JP6931575B2 - Coloring composition, coloring curable resin composition, color filter and liquid crystal display device - Google Patents

Description

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

Color filters used in display devices such as liquid crystal displays, electroluminescence display devices and plasma displays, and solid-state image sensors such as CCDs and CMOS sensors are manufactured from colored curable resin compositions. As a coloring composition contained in such a coloring curable resin composition, a composition containing a triarylmethane dye and a dispersant having an amine value of 72 mgKOH / g is known (Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-164247

The color filter formed from the above-mentioned color curable resin composition known conventionally may not have sufficiently satisfactory lightness. The present invention provides a coloring composition capable of forming a high-brightness color filter.

［式（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−ＣＨ₂−は、−Ｏ−及び−ＣＯ−の少なくとも一方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−ＣＨ₂−が同時に−Ｏ−に置き換わることはなく、末端の−ＣＨ₂−が−Ｏ−又は−ＣＯ−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−ＣＨ₂−は、−Ｏ−及び−ＣＯ−の少なくとも一方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−ＣＨ₂−が同時に−Ｏ−に置換されることはなく、末端の−ＣＨ₂−が−Ｏ−又は−ＣＯ−に置換されることはない。
環Ｔ¹は、炭素数３〜１０の芳香族複素環を表し、該芳香族複素環は、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、水素イオン、ｒ価の金属イオン又は置換若しくは非置換のアンモニウムイオンを表す。
ｋは、Ｒ⁴¹〜Ｒ⁴⁴、Ｒ⁴⁷〜Ｒ⁵⁴及び環Ｔ¹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Ｔ¹は、−ＳＯ₃ ^-又は−ＳＯ₂−Ｎ^-−ＳＯ₂−Ｒ^fを少なくとも１つ有する。］

［式（ＩＩ）中、［Ｙ²］^n-は、任意のｎ価のアニオンを表す。
Ｒ^b41〜Ｒ^b44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、炭素数２〜２０のアルキル基を構成する炭素原子間に酸素原子が挿入されている基、置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよいアラルキル基を表す。Ｒ^b41とＲ^b42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、Ｒ^b43とＲ^b44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。
Ｒ^b45〜Ｒ^b52は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、ヒドロキシル基、炭素数１〜８の飽和炭化水素基、又は炭素数２〜８のアルキル基を構成する炭素原子間に酸素原子が挿入されている基を表すか、Ｒ^b46とＲ^b50は互いに結合して、−Ｏ−、−ＮＨ−、−Ｓ−または−ＳＯ₂−を形成していてもよい。
Ｙ¹は置換基を有していてもよい芳香族複素環基を表す。
式（ＩＩ）で示される化合物が複数のカチオンを含む場合、複数のカチオンは互いに同じ構造であってもよいし、異なる構造であってもよい。
ｎは任意の自然数を表す。］
［３］ ［１］又は［２］記載の着色組成物、樹脂（Ｂ）、重合性化合物（Ｃ）及び重合開始剤（Ｄ）を含む着色硬化性樹脂組成物。
［４］ ［３］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。 [1] A coloring composition containing a triarylmethane compound having a heterocycle, a dispersant and a solvent, and having an amine value of the dispersant of 70 mgKOH / g or less.
[2] Described in [1], the triarylmethane compound having a heterocycle includes at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). Coloring composition.

[In formula (I),
R ^{41 to} R ⁴⁴ are independently hydrogen atoms, saturated hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have substituents, or substituents. an aralkyl group of carbon atoms which may 7-30 have a group, the substituents which may be possessed by the aromatic hydrocarbon group and the aralkyl group, -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, −CH ₂ − contained in the saturated hydrocarbon group may be replaced with at least one of −O− and −CO−. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent −CH ₂ − is not replaced with −O− at the same time, and the terminal −CH ₂₋ is replaced with −O− or −CO−. No. 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 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 _{-CH 2-} , which represents a group and constitutes the alkyl group, may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² are bonded to each other to form -NH-,-. It may form S- or −SO _2-. However, in the alkyl group, the adjacent −CH ₂ − is not substituted with −O− at the same time, and the terminal −CH ₂₋ is not substituted with −O− or −CO−.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle has a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or a substituent. It may have an aromatic hydrocarbon group having 6 to 20 carbon atoms. Aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^{f.
Mr +} represents a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium 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 ^1.
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 ¹ is, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f. ]

[In formula (II), [Y ² ] ^n- represents an arbitrary n-valent anion.
R ^{b41 to} R ^b44 are independently between carbon atoms constituting a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 2 to 20 carbon atoms. Represents a group into which an oxygen atom is inserted, an aromatic hydrocarbon group which may have a substituent, or an aralkyl group which may have a substituent. R ^b41 and R ^b42 may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^b43 and R ^b44 may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{b45 to} R ^b52 are independently between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Represents a group in which an oxygen atom is inserted, or R ^b46 and R ^b50 may be bonded to each other to form -O-, _{-NH-, -S- or -SO 2-} .
Y ¹ represents an aromatic heterocyclic group which may have a substituent.
When the compound represented by the formula (II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.
n represents an arbitrary natural number. ]
[3] A coloring curable resin composition containing the coloring composition, resin (B), polymerizable compound (C) and polymerization initiator (D) according to [1] or [2].
[4] A color filter formed from the color curable resin composition according to [3].
[5] A display device including the color filter according to [4].

According to the present invention, there is provided a coloring composition capable of forming a high-brightness color filter.

The coloring composition of the present invention contains a triarylmethane compound having a heterocycle, a dispersant and a solvent.
The coloring curable resin composition of the present invention contains the coloring composition of the present invention, the resin (B), the polymerizable compound (C), and the polymerization initiator (D). The coloring curable resin composition of the present invention may contain other coloring agents in addition to the coloring agent such as the triarylmethane compound having a heterocycle contained in the coloring composition of the present invention. These colorants are collectively referred to as colorant (A).

<Coloring composition>
<Triarylmethane compound having a heterocycle>
A triarylmethane compound having a heterocycle has a structure in which three aromatic rings are bonded to one carbon atom and one or more of them are aromatic heterocycles, preferably two aromatic rings to one carbon atom. It is a compound having a structure in which a hydrocarbon ring and one aromatic heterocycle are bonded.

As the triarylmethane compound having a heterocycle, a compound represented by the formula (I) (hereinafter, may be referred to as “compound (I)”) is preferable.

Compound (I) also includes its tautomers and salts thereof. In addition, each of the components and functional groups exemplified below can be used alone or in combination.

[In formula (I),
R ^{41 to} R ⁴⁴ are independently hydrogen atoms, saturated hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have substituents, or substituents. an aralkyl group of carbon atoms which may 7-30 have a group, the substituents which may be possessed by the aromatic hydrocarbon group and the aralkyl group, -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, −CH ₂ − contained in the saturated hydrocarbon group may be replaced with at least one of −O− and −CO−. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent −CH ₂ − is not replaced with −O− at the same time, and the terminal −CH ₂₋ is replaced with −O− or −CO−. No. 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 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 _{-CH 2-} , which represents a group and constitutes the alkyl group, may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² are bonded to each other to form -NH-,-. It may form S- or −SO _2-. However, in the alkyl group, the adjacent −CH ₂ − is not substituted with −O− at the same time, and the terminal −CH ₂₋ is not substituted with −O− or −CO−.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle has a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or a substituent. It may have an aromatic hydrocarbon group having 6 to 20 carbon atoms. Aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^{f.
Mr +} represents a hydrogen ion, an r-valent metal ion, or a substituted or unsubstituted ammonium 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 ^1.
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 ¹ is, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f. ]

The aromatic heterocycle represented by ring T ¹ may be a monocyclic ring or a condensed ring. The aromatic heterocycle represented by ring T ¹ has 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. 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; and a 5-membered ring containing no nitrogen atom such as a furan ring and a thiophene ring. Rings; 6-membered rings containing nitrogen atoms such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring; and the like; examples of the aromatic heterocycle of the fused ring include indole ring, benzimidazole ring, benzothiazole ring, and quinoline. A fused ring containing a nitrogen atom such as a ring; a fused ring containing no nitrogen atom such as a benzofuran ring; and the like can be mentioned.
The substituents that the aromatic heterocycle of ring T ¹ may have include a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, and substituted or unsubstituted. Examples thereof include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have an amino group or a substituent, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or the like. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent. Ring T ¹ 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. , An aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent and the like are preferable.
Among them, as the aromatic heterocyclic ring T ^1, an 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 ¹ is preferably a ring represented by the formula (t1).

[In 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 (R ⁵⁷ )-or -S-.
R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ⁴⁵ and R ⁴⁶ independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and 6 to 20 carbon atoms which may have a substituent. It represents an aralkyl group having 7 to 30 carbon atoms which may have an aromatic hydrocarbon group or a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, it is contained in the saturated hydrocarbon group. −CH ₂₋ may be replaced by at least one of −O− and −CO−. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent −CH ₂ − is not replaced with −O − at the same time, and the terminal −CH ₂ − is substituted with −O − or −CO−. Will not be done. R ⁴⁵ and R ⁴⁶ may be bonded to form a ring with the nitrogen atom to which they are bonded.
* Represents a bond with a carbocation. ]

Further, ^{it is also preferable that the ring T 1} is a ring represented by the formula (t2).

[In equation (t2),
Ring T ³ represents an aromatic heterocycle having a nitrogen atom and having 3 to 10 carbon atoms.
R ⁵⁸ is 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 group, -SO ₃ ^-, or -SO ₂ -N ^- -SO Represents _2- R ^f.
R ⁵⁹ is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent. Represents an aralkyl group having 7 to 30 carbon atoms which may have.
k2 represents 0 or 1.
* Represents a bond with a carbocation. ]

It is further preferable that the ring T ¹ is a ring represented by the formula (t2-1).

[In equation (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 synonymous with the above.
* Represents a bond with a carbocation. ]

Saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , and amino groups which may substitute ^{ring T 1 may have carbon atoms.} The saturated hydrocarbon groups 1 to 20 may be linear, branched or cyclic. The linear or branched saturated hydrocarbon group includes 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. , Linear alkyl group such as icosyl group; branched chain alkyl group such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like. The saturated hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and further preferably 1 to 6 carbon atoms.

Cyclic saturated hydrocarbon groups represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , and cyclic saturated hydrocarbon groups that may be contained in the amino group that ^{ring T 1 may have.} May be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include an alicyclic saturated hydrocarbon group 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, and more preferably 6 to 10 carbon atoms.
Methyl is a saturated hydrocarbon group represented by R ^{41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ , and an amino group which ^{ring T 1 may have.} Examples thereof include a group, an ethyl group, an isopropyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isobutyl group, a 2-ethylhexyl group, a cyclohexyl group and an adamantyl group.

The ^{saturated hydrocarbon groups represented by R 41 to} R ⁴⁶ , R ⁵⁶ and R ^{58 to} R ⁶⁰ and the saturated hydrocarbon groups that the ring T ¹ may have may be substituted or substituted. 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 dimethylamino group and a diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. 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 peroloethyl group or a perfluoropropyl group.

The alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ has 1 carbon atom among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by ^{R 41.} ~ 8 groups can be mentioned.
The alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ has 1 to 1 carbon atoms among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by ^{R 41.} There are 10 groups.

When the ^{saturated hydrocarbon group represented by R 41 to} R ⁴⁶ has 2 to 20 carbon atoms, -CH ₂ − contained in the saturated hydrocarbon group is replaced with at least one of -O- and -CO-. May be. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent −CH ₂ − is not replaced with −O − at the same time, and the terminal −CH ₂ − is substituted with −O − or −CO−. Will not be done. In this case, as the saturated hydrocarbon group, a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group) is preferable, and a linear saturated hydrocarbon group (that is, a linear) is preferable. Alkyl group) is more preferable. The _{saturated hydrocarbon group in which −CH 2} − may be replaced with at least one of −O− and −CO− has a preferred carbon number of 2 to 10, more preferably 2 to 8. Also, when −CH ₂₋ is replaced by at least one of −O− and −CO−, between the terminal and −O− or −CO−, or between −O− or −CO− and −O− or −CO−. The number of carbon atoms between is 1 or more, preferably 1 to 5, more preferably 2 to 3, and even more preferably 2.

Further, it has 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 1.} The number of carbon atoms of the aromatic hydrocarbon group which may be (however, the aromatic hydrocarbon group may have a substituent) is preferably 6 to 20, and more preferably 6 to 15. Yes, more preferably 6-12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group and the like, and preferably a phenyl group, a naphthyl group, a tolyl group and the like. It is a xsilyl group, particularly preferably a phenyl group. Further, the aromatic hydrocarbon group may have one or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom and bromine atom; haloalkyl groups having 1 to 6 carbon atoms such as chloromethyl group and trifluoromethyl group; and carbon atoms such as methoxy group and ethoxy group. Alkoxy groups 1 to 6; hydroxy groups; sulfamoyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl groups and ethoxycarbonyl groups; -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, directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, i.e., attached to an aromatic hydrocarbon ring It is preferable to replace the hydrogen atom.
Specific examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

An aralkyl group which may have a substituent represented by ^{R 41 to} R ⁴⁶ and R ^{59 and an aralkyl group which may have an amino group which ring T 1} may have (however, the aralkyl group). May have a substituent.) As the group described as the aromatic hydrocarbon group, the group has 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group, and a propylene group. ), Such as a group to which an alcandiyl group is bonded. The aralkyl group preferably has 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17 carbon atoms.

The ^{rings formed by the bonds of R 41} and R ⁴² with the nitrogen atoms to which they are bonded, the rings formed by the bonds of R ⁴³ and R ⁴⁴ with the nitrogen atoms to which they are bonded, and the rings R ⁴⁵ and R ⁴⁶ are formed. 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 morpholin ring, a piperidine ring, and a piperidine ring, and a pyrrolidine ring and a piperidine ring are preferable. Examples of such heteroatoms include 4- to 7-membered rings having only one nitrogen 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 , aromatic hydrocarbon groups having 1 to 20 carbon atoms or which may have a saturated hydrocarbon group or a substituent are preferable, and they are independent of each other. More preferably, it is 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 formulas. In the following formula, * represents a bond with a nitrogen atom.

In each of R ^{45 to} R ⁴⁶ _{, −CH 2} − constituting a saturated hydrocarbon group having 1 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms is independently contained in at least one of −O− and −CO−. It is preferably an aromatic hydrocarbon group that may have a substituted group or a substituent, or R ⁴⁵ and R ⁴⁶ are bonded to form a ring with the nitrogen atom to which they are bonded. R ^{45 to} R ⁴⁶ are independently saturated hydrocarbon groups having 1 to 8 carbon atoms, an alkyloxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ⁴⁶ are bonded to each other. It is more preferable to form a 4- to 7-membered ring having only one nitrogen atom as a heteroatom, and each independently has a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkyloxyalkyl group, or the following formula. It is more preferable that the group is represented by. In the following formula, * represents a bond with a nitrogen atom.

Further, as the alkyl group having 1 to 8 carbon atoms represented by ^{R 47 to} R ⁵⁴ , carbon among the linear or branched saturated hydrocarbon groups exemplified as the saturated hydrocarbon group represented by ^{R 41 is carbon.} The number 1 to 8 groups can be mentioned. Further, a _{group in which −CH 2} − constituting an alkyl group having 2 to 8 carbon atoms represented by ^{R 47 to} R ⁵⁴ is replaced with at least one of −O− and −CO− (provided that the alkyl groups are adjacent to each other. -CH _2- is not replaced with -O- at the same time, and the terminal -CH _2- is not replaced with -O- or -CO-), as shown in Tables ^{R 41 to} R ^{46 above.} _{Among the groups in which −CH 2} − constituting the alkyl group having 2 to 20 carbon atoms is replaced with at least one of −O− and −CO−, a group having 8 or less carbon atoms can be mentioned.

R ^{47 to} R ⁵⁴ are preferably hydrogen atoms, halogen atoms or alkyl groups having 1 to 8 carbon atoms independently, and are independently hydrogen atoms, methyl groups, fluorine atoms or chlorine atoms, respectively. Is more preferable.
Further, as R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable.
A hydrogen atom is preferable as ^{R 61.}

^{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. Typical metal ions and the like can be mentioned. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. ^{Examples of the substituted or unsubstituted ammonium ion represented by Mr +} include a quaternary ammonium ion such as a tetraalkylammonium ion.
As ^{Mr +} , hydrogen ions or r-valent metal ions are preferable, 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. preferable.

In the formula (I), the number of ^{Mr + is} 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 ^1. The number is one less than the sum of (k). Therefore, the compound (I) has a valence of 0, that is, is an electrically neutral compound.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group and a tetrafluoroethyl group. Perfluoroethyl group, monofluoropropyl group, difluoropropyl group, trifluoropropyl group, tetrafluoropropyl group, pentafluoropropyl group, hexafluoropropyl group, perfluoropropyl group, monofluorobutyl group, difluorobutyl group, trifluorobutyl group , Tetrafluorobutyl group, pentafluorobutyl group, hexafluorobutyl group, heptafluorobutyl group, octafluorobutyl group, perfluorobutyl group and the like. Of these, the perfluoroalkyl group is preferable as the fluoroalkyl group represented by ^{R f.} The ^{number of carbon atoms of the fluoroalkyl group represented by R f} is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

In formula (I), R ^{41 to} R ⁴⁴ , R ^{47 to} R ⁵⁴ and ring T ¹ have at least one _{−SO 3} ⁻ or _{− SO 2} −N ^{− −} SO ₂ −R ^{f. R 41 ~R 44, R 47 ~R} 54 and ring T ¹ -SO ₃ has ^- and -SO ₂ -N ^- sum of the number of -SO ₂ -R ^f (k) is 1 or more, preferably It is 1 to 7, more preferably 2 to 7, even 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, the following (Ia) at least one or more conditions are satisfied it is preferably selected from ~ (Id), from (Ia) and (Ib) It is more preferable that at least one of the selected conditions is satisfied.
(Ia) Any of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent represented by ^{(Ib) R 41 to} R ⁴⁴ included as any of the ^{above R 47 to} R ^54. (Ic) It ^{may have a substituent represented by R 41 to} R ^44. It is bonded to any of the aromatic groups having 7 to 30 carbon atoms and is represented by ^{(Id) T 1.} It is bonded to one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms that replaces the hydrogen atom of the aromatic heterocycle.

However -SO ₃ an aromatic hydrocarbon group or an aralkyl group ^-, or -SO ₂ -N ^- if -SO ₂ -R ^f are attached, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^{It is preferable that f} is directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or the aralkyl group. That -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is preferably substituted to the hydrogen atom bonded to an aromatic hydrocarbon ring.
-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is aromatic R ⁴¹ to R ⁴⁴ carbon atoms which may have a substituent represented 6-20 hydrocarbon radical or R ⁴¹ ~ In the aromatic hydrocarbon ring (for example, benzene ring) in the aralkyl group having 7 to 30 carbon atoms which may have a substituent representing ^{R 44, it is bonded to the para position with respect to the bond position with the nitrogen atom.} Is preferable.
If it contains -SO ₂ -R ^f, a plurality of -SO ₃ ^{- -} Compound (I) into a plurality of -SO ₃ ^- or -SO ₂ -N, or -SO ₂ -N ^- -SO ₂ -R ^f is It may be bonded to the same aromatic hydrocarbon ring, but it is preferably bonded to a different aromatic hydrocarbon ring.

Compound (I) preferably does not have an ethylenically unsaturated bond.

The compound (I) is preferably a compound represented by the following formula (I-1) (hereinafter, may be referred to as “compound (I-1)”).

[In formula (I-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 ^- represents a -SO ₂ -R ^{f -} or -SO ₂ -N.
k1 is the sum of the number of −SO ₃ ^{− and} the number of −SO ₂ −N ⁻ −SO ₂ −R ^{f possessed by R 41} , R ⁴³ , R ^{47 to} R ⁵⁴ , R ^{81 to} R ^90, and ring T ^1. show.
R ⁴¹ , R ⁴³ , R ^{47 to} R ⁵⁴ , T ¹ , ^{Mr +} , r, R ^f are synonymous with the above.
However, R ⁴¹ , R ⁴³ , R ^{47 to} R ⁵⁴ , R ^{81 to} R ⁹⁰ and ring T ¹ have at least one _{−SO 3} ⁻ or _{− SO 2} −N ^{− −} 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 those exemplified as the saturated hydrocarbon group represented by ^{R 41.} The 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 preferably a hydrogen atom, -SO ₃ ^- or −SO ₂ −N ⁻ −SO ₂ −R ^f is more preferable.

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is at least 1 or more satisfying the condition are preferable selected from (Ie) ~ (Ig), selected from (If) and (Ig) It is more preferable that the condition of at least one or more is satisfied, and it is further preferable that the condition of (If) is satisfied.
(Ie) ^{Included as any of R 47 to} R ⁵⁴ (If) Included as ^{any of R 81 to} R ⁹⁰ (Ig) 6 carbon atoms substituting the hydrogen atom of the aromatic heterocycle represented by ^{T 1.} Bonded to ~ 20 aromatic hydrocarbon groups

It is even more preferable that −SO ₃ ⁻ or _{− SO 2} −N ⁻ −SO ₂ −R ^f satisfy the condition of (If').
(If') Included as either ^{R 86} or R ⁸⁹

In the formula ^{(I-1), R 41} , R 43, R 47 ~R 54, R 81 ~R 90 and ring T ¹ -SO ₃ has ^- the number of -SO ₂ -R ^{f -} and -SO ₂ -N The sum (k1) of is preferably 1 to 7, more preferably 1 to 4, and even more preferably 1 or 2.

Examples of the compound (I-I) include compounds represented by formulas (I-I-1) to (I-I-1080) as shown in Tables 1 to 16.

In Tables 1 to 16, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, Bt represents an n-butyl group, and Ph1 to Ph19 mean a group represented by the following formula. In the formula, * represents a bond.

As the compound (I), compounds represented by formulas (I-I-136) to (I-I-270) and formulas (I-I-676) to (I-I-810) are preferable. ,
Formulas (I-I-136) to (I-I-156), Formulas (I-I-175) to (I-I-177), Formulas (I-I-190) to Formulas (I-I) -192), formulas (I-I-205) to formulas (I-I-207), formulas (I-I-220) to formulas (I-I-222), formulas (I-I-235) to formulas. Compounds represented by (I-I-237) and formulas (I-I-250) to (I-I-252) are more preferable.
Compounds represented by formulas (I-I-136) to (I-I-156) are particularly preferable.

Compound (I) can be produced, for example, by sulfonation of a compound represented by the formula (IC) (hereinafter, may be referred to as compound (IC)). The compound (IC) is preferably a hydrochloride, phosphate, perchlorate, BF ₄ salt, PF ₆ salt or the like.

[In the formula (IC),
R ^{1 to} R ⁴ independently have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group or a substituent having 6 to 20 carbon atoms which may have a substituent. It represents an aralkyl group having 7 to 30 carbon atoms which may be possessed, and in the saturated hydrocarbon group having 1 to 20 carbon atoms, the 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 —CH ₂ − contained in the saturated hydrocarbon group may be replaced with at least one of −O− and −CO−. R ¹ and R ² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ³ and R ⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{7 to} R ¹⁴ independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, and −CH ₂ − constituting the alkyl group is −O−. And -CO- may be replaced by at least one of them. R ⁸ and R ¹² may be combined with each other to form -NH-, -S-, or -SO _2- .
Ring T ¹⁰ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle has 6 to 20 carbon atoms which may have a saturated hydrocarbon group or a substituent having 1 to 20 carbon atoms. May have an aromatic hydrocarbon group of.
M ¹ is, Cl ^-, phosphate ion, perchlorate ion, BF ₄ ^- or PF ₆ ^- represents a. ]

Compound (I) is, -SO ₃ ^- has a group, -SO ₂ -N ^- compound having no -SO ₂ -R ^f is (hereinafter sometimes referred to as "compound (IA-1)".) In the case, the compound (IA-1) may be reacted with the compound represented by the formula (IB).

[In formula (IB), R ^f is synonymous with the above. ]

Further, when the compound (I) is a compound in which ^{Mr +} is a hydrogen ion in the formula (I) (hereinafter, may be referred to as a compound (IA-2)), the compound (IA-2) and the r valence are obtained. You may react with a halide (preferably chloride) containing a metal ion of the above, an acetate, a phosphate, a sulfate, a silicate, a cyanide and the like.

Various known methods for sulfonation, such as Journal of Organic Chemistry, (1994), vol. 59, # 11, p. The method described in 3232-3236 can be mentioned.

Further, as the triarylmethane compound having a heterocycle, a compound represented by the formula (II) (hereinafter, may be referred to as “compound (II)”) is also preferable.

[In formula (II), [Y ² ] ^n- represents an arbitrary n-valent anion.
R ^{b41 to} R ^b44 are independently between carbon atoms constituting a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 2 to 20 carbon atoms. Represents a group into which an oxygen atom is inserted, an aromatic hydrocarbon group which may have a substituent, or an aralkyl group which may have a substituent. R ^b41 and R ^b42 may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^b43 and R ^b44 may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{b45 to} R ^b52 are independently between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Represents a group in which an oxygen atom is inserted, or R ^b46 and R ^b50 may be bonded to each other to form -O-, _{-NH-, -S- or -SO 2-} .
Y ¹ represents an aromatic heterocyclic group which may have a substituent.
When the compound represented by the formula (II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.
n represents an arbitrary natural number. ]

[Y ² ] ^n- represents an arbitrary n-valent anion. The ^{anion represented by Y 2} is not particularly limited as long as it is an anion capable of forming a counter ion with the cation, and is preferably a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, a halogen atom such as a chlorine atom, and tungsten. , An anion having at least one element selected from the group consisting of molybdenum, silicon and phosphorus and an oxygen atom.

Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the formula (4).

[In formula (4), W ¹ and W ² each independently represent a group having two monovalent proton donating substituents. M represents boron or aluminum. ]

As a group having two monovalent proton donating substituents, a group formed by releasing protons from each of a compound having at least two monovalent proton donating substituents (for example, a hydroxy group, a carboxy group, etc.) Can be mentioned. Examples of the compound include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and a substituent. 3-Hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoe which may have a substituent. An acid, binaphthol which may have a substituent, salicylic acid which may have a substituent, benzylic acid which may have a substituent or mandelic acid which may have a substituent. Is preferable.

In each of the compounds exemplified as the compound having at least two monovalent proton donating substituents, the substituents include saturated hydrocarbon groups (for example, alkyl groups, cycloalkyl groups, etc.), halogen atoms, hydroxy groups, aminos. Examples include a group, a nitro group, an alkoxy group and the like.

Examples of salicylic acid that may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, and 3,5-di-. Monoaminosalicylic acid such as tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2) , 4-Dihydroxysalicylic acid), 5-hydroxysalicylic acid (2,5-dihydroxysalicylic acid), 6-hydroxysalicylic acid (2,6-dihydroxysalicylic acid) and other monohydroxysalicylic acids; 4,5-dihydroxysalicylic acid, 4, Dihydroxysalicylic acid such as 6-dihydroxysalicylic acid; 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid and the like. Monohalosalicylic acid; dihalosalicylic acid such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-diiodosalicylic acid; trihalosalicylic acid such as 3,5,6-trichlorosalicylic acid; and the like.

Benzilic acid, which may have a substituent, includes

As a mandelic acid that may have a substituent,

And so on.

Examples of the fluorine-containing anion include groups represented by the formulas (6), (7), (8) and (9).

[In formula (6), W ³ and W ⁴ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms, or W ³ and W ⁴ are combined to have 1 carbon atom. Represents an alkanediyl fluoride group of ~ 4. ]

[In the formula (7), W ^{5 to} W ⁷ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms. ]

Wherein (8), Y ^a represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

[In formula (9), Y ^b represents an alkyl fluoride group having 1 to 4 carbon atoms. ]

In the formulas (6), (7) and (9), the perfluoroalkyl group is preferable as the fluorinated alkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF _3). ) ₂ , -C (CF ₃ ) _3, etc.
In the formulas (6) and (8), the perfluoroalkanediyl group is preferable as the fluorinated alkanediyl group having 1 to 4 carbon atoms, and −CF ₂ −, _{−CF 2} CF ₂ −, −CF ₂ CF ₂ CF ₂ −, −C (CF ₃ ) ₂ −, −CF ₂ CF ₂ CF ₂ CF ₂ − and the like can be mentioned.

The anions represented by the formula (6) (hereinafter sometimes referred to as "anion (6)") include the anions represented by the formulas (6-1) to (6-6) (hereinafter, "anion (6)". -1) ”to“ anion (6-6) ”).

Examples of the anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an oxygen atom include a heteropolyacid anion having the element and a polyacid anion such as an isopolyacid anion having the element. ..

Examples of the anion of the heteropolyacid or isopolyacid containing tungsten as an essential element include kegin-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- , Kegin-type heterohydrogenate α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and other examples are [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. As the anion of the heteropolyacid or isopolyacid containing tungsten as an essential element, the anion of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid is preferable.

Further, an anion containing oxygen and at least one element selected from the group consisting of silicon and phosphorus is also preferable, and examples of the _{anion include SiO 3} ^2- and PO ₄ ^3-.

As [Y ² ] ^n- , a fluorine-containing anion and a polyacid anion are preferable, and more preferably an anion represented by the formula (6), [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^{6 -} , [SiW ₁₂ O ₄₀ ] ^4- or [W ₁₀ O ₃₂ ] ^4- is preferable, and more preferably an anion represented by the formulas (6-1) to (6-5), [PW ₁₂ O ₄₀ ]. ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , and particularly preferably an anion represented by the formula (6-2), [PW ₁₂ O ₄₀ ] ^3- .

n represents an arbitrary natural number and is equal to the negative charge of ^{the anion [Y 2} ] ^n-. N on the cation side is ^{defined so that the charge of the anion [Y 2} ] ^n- and the cation are equal. n is preferably a natural number from 1 to 10.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{b41 to} R ^{b44 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. be.
The linear or branched saturated hydrocarbon group includes 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. Examples thereof include branched chain alkyl groups such as an isopropyl group, an isobutyl group and a 2-ethylhexyl group. The linear or branched saturated hydrocarbon has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms.
Further, 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. The cyclic saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

The hydrogen atom of the saturated hydrocarbon group of R ^{b41 to} R ^{b44 may be substituted with a substituent.} Examples of the substituent include 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.

Among the groups represented by R ^{b41 to} R ^b44 , a group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting an alkyl group having 2 to 20 carbon atoms is represented by, for example, the following formula. Group is mentioned. In the following formula, * represents a bond with a nitrogen atom. Among them, as the group in which an oxygen atom is inserted between the methylene groups constituting the alkyl group, a group having 2 to 10 carbon atoms is preferable, and a group having 2 to 6 carbon atoms is more preferable. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^{b41 to} R ^b44 , the carbon number of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and the carbon number of the aralkyl group is preferably 7 to 20, more preferably. It preferably has 7 to 10 carbon atoms.
^Examples of the aromatic hydrocarbon group of R ^{b41 to} R b44 include a phenyl group, a naphthyl group, a toluyl group and the like.
Examples of the aromatic hydrocarbon group in the aralkyl groups of R ^{b41 to} R ^b44 include a phenyl group and a naphthyl group, and the aralkyl group includes a bond of these aromatic hydrocarbon groups and an alkanediyl group. The group is mentioned. The alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and preferably a linear alkanediyl group. Specific examples of the alkandiyl group include a methylene group, an ethylene group, a propylene group, a butanjiyl group and a pentandiyl group, and examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group and a naphthylethyl group. And so on.
Among the groups represented by R ^{b41 to} R ^b44 , in the aromatic hydrocarbon group and the alkoxy group, the substituent is a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom; the number of carbon atoms such as a methoxy group or an ethoxy group. Alkoxy groups 1 to 6; hydroxy groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups; alkoxycarbonyl groups having 2 to 6 carbon atoms such as methoxycarbonyl groups and ethoxycarbonyl groups; and the like.
Specific examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Examples of the aralkyl group which may have a substituent include a group in which an alkylene group such as a methylene group or an ethylene group is bonded to the bond of the aromatic hydrocarbon group.

The ^{ring formed by the bond between R b41} and R ^b42 together with the nitrogen atom to which they are bonded and the ring formed by the ^{bond between R b43} and R ^b44 together with the nitrogen atom to which they are bonded include a pyrrolidine ring and the like. Memberd rings; 6-membered rings such as morpholine ring, piperidine ring, piperazine ring; and the like.

Each of R ^{b41 to} R ^b44 independently has a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a substituent. It is preferable that it is an aralkyl group which may have, and each of them may independently have a saturated hydrocarbon group having 1 to 8 carbon atoms or a substituent represented by the following formula. More preferably it is a group. In the following formula, * represents a bond with a nitrogen atom.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ^{b45 to} R ^b52 may be linear, branched or cyclic, and is preferably linear or branched. .. The saturated hydrocarbon group having 1 to 8 carbon atoms R ^b45 to R ^b52, can be exemplified saturated hydrocarbon group having 1 to 8 carbon atoms among the groups exemplified as the saturated hydrocarbon group R ^b41 to R ^b44 .. As a group in which an oxygen atom is inserted between methylene groups (carbon atoms) constituting the alkyl group, an alkyl group having 2 to 8 carbon atoms is more preferable. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group, and the number of carbon atoms between the oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

From ^{the viewpoint of ease of synthesis, R b45 to} R ^b52 are preferably hydrogen atoms, halogen atoms or saturated hydrocarbon groups having 1 to 8 carbon atoms independently of each other, and are independently hydrogen atoms, respectively. More preferably, it is a methyl group, a fluorine atom or a chlorine atom.

R ^b46 and R ^b50 may combine with each other to form -O-, _{-NH-, -S- or -SO 2-} .

Y ¹ represents an aromatic heterocyclic group which may have a substituent.
The aromatic heterocycle may be either a monocyclic ring or a condensed ring, preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring.
Examples of the monocyclic aromatic heterocycle include a 5-membered ring having 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 having an oxygen atom or a 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;
And so on. Examples of the aromatic heterocycle of the fused ring include a fused ring having a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring, and a quinoline ring;
A ring having an oxygen atom such as a benzofuran ring or a sulfur atom; and the like.

As the compound (II), the compound represented by the formula (II-1) is more preferable.

[In formula (II-1), [Y ² ] ^n- , R ^{b41 to} R ^b52 , and n are the same as described above.
R ^b53 and R ^b54 are independently between carbon atoms constituting a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 2 to 20 carbon atoms. Represents a group into which an oxygen atom is inserted, an aromatic hydrocarbon group which may have a substituent, or an aralkyl group which may have a substituent.
R ^b55 represents an aromatic hydrocarbon group which may have a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent.
X1 represents an oxygen atom, -NR ^b57- or a sulfur atom.
R ^b57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
When the compound represented by the formula (II-1) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other. ]

^{Examples of} R b53, R ^b54 and R ^b57 include groups similar to those exemplified in ^{R b41 to} R ^b44.

^Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R b55 include a group similar to the group exemplified as the saturated hydrocarbon group of ^{R b41 to} R ^b44. Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

^Examples of the group represented by R b55 in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include groups similar to the groups exemplified in ^{R b41 to} R ^b44. The alkyl group into which the oxygen atom is inserted is preferably a linear alkyl group. The number of carbon atoms between oxygen atoms is preferably 1 to 4, more preferably 2 to 3.

In R ^b55 , the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 10.
^{Further, as} the aromatic hydrocarbon group of R ^{b55 , the same groups as those exemplified in R b41 to} R b44 can be mentioned, and a phenyl group is preferable.
In ^{the aromatic hydrocarbon group of R b55} , as the substituent, a halogen atom such as a fluorine atom, a chlorine atom or an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxy group; a sulfamoyl group; Examples thereof include an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group; an alkoxycarbonyl group having 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

R ^b55 is preferably an aromatic hydrocarbon group which may have a saturated hydrocarbon group or a substituent having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms or a halogen atom. , An aromatic hydrocarbon group which may have a substituent on an alkoxy group, a hydroxy group, or a methylsulfonyl group having 1 to 4 carbon atoms, and more preferably a group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

X1 represents an oxygen atom, -NR ^b57- or a sulfur atom. Examples of the cyclic structure containing X1 include a group represented by the following formula. In the formula, R ^{b53 to} R ^b55 are synonymous with the above, and * represents a bond with a carbocation. Among them, as X1, an oxygen atom or a sulfur atom is preferable, and a sulfur atom is particularly preferable.

Examples of the cation portion of the formula (II) include cations 1 to 27 represented by the formula (II-I-1) shown in the table below.
Of these, cations 1 to 6, cations 11, or cations 12 are preferable.
Cation 1, cation 2, or cation 12 is particularly preferred.

In Table 17, Ph1 to Ph12 mean a group represented by the following formula.

The coloring composition may contain only one compound (II) or two or more compounds. Compound (II) is preferably a dye that is soluble in an organic solvent.

In the coloring composition of the present invention, the content of the triarylmethane compound having a heterocycle is preferably 1 to 100% by mass, more preferably 20 to 100% by mass, based on the total amount of the coloring agent contained in the coloring composition. %, More preferably 50 to 100% by mass.

The coloring composition of the present invention may contain a dye (A1) and a pigment (A2) in addition to the triarylmethane compound having a heterocycle.

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified by the Color Index (published by The Society of Dyers and Colorists) as having hues other than pigments, and known dyes described in dyeing notes (Dyeing Co., Ltd.). Be done. According to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acrydin dye, styryl dye, coumarin. Examples include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, 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, 218, 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, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270, 274,277,280,281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1,3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41,42,43,45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 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.I., 104, 105, 106, 109, etc. I. Acid dye,
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 and the like. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse dye,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. Basic Red 9;
C. I. Basic Green 1; etc. I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; etc. I. Reactive dye C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. 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. Mordant dye,
C. I. C.I. I. Vat dyes and the like can be mentioned.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

The dye (A1) preferably contains a xanthene dye.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. The same applies to the others), 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, C.I. I. Basic Red 10, 11, C.I. I. Basic Violet 10 (Rhodamine B), 11, C.I. I. Solvent Red 218, C.I. I. Modant Red 27, C.I. I. Examples thereof include reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP-A-2010-32999, and xanthene dyes described in Japanese Patent No. 4492760. Those that dissolve in an organic solvent are preferable.

Among these, as the xanthene dye (Aa), a dye containing a compound represented by the formula (1a) (hereinafter, may be referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) 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 (Aa).

[In the formula (1a), R ^{a1 to} R ^a4 have a monovalent saturated hydrocarbon group or a substituent having 1 to 20 carbon atoms which may have a hydrogen atom and a substituent independently of each other. It represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and −CH ₂ − contained in the saturated hydrocarbon group is replaced with −O−, −CO− or −NR ^a11−. May be good. R ^a1 and R ^a2 may be combined to form a ring containing a nitrogen atom, and R ^a3 and R ^a4 may be combined to 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 Represents NR ^a9 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 from 0 to 5. When m is 2 or more, a plurality of Ra ^5s 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 ^a11s may be the same or different.
R ^a8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ^a9 and R ^a10 represent monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and are contained in the saturated aliphatic hydrocarbon group-. CH ₂ − may be replaced by −O −, −CO−, −NH− or −NR ^a8− , and R ^a9 and R ^a10 are 3 to 10 members bonded to each other and containing a nitrogen atom. It may form a heterocycle of rings.
R ^a11 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 formula (1a), -SO ₃ ^- if there is, the number is 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 xsilyl 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 +, - ^Examples thereof include CO ₂ H, -CO ₂ R ^a8 , -SR ^a8 , -SO ₂ R ^a8 , -SO ₃ R ^a8 or -SO ₂ NR ^a9 R a10. 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 preferable. In this case, as −SO ₃ ⁻ Z ⁺ , −SO ₃ ^{− +} N (R ^a11 ) ₄ is preferable. When R ^{a1 to} R ^a4 are these groups, a color filter containing less foreign matter and excellent heat resistance 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. , Octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; 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 a ^{4 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, an icosyloxycarbonyl group and the like.

Examples of the −SR ^a8 include a methylsulfanil group, an ethylsulfanil group, a butylsulfanil group, a hexylsulfanil group, a decylsulfanil group, an icosylsulfanil group and the like.
Examples of −SO ₂ R ^a8 include a methyl sulfonyl group, an ethyl sulfonyl group, a butyl sulfonyl group, a hexyl sulfonyl group, a decyl sulfonyl group and an icosyl sulfonyl group.
Examples of the -SO ₃ R ^a8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

-SO ₂ NR ^a9 R ^a10 includes, for example, sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl 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-cyclopentyl sulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- Heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- N-1-substituted sulfamoyl groups such as (1,5-dimethyl) hexyl sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl Examples thereof include N, N-2 substituted sulfamoyl groups such as groups.

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 are more preferred.
m is preferably 1 to 4, more preferably 1 or 2.

The alkyl group having 1 to 6 carbon atoms in the R ^a6 and R ^a7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

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

Z ⁺ is ⁺ N (R ^a11 ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ^a11 ) ₄ .
As the ⁺ N (R ^a11 ) ₄ , ^{it is preferable that at least two of the four R a11} are monovalent saturated hydrocarbon groups 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. ^{When +} N (R ^a11 ) ₄ is present in the compound (1a), ^{if R a11} is these groups, the color filter containing the compound (1a) and having less foreign matter can be obtained from the colored curable resin composition of the present invention. 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 represent monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms independently of each other, and the hydrogen atoms contained in the saturated hydrocarbon groups have 6 to 10 carbon atoms. It may be substituted with 10 aromatic hydrocarbon groups or halogen atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and the saturated hydrocarbon may be substituted. _{-CH 2} − contained in the hydrogen group may be replaced by −O −, −CO− or −NR ^a11−.
R ^a33 and R ^a34 independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ^a31 and R ^a33 may be combined to form a ring containing a nitrogen atom, and R ^a32 and R ^a34 may be combined to form a ring containing a nitrogen atom.
p and q represent integers 0 to 5 independently of each other. When p is 2 or more, the plurality of Ra ^33s may be the same or different, and when q is 2 or more, the plurality of Ra ^34s may be the same or different.
R ^a11 has the same meaning as above. ]

Examples of monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms in R ^a31 and R ^a32 include groups having 1 to 10 carbon atoms among those ^{in R a8.}
The aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent group, include the same groups as in R ^a1.
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.
R ^a31 and R ^a32 are preferably monovalent saturated hydrocarbon groups having 1 to 3 carbon atoms independently of each other.

^Examples of the alkyl group having 1 to 4 carbon atoms in R ^a33 and R a34 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like.
^Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ^a33 and R a34 include a methyl sulfanyl group, an ethyl sulfanyl group, a propyl sulfanyl group, a butyl sulfanyl group, an isopropyl sulfanyl group and the like.
^Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R ^a33 and R a34 include a methyl sulfonyl group, an ethyl sulfonyl group, a propyl sulfonyl group, a butyl sulfonyl group and an isopropyl sulfonyl group.
R ^a33 and R ^a34 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, preferably 0 or 1.

Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43). In the formula, ^Ra40 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.
The compound (1a) is preferably a compound represented by the formulas (1-24) to (1-36), and more preferably represented by the formulas (1-29) to (1-32). It is a compound.

As the xanthene dye (Aa), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Pharmaceutical Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used. can. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to Japanese Patent Application Laid-Open No. 2010-32999.

As the pigment (A2), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in the 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. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Blacks 1 and 7.

As the pigment, C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments are preferred. I. Pigment Blue 15: 3, 15: 6 and C.I. I. Pigment Violet 23 is more preferred, C.I. I. Pigment Blue 15: 6 is even more preferred. By including the above pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment is treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, and atomization by a sulfuric acid atomization method or the like. Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out the dispersion treatment by adding a pigment dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajinomoto Fine. Examples include Techno Co., Ltd. and Disperbyk (manufactured by Big Chemie).
When a pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content ratio of the dye (A1) to the pigment (A2) (dye (A1) / pigment (A2)) is preferably 1/99 to 99/1 on a mass basis, and 5/95 to 50 /. It is more preferably 50, and even more preferably 0/90 to 20/80.

In the coloring composition of the present invention, the content of the coloring agent is preferably 9 to 99% by mass, more preferably 20 to 90% by mass, still more preferably, based on the total solid content of the coloring composition. Is 40 to 80% by mass. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and a required amount of resin or polymerizable compound can be contained in the composition. A pattern with sufficient target strength can be formed.
Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting the content of the solvent from the total amount of the coloring composition or the coloring curable resin composition. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Dispersant>
The coloring composition contains a dispersant having an amine value of 70 mgKOH / g or less. By containing a dispersant having an amine value of 70 mgKOH / g or less, a coloring composition capable of forming a high-brightness color filter is provided. The amine value of the dispersant is preferably 65 mgKOH / g or less, more preferably 60 mgKOH / g or less, still more preferably 55 mgKOH / g or less, preferably 0 mgKOH / g or more, more preferably 5 mgKOH / g or more, and further. It is preferably 10 mgKOH / g or more.
The amine value [mgKOH / g] represents the total amount of primary _{(RNH 2} ), secondary (R ₂ NH), and tertiary (RN (CH ₃ ) ₂ , R ₂ NCH ₃ , R _{3 N) amines.} It is defined by "the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize all amines in 1 g of fats and oils". For the amine value, dissolve the sample in neutral ethanol (tetrahydrofuran, acetone, etc.), neutralize with an ethanolic hydrochloric acid solution (or perchloric acid) using bromphenol blue or crystal violet as an indicator, or measure the potential difference. Measured by.

Dispersants with an amine value of 70 mgKOH / g or less include DISPERBYK-161 (amine value: 11 mgKOH / g, manufactured by Big Chemie), DISPERBYK-162 (amine value: 13 mgKOH / g, manufactured by Big Chemie), DISPERBYK-163 (amine). Value: 10 mgKOH / g, manufactured by Big Chemie), DISPERBYK-164 (amine value: 18 mgKOH / g, manufactured by Big Chemie), DISPERBYK-166 (amine value: 20 mgKOH / g, manufactured by Big Chemie), DISPERBYK-167 (amine value:: 13 mgKOH / g, manufactured by Big Chemie), DISPERBYK-182 (amine value: 13 mgKOH / g, manufactured by Big Chemie), DISPERBYK-184 (amine value: 15 mgKOH / g, manufactured by Big Chemie), DISPERBYK-185 (amine value: 17 mgKOH /) g, manufactured by Big Chemie), DISPERBYK-2000 (amine value: 4 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2001 (amine value: 29 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2008 (amine value: 66 mgKOH / g, manufactured by Big Chemie) (Made by Big Chemie), DISPERBYK-2009 (Amine value: 4 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2022 (Amine value: 61 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2050 (Amine value: 30 mgKOH / g, manufactured by Big Chemie) , DISPERBYK-2055 (amine value: 40 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2061 (amine value: 3 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2150 (amine value: 57 mgKOH / g, manufactured by Big Chemie) , DISPERBYK-2155 (amine value: 48 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2163 (amine value: 10 mgKOH / g, manufactured by Big Chemie), DISPERBYK-2164 (amine value: 14 mgKOH / g, manufactured by Big Chemie), BYK -9077 (amine value: 48 mgKOH / g, manufactured by Big Chemie), BYKLPN-21116 (amine value: 29 mgKOH / g, manufactured by Big Chemie), BYKLPN-21324 (amine value: 0 mgKOH / g, manufactured by Big Chemie), etc. ..

The amount of the dispersant is 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 50 parts by mass, and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the triarylmethane compound having a heterocycle. It is a mass part.

<Solvent>
As the solvent, any solvent that can be used as the solvent (E) of the colored curable resin composition can be used. A particularly excellent solvent for the purpose of dispersing a triarylmethane compound having a heterocycle is, for example, an ether ester solvent, more preferably one hydroxy group of an alkylene glycol or a polyalkylene glycol is etherified and the remaining hydroxy group. Esterated solvents such as 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, diethylene glycol mono Examples thereof include butyl ether acetate and dipropylene glycol methyl ether acetate. These may be used alone or in combination of two or more.

The amount of the solvent is, for example, 1 to 50 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 10 parts by mass with respect to 1 part by mass of the triarylmethane compound having a heterocycle.

When the coloring curable resin composition described later contains a dye (A1), the coloring composition may contain a part or all, preferably all of the dye (A1) in advance, if necessary. .. Further, the coloring composition may contain a part or all, preferably all of the pigment (B2) in advance.

If necessary, the coloring composition may contain a part or all, preferably a part of the resin (B) used in the coloring curable resin composition in advance. By including the resin in advance, the dispersibility of the colored curable resin composition can be further improved. The content of the resin in the coloring composition 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 triarylmethane compound having a heterocycle. Is.

In preparing the dispersion, it is preferable to add necessary components as appropriate and then finely disperse using a dispersion device. As the disperser, a bead mill device can be used. As the beads to be used, hard beads such as zirconia beads are generally used, and the particle size thereof is selected from the range of, for example, 0.05 mm or more and 20 mm or less, preferably 0.1 to 10 mm, and more preferably. It is 0.1 to 0.5 mm.

The coloring composition is preferably composed of a triarylmethane compound having a substantially heterocycle, a dispersant having an amine value of 70 mgKOH / g or less, and a solvent, and the heterocycle is contained in 100% by mass of the coloring composition. The content of the triarylmethane compound having the above, the dispersant having an amine value of 70 mgKOH / g or less, and the solvent is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more. It is preferably 90% by mass or more. By first preparing the coloring composition and then mixing it with the resin (B), the polymerizable compound (C), the polymerization initiator (D), etc., it is expected that the heat resistance of the color filter will be improved.
From the above viewpoint, the content of the resin (B) in 100% by mass of the coloring composition is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 1% by mass. % Or less, particularly preferably 0% by mass.
The content of the polymerizable compound (C) and the polymerization initiator (D) in 100% by weight of the coloring composition is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less. , More preferably 0.1% by mass or less, and particularly preferably 0% by mass.

<Color curable resin composition>
<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 (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and 2 carbon atoms. A copolymer having a cyclic ether structure of ~ 4 and a structural unit derived from a monomer (b) having an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”);
Resin [K2]; Structural unit derived from (a), structural unit derived from (b), and monomer (c) copolymerizable with (a) (however, (a) and (b) are Different.) (Hereinafter sometimes referred to as “(c)”), a copolymer having a structural unit derived from;
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) plus (b) and a structural unit derived from (c);
Resin [K5]; A copolymer having a structural unit derived from (b) with (a) added and a structural unit derived from (c);
Resin [K6]; A copolymer having a structural unit derived from (c) and a structural unit derived from (b) with (a) added and a carboxylic acid anhydride further added.

Specifically, as (a), 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, 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic 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 valent carboxylic acids such as monosuccinate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an alkaline aqueous 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 oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. say. In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.
In addition, in this specification, "(meth) acrylic acid" represents at least one kind 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 oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a simple monomer having an oxetanyl group and an ethylenically unsaturated bond. A metric (b2) (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)"), etc. Can be mentioned.

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)”). ), Monomers (b1-2) having an alicyclic unsaturated hydrocarbon epoxidized structure (hereinafter, may be referred to as “(b1-2)”).

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and 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 (Glysidyloxymethyl) styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example,). Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II). Examples thereof include compounds represented by.

[In formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You may.
X ^a and X ^b is a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
The alkyl groups in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.
Examples of X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH _2- O- and * -CH ₂ CH _2- O-, and more preferably a single bond, * -CH ₂ CH _2- O-can be mentioned (* represents a bond with O).

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

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

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

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane. , 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

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.

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

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, it is commonly referred to as "dicyclopentanyl (meth) acrylate", and when it is referred to as "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth)
Acrylate (in the art, commonly referred to as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl. (Meta) acrylic acid esters such as (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylnitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2. 1] Hept-2-ene and the like are preferable.

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

Resin [K1] can be used, for example, in the method described in the document "Design of Experiments for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). It can be manufactured with reference to the cited references described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent, and the like used here are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) As the solvent, any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent contained in the color 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 color curable resin composition of the present invention. Therefore, the manufacturing 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 is determined in the total structural units constituting the resin [K2].
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2-95 mol%
Structural unit derived from (c); 1-65 mol%
Is preferable,
Structural unit derived from (a); 5-40 mol%
Structural unit derived from (b); 5-80 mol%
Structural unit derived from (c); 5-60 mol%
Is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the color curable resin composition, the developability when forming a color pattern, and the 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 is determined among all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (c); 40-98 mol%
Is preferable,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 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].

The resin [K4] is a carboxylic acid and / or a carboxylic acid anhydride having the cyclic ether having 2 to 4 carbon atoms of (b) obtained by obtaining a copolymer of (a) and (c). It can be manufactured by adding to.
First, the 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, the ratio of the structural units derived from each is preferably the same as that mentioned in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.
Following 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 acid anhydride and cyclic ether (for example, Tris (for example, Tris) Resin [K4] can be produced by putting (dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). Within this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance between the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are improved. Tend. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is further preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount 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 calorific value due to the polymerization and the like. As with 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 first step, the resin [K5] obtains a copolymer of (b) and (c) in the same manner as in the above-mentioned production method of the resin [K1]. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
Is preferable,
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10-90 mol%
Is more preferable.

Further, under the same conditions as the method for producing the resin [K4], the carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). The resin [K5] can be obtained by reacting an object.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is further preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic acid 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 acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl. Resin [K1] such as 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 ] decylacrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3-methyl-3- (meth) Acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, acrylic acid / 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decylacrylate / cyclohexyl maleimide / 2-hydroxyethyl methacrylate Resin such as copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, resin such as styrene / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) ) Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer with glycidyl (meth) acrylate added. Resin such as decyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer to which glycidyl (meth) acrylate is added; tricyclodecyl (meth) acrylate / glycidyl (meth) Resins such as resins obtained by reacting an acrylate copolymer with (meth) acrylic acid, and resins made by reacting a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate with (meth) acrylic acid. [K5]; Resin such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further reacting tetrahydrophthalic acid anhydride [K6]. And so on.
Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable.

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

The content of the resin (B) is preferably 20 to 70% by mass, more preferably 30 to 65% by mass, and further preferably 40 to 40% by mass, based on the total solid content of the color curable resin composition. It is 60% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and 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 compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

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

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, still more preferably 17 to 55% by mass, based on the total solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring 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 that can initiate polymerization by generating active radicals, acids, etc. by the action of light or heat, 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-acyloxime compound, and a biimidazole compound.

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

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-] (2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,, 3-dimethyl-2,) 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole] -3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane- 1-on-2-imine and the like can be mentioned. Commercially available products such as Irgacure OXE01 and OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-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-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy is preferable. -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. With these O-acyloxime compounds, a high-brightness color filter 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). -Morholinophenyl) -2-benzyl butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available 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] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl 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- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-) 2-Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. Can be mentioned.

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

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl)-. 4,4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4 , 4', 5,5'-tetraphenyl biimidazole, 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 (tri) Alkoxyphenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913).

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

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyltosilates, Examples thereof include benzointosilates.

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-acyloxime compound and a biimidazole compound is preferable, and an O-acyloxy compound is preferable. A polymerization initiator containing a compound compound is more preferable.

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

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a 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 initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4 -Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis Examples thereof include (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-di. Butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, and dichlorophenylsulfanyl acetic acid. Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiators (D1) are used, 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). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Colorant (A)>
The colorant (A) is not particularly limited, and a triarylmethane compound having a heterocycle, a dye (A1), a pigment (A2) and the like are preferable. The colorant (A) is preferably a dye (A1), more preferably a xanthene dye, and even more preferably a compound represented by the formula (1a).

Further, in the color curable resin composition of the present invention, the content of the colorant (A) is preferably 1 to 60% by mass, more preferably 1 to 60% by mass, based on the total solid content of the color curable resin composition. Is 3 to 55% by mass, more preferably 5 to 50% by mass. When the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and a required amount of resin or polymerizable compound can be contained in the composition. A pattern with sufficient target strength can be formed.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisol.

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

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.

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

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

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

Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, 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 , N-Methylpyrrolidone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the 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 surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

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

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

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1, based on the total amount of the colored curable resin composition. It is mass% or less, more preferably 0.005 mass% or more and 0.05 mass% or less. The content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The color curable resin composition of the present invention is an additive known in the art, such as a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May include.

<Manufacturing method of coloring composition and coloring curable resin composition>
In the present invention, a triarylmethane compound having a heterocycle is mixed with a dispersant and a solvent to prepare a coloring composition.
The coloring curable resin composition of the present invention is the coloring composition of the present invention, the resin (B), the polymerizable compound (C) and the polymerization initiator (D), and the coloring composition used as needed. It can be prepared by mixing a colorant (A), a solvent (E), a leveling agent (F) and other components other than the colorant contained in the above. When a coloring composition is prepared and then mixed with a resin (B), a polymerizable compound (C), a polymerization initiator (D), or the like to form a coloring curable resin composition, the heat resistance when made into a color filter is further improved. Can be enhanced.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or colored coating film thus formed can be used as the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose, application and the like. For example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5. It is ~ 6 μm.

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

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

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

A coloring pattern is formed on the substrate by developing the coloring composition layer after exposure in contact with a developing solution. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, 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 tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

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

By preparing a color curable resin composition from the color composition of the present invention, a color filter having particularly excellent brightness can be produced from the color curable resin composition. 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, an electronic paper, etc.) and a solid-state image sensor.

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,% and parts indicating the content or the amount used are based on mass unless otherwise specified.

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

Amine titers are measured according to ASTM D 2074.

[Synthesis Example 1]
The following reaction was carried out in a nitrogen atmosphere. After putting 32.2 parts of potassium thiocyanate and 160 parts of acetone into a flask equipped with a cooling tube and a stirrer, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropping, the mixture was further stirred at room temperature for 2 hours. Then, after ice-cooling the reaction mixture, 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was further stirred at room temperature for 30 minutes. Then, after the reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of the dropping, the reaction mixture was further stirred at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid was added dropwise to the reaction mixture at room temperature. After completion of the dropping, the reaction mixture was stirred under heating under reflux for 7 hours. Then, after allowing the reaction mixture to cool to room temperature, the reaction mixture was poured into 120 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, stirring was stopped and the mixture was allowed to stand for 30 minutes to separate the organic layer and the aqueous layer. After discarding the aqueous layer by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bow show was added to the organic layer, and the mixture was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was distilled off with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C. to obtain 49.9 parts of the compound represented by the formula (BI-2). The yield was 51%.

The following reaction was carried out in a nitrogen atmosphere. After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Kasei Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a cooling tube and a stirrer, the mixed solution was ice-cooled. After adding 5.7 parts of 60% sodium hydride (manufactured by Tokyo Kasei Co., Ltd.) little by little over 30 minutes under ice-cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Kasei Co., Ltd.) was added little by little to the reaction mixture, and the mixture was stirred at room temperature for 24 hours. After adding the reaction mixture to 200 parts of ice water little by little, the mixture was allowed to stand at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and then purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C. to obtain 9.8 parts of the compound represented by the formula (CI-2). The yield was 53%.

The following reaction was carried out in a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (BI-2), 10 parts of the compound represented by the formula (CI-2) and 20 parts of toluene are put into a flask equipped with a cooling tube and a stirrer. After that, 12.2 parts of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170 parts isopropanol. Then, the diluted reaction mixture was poured into 300 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, stirring was stopped and the mixture was allowed to stand for 30 minutes to separate the organic layer and the aqueous layer. After discarding the aqueous layer by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bow show was added to the organic layer, the mixture was stirred for 30 minutes, and then filtered to obtain an organic layer. The obtained organic layer was distilled off with an evaporator to obtain a bluish-purple solid. Further, the bluish purple solid was dried under reduced pressure at 60 ° C. to obtain 18.4 parts of the compound represented by the formula (X-II-2). The yield was 100%.

Identification of the compound represented by the formula (X-II-2) (mass spectrometry) Ionization mode = ESI +: m / z = 687.3 [M-Cl] ⁺
Exact Mass: 722.3

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of the compound represented by the formula (X-II-2) and 7.3 parts of dichloromethane were put into a flask equipped with a cooling tube and a stirrer, and then the reaction solution was ice-cooled. Next, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was stirred overnight while raising the temperature to room temperature. The reaction solution was then diluted with 34 parts of N, N-dimethylformamide while ice-cooled. Then, the diluted reaction solution was poured into 140 parts of toluene and then stirred for 30 minutes. Then, stirring was stopped and decantation was performed to obtain a bluish-purple viscous solid. Further, the bluish-purple viscous solid was dried under reduced pressure at 60 ° C. to obtain 2.3 parts of the compound represented by the formula (XI-2). The yield was 100%.

Identification of the compound represented by the formula (XI-2) (mass spectrometry) Ionization mode = ESI +: m / z = 847.3 [M + H] ⁺
ESI-: m / z = 845.5 [MH] ^-
Exact Mass: 846.2

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of the compound represented by the formula (XI-2) and 167 parts of ion-exchanged water were added to a flask equipped with a cooling tube and a stirrer, and the mixture was stirred at 40 ° C. for 30 minutes. 5.8 parts of barium chloride dihydrate and 35 parts of ion-exchanged water were added to the beaker, and the mixture was stirred for 30 minutes. A barium chloride aqueous solution was added dropwise to the previously prepared aqueous solution of the compound represented by the formula (XI-2) while maintaining the liquid temperature at 40 ° C., and the mixture was stirred for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the solid collected by filtration was suspended and washed with 67 parts of ion-exchanged water, and then washed with 20 parts of ion-exchanged water. The obtained solid was dried under reduced pressure at 60 ° C. to obtain 1.9 parts of the compound represented by the formula (AI-3). The yield was 89%.

[Synthesis Example 2]
20 parts of the compound represented by the formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the obtained solution was mixed at 110 ° C. The mixture was stirred for 6 hours. The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain a compound represented by the formula (1-32).

Identification of the compound represented by the formula (1-32) (mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9
Exact Mass: 658.9

[Synthesis Example 3]
A compound represented by the formula (AX-2) (hereinafter, may be referred to as compound (AX-2)) was synthesized according to the method described in JP-A-2015-382201.

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

[Synthesis Example 5]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, in the flask, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] A solution prepared by dissolving 289 parts of a mixture of decane-9-ylacrylate in 125 parts of propylene glycol monomethyl ether acetate was added dropwise using a dropping pump over about 5 hours. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate is added dropwise into the flask over about 6 hours using another dropping pump. bottom. After completion of the dropping, the mixture was kept 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 9200, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g.

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

[Method for Producing Dispersion Liquid (Coloring Compositions 1-1 to 1-5)]
10 parts of the compound represented by the formula (AI-3), 2 parts of the solid content of the dispersant P-1, and 4 parts of the (resin B-2) solution (solid content 35.1%) as the resin. After weighing 186 parts of propylene glycol monomethyl ether acetate, add 600 parts of 0.4 μm zirconia beads, shake for 1 hour using a paint conditioner (manufactured by LAU), remove the zirconia beads by filtration, and disperse the dispersion. (Coloring composition 1-1) was prepared.
The dispersion liquid (coloring composition 1-2, coloring composition) is the same as that of the colorant 1-1 except that the dispersant P-1 is used as the dispersant P-2, the dispersant P-3, and the dispersant P-4, respectively. A product 1-3 and a coloring composition 1-4) were prepared.
Coloring Composition 1-1 except that the compound represented by the formula (AI-3) was changed to the compound represented by the formula (A-X-2) and the dispersant P-1 was changed to the dispersant P-5. A dispersion liquid (coloring composition 1-5) was prepared in the same manner as in the above.

Examples 1-8, Comparative Examples 1-2
Each component was mixed so as to have the composition shown in Table 19 to obtain a colored curable resin composition.

In Table 19, each component represents the following. Further, the resin (B) showed a mass part in terms of solid content.
Colorant (A) 1-1; Coloring composition 1-1 (Amine value of dispersant: 11 mgKOH / g)
Colorant (A) 1-2; Coloring composition 1-2 (Amine value of dispersant: 30 mgKOH / g)
Colorant (A) 1-3; Coloring composition 1-3 (Amine value of dispersant: 57 mgKOH / g)
Colorant (A) 1-4; Coloring composition 1-4 (Amine value of dispersant: 0 mgKOH / g)
Colorant (A) 1-5; Coloring composition 1-5 (Amine value of dispersant: 72 mgKOH / g)
Colorant (A) A-1; Compound resin (B) represented by the formula (1-32) B-1; Resin (B-1)
Resin (B) B-2; Resin (B-2)
Polymerizable compound (C) C-1; dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization Initiator (D) D-1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE 01; BASF; oxime compound)
Solvent (E) E-1; Propylene glycol monomethyl ether acetate leveling agent (F) F-1; Polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

<Making a colored pattern>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to create an air atmosphere of 60 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} As the photomask, a photomask having a 100 μm line-and-space pattern formed was used. The colored composition layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and then in an oven at 230. Post-baking was performed at ° C. for 20 minutes to obtain a coloring pattern.

<Film thickness measurement>
With respect to the obtained coloring pattern, the film thickness (μm) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Saturation evaluation>
The obtained coloring pattern was spectrally measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the CIE XYZ color system were used using the characteristic function of the C light source. (X, y) and the stimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 20.

According to the color curable resin composition containing the color composition of the present invention, an excellent color filter having high brightness can be produced.

Claims (4)

Contains triarylmethane compounds with heterocycles, dispersants and solvents
Amine value of the dispersant is Ri der following 70mgKOH / g,
Examples triarylmethane compound having a heterocyclic ring, and the compound represented by at least one compound is colored composition that is part selected from the group consisting of compounds represented by formula (II) in the formula (I).

[In formula (I),
R ^{41 to} R ⁴⁴ are independently hydrogen atoms, saturated hydrocarbon groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have substituents, or substituents. an aralkyl group of carbon atoms which may 7-30 have a group, the substituents which may be possessed by the aromatic hydrocarbon group and the aralkyl group, -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, −CH ₂ − contained in the saturated hydrocarbon group may be replaced with at least one of −O− and −CO−. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent −CH ₂ − is not replaced with −O− at the same time, and the terminal −CH ₂₋ is replaced with −O− or −CO−. No. 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 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 _{-CH 2-} , which represents a group and constitutes the alkyl group, may be replaced with at least one of -O- and -CO-, and R ⁴⁸ and R ⁵² are bonded to each other to form -NH-,-. It may form S- or −SO _2-. However, in the alkyl group, the adjacent −CH ₂ − is not substituted with −O− at the same time, and the terminal −CH ₂₋ is not substituted with −O− or −CO−.
Ring T ¹ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle has a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group or a substituent. It may have an aromatic hydrocarbon group having 6 to 20 carbon atoms. Aromatic hydrocarbon group substituents which may be possessed by the, -SO ₃ ^- or -SO ₂ -N ^- may be -SO ₂ -R ^f.
M r ⁺ represents a hydrogen ion, r-valent metal ions or substituted or unsubstituted ammonium 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 ^1.
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 ¹ is, -SO ₃ ^- or -SO ₂ -N ^- having at least one -SO ₂ -R ^f. ]

[In formula (II), [Y ² ] ^n- represents an arbitrary n-valent anion.
R ^{b41 to} R ^b44 are independently between carbon atoms constituting a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 2 to 20 carbon atoms. Represents a group into which an oxygen atom is inserted, an aromatic hydrocarbon group which may have a substituent, or an aralkyl group which may have a substituent. R ^b41 and R ^b42 may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^b43 and R ^b44 may be bonded to form a ring with the nitrogen atom to which they are bonded.
R ^{b45 to} R ^b52 are independently between carbon atoms constituting a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. Represents a group in which an oxygen atom is inserted, or R ^b46 and R ^b50 may be bonded to each other to form -O-, _{-NH-, -S- or -SO 2-} .
Y ¹ represents an aromatic heterocyclic group which may have a substituent.
When the compound represented by the formula (II) contains a plurality of cations, the plurality of cations may have the same structure or different structures from each other.
n represents an arbitrary natural number. ] A coloring curable resin composition containing the coloring composition according to claim 1 , the resin (B), the polymerizable compound (C), and the polymerization initiator (D). A color filter formed from the colored curable resin composition according to claim 2. A display device including the color filter according to claim 3.