JP2015113421A - Colored resin composition, color filter, liquid crystal display device, and organic electroluminescence (el) display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition having high color purity and brightness and sufficient heat resistance and light fastness, and a color filter, a liquid crystal display device and an organic EL display device using the composition.SOLUTION: The colored resin composition comprises (A) a coloring material, (B) a solvent, and (C) a binder resin. The (A) coloring material comprises a triaryl methane compound represented by formula (I). Further, the coloring material includes, as a pigment, a metal phthalocyanine. In formula (I), Arepresents an anion, which is an imide anion.

Description

  The present invention resides in a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

Flat panel displays such as liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used, and color filters are used for these displays.
With the trend of energy saving, the color filter is required to have higher brightness and higher contrast.

As a color filter forming material, a colored resin composition using a pigment is mainly used. In order to obtain high luminance and high contrast, for example, in Non-Patent Document 1, the particle size of pigment particles is colored. A method of finely dispersing to 1/2 or less of the wavelength is disclosed.
On the other hand, dyes have also been developed as color materials used in colored resin compositions for color filters.

  For example, Patent Document 1 discloses using a triarylmethane derivative as a dye. Patent Documents 2, 3 and 4 disclose the use of a triarylmethane compound having a specific structure of an anion in a triarylmethane salt.

JP 2008-304766 A International Publication No. 2011/152379 Pamphlet JP 2012-83651 A JP 2013-079370 A

Kiyoshi Hashizume, “Color Material Association”, December 1967, p608

However, the method disclosed in Non-Patent Document 1 requires a further fine dispersion because the blue pigment has a shorter coloration wavelength than other red and green pigments, and increases the cost and stability after dispersion. It becomes a problem.
Further, according to the study by the present inventors, when a triarylmethane compound having a cation structure described in Patent Document 1 is used, luminance (transmittance) is a conventional material using a pigment as a colorant. However, it was found that the heat resistance in baking at 230 ° C. required in the color display manufacturing process is insufficient.

On the other hand, even when the triarylmethane-based compound having a cation structure described in Patent Documents 2 to 4 is used, the heat resistance in baking at 230 ° C. required in the color display manufacturing process and the long-term reliability of the color display. It was found that it was difficult to satisfy both required light resistance characteristics.
Accordingly, an object of the present invention is to provide a coloring composition that has high color purity and brightness, and satisfies the heat resistance required in the color display manufacturing process and the light resistance required for long-term reliability of the color display. It is another object of the present invention to provide a color filter, a liquid crystal display device, and an organic EL display device that have high color purity and brightness and satisfy heat resistance and light resistance.

As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by using a novel triarylmethane compound having a specific structure, and the present invention has been completed.
That is, the gist of the present invention is as follows.
[1] containing (A) a color material, (B) a solvent, and (C) a binder resin,
(A) A colored resin composition, wherein the color material contains a triarylmethane compound represented by the following formula (I).

(In the above formula (I),
[A ⁿ⁻ ] represents an n-valent anion.
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
However, at least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent.

At least one combination selected from the group consisting of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be linked to each other to form a ring, and the ring has a substituent. You may do it.
One of R ⁷ and R ⁸ is an optionally substituted alkyl group or a halogen atom, and the other is a hydrogen atom.

Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent.
n represents an integer of 1 to 4, and when n is 2 to 4, a plurality of cations represented by the following formula (I) _CA contained in one molecule may each independently have the same structure. , Different structures may be used. )

[2] The colored resin composition according to [1], wherein the anion is an imide anion.
[3] The colored resin composition according to [1] or [2], wherein the anion is represented by the following formula (II).

(In the formula (II), R ¹¹ and R ¹² each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
R ¹¹ and R ¹² may be connected to each other to form a ring, and the ring may have a substituent. )
[4] The colored resin composition according to [3], wherein at least one of R ¹¹ and R ¹² is a group having a fluorine atom.
[5] The content ratio of the triarylmethane compound represented by the formula (I) is 0.01% by mass or more based on the total solid content, and any one of [1] to [4] The colored resin composition as described in any one.
[6] The colored resin composition according to any one of [1] to [5], further comprising (D) a polymerizable monomer.
[7] The colored resin composition according to any one of [1] to [6], further comprising (E) a photopolymerization initiating component and / or (E ′) a thermal polymerization initiating component. object.
[8] The colored resin composition according to any one of [1] to [7], wherein (A) the colorant further contains a pigment.
[9] The colored resin composition as described in [8], wherein the pigment is metal phthalocyanine.
[10] The content ratio of the compound represented by the formula (I) in the color material (A) is 50% by mass or more based on the total mass of the color material [8] or [9] The colored resin composition described in 1.
[11] A color filter comprising a pixel formed using the colored resin composition according to any one of [1] to [10].
[12] A liquid crystal display device comprising the color filter according to [11].
[13] An organic EL display device comprising the color filter according to [11].
[14] A triarylmethane compound represented by the following formula (I).

(In the above formula (I),
[A ⁿ⁻ ] represents an n-valent anion.
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
However, at least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent.

At least one combination selected from the group consisting of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be linked to each other to form a ring, and the ring has a substituent. You may do it.
One of R ⁷ and R ⁸ is an optionally substituted alkyl group or a halogen atom, and the other is a hydrogen atom.

Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent.
n represents an integer of 1 to 4, and when n is 2 to 4, a plurality of cations represented by the following formula (I) _CA contained in one molecule are each independently the same structure, Different structures may be used. )

[15] The triarylmethane compound according to [14], wherein the anion is an imide anion.
[16] The triarylmethane compound according to [14] or [15], wherein the anion is represented by the following formula (II).

(In the formula (II), R ¹¹ and R ¹² each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
R ¹¹ and R ¹² may be connected to each other to form a ring, and the ring may have a substituent. )
[17] A dye comprising the triarylmethane compound according to any one of [14] to [16].

ADVANTAGE OF THE INVENTION According to this invention, it can provide the colored resin composition which is excellent in color purity and brightness | luminance, has the heat resistance requested | required in a color display manufacturing process, and satisfies the light resistance requested | required by long-term reliability.
Furthermore, according to the present invention, it is possible to provide a color filter, a liquid crystal display device, and an organic EL display device that have high color purity and brightness and satisfy heat resistance and light resistance.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element having the color filter of the present invention. FIG. 2 is a graph showing the transmittance of the polarizing plate used in the examples.

Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “at least one of acryl and methacryl”, “at least one of acrylate and methacrylate” and the like, for example, “( “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
A term such as “CI Pigment Green” means a color material name included in the color index (CI).

  The colored resin composition of the present invention contains (A) a color material, (B) a solvent, and (C) a binder resin, and (A) the color material is a triarylmethane type represented by the formula (I) described later. It is characterized by containing a compound. Further, it preferably contains at least one of (D) a polymerizable monomer, and (E) a photopolymerization initiation component and (E ′) a thermal polymerization initiation component, and may contain other components as necessary. .

[(A) Color material]
(Compound represented by formula (I))
The color material (A) contained in the colored resin composition of the present invention contains a triarylmethane compound represented by the following general formula (I).

In the above formula (I),
[A ⁿ⁻ ] represents an n-valent anion.
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
However, at least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent.

At least one combination selected from the group consisting of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be linked to each other to form a ring, and the ring has a substituent. You may do it.
One of R ⁷ and R ⁸ is an optionally substituted alkyl group or a halogen atom, and the other is a hydrogen atom.

Further, the benzene ring and naphthalene ring forming the triarylmethane skeleton in the above formula (I) may further have an arbitrary substituent.
n represents an integer of 1 to 4, and when n is 2 to 4, cations represented by the following formula (I) _CA contained in one molecule are independently different even in the same structure. It may be a structure.

^(R 1 ~R 6)
R ^{1 to} R ⁶ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
However, at least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent. At least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent, and any one of R ⁷ and R ⁸ has a substituent. By using an alkyl group that may be substituted and a hydrogen atom on the other side, the steepness of the absorption waveform near 500 nm, that is, while maintaining high luminance, the heat and light of the molecule represented by formula (I) Contributes to the improvement of various physical properties by the effect of these substituents inhibiting the attack from other molecules, which causes decomposition, and the effect of the molecules represented by formula (I) associating and inhibiting each other. It is thought to do.

Further, both R ⁵ and R ⁶ may be an alkyl group having a secondary carbon which may have a substituent, and either one of R ⁵ and R ⁶ may be a substituent. It is good also as an alkyl group which has secondary carbon which you may have, and it is good also as groups other than the alkyl group which has secondary carbon which may have the other. If the substituents of R ⁵ and R ⁶ are large, steric hindrance may occur, inhibiting the association between molecules represented by formula (I) and electrostatic interaction with anions, which may reduce heat resistance. Therefore, any one of R ⁵ and R ⁶ may have a substituent, an alkyl group having a secondary carbon, and the other may have a substituent, a secondary It is preferable to use a group other than an alkyl group having carbon, and it is more preferable that either one is an optionally substituted alkyl group having a secondary carbon and the other is a hydrogen atom.

Note that "at least one of R ⁵ and R ⁶ may have a substituent, an alkyl group having a secondary carbon" refers to at least one of R ⁵ or R ^6, a substituted It means an alkyl group having a group represented by the following formula (III) which may have a group. In addition, * in a formula means a bond.
Α and β in the following formula (III) each independently represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. The C-α bond represents a bond between the carbon atom and the carbon atom of the substituent α, and the C-β bond similarly represents a bond between the carbon atom and the carbon atom of the substituent β. Α and β may be linked to form a ring, and the ring may have a substituent.

The alkyl group having a secondary carbon which may have a substituent is not limited as long as it has a group represented by the above formula (III). For example, the group represented by the above formula (III) itself may be used, or an alkylene group which may have a substituent may be bonded to the group represented by the above formula (III). Good. From the viewpoint of increasing the volume around the nitrogen atom, the group itself represented by the above formula (III) is preferable. That is, the alkyl group having a secondary carbon which may have a substituent is a group itself represented by the above formula (III), and any one of R ⁷ and R ⁸ is a substituent. It is an alkyl group that may be present, and the other is a hydrogen atom, which contributes to the improvement of various physical properties because this substituent inhibits attacks from other molecules that cause decomposition by light. Tend.

  Examples of the alkyl group for α and β include a linear, branched or cyclic alkyl group. The carbon number including α and β in the carbon number is preferably 30 or less, more preferably 12 or less, further preferably 8 or less, and most preferably 6 or less, Usually one or more. By setting it to the upper limit or less, in the colored resin composition, the solubility in the solvent of the formula (I) can be appropriately adjusted, and the association between the molecules represented by the formula (I) and cations Since effective interaction with an anion occurs, heat resistance and light resistance tend to be improved.

  Specific examples of the alkyl group in α and β include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. Group, phenethyl group, 3-methylbutyl group, 2-ethoxyethyl group and the like. Among these, a linear alkyl group is preferable from the viewpoint of association between molecules represented by the formula (I) and electrostatic interaction with an anion.

  Examples of the aromatic ring group for α and β include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 28 or less, more preferably 10 or less, and even more preferably 6 or less. By setting it to the upper limit or less, the solubility in the solvent of the formula (I) can be appropriately adjusted, and the association between the molecules represented by the formula (I) and effective mutual interaction between the cation and the anion can be achieved. Since the action occurs, heat resistance and light resistance tend to be improved.

  The aromatic hydrocarbon ring group in α and β may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring having one free valence, Examples include perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence, Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring , Quinazolinone Include groups such as azulene ring.

α and β may be linked to form a ring, and the ring may have a substituent. The ring may be a ring bridged with a heteroatom. The number of carbon atoms of the ring (including C atom bonded to α and β, including α and β) is preferably 30 or less, more preferably 12 or less, still more preferably 8 or less, 3 or more. By setting it to the upper limit or less, the solubility in the solvent of the formula (I) can be appropriately adjusted, and the association between the molecules represented by the formula (I) and effective mutual interaction between the cation and the anion can be achieved. Since the action occurs, heat resistance and light resistance tend to be improved.
In the case where α and β are connected to form a ring, specific examples of the alkyl group having a secondary carbon include the following structures.

Examples of the substituent that the alkyl group in α and β may have include those in the following substituent group W1. Moreover, as a substituent which the aromatic ring group may have, the following substituent group W2 is mentioned, for example. Furthermore, as a substituent which the ring formed by mutually connecting may have, the thing of the following substituent group W3 is mentioned, for example.
As α and β, α and β are preferably included in the number of carbon atoms, and each independently a linear alkyl group having 1 to 12 carbon atoms which may have a substituent or α and β are linked to each other. To form a ring. More preferably, it is a case where an optionally substituted alkyl group having 1 to 6 carbon atoms or adjacent α and β having 3 to 12 carbon atoms are connected to each other to form a ring. When these substituents are used, association between the compounds (I) and effective interaction between the cation and the anion occur, so that heat resistance and light resistance tend to be improved.

The total number of carbon atoms in the alkyl group having a secondary carbon in R ⁵ and R ⁶ is preferably 30 or less, more preferably 12 or less, further preferably 8 or less, and 6 or less. Most preferred. Usually, it is 3 or more, preferably 4 or more, more preferably 5 or more. By being within the above range, in the colored resin composition, the interaction between the molecules represented by the formula (I) and the electrostatic capacity of the cation and anion within the molecule in the compound represented by the formula (I). Interaction tends to be appropriate and durability can be improved.

Specific examples of the alkyl group having a secondary carbon include isopropyl group, s-butyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, cyclopentyl group, 1-methylpentyl group, 1- Ethylbutyl group, 1-propylbutyl group, 1-ethylpentyl group, 1-propylpentyl group, 1-butylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-propylhexyl group, 1-butylhexyl group, 1-propylhexyl group, cyclohexyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group, 2-cyclopropylcyclohexyl group, 2-butylcyclohexyl group, 2 -S-butylcyclohexyl group, 2-t-butylcyclohexyl 2-isobutylcyclohexyl group, 2-cyclobutylcyclohexyl group, 2-pentylcyclohexyl group, 2-cyclopentylcyclohexyl group, 2-cyclohexylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,6- Dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,3, 5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 1-ethylheptyl group, 1-methylheptyl group, 1-propylheptyl group, 1-butylheptyl group, 1-pentylheptyl group, 1-hexyl Heptyl, cycloheptyl, 2-methylcycloheptyl, 3-methylcycloheptyl Group, 4-methylcycloheptyl group, 2,7-dimethylcycloheptyl group, 1-cyclohexylethyl group, 1-methyloctyl group, 1-ethyloctyl group, 1-propyloctyl group, 1-butyloctyl group, 1- Pentyloctyl group, 1-hexyloctyl group, 1-heptyloctyl group, cyclooctyl group, 1-methylcyclooctyl group, 2-methylcyclooctyl group, 3-methylcyclooctyl group, 4-methylcyclooctyl group, 2- And an adamantyl group.

  Among these, isopropyl group, s-butyl group, 1-methylpropyl group, 1-ethylpropyl group from the viewpoint of improving durability due to association between molecules represented by formula (I) and electrostatic interaction with anions. Group, 1-methylbutyl group, 1-ethylbutyl group, 1-propylbutyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, cyclopentyl group, Or a cyclooctyl group is preferable.

Examples of the alkyl group for R ^{1 to} R ⁶ include a linear, branched, or cyclic alkyl group. The number of carbon atoms is preferably 30 or less, and more preferably 12 or less. By setting it to the upper limit or less, in the colored resin composition, the solubility of the triarylmethane-based compound can be appropriately adjusted, and an effective interaction between the cation and the anion occurs. There is a tendency for light resistance to improve.

Specific examples of the alkyl group in R ^{1 to} R ⁶ include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include cyclohexylethyl group, phenethyl group, 3-methylbutyl group, 2-ethoxyethyl group and the like. Among these, a linear alkyl group is preferable from the viewpoint of association between molecules represented by the formula (I) and electrostatic interaction with an anion.

Examples of the aromatic ring group for R ^{1 to} R ⁶ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 30 or less, and more preferably 12 or less. By making it not more than the above upper limit value, the conjugate length becomes appropriate, and the absorption waveform near 500 nm becomes steep, so that a tendency to increase in brightness is seen, and in the colored resin composition, a triarylmethane compound, Since the interaction with other compounds constituting the composition is appropriate, the solubility tends to be adjusted appropriately.

The aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene having one free valence. And groups such as a ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence. , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Ring, quinazo Non rings include groups such as azulene ring.

Adjacent R ^{1 to} R ⁴ (specifically, R ¹ and R ² , R ³ and R ⁴ ) may be linked to form a ring, and the ring has a substituent. Also good.
In addition, the ring may be a ring bridged with a heteroatom, and specific examples thereof include the following structures.

From the viewpoint of chemical stability, R ^{1 to} R ⁴ are preferably each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a substituent. It is a good phenyl group or a case where adjacent R ^{1 to} R ⁴ are connected to each other to form a ring. These substituents are also preferable in terms of luminance. It has the C1-C12 alkyl group or substituent which may have a substituent more preferably at the point which improves the heat resistance of compound (I), and the heat resistance of the color filter obtained is excellent. It may be a phenyl group.

R ¹ to R ⁴ is optionally substituted alkyl group which may having 1 to 12 carbon atoms, the charge in the cation is dispersed by hyperconjugative, cations are assumed to be stabilized.
More specifically, the number of carbon atoms of the alkyl group in R ^{1 to} R ⁴ is less likely to affect the conformation of the triarylmethane skeleton (has less effect on luminance), and less likely to remove a substituent on nitrogen. (Compound (I) is stable), preferably 8 or less, more preferably 4 or less, and preferably 2 or more.

Further, when adjacent R ^{1 to} R ⁴ are connected to each other to form a ring, the substituent on N tends to be less likely to be eliminated, and thus tends to be stable.
In the case where R ^{1 to} R ⁴ are phenyl groups which may have a substituent, the conjugated system is extended, so that the charge in the cation is dispersed and the cation is stabilized. As described above, it can be considered that as a result of stabilization of the cation, the heat resistance of the obtained color filter is further improved.

On the other hand, when any one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon and the other is a group other than an alkyl group having a secondary carbon, the alkyl group having a secondary carbon Examples of other groups include hydrogen atoms, methyl groups, ethyl groups, propyl groups, butyl groups, t-butyl groups, pentyl groups and other alkyl groups having 1 to 5 carbon atoms, hydroxyethyl groups, hydroxypropyl groups and other carbons. 1 to 5 hydroxyalkyl groups, methoxyethyl groups, ethoxyethyl groups, ethoxypropyl groups, butoxyethyl groups such as alkoxyalkyl groups having 1 to 5 carbon atoms, and hydroxy groups having 1 to 5 carbon atoms such as 2-hydroxyethoxy groups C1-C5 alkoxy (C1-C5) alkoxy group, such as alkoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-sulfo Butyl group, carboxyethyl group, etc. cyanoethyl group.

R ⁵ and R ⁶ may combine with each other to form a ring, and the ring may have a substituent. The ring may be a ring bridged with a heteroatom.
As a substituent which the alkyl group in R < ¹ > -R < ⁶ > may have, the thing of the following substituent group W1 is mentioned, for example. Moreover, as a substituent which the aromatic ring group may have, the following substituent group W2 is mentioned, for example. Furthermore, as a substituent which the ring formed by mutually connecting may have, the thing of the following substituent group W3 is mentioned, for example.
Moreover, as an arbitrary substituent which the benzene ring and naphthalene ring which form the triarylmethane skeleton in Formula (I) may have, the thing of the following substituent group W2 is mentioned.

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms Carbonyloxy group, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, and alkyl group having 1 to 4 carbon atoms A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.
Among them, preferred are an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom. .

(Substituent group W2)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, C2-C9 alkylcarbonyloxy group, sulfamoyl group, C2-C9 alkylsulfamoyl group, C2-C9 alkylcarbonyl group, hydroxyethyl group, acetylamide group, C1-C1 A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.
Among them, preferably an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkyl group having 2 to 9 carbon atoms. A famoyl group and a fluorine atom;

(Substituent group W3)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, alkylcarbonyloxy group having 2 to 9 carbon atoms, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, or an alkylthio group having 1 to 8 carbon atoms, which is formed by bonding an alkyl group having 1 to 4 carbon atoms.
Among them, preferably an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, and an alkyl group having 2 to 9 carbon atoms. A famoyl group and a fluorine atom;

(About R ⁷ and R ⁸ )
One of R ⁷ and R ⁸ is an optionally substituted alkyl group or a halogen atom, and the other is a hydrogen atom. At least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent, and any one of R ⁷ and R ⁸ has a substituent. By using an alkyl group or halogen atom that may be present and the other being a hydrogen atom, the heat and light of the molecule represented by formula (I) can be maintained while maintaining the steep absorption waveform near 500 nm, that is, high luminance. Various physical properties are improved by the effect of inhibiting these substituents against the attack from other molecules, which causes the decomposition of the compound, and the effect of inhibiting the molecules represented by the formula (I) to associate with each other. It is thought that it contributes to.

Examples of the alkyl group for R ⁷ and R ⁸ include linear, branched or cyclic alkyl groups. The number of carbon atoms of the alkyl group is preferably 8 or less, more preferably 6 or less, particularly preferably 4 or less, from the viewpoint that the change in absorption spectrum due to the change in molecular conformation and the resulting decrease in luminance of the pixel are less likely to occur. Usually one or more.
Specific examples of the alkyl group in R ⁷ and R ⁸ include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples thereof include a cyclohexylethyl group and a phenethyl group. From the viewpoints of steric protection and the shape of the absorption spectrum, R ⁷ is preferably a hydrogen atom and R ⁸ is an alkyl group, particularly preferably R ⁷ is a hydrogen atom and R ⁸ is a methyl group.

The substituent that the alkyl group in R ⁷ and R ⁸ may have is preferably a halogen atom. That is, a fluoroalkyl group typified by a fluoromethyl group such as a trifluoromethyl group is preferred.
In addition, examples of the halogen atom in R ⁷ and R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of luminance due to the conformational change of the molecule derived from the size of the atom and the charge stability of the cation molecule. From the viewpoint of properties, a fluorine atom or a chlorine atom is preferable, and a chlorine atom is more preferable.
Among these, from the viewpoint of stabilizing the positive charge of the cation, either one of R ⁷ and R ⁸ is an alkyl group which may be an electron donating group and may have a substituent. preferable.

(Combination of R ^{1 to} R ⁸ )
The R ¹ to R ^8, may be suitably selected from those described above. Specific examples of combinations include those described in Table 1. The alkyl group, aromatic ring and heterocyclic ring listed in the following table may further contain an arbitrary substituent. C in the table means carbon number.

As a combination of R ^{1 to} R ⁸ , from the viewpoint of increasing the absorption waveform near 500 nm, that is, from the viewpoint of increasing the brightness, two or more of R ^{1 to} R ⁴ may have a substituent. Combinations that are groups are preferred. Furthermore, in consideration of stabilization due to electrostatic interaction with cations and anions in the colored resin composition and energy relaxation due to interaction between molecules, all of R ^{1 to} R ⁴ have substituents. A combination of alkyl groups that may be substituted, or an aryl group that is optionally substituted at two positions, and an optionally substituted alkyl group at the other two positions. Some 1 to 16 are desirable. In particular, when the viewpoints of improving heat resistance are combined, the combination of 1 to 8 is most preferable.

In the case of this combination of 1 to 8, the compound represented by the formula (I) can be decomposed by heat or light, while inhibiting the attack from other molecules, the steric hindrance of the substituent causes the formula ( There is a tendency that heat resistance and light resistance are improved without lowering the association between the molecules represented by I) and electrostatic interaction with anions. In particular, R ⁵ is a hydrogen atom, R ⁶ is an optionally substituted linear alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having a secondary carbon, and R ⁷ is It is preferably a hydrogen atom and R ⁸ is an optionally substituted alkyl group having 1 to 4 carbon atoms. From the viewpoint of a coloring material, if the R ^{1 to} R ⁸ substituents of the compound represented by the formula (I) are small, the contribution of conjugation spreading to the three aryl rings of the triarylmethane skeleton due to steric hindrance Tends to be large and can function as a preferred blue color material. From this viewpoint, R ^{1 to} R ⁴ are an optionally substituted alkyl group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group having 6 to 12 carbon atoms having a substituent, and R ⁵ is A hydrogen atom, R ⁶ optionally having a substituent, a secondary carbon having 3 to 12 carbon atoms or a cyclic alkyl group, R ⁷ being a hydrogen atom, and R ⁸ being It is preferable that it is a C1-C4 alkyl group which may have a substituent.

(About [A ⁿ⁻ ] and n)
In formula (I), [A ⁿ⁻ ] represents an n-valent anion, and n represents an integer of 1 to 4. Here, A represents an atom or an atomic group constituting an anion.
From the viewpoint of interaction with the cation, n is preferably 4 or less, more preferably 2 or less, and even more preferably 1. By setting it to the upper limit value or less, the anion and the cation are arranged close to each other, and thus physical properties such as heat resistance and light resistance tend to be improved.

  The counter anion of the triarylmethane cation is not particularly limited as long as the effects of the present invention are not impaired. Specific examples thereof include compounds containing sulfonate, phosphonate, borate, imide anion, methide anion, alkoxide, carboxylate, halogen anion, and metal anion. Among these, from the viewpoint of easily delocalizing the charge of the counter anion, a compound containing an imide anion is preferable. That is, since the charge of the anion is delocalized, the counter anion can be prevented from reacting with the triarylmethane cation with heat and light, and thus durability tends to be improved.

  Easy to manufacture, the negative charge is delocalized and the anion is stable, and the negative charge is delocalized and the electrostatic interaction with the triarylmethane cation is appropriate. And is preferably a disulfonylimide anion. Although it does not specifically limit about the structure of a disulfonyl imide anion, For example, what is represented by following formula (II) is mentioned.

R ¹¹ and R ¹² each independently represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an cycloalkyl group that may have a substituent. .
R ¹¹ and R ¹² may be connected to each other to form a ring, and the ring may have a substituent.
(About R ¹¹ and R ¹² )
R ¹¹ and R ¹² represent an alkyl group which may have a substituent and an alkenyl group which may have a substituent.

Examples of the alkyl group for R ¹¹ and R ¹² include a linear, branched or cyclic alkyl group. The carbon number is preferably 30 or less, more preferably 12 or less, and the carbon number of the linear or branched alkyl is usually 1 or more, and the carbon number of the cyclic alkyl group is usually 3 or more. It is. By setting it within the above range, the electrostatic interaction between the cation and the anion becomes appropriate, and the durability tends to be improved.

Specific examples of the alkyl group in R ¹¹ and R ¹² include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a cyclohexylethyl group, a phenethyl group, a 3-methylbutyl group, a 2-ethoxyethyl group, a trifluoromethyl group, and a perfluoroalkyl group having 1 to 12 carbon atoms.

Examples of the alkenyl group for R ¹¹ and R ¹² include linear, branched, or cyclic alkenyl groups. The carbon number is preferably 6 or less, and usually 2 or more. By setting it within the above range, the intermolecular interaction of the triarylmethane compound becomes appropriate, and the durability tends to be improved.
Specific examples of the alkenyl group for R ¹¹ and R ¹² include a vinyl group, an allyl group, 1
-Propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, etc. are mentioned.

Examples of the substituent that these groups may have include those described in the aforementioned substituent groups W1 and W2.
Among these, in particular, as the substituent of the alkyl group or alkenyl group in R ¹¹ and R ¹² , the charge of the anion is more delocalized, and the heat resistance of the colorant tends to be improved. It preferably has a fluorine atom as a substituent.
That is, R ¹¹ and R ¹² are preferably a C 1-12 perfluoroalkyl group in that the anion charge is dispersed and the anion tends to be stabilized.
More specifically, the anion represented by the formula (II) is preferably represented by the following formula (II-1).

In the above formula (II-1), m and m ′ each independently represents an integer of 1 to 8.
m and m ′ are integers of 1 to 8, but are preferably integers of 1 to 4. m and m ′ may be the same or different.
Specific examples of the sulfonylimide anion when m and m ′ are the same include bis (trifluoromethanesulfone) imide, bis (pentafluorobutanesulfone) imide, and the like.

Specific examples of the sulfonylimide anion when m and m ′ are different include pentafluoroethanesulfone trifluoromethanesulfonimide, trifluoromethanesulfone heptafluoropropanesulfonimide, fluorobutanesulfone trifluoromethanesulfonimide, and the like.
Among these, bis (pentafluoroethanesulfone) imide, in which m = m ′ = 2, is particularly preferable because the anion is most stabilized.

On the other hand, in the formula (II), R ¹¹ and R ¹² may be connected to each other to form a ring.
In the case of forming a ring, the group formed by linking R ¹¹ and R ¹² is particularly preferably a fluoroalkylene group having 2 to 12 carbon atoms.
That is, the anion represented by the formula (II) is preferably an anion represented by the following formula (II-2).

In the above formula (II-2), m ″ represents an integer of 2 to 12.
m ″ is preferably an integer of 2 to 8 and more preferably 3 in terms of good heat resistance.
An anion having a smaller number of m ″ has a smaller effect of steric repulsion and tends to allow stronger interaction. That is, it is presumed that the smaller the m ″, the greater the interaction between the anion and the cation, the more counterion is stabilized and the heat resistance of the dye is improved.

The compound represented by the formula (I) are, for example, from R ¹ to R ^6, stretched a linker, may form a like a dimer or trimer.
In addition, the presence form of the triarylmethane compound represented by the formula (I) in the colored resin composition is not particularly limited, and may be a dye and / or a pigment. From the standpoint of sufficient solubility of the dye, it is preferably present in the form of a dye.

(Molecular weight)
In the triarylmethane compound represented by the general formula (I), the molecular weight of the triarylmethane cation is preferably 270 or more, more preferably 470 or more, and usually 1970 or less. It is preferable that it is in the above-mentioned range in that the solubility in the colored resin composition is sufficient and the content in the colored resin composition can be reduced, so that the curability can be sufficiently secured.
The total molecular weight of the cation and the anion is preferably 300 or more, more preferably 500 or more, and usually 2000 or less. It is preferable that it is in the above-mentioned range in that the solubility in the colored resin composition is sufficient and the content in the colored resin composition can be reduced, so that the curability can be sufficiently secured.

(Specific examples of compounds represented by formula (I))
Examples of the compound represented by the formula (I) include those listed below.

(Method for synthesizing compound represented by formula (I))
The triarylmethane compounds represented by the formula (I) include, for example, “reviewed synthetic dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968), “theoretical manufacturing dye chemistry” (Toyo Hosoda, Gihodo, 1957). Although it can synthesize | combine according to the method as described in international publication 2009/107734 pamphlet, it is not restricted to this method.

(Content ratio in the colored resin composition of the compound represented by the formula (I))
In the colored resin composition of the present invention, only one type of compound represented by the formula (I) may be included in the color material (A), or two or more types may be included. The compound represented by formula (I) in the total solid content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and further more preferably 5% by mass. As described above, it can be contained in a proportion of preferably 8% by mass or more, preferably 70% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
It is preferable for it to be less than or equal to the above upper limit value because the curability of the coating film is unlikely to decrease and the film strength tends to be sufficient. Moreover, since it is sufficient for coloring power to be more than the said lower limit, the chromaticity of a desired density | concentration is easy to be obtained, and since it is hard to become thick, it is preferable.

(Content ratio of the compound represented by the formula (I) in the coloring material)
Further, the content ratio of the compound represented by the formula (I) in the (A) color material is not particularly limited, but is preferably 0.01% by mass or more with respect to the (A) color material. More preferably, it is more preferably 1% by weight or more, still more preferably 5% by weight or more, particularly preferably 20% by weight or more, and more preferably 50% by weight or more. Most preferred. Moreover, it is 100 mass% or less normally, it is preferable that it is 99 mass% or less, it is more preferable that it is 95 mass% or less, and it is further more preferable that it is 90 mass% or less. It is preferable for it to be less than or equal to the above upper limit value because the curability of the coating film is hardly lowered and the film strength is sufficient. Moreover, since it is sufficient for coloring power to be more than the said lower limit, the chromaticity of a desired density | concentration is easy to be obtained, and since it is hard to become thick, it is preferable.

(Other color materials)
The color material (A) contained in the colored resin composition of the present invention contains a triarylmethane compound represented by the formula (I), but other color materials may be used as long as the effects of the present invention are not impaired. You may contain. Examples of the color material include dyes and pigments.

(Content ratio of other coloring materials in the coloring resin composition and coloring materials)
The colored resin composition of the present invention may contain a coloring material other than the triarylmethane compound represented by the formula (I), and the content ratio is not particularly limited, but is preferably 70 in the total solid content. It is not more than mass%, more preferably not more than 40 mass%, still more preferably not more than 30 mass%. Moreover, the content rate with respect to (A) color material becomes like this. Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 10 mass% or less. Within the above range, the color tone, heat resistance, and light resistance of the obtained pixel are easily improved without greatly affecting the absorption waveform and luminance in the colored resin composition.

(Other dyes)
Other dyes include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, Preferred examples include dipyrromethene dyes and xanthene dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 25, C.I. I. Acid Blue 40, C.I. I. Acid Blue 80, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Vat Blue 5, those described in JP-A No. 2002-14222, JP-A No. 2005-134759, JP-A No. 2010-191358 and JP-A No. 2011-148950 are examples of quinoneimine dyes such as C . I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Examples of triarylmethane dyes include C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Acid Blue 108, International Publication No. 2009/107734 Pamphlet, International Publication No. 2011/162217 Pamphlet, and the like.
Furthermore, examples of the cyanine dye include those described in International Publication No. 2011/162217 pamphlet, and preferred embodiments thereof are also the same.

  Examples of dipyrromethene dyes include, for example, JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, JP-A-2011-158654, and JP-A-2011-158654. Examples described in JP 2012-158739 A, JP 2012-224852 A, JP 2012-224849 A, JP 2012-224847 A, JP 2012-224846 A, and the like can be given.

Examples of xanthene dyes include C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, Japanese Patent No. 3387541, Japanese Patent Application Laid-Open No. 2010-32999, Japanese Patent No. 4492760, “Review Synthetic Dye” (Horiguchi Hiroshi, Sankyo Publishing, 1968), pages 326 to 348, etc. Is mentioned.
In particular, when forming a blue pixel, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, cyanine dyes, and phthalocyanine dyes are preferable.
In the colored resin composition of the present invention, as the color material (A), only one type of compound represented by the general formula (I) may be contained, or two or more types may be contained.
Similarly, only one other dye may be included, or two or more other dyes may be included.

(Other pigments)
As the pigment, for example, when forming a pixel of a color filter, pigments of various colors such as blue and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

Among these, a phthalocyanine pigment having a central metal is preferable, and a blue copper phthalocyanine pigment is particularly preferable. Examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and the like are preferable, and C.I. I. Pigment Blue 15: 6.
For this reason, when the colored resin composition of this invention contains a blue pigment, it is 80 mass% or more with respect to the total content of a blue pigment, Especially 90 mass% or more, Especially 95-100 mass% is C.I. I. Pigment Blue 15: 6 is preferable.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
Among these, a purple dioxazine pigment is preferable, and as the dioxazine pigment, C.I. I. Pigment Violet 19 and 23 are preferable, and C.I. I. Pigment Violet 23.

For this reason, when the colored resin composition of this invention contains a purple pigment, it is 80 mass% or more with respect to the total content of a purple pigment, Especially 90 mass% or more, Especially 95-100 mass% is C.I. I. Pigment Violet 23 is preferable.
These may be used alone or in a combination of two or more in any combination and ratio.

The pigment that can be used in the colored resin composition of the present invention preferably has a small average primary particle size from the viewpoint of forming a pixel with high contrast, and specifically, the average primary particle size is 40 nm or less. Is preferable, and it is more preferable that it is 35 nm or less.
Particularly for the blue copper phthalocyanine pigment, the average primary particle size is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.

Moreover, about a dioxazine pigment, an average primary particle diameter becomes like this. Preferably it is 40 nm or less, More preferably, it is 25-35 nm. From the viewpoint that the pigment is less likely to aggregate in the colored resin composition, it is preferable that the average primary particle size is not too small.
Here, the average primary particle diameter of the pigment can be a value measured and calculated by the following method.

First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
Particle size of individual pigment particles: X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m (m is the number of particles)

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
(B) As a solvent, what is necessary is just to be able to melt | dissolve or disperse | distribute each component which comprises a colored resin composition, and it is preferable to select a thing whose boiling point is the range of 100-200 degreeC. More preferably, it has a boiling point of 120-170 ° C.

Examples of such solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;
Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Linear or cyclic esters such as butyl methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

From the viewpoint of the adhesion between the substrate and the coating film and the coating film being able to form a uniform film thickness, the solvent preferably contains glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
Further, for example, when the above-mentioned pigment is included as an optional component, the balance of coating properties, surface tension, etc. is good, and the glycol alkyl ether is further used as a solvent from the viewpoint of relatively high solubility of the constituent components in the colored resin composition. It is more preferable to use a mixture of acetates. In addition, in colored resin compositions containing pigments, glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored resin composition. For this reason, it is preferable that the amount of glycol monoalkyl ethers used is not excessively large, and the proportion of glycol monoalkyl ethers in the solvent (B) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass. .

  Further, from the viewpoint of suitability for a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of the high boiling point solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass with respect to the total amount of the solvent (B). If the amount of the high boiling point solvent is too small, for example, a dye component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying speed of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
The colored resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 mass% or more in (B) solvent. When the ratio of such a high boiling point solvent is less than 50% by mass, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited, but the upper limit is usually 99% by mass with respect to the total amount of the colored resin composition. When the content of the solvent (B) in the composition exceeds 99% by mass, the concentration of each component excluding the solvent (B) may become too low to form a coating film. On the other hand, the lower limit of the content of the solvent (B) is usually 75% by mass, preferably 80% by mass, and more preferably 82% by mass in consideration of viscosity suitable for coating.

[(C) Binder resin]
(C) What preferable binder resin changes with the hardening means of a colored resin composition.
When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-2072111, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. However, among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meta). ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (IV) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having a structure represented by the following formula (IV) contains 5 to 90 mol% in the repeating unit derived from “another radical polymerizable monomer”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

In the above formula (IV), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (V).

The formula ^{(V), R} 91 ~R ⁹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Especially, as a structure represented by Formula (V), what is represented by the following structural formula (Va), (Vb), or (Vc) is especially preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said Formula (V) may be used individually by 1 type, and may use 2 or more types together.
As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (V), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and heat resistance and film strength are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

  Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

It is preferable for it to be in the above range since the remaining film ratio and solubility during development are sufficient.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

3000-100000 are preferable and, as for the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (gel permeation chromatography) of the above-mentioned binder resin (C), 5000-50000 are especially preferable. Within the above range, heat resistance, film strength, and solubility in a developer are preferable.
Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

In addition, the acid value of binder resin (C) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.
The content rate of (C) binder resin in a colored resin composition is 0.1-80 mass% normally in a total solid, Preferably it is 1-60 mass%.
Within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is moderate, and the surface smoothness and sensitivity of the pixels are good.

[(D) Polymerizable monomer]
The colored resin composition of the present invention can further contain (D) a polymerizable monomer.
(D) The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).
The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation component described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (D) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (D) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; An ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an esterification of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the aforementioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, pentaerythritol or (meth) acrylic ester of dipentaerythritol is more preferable, and dipentaerythritol hexa (meth) acrylate is particularly preferable.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (D) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content ratio of these (D) polymerizable monomers is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more in the total solid content. Moreover, it is 80 mass% or less normally, Preferably it is 70 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less.

In addition, the content ratio of the (D) polymerizable monomer to 100 parts by mass of the (A) colorant is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass. More preferably, it is 50 parts by mass or more, and is usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.
If it is within the above range, photocuring is appropriate, poor adhesion during development is unlikely to occur, the cross-section after development is unlikely to be an inversely tapered shape, and peeling phenomenon and omission failure due to lower solubility are less likely to occur. preferable.

[(E) photopolymerization initiating component, (E ′) thermal polymerization initiating component]
The colored resin composition of the present invention preferably contains at least one of (E) photopolymerization initiation component and (E ′) thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain at least one of a photopolymerization initiating component that has a function of generating a polymerization active radical and a thermal polymerization initiating component that generates a polymerization active radical by heat. . In the present invention, the component (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiating component in the present invention is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in, for example, JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl- radical activators such as s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone Derivatives; oxime ester derivatives described in JP 2000-80068 A and the like .

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  Further, examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazol-3-yl] ethanone oxime and a compound represented by the following formula (VI).

In formula (VI), R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl having 4 to 25 carbon atoms. Group, any of which may have a substituent. Alternatively, R ¹⁰¹ may be bonded to X or Z to form a ring.
R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic hetero group formed by condensation of two or more rings which may have a substituent.
Z represents an aromatic ring group which may have a substituent.
Of the compounds represented by the formula (VI), compounds in which X is a carbazole ring which may have a substituent are preferred. Specifically, compounds represented by the following formula (VII) and the like Among them, a compound represented by the following formula (VIII) is particularly preferable.

In formula (VII), R ¹⁰¹ , R ¹⁰² and Z have the same definitions as in formula (VI). R ^{103 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent. )

In formula (VIII), R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (VIIIa).

In formula (VIIIa), R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, a phenyl group or an N-acetyl-N-acetoxyamino group. * Represents a binding site.
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Z ^a represents an even better naphthyl group optionally substituted by also a phenyl group or a morpholino group substituted with an alkyl group. )
Commercial products may be used as the oxime initiator. Examples of commercially available products include OXE-01, OXE-02 (BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Changzhou Powerful Electronic New Materials Co., Ltd.) Ltd. (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).

  Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like. Commercial products may be used as these initiators.

  Examples of the commercially available products include IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, and IRGACURE 8 It is done.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (E2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.
Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. A suitable sensitizing dye is used depending on the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc., and a coumarin dye having a heterocyclic ring; 3 described in JP-A-3-239703, JP-A-5-289335, etc.
-Ketocoumarin dyes; pyromethene dyes described in JP-A-6-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48 JP-A-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like.

(E3) A sensitizing dye may also be used alone or in combination of two or more.
In the colored resin composition of the present invention, the content ratio of these (E) photopolymerization initiating components is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.8% by mass in the total solid content. 5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, particularly preferably 10% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass. % Or less.
Within the above range, the sensitivity to the exposure light beam is good, the solubility of the unexposed part in the development station is good, and it is preferable in that it is difficult to induce poor development.

[(E ′) Thermal Polymerization Initiating Component]
Specific examples of the (E ′) thermal polymerization initiating component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, the thermal polymerization initiating component described in International Publication No. 2009/107734 pamphlet can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

[Other optional ingredients]
The colored resin composition of the present invention includes, in addition to the above components, at least one of a surfactant, an organic carboxylic acid and an organic carboxylic anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, and a storage stabilizer. , Surface protective agents, adhesion improvers, development improvers and the like may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. Moreover, when it contains a pigment, you may contain a dispersing agent and a dispersing aid.

[Dispersant]
When the colored resin composition of this invention contains a pigment, it is preferable to contain a dispersing agent further.
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among them, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having at least one of a quaternary ammonium base and an amino group in the side chain, while the solvophilic A block is a quaternary. Examples include a unit structure having no ammonium base and amino group.
The B block constituting the acrylic block copolymer has a unit structure having at least one of a quaternary ammonium base and an amino group, and has a pigment adsorption function.

Further, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good.
Examples of such block copolymers include those described in JP-A-2009-025813.

Moreover, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648.
When the colored resin composition of the present invention contains a pigment, the content ratio in the total solid content of the dispersant is 2 to 1000 parts by mass, particularly 5 to 500, when the total content of the pigment is 100 parts by mass. It is preferable to use so that it may become in the range of mass part, especially 10-250 mass part.
By making it within the above range, good pigment dispersibility can be ensured without affecting the heat resistance of the triarylmethane compound represented by the formula (I), and the dispersion stability of the pigment is also improved. It is preferable in that it becomes better.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in JP-A No. 113000, JP-A No. 2007-186681, and the like can be used.

  The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, based on the total solid content of the pigment. Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and the dispersibility and dispersion stability are better.

[Dispersion resin]
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. A synergistic effect contributes to the dispersion stability of the pigment. As a result, the amount of dispersant added may be reduced, which is preferable. Further, it is preferable because the developability is improved, the undissolved matter does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.
Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by mass, more preferably about 10 to 100% by mass, based on the total amount of the pigment in the colored resin composition.

[Preparation Method of Colored Resin Composition]
In the present invention, the colored resin composition can be prepared by an appropriate method. For example, the (A) color material and the (C) binder resin containing the compound (I), the (B) solvent and, if necessary, the It can be prepared by mixing together with optional components used.

Moreover, the (A) color material containing compound (I) and the color material containing liquid containing (B) solvent may be prepared, and (C) binder resin and arbitrary components may be mixed together there.
In addition, as a preparation method in the case of containing a pigment, in the presence of a dispersant and, if necessary, a dispersion aid added in a solvent containing a pigment, optionally together with a part of (C) a binder resin, for example, paint Using a shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while grinding. In the pigment dispersion, (A) a colorant containing compound (I), (C) a binder resin, and (D) a polymerizable monomer, (E) a photopolymerization initiating component and a thermal polymerization initiating component, if necessary A method of adding at least one or the like and mixing them can be mentioned.
On the other hand, when a pigment is not included, for example, as a preparation method in the case of using only a dye as a coloring material, a dispersing agent or a dispersion tablet is not required, and a complicated pigment dispersion step is not required. Can be manufactured at low cost.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display device using them will be described.

<Color filter>
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.
First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

In the present invention, it is particularly preferable that the pixel formed using the colored resin composition of the present invention is a blue pixel.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.

In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Among these, the slit and spin method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  The light source used for image exposure for using radiation having a wavelength of 190 to 450 nm is not particularly limited. Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / ^{m 2} is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-methylamine, Di-methylamine, tri-methylamine, mono-ethylamine, di-ethylamine, tri-ethylamine, mono-isopropylamine, di-isopropylamine, n-butylamine, mono-isopropanolamine, di-isopropanol Amines, tri - isopropanolamine, ethyleneimine, ethylene diimine, tetramethyl ammonium hydroxide (TMAH), an aqueous solution of an organic alkaline compound such as choline and the like are preferable.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred.
The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

<Organic EL display device>
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, on a blue color filter in which pixels 20 are formed on a transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is produced by laminating the organic light-emitting body 500 through the organic protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
<Synthesis of dyes>
(Synthesis Example 1: Synthesis of Dye A)

1-iodonaphthalene (Compound 1, 15.0 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.),
Cyclohexylamine (compound 2a, 4.0 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2.3 g, 24 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), tris (dibenzylideneacetone) (chloroform) dipalladium (0 ) (54 mg, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl (98 mg, 0
. 16 mmol) and toluene (50 mL) were stirred with heating at 100 ° C. for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) gave 4.0 g of Compound 3a in a yield of 89%.

Compound 4 (1.5 g, 4.4 mmol, synthesized by the method described in International Publication No. 2009/107734), Compound 3a (1.0 g, 4.5 mmol) and toluene (16 mL) are added and room temperature until dissolved. Stir with. Phosphorus oxychloride (1.8 g, 12 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 90-95 ° C. After heating and stirring for 5.5 hours, the mixture was allowed to cool to room temperature. After adding water (15 mL) and stirring at room temperature for 1 hour, chloroform (30 mL) was added and stirred, and it left still. The organic layer was extracted, water (45 mL) was added, liquid separation operation was performed, and the solvent of the obtained organic layer was distilled off. The obtained crude product was purified by silica gel column chromatography (chloroform / methanol = 100/0 to 4/1 (volume ratio)) to obtain 0.88 g of Compound 5a in a yield of 34%.

  A mixed solution of compound 5a (0.88 g, 1.5 mmol), methanol (9.0 mL) and compound 6 (0.46 g, 1.5 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added at an external temperature of 50 ° C. for 1.5 hours. Stir with heating. Cool to room temperature and release into water. The obtained precipitate was dissolved in ethyl acetate, washed with water, evaporated, purified by silica gel column chromatography (chloroform / ethyl acetate = 100/0 to 1/7 (volume ratio)), 0.82 g of dye A, Obtained in 66% yield.

  Dye A was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown in the table below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 2: Synthesis of Dye B)

Compound 1 (5.0 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 3-aminoheptane (Compound 2b, 3.4 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2
. 3 g, 24 mmol), tris (dibenzylideneacetone) (chloroform) dipalladium (0) (51 mg, 0.050 mmol), 2,2 '-(diphenylphosphino)-
A mixture of 1,1′-binaphthyl (92 mg, 0.15 mmol) and toluene (50 mL) was heated and stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) gave 3.0 g of Compound 3b in a yield of 72%.

Compound 4 (2.6 g, 5.3 mmol, synthesized by the method described in WO2009 / 107734), compound 3b (1.5 g, 7.0 mmol) and toluene (30 mL) were added and room temperature until dissolved. Stir with. Phosphorus oxychloride (1.7 g, 11 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 80-85 ° C. After stirring for 6 hours, the mixture was allowed to cool to room temperature. Water (30 mL) was added, and the mixture was stirred at room temperature for 1 hour, and then chloroform (30 mL) was added, stirred and allowed to stand. The organic layer was extracted, washed twice with water (30 mL), and the solvent of the obtained organic layer was distilled off. Purification by silica gel column chromatography chloroform / methanol = 100/0 to 6/1 (volume ratio)) gave 2.5 g of compound 5b in a yield of 62%.

  A mixed solution of compound 5b (2.5 g, 4.4 mmol), methanol (25 mL) and compound 6 (1.3 g, 4.4 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at an external temperature of 50 ° C. for 1.5 hours. did. After allowing to cool to room temperature, the solvent was distilled off, and a mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the residue, followed by filtration. A mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the solid obtained by silica gel column chromatography (chloroform / methanol = 13/1 to 6/1 (volume ratio)), followed by filtration. The solid thus obtained was dried to obtain 2.7 g of dye B in a yield of 76%.

  Dye B was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown in the table below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 3: Synthesis of Dye C)

Compound 1 (5.1 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 2-methylcyclohexylamine (Compound 2c, 4.7 g, 41 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2.4 g, 25 mmol), Tris (dibenzylideneacetone) (chloroform) dipalladium (0) (52 mg, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl (96 mg, 0.15 mmol), toluene (50 m
The mixture of L) was stirred with heating at 100 ° C. for 2.5 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) gave 3.6 g of compound 3c in a yield of 75%.

  Compound 4 (2.5 g, 7.5 mmol, synthesized by the method described in WO 2009/107734 pamphlet), compound 3c (1.8 g, 7.5 mmol) and toluene (32 mL) were added and room temperature until dissolved. Stir with. Phosphorus oxychloride (1.7 g, 11 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 80-85 ° C. After stirring with heating for 7 hours, the mixture was allowed to cool to room temperature. Water (32 mL) was added, and the mixture was stirred at room temperature for 1 hour, and then chloroform (20 mL) was added, stirred and allowed to stand. The organic layer was extracted, washed twice with water (30 mL), and the solvent of the obtained organic layer was distilled off. Purification by silica gel column chromatography (chloroform / methanol = 100/0 to 5/1 (volume ratio)) yielded 3.5 g of compound 5c in a yield of 78%.

  A mixed solution of compound 5c (3.5 g, 5.8 mmol), methanol (33 mL) and compound 6 (1.7 g, 5.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at an external temperature of 50 ° C. for 1.5 hours. did. After allowing to cool to room temperature, the solvent was distilled off, and a mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the residue, followed by filtration. To a solid obtained after silica gel column chromatography (chloroform / methanol = 7/1 to 5/1 (volume ratio)), a mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added, followed by filtration. The solid thus obtained was dried to obtain 3.2 g of dye C in a yield of 67%.

Dye C was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 4: Synthesis of Dye D)

Compound 1 (5.0 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 2-aminobutane (Compound 2d, 2.9 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2.
3 g, 24 mmol), tris (dibenzylideneacetone) (chloroform) dipalladium (0) (52 mg, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1
, 1′-binaphthyl (96 mg, 0.15 mmol) and toluene (50 mL) were heated and stirred at 95 ° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) gave 3.6 g of compound 3d in a yield of 90%.

Compound 4 (1.5 g, 4.5 mmol, synthesized by the method described in International Publication No. 2009/107734), Compound 3d (0.90 g, 4.6 mmol) and toluene (18 mL) are added and room temperature until dissolved. Stir with. Phosphorus oxychloride (1.8 g, 11 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 85-90 ° C. After carrying out the heating reaction for 6 hours, it cooled to room temperature, added water, and extracted with chloroform. The chloroform layer was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 10/1 (volume ratio)) to obtain 1.9 g of compound 5d in a yield of 75%.

  A mixture of compound 5d (1.9 g, 3.4 mmol), compound 6 (1.0 g, 3.5 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (22 mL) was stirred at 60 ° C. for 2 hours, and then cooled to room temperature. Released into the water. The obtained precipitate was dissolved in ethyl acetate, washed with water, purified by silica gel column chromatography (developing solvent: chloroform / methanol = 15/1 to 10/1 (volume ratio)), and dye D was prepared as 1. 4 g, yield 53%.

  Dye D was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 5: Synthesis of Dye E)

Compound 1 (5.0 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 2-aminopropane (Compound 2e, 2.6 g, 44 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2
. 4 g, 25 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), tris (dibenzylideneacetone) (chloroform) dipalladium (0) (55 mg, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1,1′- A mixture of binaphthyl (99 mg, 0.16 mmol) and toluene (45 mL) was heated and stirred at 85 to 90 ° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The product was purified by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 19/1 (volume ratio)) to obtain 3.1 g of Compound 3e in a yield of 85%.

  Compound 4 (1.8 g, 5.4 mmol, synthesized by the method described in WO2009 / 107734), compound 3e (1.0 g, 5.4 mmol) and toluene (23 mL) are added and room temperature until dissolved. Stir with. Phosphorus oxychloride (1.2 g, 8.1 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 80-85 ° C. After stirring for 5 hours, the mixture was allowed to cool to room temperature. Water (23 mL) was added, and the mixture was stirred at room temperature for 1 hour, and then chloroform (23 mL) was added, stirred and allowed to stand. The organic layer was extracted, washed 3 times with water (30 mL), and the solvent of the obtained organic layer was distilled off. Purification by silica gel column chromatography (chloroform / methanol = 100/0 to 3/1 (volume ratio)) yielded 1.8 g of compound 5e in a yield of 63%.

  A mixed solution of compound 5e (1.8 g, 3.4 mmol), methanol (19 mL) and compound 6 (0.97 g, 3.4 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at an external temperature of 50 ° C. for 1.5 hours. did. After allowing to cool to room temperature, the solvent was distilled off, and a mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the residue, followed by filtration. A mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the solid obtained after silica gel column chromatography (chloroform / methanol = 10/1 to 5/1 (volume ratio)), followed by filtration. The obtained solid was dried to obtain 2.0 g of dye E in a yield of 75%.

Dye E was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown in the table below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 6: Synthesis of Dye F)

Compound 1 (5.0 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 4-aminoheptane (Compound 2f, 4.6 g, 40 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2
. 3 g, 24 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), tris (dibenzylideneacetone) (chloroform) dipalladium (0) (53 mg, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1,1′- A mixture of binaphthyl (97 mg, 0.16 mmol) and toluene (50 mL) was stirred with heating at 95 ° C. for 2 hours under a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 19/1 (volume ratio)) gave 3.0 g of Compound 3f in a yield of 62%.

Add compound 4 (1.5 g, 4.5 mmol, synthesized by the method described in WO2009 / 107734), compound 3f (1.1 g, 4.5 mmol), and toluene (18 mL) until dissolved Stir at room temperature. Phosphorus oxychloride (1.7 g, 11 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 85-90 ° C. After carrying out the heating reaction for 7.5 hours, it cooled to room temperature, added water, and extracted with chloroform. The chloroform layer was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 10/1 (volume ratio)) to obtain 1.6 g of compound 5f in a yield of 60%.

  A mixture of compound 5f (1.6 g, 2.7 mmol), compound 6 (0.8 g, 2.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (24 mL) was stirred at 60 ° C. for 2 hours, and then cooled to room temperature. Released into the water. The obtained precipitate was dissolved in ethyl acetate, washed with water, evaporated, and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 10/1 (volume ratio)). Obtained at a rate of 53%.

  Dye F was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 7: Synthesis of Dye G)

Compound 1 (5.0 g, 20 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), Compound 2 g (6.2 g, 4
0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium t-butoxide (2.3 g, 24 mmol), tris (dibenzylideneacetone) (chloroform) dipalladium (0) (53 mg
, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl (0.10 g, 0.16 mmol), toluene (50 mL) under a nitrogen atmosphere.
The mixture was heated and stirred at 5 ° C. for 2 hours. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. By adding hexane and filtering, 1.7 g of compound 3g was obtained in a yield of 30%.

  Compound 4 (1.53 g, 4.52 mmol, synthesized by the method described in WO 2009/107734 pamphlet), compound 3 g (1.3 g, 4.5 mmol) and toluene (18 mL) were added and room temperature until dissolved. Stir with. Phosphorus oxychloride (1.7 g, 11 mmol, manufactured by Kishida Chemical Co.) was added dropwise, and the temperature was raised to 85-90 ° C. After carrying out the heating reaction for 7 hours, it cooled to room temperature, water was added, and chloroform extracted. The chloroform layer was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 10/1 (volume ratio)) to obtain 1.0 g of compound 5g in a yield of 36%.

  A mixture of compound 5g (1.0 g, 1.6 mmol), 4-t-butylcyclohexylamine (compound 6, 0.5 g, 1.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (18 mL) at 60 ° C. for 2 hours. After stirring, it was cooled to room temperature and released into water. The obtained precipitate was dissolved in ethyl acetate, washed with water, evaporated, and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 10/1 (volume ratio)), and 0.60 g of dye G was collected. Obtained at a rate of 43%.

Dye G was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result of liquid chromatograph-mass spectrometry (conditions: ESI, posi) (
m / z) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 8: Synthesis of Dye H)

  Compound 7 (6.0 g, 25 mmol, synthesized by the method described in International Publication No. 2008/003604 pamphlet), 1,1,1-trifluoro-4-iodobutane (Compound 8, 6.4 mL, 50 mmol, Tokyo Chemical Industry Co., Ltd.) Manufactured), potassium carbonate (6.9 g, 50 mmol), and N-methyl-2-pyrrolidone (25 mL) were heated and stirred at 110 to 125 ° C. for 4 hours. After cooling to room temperature, water was added and the mixture was extracted with toluene. The toluene layer was washed with dilute hydrochloric acid and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. It melt | dissolved in ethanol (40 mL), the aqueous solution (25 mL) of sodium hydroxide (2.0 g, 52 mmol) was added, and it stirred at 85 degreeC for 1 hour. The mixture was allowed to cool and extracted with toluene, and the toluene layer was washed with saturated brine and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and purified by silica gel column chromatography (hexane / ethyl acetate = 3/1 (volume ratio)) to obtain 6.0 g of compound 3h in a yield of 94%.

Compound 4 (1.5 g, 4.3 mmol, synthesized by the method described in WO2009 / 107734 pamphlet), compound 3h (1.1 g, 4.3 mmol) and toluene (
30 mL) was added and stirred at room temperature until dissolved. Phosphorus oxychloride (1.0 g, 6.6 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 85-90 ° C. After carrying out the heating reaction for 4 hours, it cooled to room temperature, water was added, and chloroform extracted. The chloroform layer was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform / methanol = 15/1 to 10/1 (volume ratio)), and the resulting solid was washed with hexane to obtain 1.3 g of compound 5h. Obtained at a rate of 50%.

A mixture of compound 5h (8.9 g, 15 mmol), compound 6 (4.2 g, 15 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol (50 mL) was stirred at 50 ° C. for 1.5 hours, and then concentrated under reduced pressure. The obtained solid was washed with methanol / water = 1/2 (volume ratio) to obtain 11.5 g of dye H in a yield of 92%.
Dye H was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 9: Synthesis of Dye I)

  Compound 9 (0.50 g, 1.4 mmol, synthesized by the method described in JP 2012-113218 A), compound 3a (0.32 g, 1.4 mmol) and toluene (30 mL) are added and at room temperature until dissolved. Stir. Phosphorus oxychloride (0.32 g, 2.1 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 90-95 ° C. After carrying out a heating reaction for 14 hours, it was allowed to cool to room temperature. After adding water (10 mL) and stirring at room temperature for 1 hour, chloroform (100 mL) was added and stirred, and it left still. The organic layer was extracted, water (20 mL) was added, liquid separation operation was performed, and the solvent of the obtained organic layer was distilled off. The obtained crude product was purified by silica gel column chromatography (chloroform / methanol = 100/0 to 7/1 (volume ratio)) to obtain 0.08 g of Compound 5I in a yield of 9%.

A mixed solution of Compound 5I (0.08 g, 0.13 mmol), methanol (30 mL) and Compound 6 (0.04 g, 0.14 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at an external temperature of 50 ° C. for 1 hour. After allowing to cool to room temperature, the solvent was distilled off and washed with water (100 mL). The obtained solid was dried to obtain 0.09 g of dye I in a yield of 83%.
Dye I was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 10: Synthesis of Dye J)

  Compound 10 (1.24 g, 4.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), compound 3c (0.96 g, 4.0 mmol) and toluene (17 mL) were added and stirred at room temperature until dissolved. Phosphorus oxychloride (0.92 g, 6.0 mmol, manufactured by Kishida Chemical Co., Ltd.) was added dropwise, and the temperature was raised to 80-85 ° C. After heating reaction for 5.5 hours, the mixture was allowed to cool to room temperature. Water (15 mL) was added, and the mixture was stirred at room temperature for 1 hour, and then chloroform (10 mL) was added, stirred and allowed to stand. The organic layer was extracted, water (15 mL) was added to carry out a liquid separation operation, and the solvent of the obtained organic layer was distilled off. The resulting crude product was purified by silica gel column chromatography (chloroform / methanol = 100/0 to 3/1 (volume ratio)) to obtain 2.0 g of Compound 5J in a yield of 86%.

  A mixed solution of compound 5J (2.0 g, 3.4 mmol), methanol (20 mL) and compound 6 (0.99 g, 3.4 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was heated and stirred at an external temperature of 50 ° C. for 1.5 hours. did. After allowing to cool to room temperature, the solvent was distilled off, and a mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the residue, followed by filtration. A mixed solution (30 mL) of methanol / water = 1/2 (volume ratio) was added to the solid obtained by silica gel column chromatography (chloroform / methanol = 10/1 to 5/1 (volume ratio)), followed by filtration. The solid obtained was dried to obtain 1.8 g of dye J in a yield of 63%.

  Dye J was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. Data of maximum absorption wavelength (λmax) and gram extinction coefficient (g) at this time are shown below. Moreover, the result (m / z) of liquid chromatograph-mass spectrometry (conditions: ESI, posi) is also shown. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.

(Synthesis Example 11: Synthesis of Resin A)
145 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was stirred while being purged with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 2.2′-azobis-2-methylbutyro A mixture of 8.47 parts by mass of nitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 1.1 parts by mass of trisdimethylaminomethylphenol and 0.19 parts by mass of hydroquinone were added to 67.0 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.2 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw measured by GPC of the resin solution thus obtained was about 9000, and the acid value was 25 mg-KOH / g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 40% by mass and used as Resin A.

(Synthesis Example 12: Synthesis of Resin B)
“NC3000H” (epoxy equivalent 288, softening point 69 ° C.) (manufactured by Nippon Kayaku Co., Ltd.) 400 parts by mass, acrylic acid 102 parts by mass, p-methoxyphenol 0.3 part by mass, triphenylphosphine 5 parts by mass, and propylene glycol A reaction vessel was charged with 264 parts by mass of monomethyl ether acetate (PGMEA) and stirred at 95 ° C. until the acid value was 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mg-KOH / g). Subsequently, 151 parts by mass of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain a resin solution having an acid value of 102 mg-KOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 3900 measured by GPC. . Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 44% by mass and used as Resin B.

(Synthesis Example 13: Preparation of Pigment Dispersion Liquid J)
C. I. Pigment Blue 15: 6 is 12.4 parts by mass, the dispersant is BYK-LPN21116 (produced by Big Chemie) at 7.2 parts by mass in terms of dispersant solids, and the resin B produced in Synthesis Example 10 is in terms of solids. 0.8 part by mass and 79.6 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed and stirred with a stirrer for 3 hours to prepare a mill base having a solid content concentration of 20.4% by mass. This mill base was subjected to a dispersion treatment using 600 parts by mass of 0.5 mmφ zirconia beads in a bead mill apparatus at a peripheral speed of 10 m / s and a residence time of 3 hours to obtain a blue pigment dispersion J. The solid content concentration of the blue pigment dispersion J at this time was 20.4% by mass.

(Synthesis Example 14: Synthesis of initiator)
3- (2-acetoxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toluoyl) -9H-carbazole was synthesized by the method described in International Publication No. 2009/131189. .

[Preparation 1 of colored resin composition]
The dyes A to G obtained in the synthesis examples 1 to 7, the dyes H to J obtained in the synthesis examples 8 to 10, and the resins A and B obtained in the synthesis examples 11 and 12 are described in Table 12 below. A colored resin composition was prepared by mixing with other components so as to obtain a different composition.

In addition, the numerical value of the upper stage of Table 12 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value of a lower stage is the content ratio (mass%) in the total solid of each component. Represents.
In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.
Dyes A to G were used for the colored resin compositions of Examples 1 to 8, and Dyes H to J were used for the colored resin compositions of Comparative Examples 1 to 3.

In addition, each compound in Table 12 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether F559: Perfluoroalkyl group-containing oligomer Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
JPP-100: Tetraphenyldipropylene glycol diphosphite

[Production of colored resin film and evaluation of heat resistance]
Each colored resin composition prepared in [Preparation of colored resin composition 1] is applied onto a glass substrate cut into 5 cm square by spin coating so that the y value after firing is 0.120 as follows. After drying under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ^{2 and} then baked at 230 ° C. for 60 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and luminance in the XYZ color system were calculated.

In heating after 230 ° C. and 60 minutes, in Examples 1 to 7, R ⁵ and R ⁶ in the formula (1) showed higher luminance than Comparative Example 1 using a dye having no secondary carbon, It can be seen that the heat resistance has been improved. In Example 1 using a dye in which R ⁷ in formula (1) is a hydrogen atom and R ⁸ is an alkyl group, both R ⁷ and R ⁸ in formula (1) are alkyl groups. It can be seen that the heat resistance is higher than that of Comparative Example 2 using a dye.

Next, the colored resin compositions of Example 3, Example 4, and Comparative Example 3 were applied by spin coating on a glass substrate cut into 5 cm squares, dried under reduced pressure, and then heated at 80 ° C. on a hot plate. Pre-baked for 3 minutes. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² and baked in a clean oven at 230 ° C. for 30 minutes. At this time, the y value was adjusted to 0.120 when baked at 230 ° C. for 30 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) (A). Further, the film was baked at 230 ° C. for 30 minutes in a clean oven, and the spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.) (B).
At this time, Table 14 shows the result of the color change ΔE * ab from (A) to (B) in the La * b * color system.

The color change ΔE * ab in Example 3 and Example 4 was smaller than that in Comparative Example 3 having no alkyl group at R ⁷ and R ⁸ . By using the colored resin composition of the present invention, a color filter having a small color change, a liquid crystal display device using the same, and an organic EL display even after being subjected to high-temperature baking for a long time performed in a color display manufacturing process An apparatus can be provided.

[Preparation 2 of colored resin composition]
The dyes B and C obtained in the synthesis examples 2 and 3, the dye H obtained in the synthesis example 8, the resins A and B obtained in the synthesis examples 11 to 13, and the pigment dispersion J are described in the table below. A colored resin composition was prepared by mixing with other components so as to obtain a different composition. In addition, the numerical value of the upper stage of the following table represents the content rate (mass%) in each colored resin composition of each component to add, and the numerical value of a lower stage is the content ratio (mass%) in the total solid of each component. Represents.

In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.
Dye B and C were used for the colored resin compositions of Examples 8 and 9, respectively, and Dye H was used for the colored resin composition of Comparative Example 3.

In addition, each compound in Table 15 is as follows.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether F559: Perfluoroalkyl group-containing oligomer Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
JPP-100: Tetraphenyldipropylene glycol diphosphite

[Production of colored resin film and evaluation of light resistance]
Each colored resin composition prepared in [Preparation of colored resin composition 2] is applied onto a glass substrate cut into 5 cm square by spin coating, dried under reduced pressure, and then heated on a hot plate. Pre-baked at 0 ° C. for 3 minutes. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² and baked in a clean oven at 230 ° C. for 30 minutes. At this time, the y value was adjusted to 0.120 when baked at 230 ° C. for 30 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the luminance was calculated. The weatherometer Ci4000 (manufactured by Atlas Co., Ltd.) was set through a polarizing plate having the transmittance shown in FIG. 2 and irradiated with simulated sunlight for 20 hours. Color difference before and after irradiation (ΔE * a
b) was measured as light resistance, and the evaluation results are summarized in Table 16.

  Since Examples 8 and 9 are colored resin compositions that exhibit high light resistance in addition to high luminance, they are suitable for color filters, liquid crystal display devices using the same, and organic EL display devices.

  According to the present invention, it is possible to provide a coloring composition having high luminance and satisfying heat resistance and light resistance. Further, according to the present invention, it is possible to provide a color filter having high luminance and satisfying heat resistance and light resistance, and a high-quality liquid crystal display device and organic EL display device. Therefore, the present invention is useful in applications to color filters, liquid crystal display devices, organic EL display devices, and the like.

DESCRIPTION OF SYMBOLS 100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 500 Organic light-emitting body 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode

Claims (17)

(A) contains a coloring material, (B) a solvent and (C) a binder resin,
(A) A colored resin composition, wherein the color material contains a triarylmethane compound represented by the following formula (I).

(In the above formula (I),
[A ⁿ⁻ ] represents an n-valent anion.
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
However, at least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent.
At least one combination selected from the group consisting of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be linked to each other to form a ring, and the ring has a substituent. You may do it.
One of R ⁷ and R ⁸ is an optionally substituted alkyl group or a halogen atom, and the other is a hydrogen atom.
Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent.
n represents an integer of 1 to 4, and when n is 2 to 4, a plurality of cations represented by the following formula (I) _CA contained in one molecule may each independently have the same structure. , Different structures may be used. )

  The colored resin composition according to claim 1, wherein the anion is an imide anion. The colored resin composition according to claim 1 or 2, wherein the anion is represented by the following formula (II).

(In the formula (II), R ¹¹ and R ¹² each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
R ¹¹ and R ¹² may be connected to each other to form a ring, and the ring may have a substituent. ) The colored resin composition according to claim 3, wherein at least one of R ¹¹ and R ¹² is a group having a fluorine atom.   5. The content ratio of the triarylmethane-based compound represented by the formula (I) is 0.01% by mass or more in the total solid content, according to claim 1. Colored resin composition.   Furthermore, (D) polymerizable monomer is contained, The colored resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.   The colored resin composition according to any one of claims 1 to 6, further comprising (E) a photopolymerization initiating component and / or (E ') a thermal polymerization initiating component.   Furthermore, (A) A coloring material contains a pigment, The colored resin composition as described in any one of Claims 1-7 characterized by the above-mentioned.   The colored resin composition according to claim 8, wherein the pigment is metal phthalocyanine.   The colored resin composition according to claim 8 or 9, wherein the content ratio of the compound represented by the formula (I) in the color material is 50% by mass or more based on the total amount of the color material. object.   It has a pixel formed using the colored resin composition as described in any one of Claims 1-10, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 11.   An organic EL display device comprising the color filter according to claim 11. A triarylmethane compound represented by the following formula (I).

(In the above formula (I),
[A ⁿ⁻ ] represents an n-valent anion.
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
However, at least one of R ⁵ and R ⁶ is an alkyl group having a secondary carbon which may have a substituent.
At least one combination selected from the group consisting of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be linked to each other to form a ring, and the ring has a substituent. You may do it.
One of R ⁷ and R ⁸ is an optionally substituted alkyl group or a halogen atom, and the other is a hydrogen atom.
Further, the benzene ring and naphthalene ring in the above formula (I) may further have an arbitrary substituent.
n represents an integer of 1 to 4, and when n is 2 to 4, a plurality of cations represented by the following formula (I) _CA contained in one molecule are each independently the same structure, Different structures may be used. )

  The triarylmethane compound according to claim 14, wherein the anion is an imide anion. The triarylmethane compound according to claim 14 or 15, wherein the anion is represented by the following formula (II).

(In the formula (II), R ¹¹ and R ¹² each independently represents an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
R ¹¹ and R ¹² may be connected to each other to form a ring, and the ring may have a substituent. )   A dye comprising the triarylmethane compound according to any one of claims 14 to 16.

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