkyl group has 2 to 8 carbon atoms, The methylene group contained in the alkyl group may be substituted with an oxygen atom or —CO—. However, in the alkyl group having 1 to 8 carbon atoms, adjacent methylene groups are not simultaneously substituted with oxygen atoms, and the terminal methylene group is not substituted with oxygen atoms or —CO—. R ⁴⁶ and R ⁵⁰ may be bonded to each other to form —NH—, —O—, —S—, or —SO ₂ —.
Ring T ¹ represents an aromatic hydrocarbon ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent, and the aromatic hydrocarbon which may have this substituent The aromatic heterocyclic ring which may have a ring and the substituent has two or more halogen atoms.
[Y] ^m− represents an arbitrary 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 a plurality of cations represented by the following formula are contained in one molecule, they may be the same structure or different structures.

[Wherein, rings T ¹ , R ^{41 to} R ⁴⁴ and R ^{45 to} R ⁵² have the same meanings as described above, respectively. ]] The colored resin composition according to claim 1, wherein the ring T ¹ is a ring represented by the formula (Ab2-x1).

[In the formula (Ab2-x1), R ⁵⁵ represents an aromatic hydrocarbon group which may have a substituent, and the aromatic hydrocarbon group has two or more halogen atoms.
R ⁵³ and R ⁵⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a C 6 to 20 carbon atom which may have a substituent. An aromatic hydrocarbon group or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, included in the saturated hydrocarbon group The methylene group may be substituted with an oxygen atom or -CO-. R ⁵³ and R ⁵⁴ may combine to form a ring together with the nitrogen atom to which they are bonded.
Ring T ² represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
* Represents a bond to the carbon to which the ring T ¹ in Formula (AI) is bonded. ]   Furthermore, the colored resin composition of Claim 1 or 2 containing a polymeric compound and a polymerization initiator.   The color filter formed from the colored resin composition in any one of Claims 1-3.   A display device comprising the color filter according to claim 4.