JP6432313B2 - Colored resin composition, color filter, liquid crystal display device and organic EL display device - Google Patents

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, color filters are required to have higher color purity, higher brightness, and higher contrast.
Until now, colored resin compositions using pigments have been mainly used as color filter forming materials, but in order to obtain high brightness and high contrast, for example, Non-Patent Document 1 specifies the particle size of pigment particles. A method of finely dispersing the color to a half or less of the coloration wavelength is disclosed.

  On the other hand, a dye has been developed as a coloring material used in a colored resin composition for a color filter. For example, Patent Document 1 discloses using a triarylmethane derivative as a dye. Further, Patent Documents 2 to 5 disclose that in the triarylmethane salt, the anion further has a specific structure.

JP 2008-304766 A International Publication No. 2011/152379 Pamphlet International Publication No. 2011/162217 Pamphlet JP 2011-227408 A JP 2012-17425 A

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

However, in the method described in Non-Patent Document 1, since the blue pigment has a shorter coloration wavelength than other red and green pigments, in this case, further fine dispersion is required, which increases costs and stabilizes after dispersion. Sex matters.
Further, according to the study by the present inventors, when the triarylmethane compound having a cation structure described in Patent Documents 1 to 4 is used, the light resistance required for long-term reliability of the color display is insufficient. It was found.

On the other hand, according to the study by the present inventors, when the triarylmethane compound having a cation structure described in Patent Document 5 is used, the light resistance required for the long-term reliability of the color display and the color display manufacturing process It was found that it was difficult to satisfy both of the required heat resistance in firing at 230 ° C.
The present invention has been made in view of the above-described problems of the prior art, has high color purity and brightness, and satisfies the heat resistance required in the color display manufacturing process and the light resistance required for the long-term reliability of the color display. Another object of the present invention is to provide a coloring composition that exhibits a high contrast required for a liquid crystal display device.

  Another object of the present invention is to provide a color filter, a liquid crystal display device, and an organic EL display device that have high color purity and brightness, satisfy heat resistance and light resistance, and exhibit high contrast.

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 halogenoalkylsulfonylimide anion which may have a substituent, or an n-valent halogenoalkylsulfonylmethide anion which may have a substituent.
R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁵ and R ⁶ each independently represents an aromatic ring group which may have a 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 halogenoalkyl group in the anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms.
[3] The anion is a bistrifluoromethanesulfonylimide anion, a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion, or a tristrifluoromethanesulfonylmethide anion. The colored resin composition according to [1] or [2].
[4] R ¹ to R ⁴ of the formula (I) each independently have a hydrogen atom, or a substituent is also an alkyl group, according to any one of [1] to [3] Colored resin composition.
[5] The colored resin composition according to any one of [1] to [4], wherein R ⁵ and R ^{6 in} the formula (I) are each independently a phenyl group which may have a substituent. object.
[6] The colored resin composition according to any one of [1] to [5], wherein 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. object.

[7] The colored resin composition according to any one of [1] to [6], further comprising (D) a polymerizable monomer.
[8] The colored resin composition according to any one of [1] to [7], further comprising (E) a photopolymerization initiation component and / or (E ′) a thermal polymerization initiation component.
[9] The colored resin composition according to any one of [1] to [8], wherein (A) the colorant further contains a pigment.
[10] A color filter having pixels formed using the colored resin composition according to any one of [1] to [9].
[11] A liquid crystal display device having the color filter according to [10].
[12] An organic EL display device having the color filter according to [10].

[13] A triarylmethane compound represented by the following formula (I).

(In the above formula (I),
[A ⁿ⁻ ] represents an n-valent halogenoalkylsulfonylimide anion which may have a substituent, or a halogenoalkylsulfonylmethide anion which may have a substituent.
R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁵ and R ⁶ each independently represents an aromatic ring group which may have a 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. )

[14] The triarylmethane compound according to [13], wherein the halogenoalkyl group in the anion is a C1-10 alkyl group substituted with 3 to 6 halogen atoms.
[15] The anion is a bistrifluoromethanesulfonylimide anion, a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion, or a tristrifluoromethanesulfonylmethide anion. The triarylmethane compound according to [13] or [14].
[16] The method according to any one of [13] to [15], wherein R ^{1 to} R ^{4 in the} formula (I) are each independently a hydrogen atom or an alkyl group which may have a substituent. Triarylmethane compounds.
[17] The triarylmethane according to any one of [13] to [16], wherein R ⁵ and R ^{6 in} the formula (I) are each independently a phenyl group which may have a substituent. Compounds.

According to the present invention, it has excellent color purity and brightness, has heat resistance required in a color display manufacturing process, satisfies light resistance required for long-term reliability, and has high contrast required for a liquid crystal display device. The coloring resin composition which expresses can be provided.
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, satisfy heat resistance and light resistance, and exhibit high contrast.

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 acrylic 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. Furthermore, it is preferable to contain at least one of (D) a polymerizable monomer, (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 halogenoalkylsulfonylimide anion which may have a substituent, or an n-valent halogenoalkylsulfonylmethide which may have a substituent. Represents an anion.
R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent, and R ⁵ and R ⁶ are Each independently represents an aromatic ring group which may have a 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.

(R ¹ ~R ⁴⁾
R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
Examples of the alkyl group in R ^{1 to} R ⁴ include a linear, branched or cyclic alkyl group. The carbon number is preferably 30 or less, more preferably 12 or less, and usually 1 or more. 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 include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. 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.
Specific examples of the alkyl group having a substituent include phenethyl group, 2-ethoxyethyl group, 4,4,4-trifluorobutyl group and the like.

Examples of the aromatic ring group in R ^{1 to} R ⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. 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 ³ and R ⁴ may be linked to form a ring, and the ring may have a substituent. In addition, the ring may be a ring bridged with a heteroatom, and specific examples thereof include the following structures.

From the viewpoint of heat resistance, R ^{1 to} R ⁴ are preferably each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. Or a group in which adjacent R ³ and R ⁴ are connected to each other to form a ring, and more preferably each independently a hydrogen atom or an optionally substituted alkyl group. is there. These substituents are also preferable in terms of luminance.
R ¹ is improved in that the heat resistance of the compound (I) is improved and the heat resistance of the resulting color filter is excellent.
And R ² is preferably a C 1-12 alkyl group which may have a substituent or a phenyl group which may have a substituent, and has a substituent from the viewpoint of luminance. More preferably, it is an alkyl group having 1 to 12 carbon atoms.

When R ¹ and R ² are an optionally substituted alkyl group having 1 to 12 carbon atoms, it is presumed that the charges in the cation are dispersed by hyperconjugation and the cation is stabilized.
More specifically, the number of carbon atoms of the alkyl group in R ¹ and R ² is such that it does not easily affect the conformation of the triarylmethane skeleton (has little effect on luminance), and the substituent on nitrogen is difficult to remove. (Compound (I) is stable), preferably 8 or less, more preferably 4 or less, and preferably 2 or more.

When R ¹ and R ² 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.
In view of excellent brightness of the compound (I), R ³ and R ⁴ are preferably at least one alkyl group which may have a substituent, and from the viewpoint of heat resistance, R ³ and R ⁴ It is preferable that any one of them is an alkyl group which may have a substituent, and the other is a hydrogen atom.

Further, from the viewpoint of luminance, at least one of R ³ and R ⁴ is preferably a linear alkyl group which may have a substituent. By making at least one of R ³ and R ⁴ a linear alkyl group which may have a substituent, solubility is improved, so that association between dye molecules is suppressed and luminance is improved. It is thought to do.
In this case, both R ³ and R ⁴ may be a linear alkyl group which may have a substituent, and either one of R ³ and R ⁴ has a substituent. It may be a straight-chain alkyl group, and the other may be a hydrogen atom. From the viewpoint of heat resistance, it is preferable that either one of R ³ and R ^{4 is} a linear alkyl group which may have a substituent, and the other is a hydrogen atom.

  The linear alkyl group preferably has 12 or less carbon atoms, more preferably 6 or less, and preferably 1 or more, and more preferably 3 or more. Since the interaction with other components constituting the colored resin composition is appropriate by setting the upper limit value or less, the solubility tends to be adjusted appropriately, and the upper limit value or more. There exists a tendency which can suppress the thermal decomposition of a substituent and can improve heat resistance.

Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a butyl group is preferable from the viewpoint of heat resistance.
Examples of the substituent that the linear alkyl group may have include those in the substituent group W1 described below. Among these, from the viewpoint of heat resistance, a fluorine atom, a phenyl group, or a tolyl group is preferable, and a fluorine atom is more preferable. Specific examples of the linear alkyl group having a substituent include 4,4,4-trifluorobutyl group, 2-phenylethyl group, 2-tolylethyl group and the like. Among these, 4,4,4-trifluorobutyl group is preferable from the viewpoint of heat resistance.

On the other hand, at least one of R ³ and R ⁴ is preferably an alkyl group having a secondary carbon and optionally having a substituent. By making at least one of R ³ and R ⁴ an alkyl group having a secondary carbon and optionally having a substituent, the heat and light of the molecule represented by formula (I) This substituent is considered to contribute to the improvement of heat resistance and light resistance because the substituents inhibit attacks from other molecules that cause decomposition.
Further, both R ³ and R ⁴ may be a secondary carbon, optionally substituted alkyl group, and one of R ³ and R ^{4 is} a secondary carbon. The alkyl group which may have a substituent may be used, and the other may be a group other than the alkyl group which has a secondary carbon and which may have a substituent. If the substituents of R ³ and R ⁴ 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 ³ and R ⁴ is preferably an alkyl group having a secondary carbon which may have a substituent, and the other is preferably a group other than the alkyl group, More preferably, either one is an optionally substituted alkyl group having a secondary carbon and the other is a hydrogen atom.

In addition, “at least one of R ³ and R ⁴ has a secondary carbon, may have a substituent, and is an alkyl group” means that at least one of R ^{3 and} R ⁴ is The alkyl group which has a group represented by the formula (II) and may have a substituent. In addition, * in a formula means a bond.
In the following formula (II), α and β 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 the alkyl group has a group represented by the above formula (II) and may have a substituent. May be, for example, a group itself represented by the above formula (II), or a group represented by the above formula (II) bonded to an alkylene group which may have a substituent. May be. However, from the viewpoint of increasing the volume around the nitrogen atom, the group represented by the above formula (II) is preferable. That is, since this substituent inhibits attacks from other molecules that cause decomposition by light, it tends to contribute to improvement of various physical properties.

  Examples of the alkyl group for α and β include linear, branched or cyclic alkyl groups. 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 include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, 3- A methylbutyl group etc. are mentioned. 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.
Specific examples of the alkyl group having a substituent include a phenethyl group and a 2-ethoxyethyl group.

  Examples of the aromatic ring group in α and β include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, further preferably 6 or less, and usually 4 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.

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.

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, further preferably 8 or less, usually 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 substituent group W1 described later. Moreover, as a substituent which the aromatic ring group may have, the substituent group W2 mentioned later 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 alkyl group having 2 to 6 carbon atoms which may have a substituent or adjacent α and β having 3 to 10 carbon atoms are connected to each other to form a ring. These substituents tend to improve heat resistance and light resistance because association between the compounds represented by formula (I) and effective interaction between a cation and an anion occur.

The total number of carbon atoms in the alkyl group having a secondary carbon in R ³ and R ⁴ 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-methyl Loheptyl 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 -An adamantyl group and the like.

  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.

On the other hand, when one of R ³ and R ⁴ is an alkyl group having a secondary carbon which may have a substituent, and the other is a group other than the alkyl group, the alkyl group Examples of a group other than (a group other than an alkyl group having a secondary carbon which may have a substituent) include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, C1-C5 alkyl group such as pentyl group, C1-C5 hydroxyalkyl group such as hydroxyethyl group, hydroxypropyl group, etc. Carbon such as methoxyethyl group, ethoxyethyl group, ethoxypropyl group, butoxyethyl group 1 to 5 alkoxyalkyl groups, 2-hydroxyethoxy groups, etc., C1-C5 hydroxyalkoxy groups, 2-methoxyethoxy groups, 2-ethoxyethoxy groups, etc., 1 to 5 carbon atoms Alkoxy (having 1 to 5 carbon atoms), 2-sulfoethyl group, carboxyethyl group, cyanoethyl group and the like.

As a substituent which the alkyl group in R < ¹ > -R < ⁴ > may have, 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.

(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;

(R ⁵ and R ⁶⁾
R ⁵ and R ⁶ are each independently an aromatic ring group which may have a substituent. The triarylmethane compound represented by the general formula (I) used in the colored resin composition of the present invention is R ^5.
And R ⁶ are each independently an aromatic ring group which may have a substituent, and thus the conjugated system of the cation is expanded, the charge is stabilized, and the heat resistance and light resistance are improved. It is done.

Examples of the aromatic ring group in R ⁵ and R ⁶ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. The solubility in the solvent of the formula (I) can be appropriately adjusted by setting it to the upper limit or less, and the association between the molecules represented by the formula (I) and the effective interaction between the cation and the anion Therefore, heat resistance and light resistance tend to be improved.

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.

R ⁵ and R ⁶ may be connected to R ¹ and R ² to form a ring, respectively, and the ring may have a substituent. The ring may be a ring bridged with a heteroatom. The number of carbon atoms is preferably 28 or less, more preferably 10 or less, and even more preferably 6 or less. Examples of the substituent that the rings formed by being connected to each other may have include those of the aforementioned substituent group W3. These substituents tend to improve heat resistance and light resistance because of the association between the compounds represented by formula (I) and the effective interaction between cations and anions between molecules. .

Among these, from the viewpoint of steep absorption waveform around 500 nm, that is, high brightness, an aromatic hydrocarbon ring group having one free valence is preferable, and monocyclic or bicyclic aromatic carbonization is preferable. It is more preferably a hydrogen ring group, and further preferably a benzene ring.
Examples of the substituent that the aromatic ring group in R ⁵ and R ⁶ may have include those in the above substituent group W2. In particular, from the viewpoint of steep absorption waveform around 500 nm, that is, high brightness, and from the viewpoint of improving heat resistance and light resistance by stabilizing the cation by dispersion of charges in the cation by superconjugation, R ⁵ and R ⁶ The aromatic ring group in is preferably unsubstituted, has an alkyl group as a substituent, or has an alkoxy group as a substituent, more preferably is unsubstituted or has an alkyl group as a substituent. The number of carbon atoms of the alkyl group and alkoxy group that the aromatic ring group may have is not particularly limited, but from the viewpoint of heat resistance, it is preferably 8 or less, more preferably 4 or less, still more preferably 2 or less, usually 1 That's it.

(Combination of R ^{1 to} R ⁶ )
R ^{1 to} R ⁶ may be appropriately selected from those described above. Specific examples of combinations include those described in Table 1. The alkyl group, aromatic hydrocarbon ring group and aromatic heterocyclic group listed in the table below may further contain an arbitrary substituent. C in the table means carbon number.

As a combination of R ^{1 to} R ⁶ , from the viewpoint of heat resistance, the compounds represented by formula (I) are likely to associate with each other, and from other molecules that cause thermal decomposition of the compound represented by formula (I). The number of carbon atoms in which R ³ is a hydrogen atom and R ⁴ may have a substituent, since the electrostatic interaction between the cation and anion due to the steric hindrance of the substituent is not reduced. R ¹ and R ² are each preferably an alkyl group of 1 to 12 and can inhibit attack from other molecules on the carbon atom to which the two benzene rings and naphthalene ring of the triarylmethane skeleton are bonded. An optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted aromatic hydrocarbon ring group having 4 to 12 carbon atoms, or a substituent. A good aromatic heterocyclic group having 4 to 12 carbon atoms Preferably there is.

On the other hand, from the viewpoint of steep absorption waveform near 500 nm, that is, high brightness, the spread of the π-conjugated system is avoided and the shape of the absorption spectrum becomes sharp. Therefore, R ¹ and R ² are each independently It is an alkyl group having 1 to 12 carbon atoms that may have a substituent, R ³ is a hydrogen atom, and R ⁴ is an alkyl group having 1 to 12 carbon atoms that may have a substituent. In addition, in addition, since there is no bias of the π-conjugated system and the shape of the absorption spectrum becomes sharp, R ⁵ and R ⁶ may each independently have a substituent having 4 to 12 carbon atoms. The aromatic hydrocarbon ring group is more preferable.

The triarylmethane compound represented by the formula (I) is symmetrical in which a nitrogen atom is bonded to the para position of two benzene rings forming the triarylmethane skeleton, and a hydrogen atom is bonded to the ortho position and the meta position. Therefore, it is considered that the spectral shape is better and the luminance is higher than those of other structures having a substituent at the ortho position or the meta position. In addition, compared to the case where a substituent is present at the ortho-position or meta-position, it is considered that the molecular twist due to steric hindrance is reduced and the heat resistance is improved. From the viewpoint of contrasting the molecular structure, it is preferable that R ¹ and R ² are the same group and / or R ⁵ and R ⁶ are the same group.

(About [A ⁿ⁻ ] and n)
In the formula (I), [A ⁿ⁻ ] represents an n-valent halogenoalkylsulfonylimide anion which may have a substituent, or an n-valent halogenoalkylsulfonylmethide anion which may have a substituent. N represents an integer of 1 to 4. Here, A represents an atomic group constituting an anion.
n is 4 or less, preferably 2 or less, more preferably 1 from the viewpoint of interaction with the cation. 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 an imide anion or a methide anion from the viewpoint that the charge of the counter anion is likely to be delocalized. 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.

  In particular, when the anion is a halogenoalkylsulfonylimide anion or a halogenoalkylsulfonylmethide anion, there is a tendency that the interaction with the cation becomes stronger due to the delocalization of the charge of the anion and the heat resistance tends to be improved. It is done.

  The number of carbon atoms of the halogenoalkyl group in the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion is preferably 12 or less, more preferably 10 or less, further preferably 6 or less, and usually 1 or more. is there. When the amount is not less than the lower limit value, the anion charge is dispersed and the anion tends to be stabilized. When the value is not more than the upper limit value, the effect of steric repulsion with the cation is reduced, and the cation has a stronger interaction. Tends to be possible.

The type of halogen atom that the halogenoalkyl group has is not particularly limited, but is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine or chlorine, and even more preferably fluorine. By setting the type of halogen atom as described above, the charge of the anion is more delocalized and the heat resistance of the coloring material tends to be improved.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, further preferably 6 or less, and usually 3 or more. When the amount is not less than the lower limit, the charge of the anion tends to be dispersed and the anion tends to stabilize, and when the amount is not more than the upper limit, it has appropriate solubility and influence of steric repulsion with the cation. Tend to be smaller and allow stronger interactions with cations.

  Specific examples of the halogenoalkylsulfonylimide anion include bistrifluoromethanesulfonylimide anion, bispentafluoroethanesulfonylimide anion, and bisnonafluorobutanesulfonylimide anion. From the viewpoint of the heat resistance of the anion, bistrifluoro A methanesulfonylimide anion or a bispentafluoroethanesulfonylimide anion is preferable, and a bistrifluoromethanesulfonylimide anion is more preferable.

  Specific examples of halogenoalkylsulfonylmethide anions include tristrifluoromethanesulfonylimide anion, trispentafluoroethanesulfonylimide anion, trisnonafluorobutanesulfonylimide anion, etc., but the effect of steric repulsion with the cation. From the viewpoint of being small, tristrifluoromethanesulfonylimide anion or trispentafluoroethanesulfonylimide anion is preferable, and bistrifluoromethanesulfonylimide anion is more preferable.

Further, the substituent that the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion may have is not particularly limited, but those exemplified as the substituent group W3 described above can be used, and among them, anions An aromatic ring group which may have a substituent is preferable from the viewpoint of the stability of the charge distribution therein.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Although the carbon number is not particularly limited, it is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more. By setting it to the upper limit or less, there is a tendency that steric hindrance with the cation can be suppressed and the anion can be stabilized.
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.

Among these, from the viewpoint of suppressing steric hindrance with a cation, a benzene ring, a naphthalene ring, a thiophene ring, or a triazine ring is preferable, a benzene ring or a triazine ring is more preferable, and a triazine ring is further preferable. Since the triazine ring has high planarity, it is considered that the interaction with the aromatic moiety of the dye cation and the anion moiety existing in the same system tends to be strong. Further, since it has a sulfonylimide skeleton or a sulfonylmethide skeleton, it is considered that there is little steric repulsion with a cation and a stronger ion pair can be easily formed. As a result, it is difficult to separate the cation and the anion, so the heat resistance is high, and it is easy to suppress the decrease in the interaction between the cation and the anion even in an electric field, and the voltage holding ratio of the resulting pixel tends to increase. There is.
The number of substituents that the halogenoalkylsulfonylimide anion or the halogenoalkylsulfonylmethide anion may have is not particularly limited, but is preferably 1 to 3 from the viewpoint of suppressing steric hindrance. It is more preferable that

(Anion represented by Formula (A-1) and Formula (A-2))
Among these, from the viewpoint of anion stabilization, the substituent is preferably at the end of the anion, and particularly represented by the anion represented by the following formula (A-1) or the following formula (A-2). An anion is preferred.

In the above formula (A-1), R ^1a and R ^2a each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. .
R ^3a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
R ^4a represents a halogenoalkyl group.
X ^{1 to} X ³ are each independently a direct bond, at least one group selected from the group consisting of — (CH ₂ ) —, —NH—, —O— and —S—, or a group in which two or more of these are bonded. Represents.

In the above formula (A-2), R ^5a and R ^6a each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. .
R ^7a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
R ^8a and R ^9a each independently represents a halogenoalkyl group.
X ^{4 to} X ⁶ are each independently a direct bond, at least one group selected from the group consisting of — (CH ₂ ) —, —NH—, —O— and —S—, or a group in which two or more of these are bonded. Represents.

(R ^1a , R ^2a , R ^5a , R ^6a )
R ^1a , R ^2a , R ^5a , and R ^6a each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
Among these, examples of the alkyl group include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 8 or less, more preferably 5 or less, from the viewpoint of solubility in a solvent, and preferably 2 or more from the viewpoint of solubility in a solvent.
Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, A 3-methylbutyl group etc. are mentioned. From the viewpoint of the balance between crystallinity and solubility of the salt formed in these, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
Examples of the substituent that the alkyl group may have include those of the aforementioned substituent group W1.

Of these, examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less from the viewpoint of suppressing steric hindrance, and is preferably 4 or more from the viewpoint of the balance between crystallinity and solubility, and is 6 or more. More preferably.
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.
Among these aromatic ring groups, an aromatic hydrocarbon ring group is preferable from the viewpoint of ease of production.
Examples of the substituent that the aromatic ring group may have include those in the substituent group W2.

Among these, from the viewpoint of the stability of the colored resin composition, R ^1a and R ^2a are each independently an alkyl group which may have a substituent, or an aromatic ring which may have a substituent. It is preferably a group.
R ^1a and R ^2a may be the same or different. For example, R ^1a and R ^2a may each independently be an alkyl group that may have a substituent, and R ^1a and R ^2a may each independently have a substituent. It may be a ring group, R ^1a may be an alkyl group which may have a substituent, and R ^2a may be an aromatic ring group which may have a substituent.
R ^5a and R ^6a may be the same or different. For example, R ^5a and R ^6a may each independently be an alkyl group that may have a substituent, and R ^5a and R ^6a may each independently have a substituent. It may be a cyclic group, R ^5a may be an alkyl group that may have a substituent, and R ^6a may be an aromatic ring group that may have a substituent.

(R ^3a , R ^7a )
R ^3a represents a direct bond, an alkylene group which may have a substituent, or a divalent aromatic ring group which may have a substituent.
Among these, examples of the alkylene group include a linear alkylene group, a branched alkylene group, a cyclic alkylene group, or a group obtained by bonding these. The number of carbon atoms is preferably 8 or less, more preferably 5 or less, and usually 1 or more, from the viewpoint of suppressing the bias of charge.
Specific examples include a methylene group, an ethylene group, and a propylene group. Among these, a methylene group is preferable from the viewpoint of suppressing the bias of electric charge.
Examples of the substituent that the alkylene group may have include those in the substituent group W1.

Among these, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and usually 4 or more, and preferably 6 or more, from the viewpoints of anion rigidity and heat resistance.
The divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene having two free valences. Examples include a ring, a tetracene 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 two free valences. , 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.
Among these divalent aromatic ring groups, a divalent aromatic hydrocarbon ring group is preferable, and a benzene ring is more preferable, from the viewpoint of suppressing charge bias.
Examples of the substituent that the divalent aromatic ring group may have include those in the substituent group W2.

( ^R4a , ^R8a , ^R9a )
R ^4a , R ^8a and R ^9a each independently represents a halogenoalkyl group.
The type of halogen atom that the halogenoalkyl group has is not particularly limited, but is preferably fluorine, chlorine, bromine, or iodine, more preferably fluorine or chlorine, and even more preferably fluorine. By setting the type of halogen atom as described above, the charge of the anion is more delocalized and the heat resistance of the coloring material tends to be improved.
The number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, further preferably 6 or less, and usually 3 or more. When the amount is not less than the lower limit, the charge of the anion tends to be dispersed and the anion tends to stabilize, and when the amount is not more than the upper limit, it has appropriate solubility and influence of steric repulsion with the cation. Tend to be smaller and allow stronger interactions with cations.
The number of carbon atoms of the halogenoalkyl group is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and usually 1 or more. When the amount is not less than the lower limit value, the anion charge is dispersed and the anion tends to be stabilized. When the value is not more than the upper limit value, the effect of steric repulsion with the cation is reduced, and the cation has a stronger interaction. Tends to be possible.
Specific examples include a trifluoromethyl group, a pentafluoroethyl group, a 1,1,1-trifluoroethyl group, and the like, and a trifluoromethyl group is preferable from the viewpoint of suppressing charge bias.

(X ¹ ~X ⁶⁾
X ^{1 to} X ⁶ are each independently a direct bond, at least one group selected from the group consisting of — (CH ₂ ) —, —NH—, —O— and —S—, or a group in which two or more of these are bonded. Represents.
That is, X ^{1 to} X ⁶ may each independently be a combination of two or more divalent groups selected from the above group, or a combination of two or more of one type. In the case of bonding, the number is usually 2 or more, usually 15 or less, preferably 12 or less, more preferably 10 or less.
Among these, from the viewpoint of ease of synthesis, — (CH ₂ ) — or —NH— is preferable, and —NH— is more preferable.

Among these, from the viewpoint that heat resistance is high and the effect of steric repulsion with the cation is small, the interaction with the cation with the anion becomes large, the counter ion is stabilized, and the heat resistance of the dye is improved. It is preferably a methanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion.
Further, the existence 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 viewpoint of luminance and contrast. 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 contained in the color material (A), or two or more types may be contained. 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 color material (A) is not particularly limited, but is preferably 0.01% by mass or more with respect to the color material (A), and 1% by mass. More preferably, it is more preferably 5% by mass or more. It is preferable for it to be equal to or more than the above lower limit value since the coloring power is sufficient and the desired luminance can be easily obtained. 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.

(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, 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.
Particularly when forming blue pixels, xanthene dyes, triarylmethane dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, cyanine dyes, and phthalocyanine dyes are preferable. From the viewpoint of durability, xanthene dyes Or a dipyrromethene dye is more 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, from the viewpoint of heat resistance and light resistance, 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)

  Among other color materials, it is preferable to include other pigments from the viewpoint of improving heat resistance and light resistance, and it is more preferable to include a blue pigment from the viewpoint of improving heat resistance and light resistance due to the blue color material.

[(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.

In the above solvent, it is preferable to contain glycol monoalkyl ethers from the viewpoint of adhesion between the substrate and the coating film, and the coating film can form a uniform film thickness. 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 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 ether used is not excessively large, and the proportion of glycol monoalkyl ether 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 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 70% by mass, preferably 75% by mass, and more preferably 80% 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 (III) Acrylate is preferred.

  The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (III) contains 5 to 90 mol% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

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

In the formula (IV), R ^{91 to} R ⁹⁸ each independently represent 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.
Among these, as the structure represented by the formula (IV), a structure represented by the following structural formula (IVa), (IVb), or (IVc) is particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by said Formula (IV) may be used individually by 1 type, and may use 2 or more types together.
“Other radical polymerizable monomers” other than the mono (meth) acrylate having the structure represented by the formula (IV) can improve heat resistance and strength excellent in the colored resin composition. , 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 the heat resistance and the strength of the film 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%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
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 preferably contains (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; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above 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, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  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 and (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, which is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction . 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 (V).

(In formula (V), 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 heteroaryl group having 4 to 25 carbon atoms. An alkyl group, any of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;
R ¹⁰² is an alkanoyl group having 2 to 20 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, 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 (V), compounds in which X is a carbazole ring which may have a substituent are preferred, and specifically, compounds represented by the following formula (VI), etc. Among them, the compound represented by the following formula (VII) is particularly preferable.

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

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

In formula (VIIa), R ¹¹⁰ and R ¹¹¹ each independently represents 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. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group.

  Commercial products may be used as the oxime initiator. Examples of commercially available products are 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 commercially available products include IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRAC8, IRGACURE8, 19 Is a registered trademark).

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., a coumarin dye having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dye; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, HirakiAkira 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, JP-dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818 discloses 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 portion in the developer 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 initiation 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 these, 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. A unit structure having no ammonium base and amino group can be mentioned.
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.

When the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group. .
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 parts by mass with respect to 100 parts by mass of the total pigment content. In particular, it is preferably used so as to be in the range of 10 to 250 parts by mass.
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 at the point which becomes more favorable.

[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 Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 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 containing the compound (I) and the (C) binder resin, the (B) solvent, and as necessary. 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 an arbitrary component may be mixed together there.
In addition, as a preparation method in the case of including a pigment, in the presence of a dispersant and, if necessary, a dispersion aid to be added in a solvent including a pigment, optionally together with a part of the binder resin (C), 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. Among the pigment dispersion, (A) a colorant containing compound (I), (C) a binder resin, and, if necessary, (D) a polymerizable monomer, (E) a photopolymerization initiation component, and a thermal polymerization initiation component 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 when only a dye is used as a coloring material, a dispersing agent or a dispersion aid is not required, and a complicated pigment dispersion step is not required. The composition can be produced at a 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. Of 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.

  A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, 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, further 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 manufactured 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 | combination of dye>
(Synthesis Example 1: Synthesis of Dye A)

  1-iodonaphthalene (5.1 g, 20 mmol), 2-methylcyclohexylamine (4.7 g, 41 mmol), sodium t-butoxide (2.4 g, 25 mmol), tris (dibenzylideneacetone) (chloroform) under nitrogen atmosphere 1. A mixture of dipalladium (0) (52 mg, 0.050 mmol), 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl (96 mg, 0.15 mmol), toluene (50 mL) at 100 ° C. Stir for 5 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. Purification by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) gave Compound 1 (3.6 g, yield 75%).

  Under a nitrogen atmosphere, phosphorus oxychloride (1.28 g, 8.35 mmol) was added to a mixture of compound 2 (1.51 g, 3.34 mmol), compound 1 (0.84 g, 3.34 mmol) and toluene (30 mL). And heated to 95 ° C. After stirring with heating for 12 hours, the mixture was allowed to cool to room temperature, water (10 mL) was added, and the mixture was stirred for 1 hour. After removing the toluene layer by decantation, chloroform (50 mL) was added for extraction, and the organic layer was washed three times with saturated brine (20 mL). After the organic layer was concentrated, the concentrate was purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 95/5 (volume ratio)) to obtain a blue solid compound 3 (2.00 g, yield 74). %).

  Compound 3 (2.16 g, 3.06 mmol) was dissolved in methanol (50 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.704 g, 2.45 mmol) was added. The mixed solution was heated and stirred at an external temperature of 50 ° C. for 1 hour, and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 91/9 (volume ratio)) to obtain a blue solid dye A (2.00 g, Yield 69%).

Dye A was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 639 nm, and the Gram extinction coefficient (g) was 87.9 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 670 (M + C 48 H 52 N 3)

  (Synthesis Example 2: Synthesis of Dye B)

  Under a nitrogen atmosphere, N, N-dimethylformamide (DMF) (60 mL) was added to N-ethyl-o-toluidine (21.6 g, 160 mmol) and cooled to 5 ° C. or lower. Potassium t-butoxide (18.0 g, 160 mmol) was added in several portions while maintaining the temperature at 5 ° C. or lower. Next, a solution of 4,4-difluorobenzophenone (8.73 g, 40.0 mmol) in N, N-dimethylformamide (DMF) (35 mL) was added dropwise over 30 minutes, taking care to keep the temperature below 15 ° C. After completion of dropping, the temperature was raised to room temperature, and the mixture was further heated and stirred at 50 ° C. for 3 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed with water (20 mL) three times, and then the solvent was distilled off with an evaporator. The obtained solid was purified by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 66/34 (volume ratio)) to obtain compound 4 (3.08 g, yield 17%).

  Under a nitrogen atmosphere, the mixture of compound 4 (610 mg, 1.36 mmol), compound 1 (336 mg, 1.40 mmol) and toluene (10 mL) was stirred at room temperature until dissolved. Phosphorus oxychloride (312 mg, 2.04 mmol) was added dropwise over 5 minutes. After the addition, the mixture was heated to 80 to 85 ° C., and heated and stirred as it was for 9 hours. Further, phosphorus oxychloride (208 mmol, 1.36 mmol) was added dropwise, and the mixture was heated and stirred as it was for 4 hours, and then allowed to cool to room temperature. Water (10 mL) was added and stirred at room temperature for 1 hour. Chloroform (10 mL) was added to extract the organic layer, which was washed 3 times with water (10 mL), and then the solvent was distilled off with an evaporator. The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 82/8 (volume ratio)) to obtain a blue solid compound 5 (590 mg, yield). 61%).

  Under a nitrogen atmosphere, a mixed solution of Compound 5 (0.59 g, 0.84 mmol), methanol (5 mL) and bis (trifluoromethanesulfonyl) imidolithium (0.24 g, 0.84 mmol) was added at an external temperature of 50 ° C. The mixture was heated and stirred for 5 hours. The mixture was allowed to cool to room temperature, and the solvent was distilled off with an evaporator, followed by washing with a methanol / water = 2/1 (volume ratio) mixed solution (30 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 94/6 to 87/13 (volume ratio)) to obtain a blue solid dye B (0.50 g, Yield 62%) was obtained.

Dye B was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 575 nm, and the Gram extinction coefficient (g) was 81.8 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 670 (M + C 48 H 52 N 3)

  (Synthesis Example 3: Synthesis of Dye C)

  Under a nitrogen atmosphere, a mixed solution of N-ethyl-m-toluidine (7.65 g, 49.9 mmol) N, N-dimethylformamide and N, N-dimethylformamide (DMF) (24 mL) is adjusted to 5 ° C. or lower. After cooling, potassium tert-butoxide (6.73 g, 60 mmol) was added in several portions while maintaining the temperature at 5 ° C. or lower. A DMF solution (13 mL) of 4,4'-difluorobenzophenone (3.27 g, 15.0 mmol) was added dropwise over 30 minutes, taking care to keep the temperature below 15 ° C. After completion of dropping, the temperature was raised to room temperature, and the mixture was further heated and stirred at 50 ° C. for 5 hours. After completion of the reaction, it was cooled to room temperature and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed with water (20 mL) three times, and then the solvent was distilled off with an evaporator. The obtained solid was purified by silica gel column chromatography (hexane / ethyl acetate = 92/8 to 71/29 (volume ratio)) to obtain Compound 6 (0.39 g, yield 6%).

  Under nitrogen atmosphere, a mixture of compound 6 (1.35 g, 3.00 mmol), compound 1 (0.72 g, 3.00 mmol) and toluene (22 mL) at room temperature, phosphorus oxychloride (0.69 g, 4.50 mmol) Was added dropwise over 5 minutes. After dripping, it heated to 80-85 degreeC, and heat-stirred for 8 hours as it was. Further, phosphorus oxychloride (0.46 g, 3.00 mmol) was added dropwise, and the mixture was heated and stirred as it was for 4 hours and then allowed to cool to room temperature. After adding water (30 mL) and stirring at room temperature, chloroform (30 mL) was added and stirred and allowed to stand. The organic layer was extracted and washed three times with water (20 mL), and then the solvent was distilled off with an evaporator. The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 81/19 (volume ratio)) to obtain a blue solid compound 7 (1.19 g, Yield 56%).

  Under a nitrogen atmosphere, a mixed solution of Compound 7 (1.12 g, 1.58 mmol), methanol (10 mL) and bis (trifluoromethanesulfonyl) imidolithium (1.12 g, 1.58 mmol) was added at an external temperature of 50 ° C. The mixture was heated and stirred for 5 hours. The mixture was allowed to cool to room temperature, the solvent was distilled off with an evaporator, and then washed with a methanol / water = 2/1 mixed solution (30 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 94/6 to 87/13 (volume ratio)) to obtain a blue solid dye C (0.50 g, Yield 62%) was obtained.

Dye C was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 638 nm, and the Gram extinction coefficient (g) was 80.1 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 670 (M + C 48 H 52 N 3)

  (Synthesis Example 4: Synthesis of Dye D)

  A mixture of N-ethylaniline (10.02 g, 82.5 mmol), difluorobenzophenone (4.50 g, 20 mmol), potassium tert-butoxide (9.26 g, 82.5 mmol) and DMF (40 mL) was added under nitrogen atmosphere. The mixture was heated to 0 ° C. and stirred as it was for 7 hours. After completion of the reaction, it was cooled to room temperature and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed with water (20 mL) three times, and then the solvent was distilled off with an evaporator. The obtained oil was purified by silica gel column chromatography (hexane / ethyl acetate = 86/14 to 65/35 (volume ratio)) to obtain Compound 8 (2.34 g, yield 28%).

  Under a nitrogen atmosphere, phosphorus oxychloride (2.13 g, 13.9 mmol) was added to a mixture of compound 8 (2.34 g, 5.56 mmol), compound 1 (1.33 g, 5.56 mmol) and toluene (30 mL). Then, it heated to 100 degreeC and stirred as it was for 12.5 hours. After cooling to room temperature, water (10 mL) was added and stirred for 1 hour. After removing the toluene layer by decantation, chloroform (50 mL) was added for extraction, and the organic layer was washed three times with saturated brine (20 mL). After distilling off the solvent with an evaporator, the obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 95/5 (volume ratio)), and blue Solid compound 9 (3.00 g, 81% yield) was obtained.

  Compound 9 (1.90 g, 2.80 mmol) was dissolved in methanol (50 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.88 g, 3.08 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was distilled off with an evaporator and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 95/5 (volume ratio)) to obtain a blue solid dye D (3.00 g, Yield 81%) was obtained.

Dye D was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 638 nm, and the gram extinction coefficient (g) was 75.6 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 642 (M + C 46 H 48 N 3)

  (Synthesis Example 5: Synthesis of Dye E)

  Compound 2 (synthesized by the method described in WO 2011/162217 pamphlet) (2.01 g, 4.45 mmol), Compound 10 (1.12 g, 4.45 mmol) and toluene (30 mL) under nitrogen atmosphere After adding phosphorus oxychloride (1.70 g, 11.1 mmol), the mixture was heated to 100 ° C. and stirred as it was for 9 hours. After standing to cool to room temperature, water (10 mL) was added and stirred for 1 hour. After removing the toluene layer by decantation, chloroform (50 mL) was added for extraction, and the organic layer was washed three times with saturated brine (20 mL). After the solvent was distilled off with an evaporator, the obtained solid was dissolved in chloroform (10 mL), and silica chromatography (developing solvent: hexane / ethyl acetate = 70/30, chloroform / methanol = 100/0 to 95/5 ( Purification by volume ratio)) gave blue solid compound 11 (2.13 g, 66% yield).

  Compound 11 (2.13 g, 2.96 mmol) was dissolved in methanol (50 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.93 g, 3.25 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1 hour and then allowed to cool to room temperature. The solvent was distilled off with an evaporator and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 99/1 to 92/8 (volume ratio)) to obtain a blue solid dye E (2.00 g, Yield 70%).

Dye E was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 600 nm, and the Gram extinction coefficient (g) was 81.2 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 684 (M + C 45 H 45 F 3 N 3)

  (Synthesis Example 6: Synthesis of Dye F)

  Under a nitrogen atmosphere, p-anisidine (12.3 g, 0.10 mol), propyl bromide (12.29 g, 0.10 mol), potassium carbonate (16.5 g, 0.12 mol) and N, N-dimethylformamide (DMF) ) (60 mL) was heated to 50 ° C. and stirred for 9 hours. The mixture was allowed to cool to room temperature, poured into water (100 mL), and extracted twice with toluene (50 mL). The organic layer was washed 3 times with water (20 mL), and then the solvent was distilled off with an evaporator. The concentrate was purified by silica chromatography (developing solvent: hexane / ethyl acetate = 100/0 to 82/18 (volume ratio)) to obtain compound 12 (8.58 g, yield 52%) as a pale yellow oil. It was.

  Under nitrogen atmosphere, Compound 12 (8.50 g, 51.4 mmol), dichlorobenzophenone (2.80 g, 12.8 mmol), palladium acetate (277 mg, 1.28 mmol), t-butylphosphine (517 mg, 2.56 mmol), A mixture of sodium tert-butoxide (4.33 g, 51.4 mmol) and toluene (50 mL) was heated to 90 ° C. and stirred for 5 hours. After cooling to room temperature, water (10 mL) was added to stop the reaction, and insolubles were removed by Celite filtration. After performing toluene extraction, the solvent was distilled off with an evaporator. The concentrate was purified by silica chromatography (developing solvent: hexane / ethyl acetate = 82/18 to 61/39 (volume ratio)) to obtain compound 13 (1.79 g, 27% yield) as a pale yellow solid. .

  Under a nitrogen atmosphere, phosphorus oxychloride (1.35 g, 8.80 mmol) was added to a mixture of compound 13 (1.79 g, 3.52 mmol), compound 1 (0.84 g, 3.52 mmol) and toluene (30 mL). Then, it heated to 100 degreeC and stirred as it is for 11.5 hours. After cooling to room temperature, water (5 mL) was added and stirred for 1 hour. After removing the toluene layer by decantation, chloroform (50 mL) was added for extraction, and the organic layer was washed three times with water (20 mL). After the solvent was distilled off with an evaporator, the obtained solid was dissolved in chloroform (10 mL), and silica chromatography (developing solvent: hexane / ethyl acetate = 70/30, chloroform / methanol = 100/0 to 85/15 ( The compound 14 (2.00 g, 74% yield) was obtained as a blue solid.

  Under a nitrogen atmosphere, compound 14 (2.00 g, 2.61 mmol) was dissolved in methanol (50 mL) at room temperature, and lithium bis (trifluoromethylsulfonyl) imide (0.90 g, 3.13 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 85/15 (volume ratio)) to obtain a blue solid dye F (1.70 g, Yield 64%) was obtained.

Dye F was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 639 nm, and the Gram extinction coefficient (g) was 88.8 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 730 ((M ⁺ C ₅₀ H ₅₆ N ₃ O ₂ )

  (Synthesis Example 7: Synthesis of Dye G)

  Under a nitrogen atmosphere, compound 9 (1.03 g, 1.5 mmol) was dissolved in methanol (50 mL) at room temperature, and compound 15 (0.88 g, 1.6 mmol, manufactured by Central Glass) was added. The mixed solution was heated and stirred at an external temperature of 60 ° C. for 3 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed three times with water (20 mL). The obtained solid was dissolved in chloroform (5 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 93/7 (volume ratio)) to obtain a blue solid dye G (1.15 g, Yield 74%) was obtained.

Dye G was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 639.5 nm, and the Gram extinction coefficient (g) was 70.9 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 642 (M + C 46 H 48 N 3)

  (Synthesis Example 8: Synthesis of Dye H)

  In a nitrogen atmosphere, N-ethyl-1-naphthylamine (12.9 g, 75.2 mmol) and DMF (34 mL) were added and cooled in an ice bath, and potassium tert-butoxide (9.1 g, 81.0 mmol) was stirred. However, it was added at an internal temperature of 5 ° C or lower. Thereafter, difluorobenzophenone (4.5 g, 20.8 mmol) and DMF (20 mL) were added, and the mixture was stirred at 50 ° C. for 6 and a half hours. After allowing to cool to room temperature, toluene (10 mL) and water were added to stop the reaction. After toluene extraction, the organic layer was washed with water (50 mL) twice. After distilling off the solvent with an evaporator, the solution was crystallized with methanol in an ice bath, washed with methanol, then washed with ethyl acetate, and purified to obtain Compound 16 (2.1 g, yield 20%) as a pale yellow solid. It was.

  Under a nitrogen atmosphere, phosphorus oxychloride (0.824 g, 5.37 mmol) was added to a mixture of compound 16 (1.12 g, 2.15 mmol), compound 1 (0.51 g, 2.15 mmol) and toluene (30 mL). Then, it heated at 100 degreeC and stirred as it was for 12 hours. After allowing to cool to room temperature, water (20 mL) was added and stirred for 1 hour. Chloroform (50 mL) was added for extraction, and the organic layer was washed 3 times with water (20 mL). After the solvent was distilled off with an evaporator, the obtained solid was dissolved in chloroform (5 mL), and silica chromatography (developing solvent: hexane / ethyl acetate = 70/30, chloroform / methanol = 100/0 to 80/20 ( Purification by volume ratio)) gave blue solid compound 17 (1.92 g).

  Compound 17 (1.92 g, 2.15 mmol) was dissolved in methanol (50 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.68 g, 2.37 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1 hour and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 96/4 to 80/20 (volume ratio)) to obtain a blue solid dye H (1.87 g, Yield 85%).

Dye H was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 636.5 nm, and the Gram extinction coefficient (g) was 71.6 Lg ⁻¹ cm ⁻¹ .

  (Synthesis Example 9: Synthesis of Dye I)

  Under a nitrogen atmosphere, aniline (9.4 g, 0.1 mol), 2-bromoethyl ethyl ether (15.5 g, 0.1 mol), potassium carbonate (15.6 g, 0.11 mol) and N-methyl-2-pyrrolidone A mixture of (NMP) (80 mL) was heated to 80 ° C. and stirred for 4 hours, then at room temperature for 9 hours. Then, water (100 mL) was poured and extracted with toluene (100 mL). The organic layer was washed twice with saturated brine (100 mL), and then the solvent was distilled off with an evaporator. The concentrate was purified by silica chromatography (developing solvent: hexane / ethyl acetate = 95 / 5-74 / 26 (volume ratio)) to obtain compound 18 (7.08 g, 43% yield) as a pale yellow oil. It was.

  Under a nitrogen atmosphere, compound 18 (7.0 g, 42.3 mmol) and DMF (16 mL) were added and cooled in an ice bath, and potassium tert-butoxide (4.7 g, 42.0 mmol) was stirred at an internal temperature of 5 ° C. Added below. Thereafter, difluorobenzophenone (2.18 g, 10.0 mmol) and DMF (26 mL) were added, and the mixture was heated and stirred at 50 ° C. for 4 hours. After allowing to cool to room temperature, toluene (10 mL) and water were added to stop the reaction. After toluene extraction, the organic layer was washed with water (30 mL) twice. After evaporating the solvent with an evaporator, the solution was crystallized in an ice bath, washed with methanol, dissolved in toluene, crystallized in methanol, and purified to give a pale yellow solid compound 19 (2.3 g, yield 46). %).

  Under a nitrogen atmosphere, phosphorus oxychloride (1.01 g, 6.6 mmol) was added to a mixture of compound 19 (1.31 g, 2.6 mmol), compound 1 (0.64 g, 2.7 mmol) and toluene (20 mL). Then, it heated at 100 degreeC and stirred as it was for 28.5 hours. After cooling to room temperature, water (5 mL) was added and stirred for 1 hour. Chloroform (50 mL) was added for extraction, and the organic layer was washed with saturated brine (50 mL). After the solvent was distilled off with an evaporator, the obtained solid was dissolved in chloroform (10 mL), and silica chromatography (developing solvent: (first time) ethyl acetate only, (second time) chloroform / methanol = 100/0 to 90 / 10 (volume ratio)) to obtain a blue solid compound 20 (1.60 g, yield 81%).

  Compound 20 (1.60 g, 2.1 mmol) was dissolved in methanol (20 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.67 g, 2.3 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 5 hours and then allowed to cool to room temperature. Water (20 mL) was added and stirred, followed by filtration. The resulting solid was dissolved in ethyl acetate and washed with water. After evaporation of the solvent, the residue was dissolved in chloroform (10 mL) and silica chromatography (developing solvent: chloroform / methanol). = 100/0 to 86/14 (volume ratio)) to obtain a blue solid dye I (0.54 g, yield 26%).

Dye I was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 641 nm, and the Gram extinction coefficient (g) was 76.2 Lg ⁻¹ cm ⁻¹ .

  (Synthesis Example 10: Synthesis of Dye J)

  1-naphthylamine (0.5 g, 3.5 mmol) and 3-pentanone (0.3 g, 3.5 mmol) are dissolved in acetic acid (4 mL) and chloroform (4 mL) at room temperature under a nitrogen atmosphere, and triacetoxyborohydride Sodium (0.74 g, 3.5 mmol) was added little by little and stirred at room temperature for 12 hours. After completion of the reaction, it was mixed with water (10 mL). After extraction with chloroform, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The desiccant was filtered off and the solvent was distilled off to give oily compound 21.

  Under a nitrogen atmosphere, phosphorus oxychloride (1.57 g, 10.3 mmol) was added to a mixture of compound 4 (1.54 g, 3.43 mmol), compound 21 and toluene (23 mL), and then heated to 100 ° C. and left as it was. Stir for 2 hours. After the reaction solution was cooled to room temperature, water (10 mL) was added and stirred for 1 hour. After removing the toluene layer by decantation, chloroform (30 mL) was added for extraction, and the organic layer was washed 3 times with saturated brine (20 mL). After the solvent was distilled off, the obtained solid was dissolved in chloroform (10 mL) and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 to 86/14 (volume ratio)) to obtain a blue solid. Of compound 22 (1.85 g, 79%).

Under a nitrogen atmosphere, compound 22 (1.85 g, 2.72 mmol) was dissolved in methanol (27 mL) at room temperature, and lithium bis (trifluoromethylsulfonyl) imide (0.79 g, 2.74 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with a mixed solvent (30 mL) of methanol / water = 1/2 (volume ratio). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 86/14 (volume ratio)) to obtain a blue solid dye J (1.98 g, Yield 79%).
Dye J was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 575 nm, and the Gram extinction coefficient (g) was 79.2 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 644 ((M ⁺ C ₄₆ H ₅₀ N ₃ )

  (Synthesis Example 11: Synthesis of Dye K)

  In a nitrogen atmosphere, 1-naphthylamine (0.5 g, 3.5 mmol) and 2-heptanone (0.4 g, 3.5 mmol) are dissolved in acetic acid (4 mL) and chloroform (4 mL) at room temperature, and triacetoxyborohydride Sodium (0.74 g, 3.5 mmol) was added little by little and stirred at room temperature for 12 hours. After completion of the reaction, it was mixed with water (10 mL). After extraction with chloroform, the organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The desiccant was filtered off and the solvent was distilled off to give oily compound 23.

  Under a nitrogen atmosphere, phosphorus oxychloride (1.57 g, 10.3 mmol) was added to a mixture of compound 4 (1.54 g, 3.43 mmol), compound 23 and toluene (23 mL), and then heated to 100 ° C. and left as it was. Stir for 3.5 hours. After the reaction solution was cooled to room temperature, water (10 mL) was added and stirred for 1 hour. After removing the toluene layer by decantation, chloroform (30 mL) was added for extraction, and the organic layer was washed 3 times with saturated brine (20 mL). After the solvent was distilled off, the obtained solid was dissolved in chloroform (10 mL) and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 to 90/10 (volume ratio)) to give a blue solid. Of compound 24 (1.88 g, 76%).

  Under a nitrogen atmosphere, compound 24 (1.88 g, 2.60 mmol) was dissolved in methanol (26 mL) at room temperature, and lithium bis (trifluoromethylsulfonyl) imide (0.77 g, 2.68 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with a mixed solvent (30 mL) of methanol / water = 1/2 (volume ratio). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 85/15 (volume ratio)) to obtain a blue solid dye K (2.07 g, Yield 84%) was obtained.

Dye K was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 576 nm, and the Gram extinction coefficient (g) was 79.9 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 672 ((M + C 48 H 54 N 3)

  (Synthesis Example 12: Synthesis of Dye L)

Compound 25 was synthesized by the method described in JP2013-087248A.
Under a nitrogen atmosphere, compound 9 (0.20 g, 0.30 mmol) was dissolved in methanol (3 mL) at room temperature, and compound 25 (0.18 g, 0.33 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with water (10 mL). The obtained solid was dissolved in chloroform (2 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 82/18 (volume ratio)) to obtain a blue solid dye L (0.30 g, Yield 87%).

Dye L was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 640 nm, and the Gram extinction coefficient (g) was 58.0 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 642 ((M ⁺ C ₄₆ H ₄₈ N ₃ )

  (Synthesis Example 13: Synthesis of Dye M)

  Under a nitrogen atmosphere, compound 5 (0.53 g, 0.8 mmol) was dissolved in methanol (20 ml) at room temperature, and compound 25 (0.75 g, 1.3 mmol) was added. The mixed solution was stirred at an external temperature of 70 ° C. for 5.5 hours, and then allowed to cool to room temperature. Water (100 mL) was added and stirred, followed by filtration. The resulting solid was washed with water, dissolved in chloroform (10 mL), and silica chromatography (developing solvent: chloroform / methanol = 100/0 to 93/7 (volume). Ratio)) to obtain a blue solid dye M (0.55 g, yield 60%).

Dye M was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 635 nm, and the Gram extinction coefficient (g) was 57.0 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 670 (M + C 48 H 52 N 3)

  (Synthesis Example 14: Synthesis of Dye N)

The solution of compound 26 was synthesized by the method described in JP2013-087248A.
Water (17 mL) was added to a solution of compound 26 (2.72 mmol), and a solution obtained by suspending cyanuric chloride (0.5 g, 2.72 mmol) in acetone (2 mL) was added at 0 to 5 ° C. at pH = 4-6. Was added while stirring and further stirred for 1.5 hours. Next, at pH = 6-7 at room temperature, a solution prepared by dissolving a mixture of aniline (0.25 g, 2.72 mmol) and hydrochloric acid (0.28 mL) in water (1 ml) was added, and the mixture was further stirred for 0.5 hour. . Thereafter, a solution obtained by dissolving a mixture of aniline (1.0 g, 10.88 mmol) and hydrochloric acid (1.12 mL) in water (2 mL) was added, and the mixture was stirred at an external temperature of 70 ° C. to pH = 8 to 9 for 8 hours. The resulting reaction solution was cooled to room temperature and then filtered to obtain compound 27 (1.22 g, yield 76%).

Under a nitrogen atmosphere, compound 9 (0.20 g, 0.30 mmol) was dissolved in methanol (3 mL) at room temperature, and compound 27 (0.19 g, 0.33 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with water (10 mL). The obtained solid was dissolved in chloroform (2 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 94/6 (volume ratio)) to obtain a blue solid dye N (0.18 g, Yield 51%).
The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 642 ((M ⁺ C ₄₆ H ₄₈ N ₃ )

  (Synthesis Example 15: Synthesis of Dye O)

  Water (17 mL) was added to a solution of compound 26 (2.72 mmol), and a solution obtained by suspending cyanuric chloride (0.5 g, 2.72 mmol) in acetone (2 mL) was added at 0 to 5 ° C. at pH = 4-6. Was added while stirring and further stirred for 1.5 hours. Next, a solution of 2-ethylhexylamine (0.35 g, 2.72 mmol) and hydrochloric acid (0.28 mL) dissolved in water (1 mL) at pH = 6 to 7 at room temperature was added. Stir for hours. Thereafter, a solution prepared by dissolving a mixture of 2-ethylhexylamine (0.40 g, 3.13 mmol) and hydrochloric acid (0.32 mL) in water (1 mL) was added, and the pH was adjusted to 8 to 9 at an external temperature of 70 ° C. for 10 hours. Stir. The resulting reaction solution was cooled to room temperature and then salted out with sodium chloride to obtain Compound 28 (1.78 g, yield 99%).

Under a nitrogen atmosphere, compound 9 (0.20 g, 0.30 mmol) was dissolved in methanol (3 mL) at room temperature, and compound 28 (0.21 g, 0.33 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with water (10 mL). The obtained solid was dissolved in chloroform (2 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 94/6 (volume ratio)) to obtain a blue solid dye N (0.19 g, Yield 49%) was obtained.
The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 642 ((M ⁺ C ₄₆ H ₄₈ N ₃ )

  (Synthesis Example 16: Synthesis of Comparative Dye 1)

  Compound 29 (2.00 g, 3.40 mmol, synthesized by the method described in WO 2011/158794 pamphlet) was dissolved in methanol (20 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.99 g, 3.40 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator and then washed with a mixed solvent (30 mL) of methanol / water = 1/2 (volume ratio). The obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 10/1 to 5/1 (volume ratio)) to obtain a blue solid comparative dye 1 (1.80 g). Yield 63%).

Comparative dye 1 was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 628 nm, and the Gram extinction coefficient (g) was 111 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 546 ((M ⁺ C ₃₈ H ₄₈ N ₃ )

(Synthesis Example 17: Synthesis of Comparative Dye 2)
The following comparative dye 2 was synthesized by the method described in WO 2011/162217 pamphlet.

  (Synthesis Example 18: Synthesis of Comparative Dye 3)

  Under a nitrogen atmosphere, p-iodotoluene (5.00 g, 33.9 mmol) and N-ethyl-m-toluidine (3.72 g, 27.5 mmol) were dissolved in toluene (50 mL). Separately, tris (dibenzylideneacetone) (chloroform) dipalladium (0) (0.474 g, 0.458 mmol) and toluene (6 mL) were placed in a container purged with nitrogen, and tri-t-butylphosphine (0.370 g) was placed therein. , 1.83 mmol) in toluene (2 mL) was added dropwise, and the temperature was raised to 40 ° C. When the redness disappeared and the transparency appeared, it was added to the toluene solution system prepared first. Furthermore, after adding t-butoxy sodium (4.84 g, 50.4 mmol), it heated up to toluene recirculation | reflux and was made to react for 2 hours. After cooling to room temperature, it was poured into water (100 mL) and extracted twice with toluene (50 mL). After drying over anhydrous magnesium sulfate, filtration was performed, and the filtrate was concentrated with an evaporator. The concentrate was purified by silica chromatography (developing solvent: hexane / toluene = 10/1 (volume ratio)) to obtain an oily compound 30 (5.0 g, yield 97%).

  Under a nitrogen atmosphere, a mixture of anhydrous aluminum chloride (3.55 g, 26.6 mmol) and 1,2-dichloroethane (5 mL) was ice-cooled to 0 ° C. or lower, and 4-bromobenzoyl chloride (4.85 g, 22.1 mmol). Was added dropwise over 20 minutes. Next, compound 30 (4.82 g, 22.1 mmol) was added dropwise over a period of 25 minutes between −2 to 2 ° C., and the mixture was stirred for 1 hour. Next, stirring was continued for 2.5 hours while raising the temperature to room temperature. After completion of the reaction, the reaction solution was poured into ice water (200 mL). Chloroform (50 mL) was added for extraction, washed with 1N aqueous sodium hydroxide solution (10 mL) three times, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated with an evaporator, and then the concentrate was purified by silica chromatography (developing solvent: hexane / ethyl acetate = 15/1 to 10/1 (volume ratio)) to obtain an oily compound 31 ( 5.3 g, yield 59%).

  Under a nitrogen atmosphere, compound 31 (5.3 g, 13.0 mmol) was dissolved in toluene (55 mL), into which N-ethyltoluidine (4.99 g, 37.9 mmol), sodium tert-butoxide (2.49 g, 26.0 mmol), palladium acetate (0.175 g, 0.778 mmol) and tri-tert-butylphosphine (0.315 g, 1.56 mmol) were added, and the mixture was heated to 100 ° C. and reacted for 3 hours. Water (10 mL) was added after standing_to_cool to room temperature, and cerite filtration was performed. Toluene was added to the filtrate for extraction, followed by drying over anhydrous sodium sulfate. After performing filtration and concentrating the filtrate with an evaporator, the concentrate was purified by silica chromatography (developing solvent: hexane / ethyl acetate = 10/1 (volume ratio)) to obtain an oily compound 32 (4.5 g, Yield 66%).

  Under a nitrogen atmosphere, phosphorus oxychloride (2.93 g, 19.4 mmol) was added to a mixture of compound 32 (4.5 g, 9.72 mmol), compound 10 (2.46 g, 9.72 mmol) and toluene (50 mL). Thereafter, the mixture was heated to reflux and stirred for 5 hours. After cooling to room temperature, water (10 mL) was added and stirred for 1 hour. Chloroform (50 mL) was added for extraction, and the organic layer was washed twice with saturated brine (10 mL). After evaporating the solvent with an evaporator, the obtained solid was dissolved in chloroform (10 mL) and purified by silica chromatography (developing solvent: chloroform / methanol = 100/0 to 20/1 (volume ratio)), and tar was added. Compound 33 (1.32 g, yield 19%) was obtained.

  Compound 33 (1.30 g, 1.77 mmol) was dissolved in methanol (33 mL) at room temperature under a nitrogen atmosphere, and lithium bis (trifluoromethylsulfonyl) imide (0.508 g, 1.77 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1.5 hours and then allowed to cool to room temperature. The solvent was concentrated with an evaporator, washed with methanol / water = 1/3 to 1/2 (volume ratio), and filtered. By vacuum drying at 40 ° C., a blue-violet solid comparative dye 3 (1.40 g, yield 81%) was obtained.

Comparative dye 3 was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 637 nm, and the Gram extinction coefficient (g) was 77.2 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 698 ((M ⁺ C ₄₆ H ₄₇ F ₃ N ₃ )

  (Synthesis Example 19: Synthesis of Comparative Dye 4)

  Compound 9 (0.65 g, 0.96 mmol) was dissolved in methanol (20 mL) at room temperature under a nitrogen atmosphere, and potassium hexafluorophosphate (0.21 g, 1.15 mmol) was added. The mixed solution was stirred at an external temperature of 50 ° C. for 1 hour and then allowed to cool to room temperature. The reaction solution was added to water (100 mL), and the precipitated solid was filtered and washed with water to obtain a comparative dye 4 (0.38 g, yield 59%, LC purity 93%) as a blue solid.

Comparative dye 4 was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 638.5 nm, and the Gram extinction coefficient (g) was 89.9 Lg ⁻¹ cm ⁻¹ . The results of liquid chromatography-mass spectrometry of this compound are shown below. In addition, the mass at this time has shown the mass of the triarylmethane cation site | part.
LCMS (ESI, posi) m / z 642 (M + C 46 H 48 N 3)

(Synthesis Example 20: Synthesis of Resin A)
145 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was stirred while being replaced 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 21: 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). Next, 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 22: Synthesis of Resin G)
A resin was synthesized based on the method described in Example 1 of JP-A-2008-248142. Propylene glycol monomethyl ether acetate was added so that the solid content of the resin was 38.2% by mass and used as Resin G.

(Synthesis Example 23: 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 O obtained in Synthesis Examples 1 to 15, the comparative dyes 1 to 4 obtained in Synthesis Examples 16 to 19, and the resins A and B obtained in Synthesis Examples 20 and 21 are shown in Tables 2 and 3 below. A colored resin composition was prepared by mixing with other components so that the composition described in 1) was obtained.

In addition, the numerical value of the upper stage of Table 2 and 3 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value in () of the lower stage is the total solid content of each component. The content ratio (% by mass) is expressed.
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.
The dyes A to O were used for the colored resin compositions of Examples 1 to 15, and the comparative dyes 1 to 4 were used for the colored resin compositions of Comparative Examples 1 to 4.

In addition, each compound of Table 2 and 3 is as follows, respectively.
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

[Preparation 2 of colored resin composition]
<Preparation of pigment dispersion>
(Preparation of blue pigment dispersion (1))
As a blue pigment, C.I. I. Pigment Blue 15: 6 is 11.36 parts by mass, 57.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and “Disperbic 2000” (manufactured by BYK Chemie) as a dispersant is 3.02 parts by mass in terms of solid content. A stainless steel container was filled with 215.7 parts by weight of 0.5 mm zirconia beads and dispersed for 6 hours with a paint shaker to prepare a blue pigment dispersion (1).

(Preparation of blue pigment dispersion (2))
As a blue pigment, C.I. I. Pigment Blue 15: 6 and Violet 23 at a mass ratio of 9.20: 3.81, 11.36 parts by mass, 57.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and “Disperbic 2000” (Bic Chemie) as a dispersant Made of 3.02 parts by mass in terms of solid content and 215.7 parts by mass of zirconia beads having a diameter of 0.5 mm in a stainless steel container, and dispersed in a paint shaker for 6 hours to obtain a blue pigment dispersion (2). Prepared.

<Preparation of colored resin composition>
A colored resin composition was prepared by mixing at a ratio shown in Table 4 below.
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.
In addition, the numerical value of the upper stage in Table 4 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value in () of the lower stage is content in the total solid content of each component. The ratio (mass%) is expressed. In Table 4, (E) photopolymerization initiation component, other components, and (B) solvent are the same as those in Table 2.

[Production of colored resin film and evaluation of heat resistance]
Each colored resin composition prepared in the above [Preparation of colored resin composition 1] and [Preparation of colored resin composition 2] on a glass substrate cut into 5 cm square was subjected to the following y after baking by spin coating. After applying to a value of 0.120 and 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 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 chromaticity (C light source) and luminance in the XYZ color system were calculated.

In heating at 230 ° C. and 30 minutes later, Examples 1 to 15 showed higher luminance than Comparative Example 3 using a dye having an orthomethyl group and Comparative Example 4 using a dye having an anion of PF ₆ ⁻ . It can be seen that the heat resistance is high.

[Production of colored resin film and evaluation of light 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, 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 at an exposure amount of 60 mJ / cm ² and baked at 230 ° C. for 30 minutes in a clean oven. At this time, the y value was adjusted to 0.120 when baked at 230 ° C. for 30 minutes in a clean oven. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ^{2 and} then baked at 230 ° C. for 30 minutes. 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. The color difference (ΔE * ab) before and after irradiation was measured as light resistance, and the evaluation results are summarized in Table 6.

The color change ΔE * ab of Examples 1 to 13 was smaller than those of Comparative Examples 1 and 2 having no aromatic ring group in R ⁵ and R ⁶ of the formula (I). 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.

  From Tables 5 and 6, the colored resin compositions of Examples 1 to 15 according to the present invention have the light resistance required for the long-term reliability of the color display and the baking at 230 ° C. required in the color display manufacturing process. It can be seen that it satisfies both the heat resistance in.

[Manufacture of colored resin film and measurement of contrast ratio]
Each colored resin composition prepared in [Preparation of colored resin composition 1] and [Preparation of colored resin composition 2] is applied onto a glass substrate cut into 5 cm square by spin coating, and dried under reduced pressure. Then, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² and baked at 230 ° C. for 60 minutes in a clean oven. The obtained substrate before and after heating is sandwiched between two polarizing plates, and the polarizing plate on the front side is rotated while irradiating with light in the wavelength range of 380 to 780 nm from the back side, and the transmitted light intensity is measured by the luminance meter BM-5AS. The maximum value and the minimum value were measured by (Topcon). A value obtained by dividing the maximum value by the minimum value was evaluated as the contrast ratio.

In Examples 1, 2, and 4, the contrast was as high as 10,000 or more, whereas in Comparative Example 5, it was as low as 8000.
From the above, since Examples 1 to 15 are colored resin compositions exhibiting high light resistance and high heat resistance in addition to high brightness and contrast ratio, color filters and liquid crystal display devices using the same Suitable for organic EL display devices.

[Measurement of voltage holding ratio by liquid crystal]
<Preparation of colored resin composition for measuring voltage holding ratio>
The following components were mixed to prepare a colored resin composition for measuring voltage holding ratio.
-(A) Coloring material Dye 1-L2.7 parts by mass-(C) Binder resin Resin 1-G18 parts by mass-(D) Polymerizable monomer Dipentaerythritol hexaacrylate 6.9 parts by mass-(E) Start photopolymerization Agent 3- (2-acetoxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toluoyl) -9H-carbazole 1.5 parts by mass Other components F559 (manufactured by DIC) ) 0.02 parts by mass / (B) Solvent 52.7 parts by mass of PGMEA, 9.1 parts by mass of PGME, 9.1 parts by mass of ethyl 3-ethoxypropionate

<Preparation of composition for forming protective layer>
The following components were mixed to prepare a protective layer forming composition.
Polymerizable monomer Dipentaerythritol hexaacrylate 7.1 parts by mass Binder resin ZAR10357.1 parts by mass Nippon Kayaku Co., Ltd. Photopolymerization initiator 2- [4- (Methylthio) benzoyl] -2- (4- Morpholinyl) propane 0.75 parts by mass, other components F559 (manufactured by DIC) 0.04 parts by mass, solvent PGMEA 85 parts by mass

<Measurement of voltage holding ratio>
The colored resin composition prepared in the above <Preparation of colored resin composition for measuring voltage holding ratio> is applied to a glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited on the entire surface (evaluation glass ITO manufactured by ECH). The number of revolutions was set to be MN-1392) so that the thickness of the coating film was 2 to 3 μm (the film thickness after thermosetting was about 2 μm) (300 rpm to 700 rpm), and the coating was performed using a spin coater. The sample was pre-baked for 3 minutes on a hot plate and then dried in a vacuum chamber for 1 minute.

Next, using a high-pressure mercury lamp, a photomask was applied to the outer periphery to be an electrode, and the coating film was exposed with radiation including each wavelength of 303 nm, 313 nm, 334 nm, 365 nm, 405 nm, and 436 nm at an exposure amount of 32 mW and 60 mJ / cm ^2. Further, post baking was performed at 230 ° C. for 60 minutes to cure the coating film, thereby obtaining a blue pixel substrate.

The protective layer-forming composition prepared in <Preparation of protective layer-forming composition> is applied to a blue pixel substrate with a coating film thickness of 1.5 to 2.0 μm (the film thickness after thermosetting is about It was applied using a spin coater whose rotation speed was set to be 1.6 μm (300 to 400 rpm), dried under reduced pressure, and then pre-baked for 1 minute and 40 seconds on a hot plate at 100 ° C.
Next, using a high-pressure mercury lamp, a photomask was applied to the outer periphery to be an electrode, and the coating film was exposed with radiation including each wavelength of 303 nm, 313 nm, 334 nm, 365 nm, 405 nm, and 436 nm at an exposure amount of 32 mW and 60 mJ / cm ^2. Further, post-baking was performed at 230 ° C. for 30 minutes to cure the coating film to obtain a blue pixel substrate for liquid crystal evaluation.

After washing the blue pixel substrate for liquid crystal evaluation and an electrode substrate (eetchy evaluation glass SZ-B11MIN (B) MN11396) simply deposited in a predetermined shape with water and hot water at 45 ° C. After drying in an oven at 105 ° C. and pasting together with a sealant mixed with 5 μm glass beads (gap is 5 μm), liquid crystal MLC-7021-000 (in a cell obtained by annealing in an oven at 180 ° C. for 2 hours) A liquid crystal cell having an electrode area of 1 cm ² was prepared.

Next, the voltage holding ratio of the liquid crystal cell was measured at 25 ° C. using a liquid crystal physical property evaluation system 6254 type (manufactured by Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.0 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is usually expressed in two ways: area ratio and voltage ratio. In this case, the value of the area ratio is adopted (voltage of 0 milliseconds is observed time 16.7 mm). The ratio of the area surrounded by the voltage trajectory and the voltage zero level from 0 milliseconds to 16.7 milliseconds with respect to the area obtained by maintaining for 2 seconds).
As a result, the voltage holding ratio at 60 Hz was as high as 90%.

[Preparation 3 of colored resin composition]
Each component was mixed at the ratio described in Table 8 below to prepare a colored resin composition.
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.
In addition, the numerical value of the upper stage in Table 8 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value in () of the lower stage is content in the total solid content of each component. The ratio (mass%) is expressed. In Table 7, (E) photopolymerization initiation component, other components, and (B) solvent are the same as those in Table 2.

In addition, each compound in Table 8 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]
The colored resin composition prepared in [Preparation of colored resin composition 3] above was applied onto a glass substrate cut into 5 cm square by spin coating so that the y value after firing was 0.120 as described below. 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 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 chromaticity (C light source) and luminance in the XYZ color system were calculated. The measurement results of Example 16 together with Example 4 are shown below.

  In Example 16, although it was shown that the brightness | luminance equivalent to the case of only the dye of Example 4 was hold | maintained irrespective of the dispersion system with a pigment, it turned out that high brightness | luminance can be maintained.

  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

Claims (13)

(A) 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 halogenoalkylsulfonylimide anion which may have a substituent, or an n-valent halogenoalkylsulfonylmethide anion which may have a substituent.
R ¹ and R ² each independently represents an alkyl group which may be substituted with an alkoxy group.
R ³ and R ⁴ each independently represents a hydrogen atom, a group represented by the following formula (II), or an alkyl group optionally substituted with a fluorine atom.
R ⁵ and R ⁶ each independently represents a phenyl group which may be substituted with an alkyl group or an alkoxy group, or a naphthyl group .
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. )

(In the above formula (II),
α and β each independently represents an alkyl group. α and β may be linked to form a ring. )

  The colored resin composition according to claim 1, wherein the halogenoalkyl group in the anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms.   The anion is a bistrifluoromethanesulfonylimide anion, a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion, or a tristrifluoromethanesulfonylmethide anion. Item 3. The colored resin composition according to Item 1 or 2.   The coloring resin composition as described in any one of Claims 1-3 whose content rate of the triarylmethane type compound represented by the said formula (I) is 0.01 mass% or more in a total solid.   (D) The colored resin composition according to any one of claims 1 to 4, further comprising a polymerizable monomer.   The colored resin composition according to any one of claims 1 to 5, further comprising (E) a photopolymerization initiation component and / or (E ') a thermal polymerization initiation component.   (A) The colored resin composition according to any one of claims 1 to 6, wherein the coloring material further contains a pigment.   The color filter which has a pixel formed using the colored resin composition as described in any one of Claims 1-7.   A liquid crystal display device comprising the color filter according to claim 8.   An organic EL display device comprising the color filter according to claim 8. A triarylmethane compound represented by the following formula (I).

(In the above formula (I),
[A ⁿ⁻ ] represents an n-valent halogenoalkylsulfonylimide anion which may have a substituent, or a halogenoalkylsulfonylmethide anion which may have a substituent.
R ¹ and R ² each independently represents an alkyl group which may be substituted with an alkoxy group.
R ³ and R ⁴ each independently represents a hydrogen atom, a group represented by the following formula (II), or an alkyl group optionally substituted with a fluorine atom.
R ⁵ and R ⁶ each independently represents a phenyl group which may be substituted with an alkyl group or an alkoxy group, or a naphthyl group .
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. )

(In the above formula (II),
α and β each independently represents an alkyl group. α and β may be linked to form a ring. )

  The triarylmethane compound according to claim 11, wherein the halogenoalkyl group in the anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms.   The anion is a bistrifluoromethanesulfonylimide anion, a 2,6-diphenylamino-4-butylamino-1,3,5-triazine ring-containing trifluoromethanesulfonylimide anion, or a tristrifluoromethanesulfonylmethide anion. Item 13. The triarylmethane compound according to Item 11 or 12.

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