JP2017171784A - Coloring composition, cured film, color filter, method for producing color filter, solid state image sensor, image display device and compound - Google Patents

Abstract

Colored composition having good heat resistance and solvent resistance and capable of producing a cured film having high contrast, cured film using the same, color filter, method for producing color filter, solid-state imaging device, and image display device And provision of coloring compounds.
A coloring composition comprising a compound represented by the following formula and a resin.

[R ¹ and R ² are each independently a substituent; R ^{3 to} R ⁶ are each independently H or a substituent; R ^{7 to} R ¹¹ are each independently a substituent; at least of R ^{1 to} R ¹¹ One is a group containing a carboxyl group; n1 to n4 are each independently an integer of 0 to 4; n5 is an integer of 0 to 6; X is an anion]
[Selection figure] None

Description

  The present invention relates to a colored composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, and a compound.

The coloring composition is used for manufacturing a color filter and the like.
In recent years, color filters tend to be used not only for monitors but also for televisions in liquid crystal display device applications. Furthermore, in the coloring composition for color filters, using a triarylmethane compound as a coloring agent is examined.

  Patent Document 1 describes that a color filter is produced using a colored composition containing a triarylmethane compound having an aryl group as a substituent on a nitrogen atom, a solvent, and a binder.

JP 2015-127407 A

  A coloring composition used for a color filter or the like is desired to have good heat resistance and solvent resistance when used as a cured film and high contrast. However, with the colored composition described in Patent Document 1, it is difficult to produce a cured film having good heat resistance and solvent resistance and high contrast.

  Accordingly, an object of the present invention is to provide a coloring composition that has good heat resistance and solvent resistance and can produce a cured film having high contrast. Another object of the present invention is to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, and a compound using the colored composition.

The inventors have found that the object can be achieved by using a compound represented by the formula (1) described later, and have completed the present invention. The present invention provides the following.
<1> A colored composition comprising a compound represented by formula (1) and a resin;
Formula (1)
In formula (1), R ¹ and R ² each independently represent a substituent,
R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent,
R ^{7 to} R ¹¹ each independently represents a substituent,
Represents a group containing at least one carboxyl group among R ^{1 to} R ¹¹ ;
n1 to n4 each independently represents an integer of 0 to 4, and n5 represents an integer of 0 to 6;
X represents an anion.
<2> The colored composition according to <1>, wherein at least one of R ³ and R ⁴ is a group containing a carboxyl group.
<3> The colored composition according to <1> or <2>, wherein the compound represented by the formula (1) has one carboxyl group.
<4> The colored composition according to any one of <1> to <3>, wherein the compound represented by the formula (1) is a compound represented by the formula (2);
Formula (2)
In formula (2), each R ²⁰¹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms,
R ²⁰² and R ²⁰³ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
^R204 and ^R205 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L ¹ represents a divalent linking group, and X represents an anion.
<5> The colored composition according to any one of <1> to <4>, wherein X is a bis (trifluoromethanesulfonyl) imide anion or a tris (trifluoromethanesulfonyl) methide anion.
<6> The colored composition according to any one of <1> to <5>, further containing a crosslinking agent.
<7> The colored composition according to any one of <1> to <6>, further comprising a polymerizable compound and a photopolymerization initiator.
<8> The colored composition according to <7>, wherein the photopolymerization initiator contains an oxime compound.
<9> The colored composition according to any one of <1> to <8>, further comprising at least one selected from a xanthene dye and a dipyrromethene dye.
<10> The colored composition according to any one of <1> to <9>, further containing a pigment.
<11> A cured film obtained by curing the colored composition according to any one of <1> to <10>.
<12> A color filter having the cured film according to <11>.
<13> A step of forming a colored composition layer on a substrate using the colored composition according to any one of <1> to <10>;
Forming a pattern on the colored composition layer by a photolithography method or a dry etching method.
<14> A solid-state imaging device having the color filter according to <12>.
<15> An image display device having the color filter according to <12>.
<16> The image display device includes at least a red color filter, a blue color filter, and a green color filter, and the blue color filter is the color filter according to <12>. The image display device described.
<17> a compound represented by formula (1);
Formula (1)
In formula (1), R ¹ and R ² each independently represent a substituent,
R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent,
R ^{7 to} R ¹¹ each independently represents a substituent,
At least one of R ^{1 to} R ¹¹ represents a group containing a carboxyl group;
n1 to n4 each independently represents an integer of 0 to 4, and n5 represents an integer of 0 to 6;
X represents an anion.
<18> The compound according to <17>, wherein the compound represented by formula (1) is a compound represented by formula (2);
Formula (2)
In formula (2), each R ²⁰¹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms,
R ²⁰² and R ²⁰³ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
^R204 and ^R205 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L ¹ represents a divalent linking group, and X represents an anion.
<19> The compound according to <17> or <18>, wherein X represents a bis (trifluoromethanesulfonyl) imide anion or a tris (trifluoromethanesulfonyl) methide anion.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the coloring composition which can manufacture the cured film with favorable heat resistance and solvent resistance, and high contrast. In addition, it has become possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, an image display device, and a compound using the colored composition.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Ph represents a phenyl group, and Ac represents an acetyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

<Coloring composition>
The coloring composition of this invention contains the compound represented by Formula (1) mentioned later, and resin.
By using the colored composition of the present invention, a cured film having good heat resistance and solvent resistance and high contrast can be produced. The mechanism for obtaining such an effect is assumed to be as follows.
In the compound represented by the formula (1) (hereinafter also referred to as triarylmethane compound (1)), at least one of the nitrogen atoms in the formula (1) is bonded to an aryl group having a substituent at the ortho position. Thus, as shown in the following structure, the aryl group is twisted with respect to the plane formed by the bond of the nitrogen atom, and the p-orbital of the nitrogen atom is effectively shielded by the substituent at the ortho position of the aryl group. As a result, the compound that acts on the p orbital of the nitrogen atom and promotes the decomposition of the triarylmethane compound (1) becomes difficult to approach the triarylmethane compound (1), and a cured film having excellent heat resistance can be produced. I guess.
In addition, the carboxyl group of the triarylmethane compound (1) reacts with a film-forming component other than the triarylmethane compound (1) in the colored composition, and is easily taken into the film. It is estimated that a cured film having excellent properties could be produced.
Further, it is considered that the solubility of the triarylmethane compound (1) in the solvent is improved by twisting the aryl group of the triarylmethane compound (1) with respect to the plane formed by the bond of the nitrogen atom. Furthermore, it is thought that compatibility with components other than the triarylmethane compound (1) in the colored composition is improved because the triarylmethane compound (1) has a carboxyl group. For this reason, it is estimated that the dispersibility of the triarylmethane compound (1) in the cured film can be increased, and a cured film having a high contrast could be produced.

In addition, since a carboxyl group is a group with high hydrophilicity, it was thought that solvent resistance will fall when the compound which has a carboxyl group is used. It is a surprising effect that a cured film having excellent solvent resistance can be obtained by using a triarylmethane compound having a carboxyl group.

  Hereinafter, each component of the coloring composition of the present invention will be described.

<< Compound Represented by Formula (1) (Triarylmethane Compound (1)) >>
The coloring composition of the present invention contains a compound represented by the formula (1) (also referred to as a triarylmethane compound (1)). The triarylmethane compound (1) is also a compound of the present invention.
Formula (1)
In formula (1), R ¹ and R ² each independently represent a substituent,
R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent,
R ^{7 to} R ¹¹ each independently represents a substituent,
At least one of R ^{1 to} R ¹¹ represents a group containing a carboxyl group;
n1 to n4 each independently represents an integer of 0 to 4, and n5 represents an integer of 0 to 6;
X represents an anion.

In Formula (1), R ¹ and R ² each independently represent a substituent. Examples of the substituent include substituents defined in Substituent Group A described later. The substituent represented by R ¹ and R ² is preferably a bulky substituent than a hydrogen atom, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group.
The alkyl group represented by R ¹ and R ² may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. 1-12 are preferable, as for carbon number of an alkyl group, 1-10 are more preferable, 1-8 are more preferable, 1-6 are more preferable, 1-4 are still more preferable, 1-3 are still more preferable. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include a substituent defined in Substituent Group A described later, and a group represented by the following formula (L-100).
R ¹ and the carbon number of the aryl group represented by R ^2, 6-12, more preferably 6-10, 6 is more preferable. Examples of the aryl group represented by R ¹ and R ² include a phenyl group and a naphthyl group, and a phenyl group is preferable. The aryl group may be a single ring or a condensed ring. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a substituent defined in Substituent Group A described later, and a group represented by the following formula (L-100).

* -L ^a -COOH Formula (L-100)

In the formula (L-100), * represents a bond to the formula (1), L ^a represents a divalent linking group.
Examples of the divalent linking group L ^a represents an alkylene group; alkenylene group; an arylene group; an alkylene group, formed by combining two or more selected from the alkenylene group and the arylene group group; an alkylene group, the alkenylene group and the arylene group At least one selected from —O—, —S—, —SO—, —CO—, —COO—, —OCO—, —SO ₂ — and —NR ^X — (R ^X represents a hydrogen atom or an alkyl group; And a group formed by combining at least one kind selected from:

1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents exemplified in Substituent group A. For example, a hydroxy group, a halogen atom, etc. are mentioned. The alkylene group may be linear, branched or cyclic. Further, the cyclic alkylene group may be any of a monocyclic ring, a condensed ring, and a polycyclic ring. The cyclic alkylene group may have a crosslinked structure.
2-30 are preferable, as for carbon number of an alkenylene group, 2-15 are more preferable, and 2-10 are more preferable. The alkenylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents exemplified in Substituent group A. For example, a hydroxy group, a halogen atom, etc. are mentioned. The alkenylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents exemplified in Substituent group A.

Specific examples of the divalent linking group L ^a represents the following formulas (L-1) ~ (L -12) are exemplified by the following formulas (L-1), (L -2), (L-3 ), (L-4), (L-9), (L-10), (L-12) are preferred, and the following formulas (L-1), (L-2), (L-4), (L -9) and (L-12) are more preferable, and the following formulas (L-1), (L-9) and (L-12) are more preferable.

In the above formula, A ¹ , B ¹ and C ¹ each independently represent an alkylene group, an alkenylene group or an arylene group, and R ^X1 represents a hydrogen atom or an alkyl group. * ¹ represents a bond with the formula (1), and * ² represents a bond with the carboxyl group of the formula (L-100).

A ^1, B ¹ and C ¹ alkylene group represented, the details of the alkenylene group and the arylene group, an alkylene group described in L ^a, is synonymous with alkenylene group and an arylene group. A ¹ is preferably a cyclic alkylene group or a tertiary or higher alkylene group, more preferably a cyclic alkylene group, and even more preferably a cyclic alkylene group having 6 carbon atoms. B ¹ and C ¹ are preferably each independently an alkylene group or an alkenylene group. The alkylene group and alkenylene group represented by B ¹ and C ¹ are preferably linear or branched, and more preferably linear.

1-30 are preferable, as for carbon number of the alkyl group which R ^<X1> represents, 1-15 are more preferable, and 1-10 are more preferable. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched.

The group represented by the formula (L-100) is more preferably a group represented by the following formula (L-200).
Formula (L-200)
In formula (L-200), L ^a1 represents a single bond or a divalent linking group, and * represents a bond with formula (1).

Examples of the divalent linking group L ^a1 represents an alkylene group; alkenylene group; an arylene group; an alkylene group, formed by combining two or more selected from the alkenylene group and the arylene group group; an alkylene group, the alkenylene group and the arylene group At least one selected from —O—, —S—, —SO—, —CO—, —COO—, —OCO—, —SO ₂ — and —NR ^X — (R ^X represents a hydrogen atom or an alkyl group; And a group formed by combining at least one kind selected from:

1-30 are preferable, as for carbon number of an alkylene group, 1-15 are more preferable, and 1-10 are more preferable. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents exemplified in Substituent group A. For example, a hydroxy group, a halogen atom, etc. are mentioned. The alkylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
2-30 are preferable, as for carbon number of an alkenylene group, 2-15 are more preferable, and 2-10 are more preferable. The alkenylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents exemplified in Substituent group A. For example, a hydroxy group, a halogen atom, etc. are mentioned. The alkenylene group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
6-18 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents exemplified in Substituent group A.

In the formula (1), R ³ and R ⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent include those defined in Substituent Group A. The substituent represented by R ³ and R ⁴ is preferably an alkyl group or an aryl group, and more preferably an alkyl group. One of R ³ and R ⁴ is a hydrogen atom, and the other is preferably a substituent, and one of R ³ and R ⁴ is a hydrogen atom, and the other is more preferably an alkyl group or an aryl group. More preferably, one of R ³ and R ⁴ is a hydrogen atom, and the other is an alkyl group having a substituent or an aryl group having a substituent.
The alkyl group represented by R ³ and R ⁴ may be linear, branched or cyclic, but is preferably cyclic. R ³ and R ⁴ carbon atoms in the alkyl group represented by the 12, more preferably 4 to 12, more preferably 5 to 12, 6 to 12 are particularly preferred. The alkyl group represented by R ³ and R ⁴ may have a substituent or may be unsubstituted. It preferably has a substituent. Examples of the substituent include a substituent defined in the substituent group A and a group represented by the above-described formula (L-100). The alkyl group preferably has a group represented by the above formula (L-100) (preferably a group represented by the above formula (L-200)).

In formula (1), R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent. Examples of the substituent include substituents defined in Substituent Group A described later. The substituent represented by R ⁵ and R ⁶ is more preferably an alkyl group or an aryl group, and further preferably an alkyl group. Details of the alkyl group and aryl group represented by R ⁵ and R ⁶ are the same as the ranges described for R ¹ and R ² .
R ⁵ and R ⁶ are each independently preferably a hydrogen atom or an alkyl group, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms). More preferably, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) is more preferable. The alkyl group represented by R ⁵ and R ⁶ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ⁵ and R ⁶ may have a substituent or may be unsubstituted. Examples of the substituent include a substituent defined in the substituent group A and a group represented by the above-described formula (L-100).

In Formula (1), R ^{7 to} R ¹⁰ each independently represent a substituent. Examples of the substituent include substituents defined in Substituent Group A described later.

The substituent represented by R ⁷ and R ⁸ is preferably a bulky substituent than a hydrogen atom, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group. The details of the alkyl group and aryl group represented by R ⁷ and R ⁸ are the same as the ranges described for R ¹ and R ² .
R ⁷ and R ⁸ are preferably each independently an alkyl group having 1 to 4 carbon atoms. The alkyl group represented by R ⁷ and R ⁸ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ⁷ and R ⁸ may have a substituent or may be unsubstituted. Examples of the substituent include a substituent defined in the substituent group A and a group represented by the above-described formula (L-100).

In the formula (1), the substituent represented by R ^{9 to} R ¹¹ is not particularly limited. For example, an alkyl group, a halogen atom, and —NHCOCH ₃ are preferable.

<Substituent group A>
The substituent group A includes a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, preferably a chlorine atom, a fluorine atom, more preferably a fluorine atom), an alkyl group (preferably having 1 to 48 carbon atoms, more preferably a carbon atom). A linear, branched or cyclic alkyl group having 1 to 24, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl Group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably carbon number) An alkenyl group having 2 to 48, more preferably 2 to 18 carbon atoms, such as vinyl group, allyl group, 3-butene-1 Yl group), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 32 carbon atoms, or more). Preferably it is a C1-C18 heterocyclic group, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group , T-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxy group, cyano group, nitro group, alkoxy group (preferably carbon number) To 48, more preferably an alkoxy group having 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy Group, for example, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenoxy group, 1-naphthoxy group) A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group or 2-tetrahydropyranyloxy group), A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, A trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group or a pivaloyloxy group. , Benzoyloxy group, dodecanoyloxy group), alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, t-butoxycarbonyl group) An oxy group or a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). Group, for example, phenoxycarbonyloxy group), carbamoyloxy group (preferably carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dimethylcarbamoyloxy group, N- Butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms) An oxy group, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group), alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably alkyl having 1 to 24 carbon atoms) A sulfonyloxy group such as methylsulfonyloxy group, hexadecyl Nyloxy group, cyclohexylsulfonyloxy group), arylsulfonyloxy group (preferably arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfonyloxy group), acyl group (preferably An acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, a cyclohexanoyl group), an alkoxycarbonyl group (preferably An alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, 2,6-di-t-butyl- 4-methylcyclohexyloxycar A carbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group), a carbamoyl group (preferably having 1 to 48 carbon atoms, More preferably, it is a carbamoyl group having 1 to 24 carbon atoms, such as a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N -Phenylcarbamoyl group, N-methyl N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group), amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, , Methylamino group, N, N-dibutylamino group, tetradecylamino , 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24, for example, anilino group, N-methylanilino group), a heterocyclic amino group (Preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 4-pyridylamino group), a carbonamide group (preferably having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. An amide group, for example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group), a ureido group (preferably a C1-C32, more preferably a C1-C24 ureido group, Ureido group, N, N-dimethylureido group, N-phenylureido group), imide group (preferably Is an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as an N-succinimide group or an N-phthalimide group, or an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). To 24 alkoxycarbonylamino groups, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably carbon An aryloxycarbonylamino group having 7 to 32, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group, and a sulfonamide group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). A sulfonamide group, For example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group), sulfamoylamino group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Sulfamoylamino groups such as N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group, azo group (preferably having 1 to 32 carbon atoms, more preferably carbon An azo group having 1 to 24, for example, a phenylazo group, a 3-pyrazolylazo group, an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, such as a methylthio group, Ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably An arylthio group having 6 to 48 prime atoms, more preferably 6 to 24 carbon atoms, such as a phenylthio group, a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms) For example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms) And, for example, dodecanesulfinyl group), arylsulfinyl group (preferably arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms such as phenylsulfinyl group), alkylsulfonyl group (preferably carbon number) 1 to 48, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example methyl A sulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably having 6 to 48 carbon atoms). More preferably, it is an arylsulfonyl group having 6 to 24 carbon atoms, such as a phenylsulfonyl group or 1-naphthylsulfonyl group, a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, For example, sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, N- (2 -Ethylhexyl Sulfamoyl group), phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphine group Phinoylamino group (preferably phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group), epoxy group , (Meth) acryloyl group, —NHCOCH ₃ , —SO ₂ NHC ₂ H ₄ OCH ₃ , —NHSO ₂ CH ₃ , a carboxyl group.

In Formula (1), at least one of R ^{1 to} R ¹¹ represents a group containing a carboxyl group. At least one of R ^{3 to} R ⁶ is preferably a group containing a carboxyl group, more preferably at least one of R ³ or R ⁴ is a group containing a carboxyl group, and R ³ or R ⁴ represents a carboxyl group. More preferably, it is a group containing.

In Formula (1), n1 and n2 each independently represent an integer of 0 to 5, an integer of 1 to 3 is preferable, and 1 or 2 is more preferable.
In Formula (1), n3 and n4 each independently represent an integer of 0 to 4, an integer of 0 to 3 is preferable, an integer of 0 to 2 is more preferable, and 0 is more preferable.
In Formula (1), n5 represents an integer of 0 to 6, an integer of 0 to 4 is preferable, an integer of 0 to 2 is more preferable, and 0 is more preferable.

In the formula (1), X represents a monovalent anion. The anion is not particularly limited. For example, fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, sulfonate anion (preferably fluoroalkylsulfonate anion), carboxylate anion, sulfonylimide anion, bis (sulfonyl) imide Anion (preferably bis (fluoroalkylsulfonyl) imide anion), tris (sulfonyl) methide anion (preferably tris (fluoroalkylsulfonyl) methide anion), carboxylate anion, tetraarylborate anion, tetracyanoborate anion, PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ³ — and the like. The anion is preferably a low nucleophilic anion. The low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated.

  The anion represented by X may be an organic anion or an inorganic anion. The anion represented by X is preferably an organic anion. Examples of the anion include the anion described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein.

  The anion represented by X may have a crosslinkable group. Examples of the crosslinkable group include groups that can be cross-linked by radicals, acids, and heat. Specifically, a (meth) acryloyl group, a styryl group, a vinyl group, a cyclic ether group, and a group represented by —C—O—R (where R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). And at least one selected from a (meth) acryloyl group, a styryl group, a vinyl group, and a cyclic ether group is preferable, and one type selected from a (meth) acryloyl group, a styryl group, and a vinyl group is more preferable. . 1-3 are preferable and, as for the number of the crosslinkable group which an anion has, 1 is more preferable.

The anion represented by X is a sulfonate anion, a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion, a tetraarylborate anion, B ⁻ (CN) _n1 (OR ^a ) _4-n1 (R ^a has 1 to 10 carbon atoms) Or an aryl group having 6 to 10 carbon atoms, n1 represents 1 to 4) and PF _n2 R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms _). , N2 represents an integer of 1 to 6), sulfonate anion, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, and tetraarylborate anion are more preferable, bis (sulfonyl) imide anion and tris (sulfonyl) ) Methide anion is more preferred.

As the bis (sulfonyl) imide anion, an anion represented by the following formula (AN-1) is preferable, a bis (fluoroalkylsulfonyl) imide anion is more preferable, and a bis (trifluoromethanesulfonyl) imide anion is more preferable.
Formula (AN-1)
In formula (AN-1), X ¹ and X ² each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X ¹ and X ² may be bonded to each other to form a ring.

X ¹ and X ² are each independently preferably a C 1-10 alkyl group having a fluorine atom, more preferably a C 1-10 perfluoroalkyl group, and a C 1-4 perfluoroalkyl group. Are more preferable, and a trifluoromethyl group is particularly preferable.

The tris (sulfonyl) methide anion is preferably an anion represented by the following formula (AN-2), more preferably a tris (fluoroalkylsulfonyl) methide anion, and still more preferably a tris (trifluoromethanesulfonyl) methide anion.
Formula (AN-2)
In formula (AN-2), X ³ , X ⁴ and X ⁵ each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.

X ³ , X ⁴ and X ⁵ are each independently preferably a C 1-10 alkyl group having a fluorine atom, more preferably a C 1-10 perfluoroalkyl group, and a C 1-4 perfluoroalkyl group. A fluoroalkyl group is more preferred, and a trifluoromethyl group is particularly preferred.

The sulfonate anion is preferably an anion represented by the following formula (AN3), more preferably a fluoroalkylsulfonate anion, and even more preferably a perfluoromethanesulfonate anion.
Formula (AN3)
R-SO ₃ ^-
In formula (AN3), R represents a perfluoroalkyl group or a perfluoroaryl group. When R represents a perfluoroalkyl group, the number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3. When R represents a perfluoroaryl group, the carbon number of R is preferably 6 to 18, and more preferably 6 to 12.

As the tetraarylborate anion, an anion represented by the following formula (AN-5) is preferable.
Formula (AN-5)
In formula (AN-5), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an aryl group.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, and a nitro group. A halogen atom and an alkyl group are preferable, and fluorine An atom and an alkyl group are more preferable, and a fluorine atom and a C1-C4 fluoroalkyl group are still more preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a phenyl group having a halogen atom or a phenyl group having an alkyl group having a halogen atom, and a phenyl group having a fluorine atom or an alkyl having fluorine More preferred is a phenyl group having a group (fluoroalkyl group).

The anion is —B (CN) _n1 (OR ^a ) _4-n1 ⁻ (R ^a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents an integer of 1 to 4. ) Is preferable. 1-6 are preferable and, as for carbon number of the alkyl group which ^Ra represents, 1-4 are more preferable. The aryl group represented by ^Ra is preferably a phenyl group or a naphthyl group. n1 is preferably 1 to 4, and more preferably 1 or 2.

The anion is preferably —PF ₆ R ^P _(6-n2) ⁻ (R ^P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6). R ^P is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.
n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.

  100-1,000 are preferable and, as for the mass per molecule | numerator of the anion which X represents, 200-500 are more preferable.

Although the specific example of an anion is shown below, this invention is not limited to this.

The compound represented by formula (1) (triarylmethane compound (1)) is preferably a compound represented by formula (2).
Formula (2)
In formula (2), each R ²⁰¹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms,
R ²⁰² and R ²⁰³ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
^R204 and ^R205 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L ¹ represents a divalent linking group, and X represents an anion.

  Examples of X in the formula (2) include the anions described for X in the formula (1), and the preferred range is also the same.

In Formula (2), the alkyl group represented by R ²⁰¹ preferably has 1 to 3 carbon atoms. The alkyl group is preferably a straight chain. The alkyl group represented by R ²⁰¹ may have a substituent or may be unsubstituted. Examples of the substituent include those defined in Substituent Group A. When the alkyl group represented by ^R201 has a substituent, the substituent is preferably a group other than a carboxyl group.

In Formula (2), R ²⁰² and R ²⁰³ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms. It preferably represents an alkyl group. 1-4 are preferable and, as for carbon number of an alkyl group, 1-3 are more preferable. The alkyl group is preferably a straight chain. The alkyl group represented by R ²⁰² and R ²⁰³ may have a substituent or may be unsubstituted. Examples of the substituent include those defined in Substituent Group A. When the alkyl group represented by R ²⁰² and R ²⁰³ has a substituent, the substituent is preferably a group other than a carboxyl group.

In Formula (2), ^R204 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As for carbon number of an alkyl group, 1-3 are preferable. The alkyl group is preferably a straight chain. Alkyl group R ²⁰⁴ represents may have a substituent or may be unsubstituted. Examples of the substituent include those defined in Substituent Group A. When the alkyl group R ²⁰⁴ represents has a substituent, the substituent group other than a carboxyl group.

In Formula (2), ^R205 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom.

In Formula (2), L ¹ represents a divalent linking group. Examples of the divalent linking group, include divalent linking groups as those described above for L ^a in formula (L-100), and preferred ranges are also the same.

The compound represented by formula (1) (triarylmethane compound (1)) is preferably a compound represented by formula (3). According to this aspect, it is easy to produce a cured film having good heat resistance and solvent resistance and high contrast.
Formula (3)
In formula (3), R ²⁰¹ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms,
R ²⁰² and R ²⁰³ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
^R204 and ^R205 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L ² represents a divalent linking group, and X represents an anion.

R ²⁰¹ to R ²⁰⁵ and X of formula (3) has the same meaning as R ²⁰¹ to R ²⁰⁵ and X in formula (2), and preferred ranges are also the same.

In Formula (3), L ² represents a divalent linking group. As a bivalent coupling group, the bivalent coupling group ^demonstrated by ^La1 of the said formula (L-200) is mentioned, A preferable range is also the same.

  The number of carboxyl groups in the triarylmethane compound (1) is preferably 1 or 2 and more preferably 1 in one molecule. When the number of carboxyl groups is within the above range, the resulting cured film is particularly excellent in heat resistance, solvent resistance and contrast.

  The triarylmethane compound (1) is preferably a compound having one triarylmethane skeleton in one molecule.

Specific examples of the triarylmethane compound (1) include the following compounds. In the following structural formulas, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, and Ac represents an acetyl group.

  In the colored composition of the present invention, the content of the triarylmethane compound (1) is preferably 10 to 60% by mass and more preferably 10 to 40% by mass with respect to the total solid content of the colored composition of the present invention. .

<< other colorants >>
The coloring composition of the present invention may further contain other coloring agent in addition to the triarylmethane compound (1). Other colorants include dyes, pigments and dispersions thereof. When the pigment is blended as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

  Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, triarylmethane dyes, methine dyes, xanthene dyes, and dipyrromethene dyes.

Examples of the pigment include perylene pigment, perinone pigment, quinacridone pigment, quinacridone quinone pigment, anthraquinone pigment, anthanthrone pigment, benzimidazolone pigment, disazo condensation compound pigment, disazo pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triaryl carbo Examples thereof include nium pigments, dioxazine pigments, aminoanthraquinone pigments, diketopyrrolopyrrole pigments, indigo pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, pyranthrone pigments, and isoviolanthrone pigments. More specifically, for example, Color Index (CI) Pigment Red 190, C.I. I. Pigment red 224, C.I. I. Perylene pigments such as C.I. Pigment Violet 29; I. Pigment orange 43, C.I. I. Perinone pigments such as C.I. Pigment Red 194; I. Pigment violet 19, C.I. I. Pigment violet 42, C.I. I. Pigment red 122, C.I. I. Pigment red 192, C.I. I. Pigment red 202, C.I. I. Pigment red 207, C.I. I. Quinacridone pigments such as CI Pigment Red 209; I. Pigment red 206, C.I. I. Pigment orange 48, C.I. I. Quinacridone quinone pigments such as C.I. Pigment Orange 49; I. Anthraquinone pigments such as C.I. Pigment Yellow 147; I. Anthanthrone pigments such as C.I. Pigment Red 168; I. Pigment brown 25, C.I. I. Pigment violet 32, C.I. I. Pigment orange 36, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment orange 62, C.I. I. Benzimidazolone pigments such as CI Pigment Red 185; I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 166, C.I. I. Pigment orange 34, C.I. I. Pigment orange 13, C.I. I. Pigment orange 31, C.I. I. Pigment red 144, C.I. I. Pigment red 166, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 242, C.I. I. Pigment red 248, C.I. I. Pigment red 262, C.I. I. Disazo condensation compound pigments such as C.I. Pigment Brown 23; I. Pigment yellow 13, C.I. I. Pigment yellow 83, C.I. I. Disazo pigments such as CI Pigment Yellow 188; I. Pigment red 187, C.I. I. Pigment red 170, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 150, C.I. I. Pigment red 48, C.I. I. Pigment red 53, C.I. I. Pigment orange 64, C.I. I. Azo pigments such as C.I. Pigment Red 247, C.I. I. Indanthrone pigments such as CI Pigment Blue 60; I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. Pigment green 58, C.I. I. Pigment blue 16, C.I. I. Pigment blue 75, C.I. I. Phthalocyanine pigments such as CI Pigment Blue 15; I. Pigment blue 56, C.I. I. Triarylcarbonium pigments such as C.I. Pigment Blue 61; I. Pigment violet 23, C.I. I. Dioxazine pigments such as C.I. Pigment Violet 37; I. Aminoanthraquinone pigments such as C.I. Pigment Red 177; I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 272, C.I. I. Pigment orange 71, C.I. I. Diketopyrrolopyrrole pigments such as C.I. Pigment Orange 73; I. Thioindigo pigments such as CI Pigment Red 88; I. Pigment yellow 139, C.I. I. Pigment Orange 66 and other isoindoline pigments, C.I. I. Pigment yellow 109, C.I. I. Isoindolinone pigments such as CI Pigment Orange 61; I. Pigment orange 40, C.I. I. Pyranthrone pigments such as C.I. Pigment Red 216; I. And isoviolanthrone pigment such as CI Pigment Violet 31.
Examples of the pigment include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like, and C.I. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred. I. Pigment Blue 15: 3, 15: 6 and Pigment Violet 23 are more preferable. I. Pigment Blue 15: 6 is more preferable.

  When a dye or pigment is blended as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.

  The content of the other colorant can be used within a range not impairing the effects of the present invention, and is preferably 0.5 to 70% by mass with respect to the total solid content of the colored composition of the present invention. Moreover, it is preferable to add to the coloring composition of this invention so that absorption-intensity ratio (absorption of 450 nm / 650 nm absorption) may become the range of 0.95-1.05.

  In particular, the other colorant preferably includes at least one selected from a xanthene dye, a dipyrromethene dye, an oxazine dye, and a phthalocyanine dye, and more preferably includes at least one selected from a xanthene dye and a dipyrromethene dye.

(Xanthene dye)
A xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes include C.I. I. Acid Red 51, 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 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like. The xanthene dye is preferably a compound that dissolves in an organic solvent.

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

Formula (xt)
In formula (xt), R ^{1 to} R ⁴ may each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a good monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be substituted with —O—, —CO— or —NR ¹¹ —. Good;
R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom;
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ ;
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms;
m1 represents the integer of 0-5. when m1 is 2 or more, the plurality of R ⁵ may be the same or different;
m2 and m3 each independently represents an integer of 0 to 3. when m2 and m3 are each independently 2 or 3, a plurality of R ⁶ and R ⁷ may be independently the same or different;
a represents 0 or 1; when a represents 0, any group of R ^{1 to} R ⁷ has an anion;
X ⁻ represents an anion;
Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different;
R ⁸ 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 ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, -CO -, - NH- or -NR ⁸ - may optionally be substituted with, R ⁹ and R ^10, may form a heterocyclic ring of 3 to 10-membered ring containing a nitrogen atom bonded to each other ;
R ¹¹ 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.

Regarding the details of the formula (xt), the description of paragraph numbers 0127 to 0143 of International Publication No. 2015/141536 can be referred to, and the contents thereof are incorporated in the present specification. Specific examples of the compound (xt) include the following compounds. Further, compounds represented by formula (1-1) to formula (1-43) described in paragraph numbers 0144 to 0147 of International Publication No. 2015/141536 may be mentioned, the contents of which are incorporated herein. I will do it.

  As the xanthene dye, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink R—H / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. . Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

(Dipyrromethene dye)
The dipyrromethene dye is a dye containing a compound having a dipyrromethene skeleton in the molecule. As the dipyrromethene dye, a compound represented by the formula (pm) and a compound coordinated to a metal atom or a metal compound (dipyrromethene metal complex compound) to the compound represented by the formula (pm) are preferable.

Formula (pm)

In formula (pm), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  Examples of the substituent include the substituents described in the above-described substituent group A. When the substituent is a further substitutable group, it may be further substituted with any of the substituents described in the substituent group A. In addition, when it has two or more substituents, those substituents may be the same or different.

In the formula (pm), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered ring. May be formed. Examples of the ring formed include a saturated ring and an unsaturated ring. For example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring And a benzene ring and a pyridine ring are preferable. In addition, when the 5-membered, 6-membered and 7-membered rings formed have a structure that can be further substituted, they may be substituted with any of the substituents described in the above-mentioned Substituent group A.

  Regarding the details of the formula (pm), the description of paragraph numbers 0151 to 0158 of International Publication No. 2015/141536 can be referred to, and the contents thereof are incorporated in the present specification.

The metal atom or metal compound that forms the dipyrromethene metal complex compound may be any metal atom or metal compound that can form a complex with the compound represented by the formula (pm). For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, metal atoms such as B, AlCl, InCl, FeCl, TiCl 2, SnCl 2, SiCl 2 Metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ . Among them, from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is further included. Zn is particularly preferable.

A preferred embodiment of the dipyrromethene metal complex compound coordinated to the metal atom or the metal compound to the compound represented by the formula (pm) is a compound represented by the general formula (I-1) described in paragraphs 0153 to 0176 of JP2012-237985A. ), (I-2) or (I-3) can be referred to, the contents of which are incorporated herein. Specific examples of the dipyrromethene metal complex compound include the following compounds. In addition, the description of paragraph numbers 0179 to 0186 in JP 2012-237985 A can be referred to, and the contents thereof are incorporated in the present specification.

  When the colored composition of the present invention contains at least one selected from a xanthene dye and a dipyrromethene dye, the mass ratio of the total amount of the compound represented by the formula (1), the xanthene dye and the dipyrromethene dye is 1 0.0: 0.05 to 1.0: 1.0 is preferable, and 1.0: 0.1 to 1.0: 0.6 is more preferable.

<< Resin >>
The coloring composition of the present invention contains a resin. There is no limitation in particular as a kind of resin. For example, (meth) acrylic resin, styrene resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide Examples thereof include resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and siloxane resins. One kind of these resins may be used alone, or two or more kinds may be mixed and used. In the present invention, the resin preferably contains an alkali-soluble resin.

The alkali-soluble resin can be appropriately selected from alkali-soluble resins having a group that promotes alkali solubility. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxyl group is preferable. There may be only one type of acid group, or two or more types of acid groups.
Examples of the alkali-soluble resin include polymers having a carboxyl group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer described in JP-A-59-53836 and JP-A-59-71048 Examples thereof include a polymer and a partially esterified maleic acid copolymer.

  Alkali-soluble resins include resins obtained by adding an acid anhydride to a polymer having a hydroxy group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, Polyethylene oxide, polyvinyl alcohol and the like are also useful. The alkali-soluble resin may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate or phenoxyhydroxypropyl (meth) acrylate. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfo group and salts thereof, morpholinoethyl group, etc. Also useful are monomers comprising

  As the alkali-soluble resin, a copolymer of maleimide and ethylene oxide as shown in the following formulas (b1) and (b2) can also be preferably used.

Formula (b1)
In formula (b1), R ¹ represents a hydrogen atom, an aryl group, or an alkyl group.
Examples of the alkyl group when R ¹ represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. Can be mentioned. The alkyl group may have a substituent.
Examples of the aryl group when R ¹ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, and a heteroaryl group containing a hetero atom. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, and the like can be given. The aryl group may have a substituent.

Formula (b2)
In formula (b2), R ² represents a hydrogen atom or a methyl group. R ³ is an alkylene group having 2 or 3 carbon atoms, R ⁴ represents a hydrogen atom, an aryl group, or an alkyl group, and m represents an integer of 1 to 15.

Examples of the alkyl group when R ⁴ represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. Can be mentioned. The alkyl group may have a substituent.
Examples of the aryl group when R ⁴ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, and a heteroaryl group containing a hetero atom. More specifically, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, and the like can be given. The aryl group may have a substituent.

  The alkali-soluble resin may have a polymerizable group in the side chain. For example, a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Corporation), and the like. Also useful are alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin.

  Among these various alkali-soluble resins, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are more preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  In particular, a copolymer having a repeating unit represented by the following formula (200) and an acid group is preferred, and has a repeating unit represented by the formula (201) in addition to the repeating unit represented by the formula (200) and the acid group. A copolymer is more preferred.

In Formula (200), R ²⁰ represents a hydrogen atom or a methyl group, and R ^{21 to} R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group.

In formula (201), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure, and both R ¹² and R ¹³ are hydrogen atoms. Absent. When at least one of R ¹² and R ¹³ represents a carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure, it may further contain a carboxyl group as a partial structure.

Moreover, alkali-soluble resin may contain the repeating unit derived from a compound by following formula (X).
Formula (X)
In the formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

In the formula (X), the number of carbon atoms of the alkylene group represented by R ₂ is preferably 2 to 3. Although the carbon number of the alkyl group of R ₃ is 1 to 20, more preferably 1 to 10, alkyl group of R ₃ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso) propyl group.

The alkali-soluble resin preferably has a weight average molecular weight of 1,000 to 200,00, more preferably 2,000 to 100,000, and 5,000 to 50,000 from the viewpoints of developability, liquid viscosity, and the like. Is particularly preferred.
The acid value of the alkali-soluble resin is preferably 10 to 1000 mgKOH / g, more preferably 50 to 300 mgKOH / g, further preferably 50 to 200 mgKOH / g, and particularly preferably 105 to 200 mgKOH / g.

  The content of the alkali-soluble resin is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the colored composition. The coloring composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< polymerizable compound >>
The coloring composition of the present invention preferably contains a polymerizable compound. The polymerizable compound is preferably a radical polymerizable compound. Examples of the polymerizable compound include compounds having a group having an ethylenically unsaturated bond. The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond (bifunctional or more polymerizable compound), and ethylene. A compound having three or more groups having a polymerizable unsaturated bond (a trifunctional or higher functional polymerizable compound) is more preferable. The upper limit of the group having an ethylenically unsaturated bond is preferably 15 or less, and more preferably 6 or less.

  The polymerizable compound may be in the form of either a monomer or a polymer, but is preferably a monomer. The monomer type polymerizable compound preferably has a molecular weight of 100 to 3,000. The upper limit of the molecular weight is more preferably 2000 or less, and further preferably 1500 or less. The lower limit of the molecular weight is more preferably 150 or more, and further preferably 250 or more. The polymerizable compound is preferably a 3-15 functional (meth) acrylate compound, and more preferably a 3-6 functional (meth) acrylate compound.

  Examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and (co) polymers thereof. It is done. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and (co) polymers thereof. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also suitable. Also, addition reaction product of unsaturated carboxylic acid ester or amide having an electrophilic substituent such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols, amines or thiols, halogen atom or tosyloxy A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. Moreover, it is also possible to use the compound replaced with unsaturated phosphonic acid, styrene, vinyl ether, etc. instead of said unsaturated carboxylic acid. As specific examples of these compounds, paragraph numbers 0156 to 0159 in JP-A No. 2014-208808 can be referred to, and the contents thereof are incorporated in the present specification.

  As a polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku) And a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.

  About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored composition. For example, a bifunctional or higher polymerizable compound is preferable from the viewpoint of sensitivity. Further, from the viewpoint of increasing the strength of the cured film, a trifunctional or higher functional polymerizable compound is preferable. In addition, a method of adjusting both sensitivity and strength by using polymerizable compounds having different types and numbers of functional groups is also effective. In addition, the selection of the polymerizable compound is also an important factor for the compatibility and dispersibility with other components (eg, resin, photopolymerization initiator, colorant) contained in the colored composition, For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

  10-80 mass% is preferable, as for content of the polymeric compound in the total solid of a coloring composition, 15-75 mass% is more preferable, and 20-60 mass% is especially preferable. The coloring composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<< photopolymerization initiator >>
The coloring composition of the present invention preferably contains a photopolymerization initiator. When the coloring composition of this invention contains a polymeric compound, it is preferable that a photoinitiator is included. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, and oxime compounds. Specific examples of the photopolymerization initiator include compounds described in paragraph numbers 0070 to 0077 of JP-A No. 2004-295116. Among these, the photopolymerization initiator is preferably an oxime compound or a biimidazole compound, and more preferably an oxime compound from the viewpoint of rapid polymerization reaction.

  As specific examples of the biimidazole compound, the description of paragraph numbers 0061 to 0070 of JP2013-182213A can be referred to, and the contents thereof are incorporated herein.

  There is no limitation in particular as an oxime compound (henceforth an oxime system photoinitiator). Examples thereof include compounds described in JP-A No. 2000-80068, WO 2002/100903, JP-A No. 2001-233842, JP-A No. 2013-253224, JP-A No. 2006-21012, and the like. . As specific examples of the oxime compound, the description in paragraph No. 0053 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.

  Moreover, in this invention, the compound represented by a formula (OX-1) or a formula (OX-2) can also be used as an oxime compound from a viewpoint of a sensitivity, temporal stability, and the coloring at the time of post-heating.

In formula (OX-1), R and X each represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specific examples thereof include an acetyl group, a propionyl group, a benzoyl group, and a toluyl group.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a t-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloring over time. , An alkylene group substituted with an alkenyl group (eg, vinyl group, allyl group), an aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring over time. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthioxy group, an arylthioxy group or an amino group from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. preferable. Further, n in the formula (OX-1) is preferably 1 or 2.

In the formula (OX-2), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heterocyclic oxycarbonyl group, an alkylthiocarbonyl group, an arylthio A carbonyl group, a heterocyclic thiocarbonyl group, a heterocyclic thiocarbonyl group, or CO—CO—Rf is represented. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

^R102 represents an alkyl group, an aryl group or a heterocyclic group, which may be substituted.
R ¹⁰³ and R ¹⁰⁴ each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.

R ¹⁰⁵ to R ¹¹¹ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, heteroarylthio acryloyl group, an alkylthio group, aryl Roy thio group, heteroarylthio Roy heteroarylthio Group, alkylcarbonyl group, arylcarbonyl group, heterocyclic carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfo group, hydroxy group, carboxyl group, amide group, carbamoyl group Or represents a cyano group.
A coloring composition having higher curability when one or two of R ^{105 to} R ¹¹¹ is an electron-withdrawing substituent, that is, a nitro group, a cyano group, an alkylcarbonyl group or an arylcarbonyl group. Is preferable.

  Specific examples of the compound represented by the formula (OX-2) include the compounds described in JP-A-2014-177502, paragraphs 0087 to 0088, the contents of which are incorporated herein. To do. The compound represented by the formula (2) can be synthesized according to the synthesis method described in, for example, International Publication No. 2014/05050738.

  Commercially available oxime photopolymerization initiators include IRGACURE OX-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) can be used.

In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the colored composition of the present invention.
In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. (C-3) and the like. This content is incorporated herein.

  In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP2013-114249A, paragraph numbers 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4230711, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

  As for content of a photoinitiator, 0.1-50 mass% is preferable with respect to the total solid of a coloring composition, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass%. is there. Within this range, better sensitivity and pattern formability can be obtained. The colored composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Solvent >>
The coloring composition of the present invention preferably contains a solvent. The solvent is basically not particularly limited as long as it can satisfy the solubility of each component and the coating property when used as a colored composition, and considers the solubility of each component and the coating property of the colored composition. Is preferably selected.

  As the solvent, organic solvents such as esters, ethers, ketones, and aromatic hydrocarbons are used. Specific examples include organic solvents described in paragraph numbers 0161 to 0162 of JP2012-032754A. Is done. Organic solvents are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl It is preferably at least one selected from carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, and methyl ethyl diglycol.

  As content in the coloring composition of a solvent, the quantity from which the solid content density | concentration of a coloring composition becomes 10-80 mass% is preferable, and the quantity from which the solid content density | concentration of a coloring composition becomes 15-60 mass% is more preferable. . The colored composition of the present invention may contain only one type of solvent or two or more types of solvents. When two or more types are included, the total amount is preferably within the above range.

<< Crosslinking agent >>
It is preferable that the coloring composition of this invention contains a crosslinking agent. When the coloring composition of the present invention contains a crosslinking agent, the carboxyl group of the triarylmethane compound (1) reacts with the crosslinking agent, so that the triarylmethane compound (1) is easily taken into the cured film. Become. For this reason, solvent resistance can be improved more. Moreover, the dispersibility of the triarylmethane compound (1) can be increased in the cured film, and the contrast of the cured film can be further increased.

  The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction. For example, epoxy compounds (compounds having an epoxy group), oxetanyl compounds (compounds having an oxetanyl group), alkoxymethyl compounds (compounds having an alkoxymethyl group), methylol compounds (compounds having a methylol group), blocked isocyanate compounds (block isocyanates) A compound having a group). Among these, an epoxy compound is preferable because it is easy to produce a cured film excellent in heat resistance, solvent resistance and contrast.

(Epoxy compound)
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The number of epoxy groups is preferably 2 to 100 per molecule. For example, the upper limit may be 10 or less, and may be 5 or less.

  The epoxy compound preferably has an epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) of 500 g / equivalent or less, more preferably 100 to 400 g / equivalent, and 100 to 300 g / equivalent. More preferably it is.

  In the present invention, the epoxy compound may be a low molecular compound (for example, a molecular weight of less than 1000, preferably 100 or more and less than 1000, more preferably 150 or more and less than 1000), or a macromolecule (for example, a molecular weight of 1000 In the case of a polymer, the weight average molecular weight is 1000 or more (preferably 1000 or more and 100000 or less, more preferably May be any of 1500 to 10000, more preferably 1500 to 8000). The epoxy compound is preferably a low molecular compound.

  In the present invention, the epoxy compound is preferably a compound having at least one of an aromatic ring and an aliphatic ring, more preferably a compound having an aliphatic ring, and still more preferably a compound having a 1,2-epoxycyclohexane structure.

  When the epoxy compound is a low molecular compound, examples of the epoxy compound include compounds represented by the following formula (EP1).

In the formula (EP1), R ^{EP1 to} R ^EP3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group. The alkyl group may have a cyclic structure or may have a substituent. R ^EP1 and R ^EP2 , R ^EP2 and R ^EP3 may be bonded to each other to form a ring. ^QEP represents a single bond or an ^nEP- valent group. R ^EP1 to R ^EP3 is combined with Q ^EP may form a ring. n ^EP represents an integer of 2 or more, preferably an integer of 2 to 10, more preferably an integer from 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.
Regarding the details of R ^{EP1 to} R ^EP3 and Q ^EP , the description of paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408 can be referred to, and the contents thereof are incorporated in the present specification. Specific examples of the compound represented by the formula (EP1) include a compound described in paragraph No. 0090 of JP2014-089408A, the contents of which are incorporated herein.

The epoxy compound is preferably a compound represented by the following formula (EP2).
In the formula (EP2), R ^EP100 represents a halogen atom or an alkyl group,
p represents an integer of 0 to 7, and when p is 2 or more, the plurality of ^REP100s may be the same or different,
Q ^EP2 represents a q-valent hydrocarbon group which may contain an oxygen atom,
q represents an integer of 2 to 4.

q represents an integer of 2 to 4, preferably 2 or 3, and more preferably 2.
^Examples of the alkyl group represented by ^REP100 include linear, branched and cyclic alkyl groups. 1-15 are preferable, as for carbon number of the alkyl group which ^REP100 represents, 1-10 are more preferable, 1-5 are more preferable, and 1-3 are especially preferable.
Examples of the halogen atom represented by ^REP100 include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
p represents an integer of 0 to 7, an integer of 0 to 3 is preferable, and 0 or 1 is more preferable.

Q ^EP2 represents a q-valent hydrocarbon group which may contain an oxygen atom.
Examples of the divalent hydrocarbon group include an alkylene group and an arylene group, and an alkylene group is preferable.
1-15 are preferable and, as for carbon number of an alkylene group, 1-10 are more preferable. The alkylene group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear. The alkylene group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the substituent group A.
6-30 are preferable, as for carbon number of an arylene group, 6-20 are more preferable, and 6-12 are still more preferable. The arylene group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described in the substituent group A.
Examples of the trivalent hydrocarbon group and the tetravalent hydrocarbon group include groups obtained by removing one or two hydrogen atoms from the above-described divalent hydrocarbon group.
Examples of the hydrocarbon group containing an oxygen atom include a group formed by combining the above-described hydrocarbon group and at least one group selected from —O—, —CO—, —COO—, and —OCO—, A group formed by combining the above-described hydrocarbon group and at least one selected from —O—, —COO—, and —OCO— is more preferable. The above-described hydrocarbon group and —COO— or —OCO— A combination group is more preferable.

  Epoxy compounds are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. Compounds can also be used. These contents are incorporated herein. Commercially available products include, for example, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, And EPICLON 1051, EPICLON 1055 (manufactured by DIC Corporation). Further, as bisphenol F type epoxy compounds, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE- 602S (Nippon Kayaku Co., Ltd.) etc. are mentioned. Moreover, as a phenol novolak-type epoxy compound, jER152, jER154, jER157S70, jER157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation) Etc. Moreover, as a cresol novolak type epoxy compound, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, DIC Corporation) Product), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like. Moreover, as an aliphatic epoxy compound, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600 PB 4700 (manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (manufactured by Nagase ChemteX Corporation), and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.

(Oxetanyl compounds)
The oxetanyl compound is preferably a compound having two or more oxetanyl groups in one molecule. The number of oxetanyl groups is preferably 2 to 100 in one molecule. For example, the upper limit may be 10 or less, and may be 5 or less. Specific examples of the compound having two or more oxetanyl groups in one molecule include Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.), ETERNACOLL (registered trademark) OXMA, ETERNACOLL (registered trademark) OXBP (manufactured by Ube Industries, Ltd.) can be used.

(Alkoxymethyl compounds, methylol compounds)
Examples of the alkoxymethyl compound and methylol compound include compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom or a carbon atom that forms an aromatic ring.

  Compounds having an alkoxymethyl group or a methylol group bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethyl Urea urea, methylolated urea and the like are preferable. In addition, the descriptions of paragraph numbers 0134 to 0147 in JP-A-2004-295116 and paragraph numbers 0095 to 0126 in JP-A-2014-089408 can be referred to, and the contents thereof are incorporated in the present specification.

As a preferred structure of the compound in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom, compounds represented by the following formulas (100-1) to (100-4) can be exemplified. In the formula, R ⁷ represents a hydrogen atom or a monovalent organic group.

  Examples of the compound in which an alkoxymethyl group or a methylol group is bonded to a carbon atom that forms an aromatic ring include compounds represented by the following formulas (101-1) and (101-2).

Formula (101-1)
In formula (101-1), X represents a single bond or a 1 to 4 valent organic group, R ¹¹ and R ¹² each independently represents a hydrogen atom or a monovalent organic group, and n is an integer of 1 to 4. And p and q are each independently an integer of 0 to 4.

Formula (101-2)
In the formula (101-2), the two Y each independently represent a hydrogen atom or an alkyl group, the alkyl group may contain an oxygen atom or a fluorine atom, R ¹³ to R ¹⁶ each independently represent a hydrogen atom Alternatively, it represents a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently an integer of 0 to 4.

  Examples of commercially available products of alkoxymethyl compounds and methylol compounds include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174. , UFR65, 300 (Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, -750LM, Nicarak MS- 11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.).

(Block isocyanate compound)
The blocked isocyanate compound is preferably a compound having two or more blocked isocyanate groups in one molecule. In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that a blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90-260 degreeC.

  The skeleton of the blocked isocyanate compound is not particularly limited, and may be an aliphatic, alicyclic or aromatic polyisocyanate. With respect to specific examples of the skeleton, the description in paragraph number 0144 of JP 2014-238438 A can be referred to, and the contents thereof are incorporated in the present specification.

  Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type. Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. Can do. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable. As a specific example of the blocking agent, description in paragraph No. 0146 of JP-A No. 2014-238438 can be referred to, and the contents thereof are incorporated in the present specification.

  The block isocyanate compound is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X, L3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co.) can be preferably used, and the like.

  As for content of a crosslinking agent, 1-50 mass% is preferable with respect to the total solid of the coloring composition of this invention. The lower limit is preferably 2% by mass or more. The upper limit is more preferably 40% by mass or less, and further preferably 30% by mass or less.

<< Dye stabilizer >>
The coloring composition of the present invention may contain a dye stabilizer. Examples of the dye stabilizer include (co) polymers of unsaturated carboxylic acid esters such as (meth) acrylic acid esters; (parts) of (co) polymers of unsaturated carboxylic acid such as (meth) acrylic acid Amine salts, (partially) ammonium salts and (partially) alkylamine salts; hydroxy group-containing (meth) acrylic acid esters and other hydroxy group-containing unsaturated carboxylic acid ester (co) polymers and their modified products; crosslinkable groups And sulfonic acid and phosphoric acid polymers having
It is also effective to add the following anion salts (lithium salt, sodium salt, potassium salt, etc.) as a dye stabilizer.

  When the coloring composition of this invention contains a dye stabilizer, 0.01-50 mass% is preferable with respect to the total solid of a coloring composition, and 0.5- 30 mass% is more preferable.

<< Surfactant >>
The coloring composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The surfactant is preferably a surfactant having an ethylene oxide structure or a fluorosurfactant. In particular, surfactants having an ethylene oxide structure and fluorosurfactants having an HLB (Hydrophile-Lipophile Balance) value in the range of 9.2 to 15.5 are preferable.

  The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass. The lower limit is more preferably 5% by mass or more, and further preferably 7% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 25% by mass or less. When the fluorine content is within the above-described range, it is effective in terms of uniformity of coating film thickness and liquid-saving properties, and good solubility.

  Examples of the fluorosurfactant include surfactants described in paragraph numbers 0060 to 0064 of JP 2014-41318 A (paragraph numbers 0060 to 0064 of international publication 2014/17669), JP 2011 The surfactants described in paragraph Nos. 0117 to 0132 of JP-A-132503 can be mentioned, the contents of which are incorporated herein. Commercially available fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.

A block polymer can also be used as the fluorosurfactant. For example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention.
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. % Which shows the ratio of a repeating unit in said compound is the mass%.

  Further, as the fluorosurfactant, a fluoropolymer having a group having an ethylenically unsaturated bond in the side chain can also be used. As specific examples, compounds described in paragraph numbers 0050 to 0090 and 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K, RS manufactured by DIC Corporation. -72-K and the like. As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

  Only one type of surfactant may be used, or two or more types may be combined. 0.0001-2.0 mass% is preferable with respect to the total solid of a coloring composition, and, as for content of surfactant, 0.005-1.0 mass% is more preferable.

<< Curing accelerator >>
The coloring composition of the present invention can contain a curing accelerator. As the curing accelerator, for example, at least one compound selected from the group consisting of thiol compounds, aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds and imidazole ring-containing compounds is used. Can do. As a hardening accelerator, a thiol compound is preferable. The thiol compound is preferably a compound having 2 or more (preferably 2 to 8, more preferably 3 to 6) thiol groups in the molecule. Specific examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N-phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, thiol compounds having a heterocyclic ring, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercapto) And aliphatic thiol compounds such as butyryloxy) butane. Examples of commercially available curing accelerators include Karenz MT series such as Karenz MTBD-1 (manufactured by Showa Denko KK).
In this invention, a hardening accelerator can be used individually or in mixture of 2 or more types. 0.01-20 mass parts is preferable with respect to 100 mass parts of polymerizable compounds, and, as for content of a hardening accelerator, 0.1-10 mass parts is more preferable.

<Polymerization inhibitor>
The coloring composition of the present invention may contain a polymerization inhibitor. A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the composition by light or heat. ) And the like, inactivate the polymerization initiating species, and play a role of suppressing unintentional initiation of polymerization. As the polymerization inhibitor, for example, polymerization inhibitors described in paragraph numbers 0154 to 0173 of JP-A-2007-334322 can be used. Among these, as a polymerization inhibitor, paramethoxyphenol is mentioned preferably.
The content of the polymerization inhibitor in the colored composition of the present invention is preferably 0.0001 to 5% by mass, more preferably 0.001 to 5% by mass, and more preferably 0.001 to 5% by mass with respect to the total mass of the polymerizable compound. 1% by mass is more preferable.

<< Adhesion improver >>
The coloring composition of the present invention may contain an adhesion improving agent. The adhesion improver is a compound that improves the adhesion between an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film. Specific examples include silane coupling agents and thiol compounds. As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable. For example, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are preferable. Only one type of adhesion improver may be used, or two or more types may be combined.
0.1-20 mass% is preferable with respect to the total solid of a coloring composition, and, as for content of the contact | adherence improving agent in the coloring composition of this invention, 0.2-5 mass% is more preferable.

<< Antioxidant >>
The coloring composition of the present invention may contain an antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.

  Examples of the radical scavenger include phenolic antioxidants and hindered amine antioxidants. Examples of phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics. As the radical scavenger, compounds described in paragraphs 0013 to 0034 of JP2012-155243A and paragraphs 0030 to 0042 of JP2013-14748A can be preferably used.

  A peroxide decomposer is a compound that decomposes peroxides generated by exposure to light into harmless substances and prevents the generation of new radicals. For example, phosphorus antioxidants, sulfur And system antioxidants. Among these, sulfur-based antioxidants are preferable from the viewpoint of the stability of color characteristics. Examples of the sulfur antioxidant include thiopropionate compounds and mercaptobenzimidazole compounds. Of these, thiopropionate compounds are preferred from the viewpoint of the stability of color characteristics.

  Examples of ultraviolet absorbers include salicylic acid ester antioxidants and benzophenone antioxidants.

A singlet oxygen quencher is a compound that can deactivate singlet oxygen by energy transfer from oxygen in a singlet state. For example, ethylenic compounds such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, 1,4- Amines such as diazabicyclooctane (DABCO), N-ethylimidazole, condensed polycyclic aromatic compounds such as optionally substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene, diphenylanthracene; 1,3-diphenylisobenzofuran In addition to aromatic compounds such as 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenylcyclopentadiene, Harry H. et al. wasserman, Single Oxygen, Chapter 5, Academic Press (1979), Nicholas J. et al. Turro, Modern Molecular Photochemistry, Chapter 14, The Benjamin Cummings Publishing Co. , Inc. (1978), and CMC Co., Ltd., High Performance Chemicals for Color Photosensitive Materials, Chapter 7 (2002) can include compounds exemplified as singlet oxygen quenchers.
In addition, examples of the singlet oxygen quencher include a metal complex having a sulfur atom-containing compound as a ligand. Specific examples include transition metal chelate compounds such as nickel complexes, cobalt complexes, copper complexes, manganese complexes, and platinum complexes having bisdithio-α-diketone, bisphenyldithiol, and thiobisphenol as ligands. .

  In the present invention, only one type of antioxidant may be used, or two or more types may be combined. The content of the antioxidant is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the triarylmethane compound (1).

<< Bis (trifluoromethanesulfonyl) imide salt >>
The coloring composition of the present invention may further contain a bis (trifluoromethanesulfonyl) imide salt. Heat resistance can be improved by including a bis (trifluoromethanesulfonyl) imide salt. Examples of the bis (trifluoromethanesulfonyl) imide salt include potassium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, and lithium (bistrifluoromethanesulfonyl) imide.
The content of the bis (trifluoromethanesulfonyl) imide salt is preferably 0.3 to 10% by mass with respect to the total solid content of the colored composition. The upper limit is more preferably 5% by mass or less, and further preferably 4% by mass or less. The lower limit is more preferably 1% by mass or more, and further preferably 1.5% by mass or more.
The content of the bis (trifluoromethanesulfonyl) imide salt is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the triarylmethane compound (1). The upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less. The lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and further preferably 6 parts by mass or more.

<< Other ingredients >>
The coloring composition of the present invention further contains various additives such as a reduction inhibitor, an acid generator, a filler, an ultraviolet absorber, an aggregation inhibitor, a sensitizer, a light stabilizer, and a development accelerator as necessary. It may be included. As a reduction inhibitor, an acid generator, and a development accelerator, the description of paragraph numbers 0223 to 0228 of WO 2015/046285 and paragraph numbers 0219 to 0230 of WO 2015/141536 can be referred to. It will be incorporated herein.

<Method for preparing colored composition>
The coloring composition of the present invention can be prepared by mixing the aforementioned components.
In preparing the colored composition, the components constituting the colored composition may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, fluorine resins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. These filters are listed. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

  Since the colored composition of the present invention can form a cured film excellent in hue and contrast, for forming a colored layer (for forming colored pixels) such as a color filter used in an image display device or a solid-state imaging device, Moreover, it can use suitably as preparation uses, such as printing ink, inkjet ink, and a coating material.

<Method for producing cured film, color filter, color filter>
The cured film of the present invention is formed by curing the colored composition of the present invention. This cured film is preferably used for a color filter.

  The color filter of the present invention may be any method as long as it can form a colored region (colored pattern) cured by applying the colored composition of the present invention onto a substrate, and may be formed by any method. Preferably, it is produced using the coloring composition of the present invention. For example, the manufacturing method described in paragraphs 0359 to 0371 of JP2011-252065A can also be employed.

  The method for producing a color filter of the present invention includes a step of forming a colored composition layer on a substrate using the colored composition of the present invention, and a pattern formed on the colored composition layer by a photolithography method or a dry etching method. Forming a step.

  The pattern forming method may be a pattern forming method by a photolithography method or a pattern forming method by a dry etching method. In the case of manufacturing a color filter in which a plurality of colored cured films (colored patterns) are formed, all the colored patterns may be formed by photolithography or dry etching. The color (first layer) may be patterned by a dry etching method, and the second and subsequent colors (second layer and later) may be patterned by a photolithography method.

Pattern formation by the photolithography method includes a step of forming a colored composition layer on a substrate using the colored composition, a step of exposing the colored composition layer in a pattern, and an unexposed portion of the colored composition layer. And developing a pattern to form a pattern. If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (post-bake step) may be provided.
The pattern formation by the dry etching method includes forming a colored composition layer on a substrate using the colored composition and curing to form the colored layer, and forming a photoresist layer on the colored layer. Preferably, the method includes a step, a step of patterning a photoresist layer by exposure and development to obtain a resist pattern, and a step of forming a pattern by dry etching the colored layer using the resist pattern as an etching mask. Hereinafter, each step will be described.

<< Step of Forming Colored Composition Layer >>
In the step of forming the colored composition layer, the colored composition layer is formed by applying the colored composition of the present invention on the substrate.

As the substrate, for example, non-alkali glass, sodium glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, solid imaging elements, etc. Examples thereof include a photoelectric conversion element substrate, a silicon substrate, and a plastic substrate. Moreover, on these base materials, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be formed on the base material in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.
The plastic substrate preferably has a gas barrier layer or a solvent resistant layer on the surface.

  In addition, a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) can also be used as a base material. Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates can be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum vapor deposition and the like. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

  As a method of applying the coloring composition to the substrate, coating is preferable, and it is preferable to apply by a method such as spin coating, slit coating, cast coating, roll coating, bar coating, and ink jet.

  The colored composition layer formed on the substrate is preferably dried (prebaked). Pre-baking can be performed using a hot plate, an oven, or the like. The drying temperature is preferably 50 to 140 ° C, more preferably 70 to 110 ° C. The drying time is preferably 10 seconds to 300 seconds. Note that pre-baking may be performed in combination with high-frequency processing. The high frequency treatment can be used alone. If necessary, vacuum treatment can be performed before pre-baking. As for the conditions for vacuum drying, the degree of vacuum is preferably 13 to 133 Pa, and more preferably 26 to 66.5 Pa.

  The thickness of the colored composition layer formed from the colored composition is appropriately selected according to the purpose. In the case of a color filter for an image display device, a range of 0.2 to 5.0 μm is preferable, a range of 1.0 to 4.0 μm is more preferable, and a range of 1.5 to 3.5 μm is most preferable. Moreover, in the case of the color filter for solid-state image sensors, the range of 0.2-5.0 micrometers is preferable, The range of 0.3-2.5 micrometers is more preferable, The range of 0.3-1.5 micrometers is the most preferable. In addition, the thickness of a coloring composition layer is a film thickness after prebaking.

(Pattern formation by photolithography)
<< Exposure Step >>
Subsequently, in the method for producing a color filter of the present invention, the film (colored composition layer) made of the colored composition formed on the substrate as described above is exposed through, for example, a photomask. As light or radiation applicable to exposure, g-line, h-line, i-line, j-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

In an exposure method using a laser light source, it is preferable to use an ultraviolet laser as the light source. The irradiation light is preferably an ultraviolet laser having a wavelength of 300 to 380 nm, and more preferably an ultraviolet laser having a wavelength of 300 to 360 nm. Specifically, the third harmonic (355 nm) of an Nd: YAG (yttrium, aluminum, garnet) laser, which is a relatively inexpensive solid laser with a large output, and the XeCl (308 nm), XeF (353 nm) of an excimer laser. Can be suitably used.
The exposure amount of the exposure object (pattern), preferably from ^{1mJ / cm 2 ~100mJ / cm 2} , 1mJ / cm 2 ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), DF2200G (Dainippon Screen) can be used. It is. Further, devices other than those described above are also preferably used.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used is for forming a depression such as a through hole in addition to a pattern for forming a pixel (colored pattern). Those provided with a pattern are used.

  The colored composition layer exposed as described above may be heated. The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored composition layer.

<< Process to develop >>
Subsequently, the colored composition layer after exposure is developed with a developer. A pattern can be formed. In the development step, the uncured portion of the colored composition layer after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the uncured portion of the colored composition layer and does not dissolve the cured portion. For example, an alkaline aqueous solution can be used.
Examples of the alkaline aqueous solution include tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltrimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate Sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene Alkaline compound in which the concentration of the alkaline compound is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Solution, and the like. When the developer is an alkaline aqueous solution, the pH is preferably adjusted to 11 to 13, and more preferably adjusted to pH 11.5 to 12.5.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development temperature is preferably 20 ° C to 30 ° C. The development time is preferably 20 to 90 seconds.
The development may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent development unevenness by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

  After the development process, it is preferable to perform a rinsing process for washing and removing excess developer. The rinse treatment is usually performed with pure water, but to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. You may use the method of using ultrasonic irradiation together.

  After the development, after drying, a heat treatment (post-bake) can be performed. Post-baking is a heat treatment after development for complete film curing. When performing post-baking, the heating temperature is preferably 100 to 300 ° C, more preferably 150 to 250 ° C, and still more preferably 200 to 250 ° C. The heating time is preferably 10 minutes to 120 minutes. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

  In the method for producing a color filter of the present invention, the pattern (pixel) after development can be further subjected to ultraviolet irradiation (post-exposure). Further, post-exposure and post-bake can be used in combination. For example, post-baking is preferably performed after post-exposure.

The pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having pixels of a plurality of hues, the above steps may be repeated according to a desired number of colors.
In addition, every time the formation, exposure, and development of a monochromatic coloring composition layer are completed (for each color), the above-described post-exposure and post-bake treatment may be performed, or all coloring compositions having a desired number of colors may be performed. After the layer formation, exposure, and development are completed, the post-exposure and post-bake processes may be performed collectively.

  By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.

(Pattern formation by dry etching)
Moreover, the coloring composition of this invention is applicable also to the manufacturing method of the color filter containing a dry etching process. As an example of such a manufacturing method, a step of forming a colored layer using the colored composition of the present invention, a step of forming a photoresist layer on the colored layer, a photoresist layer by exposing and developing. Examples include a manufacturing method including a step of patterning to obtain a resist pattern and a step of dry etching the colored layer using the resist pattern as an etching mask.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) has good hue and contrast, and is excellent in heat resistance and solvent resistance.
The color filter of the present invention can be used for an image display device or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image having excellent spectral characteristics and contrast while achieving a good hue.

<Image display device>
The image display device of the present invention has the color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device. It is particularly suitable for liquid crystal display devices. The liquid crystal display device having the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics. Among them, the blue color filter of the image display device having at least a red color filter, a blue color filter, and a green color filter is constituted by the color filter of the present invention, so that the color of the display image is improved. It is possible to display a high-quality image that is good and excellent in display characteristics.

  For the definition of the image display device and details of the image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-Chip Spacer), FFS (Fringe Field Switching), and R-OCB (Reflective Optical Compensation Compliant Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensated Compensation
The color filter of the present invention can also be used for a bright and fine COA (Color-filter On Array) system.

  When the color filter of the present invention is used in an image display device, a high contrast can be realized when combined with a conventionally known three-wavelength cold-cathode tube. By doing so, it is possible to provide an image display device with high luminance and high color purity and good color reproducibility.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

The support has a transfer electrode made of a plurality of photodiodes and polysilicon forming a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.), and a photo is formed on the photodiode and the transfer electrode. A device having a light-shielding film made of tungsten or the like that is open only in the light-receiving portion of the diode, and a device protective layer made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion; The color filter of the present invention is provided on the protective layer.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light condensing means on the color filter. Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis example>
(Synthesis of TAM-001)
4,4'-dichlorobenzophenone (Tokyo Chemical Industry Co., Ltd.) 12.5 g, 2,4,6-trimethylaniline (Tokyo Chemical Industry Co., Ltd.) 15.0 g, t-butoxy sodium 14.4 g, toluene 150 mL It put into the flask and stirred at room temperature under nitrogen atmosphere. To this was added 56 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 266 mg of tri-t-butylphosphonium tetrafluoroborate (t-Bu ₃ P) (manufactured by Wako Pure Chemical Industries, Ltd.), followed by heating to reflux. Stir for 4 hours under conditions. After cooling, 200 mL of ethyl acetate and 200 mL of water were added, and the precipitated crystals were collected by filtration. The crystals were heated and washed with 100 mL of ethyl acetate, and 8.0 g of the obtained TAM-001A crystals were collected by filtration.

To a mixed solution of TAM-001A (2.6 g), sodium hydride (oil mixture, 60% by mass, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methylpyrrolidone 25 mL, methyl p-toluenesulfonate (Wako Pure Chemical Industries, Ltd.) 15.3 g (manufactured by Co., Ltd.) was added dropwise at room temperature. The solution after dropping was stirred at 75 ° C. for 2 hours. After cooling the reaction solution to room temperature, 100 mL of water was added. After the pH of the solution was adjusted to 6-7 with hydrochloric acid, the precipitated crude crystals were filtered. The crude crystals were suspended and washed with n-hexane to obtain 2.0 g of TAM-001B crystals.

50 g of 1-aminonaphthalene, 38 g of 1,2-epoxycyclohexane, and 150 mL of 1,3-hexafluoro-2-propanol were added to the flask and stirred for 5 hours under heating and refluxing conditions. After cooling to room temperature, the solvent was concentrated, washed with suspension by heating with 200 mL of hexane, and the resulting crystals were filtered and further washed with isopropyl alcohol to obtain TAM-001C (56 g).

To a mixed solution of TAM-001C (53.1 g) and acetonitrile 130 mL, 24.7 g of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After cooling in an ice bath, 25.32 g of N-methylimidazole (NMIm) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at an internal temperature of 20 ° C. or less. After maintaining at 10 ° C. and stirring for 1 hour, 41.3 g of water was added dropwise at an internal temperature of 10 ° C. to 15 ° C. After maintaining at 10 ° C. and stirring for 30 minutes, 41.3 g of water was further added dropwise at an internal temperature of 10 ° C. to 15 ° C. After stirring at 5 ° C. or lower for 1 hour, the precipitated crude crystals were filtered and washed with water to obtain 60.32 g of TAM-001D crystals.

22.2 g of phosphoryl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a mixed solution of TAM-001B (23 g), TAM-001D (13.7 g), and acetonitrile 71 mL, and the mixture was stirred for 3 hours under heating and refluxing conditions. . After cooling in an ice bath, water (24.2 g) was added dropwise at 20 ° C. or lower, then 48.3 mL of methanol was added, and the mixture was stirred for 1 hour under heating and refluxing conditions. After cooling to room temperature, ethyl acetate (161 mL), sodium chloride (21.9 g), water (193 g), and methanol (7.8 mL) were added for extraction. Extraction was performed by adding water (193 g) and 7.36 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to the organic layer, followed by extraction by adding water (193 g) and sodium chloride (10 g). . The organic layer was dehydrated and concentrated with anhydrous sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain TAM-001E (32 g).

Bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.0 g and methanol 250 mL were placed in a flask and stirred at room temperature for dissolution. TAM-001E (29.5 g) was added thereto and stirred for 30 minutes, and then 1000 mL of water was added dropwise to cause precipitation. The obtained crystal was purified by silica gel column chromatography to obtain TAM-001F (35.0 g).

After cooling a mixed solution of TAM-001F (9.81 g), 2.5 g of succinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 25 mL of acetonitrile in an ice bath, N-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 5.1 g was added dropwise at an internal temperature of 20 ° C or lower. After reacting at room temperature for 1 hour, ethyl acetate (75 mL), sodium chloride (7.5 g), and water (75 mL) were added and extracted. The organic layer was dehydrated with anhydrous sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.). After concentration, purification by silica gel chromatography gave 10 g of TAM-001 crystals. MALDI-MASS (matrix-assisted laser desorption / ionization mass spectrometry) (posi): 781.43.
The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-001 was 567 nm, and the molar extinction coefficient was 74200.

(Synthesis of TAM-003)
TAM-003 was obtained by the same method except that succinic anhydride was changed to glutaric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) in the synthesis of TAM-001. MALDI-MAS (posi): 815.45. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-003 was 567 nm, and the molar extinction coefficient was 72800.

(Synthesis of TAM-004)
In the synthesis of TAM-001, TAM-004 was obtained by the same method except that succinic anhydride was changed to diglycolic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). MALDI-MASS (posi): 817.43. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-004 was 567 nm, and the molar absorption coefficient was 74800.

(Synthesis of TAM-006)
In the synthesis of TAM-001A, TAM-006-A was obtained in the same manner except that 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2,4,6-trimethylaniline. It was.
In the synthesis of TAM-001B, TAM-006B was obtained in the same manner except that TAM-001A was changed to TAM-006A.
In the synthesis of TAM-001C, TAM-006C was obtained in the same manner except that TAM-001B was changed to TAM-006B.
In the synthesis of TAM-001D, TAM-006D was obtained in the same manner except that TAM-001C was changed to TAM-006C.
In the synthesis of TAM-001E, TAM-006E was obtained in the same manner except that TAM-001D was changed to TAM-006D.
TAM-006F was obtained by the same method except that TAM-001E was changed to TAM-006E in the synthesis of TAM-001F.
In the synthesis of TAM-001, TAM-006 was obtained in the same manner except that TAM-001F was changed to TAM-006F. MALDI-MASS (posi): 773.40. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-006 was 562 nm, and the molar extinction coefficient was 66300.

(Synthesis of TAM-007)
In the synthesis of TAM-001A, TAM-007-A was obtained in the same manner except that 2,6-diethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2,4,6-trimethylaniline. It was.
In the synthesis of TAM-001B, TAM-007B was obtained in the same manner except that TAM-001A was changed to TAM-007A.
In the synthesis of TAM-001C, TAM-007C was obtained in the same manner except that TAM-001B was changed to TAM-007B.
In the synthesis of TAM-001D, TAM-007D was obtained in the same manner except that TAM-001C was changed to TAM-007C.
In the synthesis of TAM-001E, TAM-007E was obtained in the same manner except that TAM-001D was changed to TAM-007D.
TAM-007F was obtained by the same method except that TAM-001E was changed to TAM-007E in the synthesis of TAM-001F.
In the synthesis of TAM-001, TAM-007 was obtained in the same manner except that TAM-001F was changed to TAM-007F. MALDI-MASS (posi): 829.47. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-007 was 564 nm, and the molar extinction coefficient was 62100.

(Synthesis of TAM-008)
In the synthesis of TAM-001A, TAM-008-A was obtained in the same manner except that 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2,4,6-trimethylaniline. It was.
TAM-008B was obtained by the same method except that TAM-001A was changed to TAM-008A in the synthesis of TAM-001B.
TAM-008C was obtained by the same method except that TAM-001B was changed to TAM-008B in the synthesis of TAM-001C.
In the synthesis of TAM-001D, TAM-008D was obtained in the same manner except that TAM-001C was changed to TAM-008C.
In the synthesis of TAM-001E, TAM-008E was obtained in the same manner except that TAM-001D was changed to TAM-008D.
TAM-008F was obtained by the same method except that TAM-001E was changed to TAM-008E in the synthesis of TAM-001F.
In the synthesis of TAM-001, TAM-008 was obtained in the same manner except that TAM-001F was changed to TAM-008F. MALDI-MASS (posi): 885.53. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-008 was 564 nm, and the molar extinction coefficient was 63200.

(Synthesis of TAM-044)
In the synthesis of TAM-001F, TAM-044F was obtained by the same method except that bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to sodium trifluoromethanesulfonate.
In the synthesis of TAM-001, TAM-044 was obtained by the same method except that TAM-001F was changed to TAM-044F. MALDI-MASS (posi): 781.43. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-044 was 567 nm, and the molar absorption coefficient was 71100.

(Synthesis of TAM-049)
In the synthesis of TAM-006F, TAM-049F was obtained by the same method except that bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to sodium trifluoromethanesulfonate.
In the synthesis of TAM-006, TAM-049 was obtained in the same manner except that TAM-006F was changed to TAM-049F. MALDI-MASS (posi): 773.40. The maximum absorption wavelength (methanol solution) of the absorption spectrum of TAM-049 was 562 nm, and the molar extinction coefficient was 65800.

<Preparation of coloring composition>
Raw materials having the following composition were mixed to prepare a colored composition.
-Composition-
Colorants listed in the following table: parts by mass listed in the following table: polymerizable compound (T-1): 6.0 parts by mass alkali-soluble resin (U-2): 5.3 Mass parts / photopolymerization initiator (V-4) 0.3 mass parts / curing accelerator (V-5) 0.2 mass parts / crosslinking agent (U-1) or crosslinking agent (U -2) ... parts by mass and additives (W-1) listed in the table below 0.5 parts by mass, solvent (X-1) ... 71 parts by mass, solvent (X-3)・ ・ 13 parts by mass ・ Surfactant (Z-1): 0.01 parts by mass

Polymerizable compound (T-1): KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Alkali-soluble resin (U-2): allyl methacrylate / methacrylic acid (77/23 “mass ratio” copolymer, weight average molecular weight 37,000, acid value 137 mg KOH / g)
Photopolymerization initiator (V-4): IRGACURE OXE-02 (manufactured by BASF)
Curing accelerator (V-5): Karenz MTBD-1 (manufactured by Showa Denko KK)
Crosslinking agent (U-1): Celoxide 2021P (manufactured by Daicel Corporation, epoxy compound)
-Crosslinking agent (U-2): jER1031S (Mitsubishi Chemical Corporation, epoxy compound)
Solvent (X-1): Propylene glycol monomethyl ether acetate Solvent (X-3): Methyl ethyl diglycol (manufactured by Nippon Emulsifier Co., Ltd.)
Additive (W-1): Potassium bis (trifluoromethanesulfonyl) imide (Mitsubishi Materials Corporation)
Surfactant (Z-1): The following mixture (Mw = 14000,% indicating the ratio of repeating units is% by mass)

<Production of cured film>
The colored composition obtained above was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the maximum absorbance at 600 to 700 nm was 1.5 to 2.0. The film was dried in an oven for 180 seconds to produce a cured film (colored film). The following evaluation was performed about the cured film obtained above.

<Heat resistance>
The ratio of absorbance at a wavelength of 600 nm between the transmission spectrum of the cured film obtained above and the transmission spectrum after additionally baking the cured film obtained above at 230 ° C. for 160 minutes was evaluated as a residual color rate (%). did. The higher the residual color rate, the better the heat resistance.
Residual color rate (%) = {absorbance at 600 nm of cured film after additional baking / absorbance at 600 nm of cured film before additional baking} × 100
Remaining color rate is 95% or more ... 8
Residual color rate is 90% or more and less than 95% ... 7
Residual color rate is 85% or more and less than 90% ... 6
Residual color rate is 80% or more and less than 85% ... 5
Residual color rate is 75% or more and less than 80% ... 4
Residual color rate is 70% or more and less than 75% 3
Residual color rate is 60% or more and less than 70% ... 2
Residual color rate is less than 60% ... 1

<Solvent resistance (color difference)>
The cured film obtained above is heated at 230 ° C. for 30 minutes, then immersed in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. for 60 minutes, and the chromaticity before and after immersion is measured. A change index ΔEab was calculated. The ΔEab value was calculated from the transmission spectrum of the cured film before and after being immersed in PGMEA. The lower the value of ΔEab, the smaller the hue change and the better the solvent resistance.
ΔEab is less than 0.5 ... 8
ΔEab is 0.5 or more and less than 1, 7
ΔEab is 1 or more and less than 1.5 6
ΔEab is 1.5 or more and less than 2, 5
ΔEab is 2 or more and less than 3, 4
ΔEab is 3 or more and less than 4 3
ΔEab is 4 or more and less than 5, 2
ΔEab is 5 or more ・ ・ ・ 1

<Contrast>
When the obtained cured film is sandwiched between two polarizing films, the luminance value when the polarizing axes of the two polarizing films are parallel and perpendicular is measured by a color luminance meter (manufactured by Topcon Corporation, model number: BM-5A) was measured, and the brightness when the polarization axes of the two polarizing films were parallel was divided by the brightness when vertical, and the obtained value was obtained as contrast. A higher contrast indicates better performance as a color filter for a liquid crystal display device. The contrast value is preferably 30,000 or more, more preferably 35,000 or more, and further preferably 40,000 or more.

From the above results, the Examples were able to produce a cured film having good heat resistance and solvent resistance and high contrast. Moreover, the heat resistance of the cured film, solvent resistance, and contrast were further improved by using the coloring composition which further contains a crosslinking agent.
On the other hand, the comparative example was inferior in at least one of heat resistance, solvent resistance, and contrast.

The colorants shown in the above table are as follows.
TAM001, TAM-003, TAM-004, TAM-006, TAM-007, TAM-008, TAM-011, TAM-012, TAM-018, TAM-026, TAM-027, TAM-044, TAM-049: Compounds with the following structure
Comparative compound 1: Compound having the following structure
Comparative compound 2: Compound having the following structure (compound described in JP-A-2015-127407)
Dye001, Dye002: Compounds having the following structure
PB15: 6: CI Pigment Blue 15: 6

Claims (19)

A coloring composition comprising a compound represented by formula (1) and a resin;
Formula (1)
In formula (1), R ¹ and R ² each independently represent a substituent,
R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent,
R ^{7 to} R ¹¹ each independently represents a substituent,
Represents a group containing at least one carboxyl group among R ^{1 to} R ¹¹ ;
n1 to n4 each independently represents an integer of 0 to 4, and n5 represents an integer of 0 to 6;
X represents an anion. The colored composition according to claim 1, wherein at least one of R ³ and R ⁴ is a group containing a carboxyl group.   The colored composition according to claim 1 or 2, wherein the compound represented by the formula (1) has one carboxyl group. The coloring composition according to any one of claims 1 to 3, wherein the compound represented by the formula (1) is a compound represented by the formula (2);
Formula (2)
In formula (2), each R ²⁰¹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms,
R ²⁰² and R ²⁰³ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
^R204 and ^R205 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L ¹ represents a divalent linking group, and X represents an anion.   The coloring composition according to any one of claims 1 to 4, wherein X is a bis (trifluoromethanesulfonyl) imide anion or a tris (trifluoromethanesulfonyl) methide anion.   Furthermore, the coloring composition of any one of Claims 1-5 containing a crosslinking agent.   Furthermore, the coloring composition of any one of Claims 1-6 containing a polymeric compound and a photoinitiator.   The coloring composition of Claim 7 in which the said photoinitiator contains an oxime compound.   Furthermore, the coloring composition of any one of Claims 1-8 containing at least 1 sort (s) chosen from a xanthene pigment and a dipyrromethene pigment.   Furthermore, the coloring composition of any one of Claims 1-9 containing a pigment.   The cured film formed by hardening | curing the coloring composition of any one of Claims 1-10.   A color filter having the cured film according to claim 11. Forming a colored composition layer on a substrate using the colored composition according to any one of claims 1 to 10, and
Forming a pattern on the colored composition layer by a photolithography method or a dry etching method.   A solid-state imaging device having the color filter according to claim 12.   An image display device comprising the color filter according to claim 12.   The image display device according to claim 15, wherein the image display device includes at least a red color filter, a blue color filter, and a green color filter, and the blue color filter is the color filter according to claim 12. Image display device. A compound represented by formula (1);
Formula (1)
In formula (1), R ¹ and R ² each independently represent a substituent,
R ^{3 to} R ⁶ each independently represent a hydrogen atom or a substituent,
R ^{7 to} R ¹¹ each independently represents a substituent,
At least one of R ^{1 to} R ¹¹ represents a group containing a carboxyl group;
n1 to n4 each independently represents an integer of 0 to 4, and n5 represents an integer of 0 to 6;
X represents an anion. The compound of Claim 17 whose compound represented by Formula (1) is a compound represented by Formula (2);
Formula (2)
In formula (2), each R ²⁰¹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms,
R ²⁰² and R ²⁰³ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms,
^R204 and ^R205 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L ¹ represents a divalent linking group, and X represents an anion.   19. A compound according to claim 17 or 18, wherein X represents a bis (trifluoromethanesulfonyl) imide anion or a tris (trifluoromethanesulfonyl) methide anion.