TWI644172B - Colored resin composition, color filter, liquid crystal display, and organic el display - Google Patents

Abstract

An object of the present invention is to provide a colored resin composition having high color purity, satisfying light resistance, and exhibiting high contrast. In addition, a color filter, a liquid crystal display device, and an organic EL display device having high color purity and brightness, satisfying heat resistance and light resistance, and exhibiting high contrast are provided. The present invention relates to a coloring resin composition containing (A) a color material, (B) a solvent, and (C) a binder resin, and (A) the color material contains a compound represented by a specific structural formula.

Description

Colored resin composition, color filter, liquid crystal display device, and organic EL display device

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

Flat panel displays including liquid crystal display devices and organic EL (Electroluminescence) display devices are widely used. These displays use color filters. In consideration of the trend of the times of energy saving, the industry is pursuing further improvements in color purity, brightness and contrast for color filters.

Heretofore, as a material for forming a color filter, a colored resin composition using a pigment has been mainly used, but in order to achieve high brightness and high contrast, for example, Non-Patent Document 1 discloses that the particle size of pigment particles is finely dispersed therein The method of the color development wavelength is less than 1/2.

On the other hand, dyes are also being developed for color materials used in color resin compositions for color filters. For example, Patent Document 1 discloses a case where a triarylmethane derivative is used as a dye. In addition, Patent Documents 2 to 5 disclose cases in which a triarylmethane salt has an anion having a specific structure.

Further, Patent Document 6 discloses a triarylmethane salt having an anion having a specific structure. Furthermore, Patent Document 7 discloses a triarylmethane compound having an anion in the molecule.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2008-304766

Patent Document 2: International Publication No. 2011/152379

Patent Document 3: International Publication No. 2011/162217

Patent Document 4: Japanese Patent Laid-Open No. 2011-227408

Patent Document 5: Japanese Patent Laid-Open No. 2012-17425

Patent Document 6: Japanese Patent Laid-Open No. 2012-57055

Patent Document 7: International Publication No. 2013/147099

Non-Patent Document 1: Hashizume Kiyoshi, "Color Materials Association Journal", December 1967, p608

However, in the method described in Non-Patent Document 1, especially since blue pigments have shorter color rendering wavelengths than other red and green pigments, in this case, further fine dispersion is required, and the cost is increased. And the stability after dispersion becomes a problem.

In addition, according to research by the present inventors, when a triarylmethane-based compound having a cationic structure described in Patent Documents 1 to 4 was used, light resistance required for long-term reliability of a color display was insufficient.

On the other hand, according to research by the present inventors, when using a triarylmethane-based compound having a cationic structure described in Patent Document 5, it is difficult to satisfy the light resistance required for long-term reliability of a color display, and Both the heat resistance to baking at 230 ° C. required for the color display manufacturing steps.

In addition, according to research by the present inventors, when the triarylmethane-based compound described in Patent Document 6 is used, the light resistance and voltage retention required for the long-term reliability of a color display are insufficient.

On the other hand, according to research by the present inventors, it has been found that when using the triarylmethane-based compound described in Patent Document 7, it is difficult to satisfy the long-term availability of a color display. Reliability requires both light resistance and voltage retention.

The present invention has been made in view of the above-mentioned problems in the prior art, and its object is to provide a color with high color purity, satisfying the light resistance required by the long-term reliability of a color display, and exhibiting a high contrast required for a liquid crystal display device. combination.

Another object of the present invention is to provide a color filter having high color purity, satisfying light resistance, and exhibiting high contrast, and a liquid crystal display device and an organic EL display device.

The inventors of the present invention have worked hard and found that the use of a novel triarylmethane compound having a specific structure can solve the above-mentioned problems, thereby completing the present invention.

That is, the present invention is directed to the following.

[1]

A colored resin composition, comprising: (A) a color material, (B) a solvent, and (C) a binder resin; and (A) the color material contains a triarylmethane represented by the following formula (I-1) Department of compounds,

(In the above formula (I-1), [A ^n- ] represents an n-valent halogenated alkylsulfonimide anion which may have a substituent, or an n-valent halogenated alkylsulfonylmethyl group which may have a substituent. Anions; 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; R ⁵ and R ⁶ each independently represent an aromatic group which may have a substituent A cyclic group; n represents an integer of 1 to 4, and when n is 2 to 4, the plurality of cations represented by the following formula (I-1) _CA contained in one molecule are each independently the same structure, or Different structures; furthermore, R ¹ to R ^{6 in} _CA (I-1) have the same meaning as above)

[2]

The colored resin composition as in [1], wherein the halogenated alkyl group in the above anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms.

[3]

The colored resin composition according to [1] or [2], wherein the above anion is a bistrifluoromethanesulfinimide anion, and contains 2,6-diphenylamino-4-butylamino-1,3, 5-three Ring trifluoromethanesulfonylimide anion, or tris (trifluoromethanesulfonyl) methylate anion.

[4]

The colored resin composition according to any one of [1] to [3], wherein R ¹ to R ^{4 in} the formula (I-1) are each independently a hydrogen atom or an alkyl group which may have a substituent.

[5]

The colored resin composition according to any one of [1] to [4], wherein each of R ⁵ and R ^{6 in the} above formula (I-1) is independently a phenyl group which may have a substituent.

[6]

The colored resin composition according to any one of [1] to [5], wherein the content ratio of the triarylmethane-based compound represented by the formula (I-1) is 0.01% by mass or more in the total solid content.

[7]

A colored resin composition, comprising: (A) a color material, (B) a solvent, and (C) a binder resin; and (A) the color material contains a triarylmethane represented by the following formula (I-2) Department of compounds,

(In the above formula (I-2), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent; R ⁵ and R ⁶ each independently represent An aromatic ring group which may have a substituent; adjacent R ¹ to R ⁶ may be connected to each other to form a ring, and the ring may also have a substituent; M ⁺ represents a monovalent cation; m represents an integer of 0 to 4).

[8]

The colored resin composition according to [7], wherein R ¹ to R ^{4 in} the formula (I-2) are each independently a hydrogen atom or an alkyl group which may have a substituent, and R ⁵ and R ⁶ are each independently Substituted phenyl.

[9]

The colored resin composition according to [7] or [8], wherein the content ratio of the triarylmethane-based compound represented by the formula (I-2) is 0.01% by mass or more in the total solid content.

[10]

The colored resin composition according to any one of [1] to [9], which further contains (D) a polymerizable monomer.

[11]

The colored resin composition according to any one of [1] to [10], which further contains (E) a photopolymerization starting component and / or (E ') a thermal polymerization starting component.

[12]

The colored resin composition according to any one of [1] to [11], wherein the (A) color material further contains a pigment.

[13]

A color filter having a pixel formed using the colored resin composition according to any one of [1] to [12].

[14]

A liquid crystal display device having a color filter as in [13].

[15]

An organic EL display device having a color filter as in [13].

[16]

A triarylmethane-based compound represented by the following formula (I-1), [Chem. 4]

(In the above formula (I-1), [A ^n- ] represents an n-valent halogenated alkylsulfonimide anion which may have a substituent, or an n-valent halogenated alkylsulfonylmethyl group which may have a substituent. Anions; 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; R ⁵ and R ⁶ each independently represent an aromatic group which may have a substituent A cyclic group; n represents an integer of 1 to 4, and when n is 2 to 4, the plurality of cations represented by the following formula (I-1) _CA contained in one molecule are each independently the same structure, or Different structures; furthermore, R ¹ to R ^{6 in} _CA (I-1) have the same meaning as above)

[17]

For example, the triarylmethane compound of [16], wherein the halogenated alkyl group in the above anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms.

[18]

For example, the triarylmethane compound of [16] or [17], wherein the above anion is a bistrifluoromethanesulfonylimide anion, and contains 2,6-diphenylamino-4-butylamino-1,3 , 5-three Ring trifluoromethanesulfonylimide anion, or tris (trifluoromethanesulfonyl) methylate anion.

[19]

The triarylmethane-based compound according to any one of [16] to [18], wherein R ¹ to R ^{4 in} the formula (I-1) are each independently a hydrogen atom or an alkyl group which may have a substituent.

[20]

The triarylmethane compound according to any one of [16] to [19], wherein each of R ⁵ and R ^{6 in} the formula (I-1) is independently a phenyl group which may have a substituent.

[twenty one]

A triarylmethane-based compound represented by the following formula (I-2),

(In the above formula (I-2), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent; R ⁵ and R ^{6 each} may have a substituent Is an aromatic ring group; adjacent R ¹ to R ⁶ may be connected to each other to form a ring, and the ring may have a substituent; M ⁺ represents a monovalent cation; m represents an integer of 0 to 4).

[twenty two]

For example, the triarylmethane compound of [21], wherein each of R ¹ to R ^{4 of} the formula (I-2) is independently a hydrogen atom or an alkyl group which may have a substituent, and each of R ⁵ and R ^{6 is} independently A phenyl group having a substituent.

According to the present invention, a colored resin composition having excellent color purity, satisfying light resistance required for long-term reliability, and exhibiting a high contrast ratio required for a liquid crystal display device 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, satisfy light resistance, and exhibit high contrast.

10‧‧‧ transparent support substrate

20‧‧‧ pixels

30‧‧‧ Organic protective layer

40‧‧‧ inorganic oxide film

50‧‧‧ transparent anode

51‧‧‧ Hole injection layer

52‧‧‧ Hole Transmission Layer

53‧‧‧Light-emitting layer

54‧‧‧ Electron injection layer

55‧‧‧ cathode

100‧‧‧Organic EL element

500‧‧‧Organic luminous body

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element having a color filter of the present invention.

FIG. 2 is a graph showing the transmittance of a polarizing plate used in Examples.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to these contents.

Furthermore, in the present invention, "(meth) acrylic group", "(meth) acrylate" and the like mean "at least one of an acrylic group and a methacrylic group", "acrylate and methacrylate" At least one of them ", for example," (meth) acrylic acid "means" at least one of acrylic acid and methacrylic acid ".

In addition, the "total solid content" means the present invention other than the solvent components described below. All components of bright colored resin composition.

Furthermore, the "aromatic ring" means both an "aromatic hydrocarbon ring" and an "aromatic heterocyclic ring".

In addition, terms such as "C.I. Pigment Green" mean the name of the color material described in the chromaticity index (C.I.).

The colored resin composition of the present invention in the first aspect is characterized in that it contains (A) a color material, (B) a solvent, and (G) a binder resin, and (A) the color material contains the following formula (I-1) The indicated triarylmethane compounds. Furthermore, it is preferable to contain at least one of (D) a polymerizable monomer, (E) a photopolymerization starting component, and (E ') a thermal polymerization starting component, and may contain other components as needed.

[(A) Color material]

(Compound represented by general formula (I-1))

The color material (A) contained in the colored resin composition of the present invention in the first aspect contains a triarylmethane-based compound represented by the following general formula (I-1).

The colored resin composition of the present invention in the first aspect can satisfy a color display manufacturing process by containing a specific triarylmethane-based compound represented by the following general formula (I-1), and having high color purity and brightness. The required heat resistance and the light resistance required for the long-term reliability of a color display show the high contrast required for a liquid crystal display device.

In the above formula (I-1), [A ^n- ] represents an n-valent halogenated alkylsulfonimide anion which may have a substituent, or an n-valent halogenated alkylsulfonimide methylate which may have a substituent. 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 each independently represent 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-1) _CA contained in one molecule each independently have the same structure or different structures. In addition, R ¹ to R ⁶ in the formula (I-1) _CA have the same meanings as described above.

(R ¹ ~ R ⁴ )

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.

Examples of the R ¹ to R ⁴ alkyl group include a linear, branched, or cyclic alkyl group. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and usually 1 or more. By setting it below the above upper limit value, the solubility of the triarylmethane-based compound can be adjusted to be appropriate in the colored resin composition, and since the effective interaction between the cation and the anion is generated, heat resistance and light resistance are improved. tendency.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, third butyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl. , 3-methylbutyl and the like. Among these, a linear alkyl group is preferred from the viewpoint of the association of molecules represented by formula (I-1) with each other or electrostatic interaction with anions.

Specific examples of the alkyl group having a substituent include phenethyl, 2-ethoxyethyl, 4,4,4-trifluorobutyl, and the like.

Examples of the aromatic ring group of 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 setting it below the above-mentioned upper limit value, the conjugate length becomes appropriate, and the absorption waveform near 500 nm becomes steep. Therefore, a tendency of high brightness can be seen. In the colored resin composition, a triarylmethane-based compound is used. Since the interaction with other compounds constituting the composition becomes appropriate, there is a tendency that the solubility can be adjusted to be appropriate.

The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, and a fluorene ring having one free atomic valence. , Benzopyrene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring having one free atomic valence, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyridine. Azole ring, imidazole ring, Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thieno Furan ring, benzoiso Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine Ring Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinine Phenoline ring, morphine ring, benzimidazole ring, Pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

Adjacent R ³ and R ⁴ may be linked to form a ring, and the ring may have a substituent. The ring may be a ring cross-linked with a hetero atom, and specific examples thereof include the following structures.

In terms of heat resistance, R ¹ to R ⁴ are each preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or an adjacent R ³ When R ^{4 is} bonded to each other to form a ring, an alkyl group which is each independently a hydrogen atom or a substituent may be more preferable. These substitutions are better in terms of brightness.

In terms of improving the heat resistance of the compound (I-1) and making the obtained color filter excellent in heat resistance, R ¹ and R ^{2 are} preferably alkyl groups having 1 to 12 carbon atoms which may have a substituent. Or, a phenyl group which may have a substituent, and from the viewpoint of brightness, an alkyl group having 1 to 12 carbon atoms which may have a substituent is more preferable.

When R ¹ and R ² are alkyl groups having 1 to 12 carbon atoms which may have a substituent, the charge in the cation is dispersed due to super-conjugation, and it is estimated that the cation is a stabilized one.

More specifically, regarding the carbon numbers of the alkyl groups of R ¹ and R ² , it is difficult to be affected by the configuration of the triarylmethane skeleton (the effect on brightness is small) and the substituent on the nitrogen is difficult to detach ( The compound (I-1) is preferably 8 or less, more preferably 4 or less, and still more preferably 2 or more.

When R ¹ and R ² are a phenyl group which may have a substituent, it is considered that the charge in the cation is dispersed and the cation is stabilized due to the extension of the conjugated system. In this way, the cation is stabilized, and as a result, it is considered that the heat resistance of the obtained color filter becomes more excellent.

In terms of excellent brightness of the compound (I-1), 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 is} preferable. And any of R ⁴ is an alkyl group which may have a substituent, and the other is a hydrogen atom.

From the viewpoint of brightness, it is preferable that at least one of R ³ and R ⁴ is a linear alkyl group which may have a substituent. By setting at least one of R ³ and R ⁴ as a linear alkyl group which may have a substituent, the solubility is improved. Therefore, it is considered that the association between the dye molecules is suppressed and the brightness is improved.

In this case, both R ³ and R ⁴ may be a linear alkyl group which may have a substituent, and either R ³ and R ⁴ may be a substituent which may have a substituent. A linear alkyl group, and the other is a hydrogen atom. From the viewpoint of heat resistance, one of R ³ and R ⁴ is preferably a linear alkyl group which may have a substituent, and the other is a hydrogen atom.

The number of carbon atoms of the linear alkyl group is preferably 12 or less, more preferably 6 or less, and more preferably 1 or more, and more preferably 3 or more. By making it below the said upper limit, since interaction with other components which comprise a colored resin composition becomes appropriate, there exists a tendency for the solubility to be adjusted suitably. When it is at least the above lower limit value, thermal decomposition of the substituent is suppressed, and the heat resistance tends to be improved.

Specific examples include methyl, ethyl, propyl, and butyl. Among these, butyl is preferable from the viewpoint of heat resistance.

Examples of the substituent which the linear alkyl group may have include those in the following substituent group W1. 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, 2-phenylethyl, and 2-tolylethyl. Among these, 4,4,4-trifluorobutyl is preferred from the viewpoint of heat resistance.

On the other hand, it is preferred that at least one of R ³ and R ⁴ is an alkyl group which may have a substituent having a secondary carbon. By setting at least one of R ³ and R ⁴ as an alkyl group which may have a substituent having a second-order carbon, the substituent is suppressed from becoming a molecule represented by formula (I-1) due to heat or light. The reason for the decomposition comes from the attack of other molecules, so it is thought to contribute to the improvement of heat resistance and light resistance.

In addition, both R ³ and R ⁴ may be substituted alkyl groups having a second-order carbon, and any of R ³ and R ⁴ may be second-order groups. An alkyl group which may have a substituent on the carbon, and the other is a group other than the alkyl group which may have a substituent on the second carbon. If the substituents of R ³ and R ^{4 are} large, they will become steric hindrances, and inhibit the association of molecules represented by formula (I-1) or the electrostatic interaction with anions, and it is considered that the heat resistance may decrease. Therefore, it is preferable that one of R ³ and R ⁴ is an alkyl group having a second carbon which may have a substituent, and the other is a group other than the alkyl group, and more preferably Either is an alkyl group having a second carbon which may have a substituent, and the other is a hydrogen atom.

In addition, "at least one of R ³ and R ⁴ is an alkyl group which may have a substituent having a secondary carbon" means that at least one of R ³ or R ⁴ has the following formula (II) The represented group may have an alkyl group having a substituent. Furthermore, * in the formula means bond-to-bond.

Α and β in the following formula (II) each independently represent 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 a carbon atom and a carbon atom of the substituent α, and the C-β bond also represents a bond between a carbon atom and a carbon atom of the substituent β. In addition, α and β may be connected to form a ring, and the ring may have a substituent.

The alkyl group having a secondary carbon group which may have a substituent is not limited as long as it is an alkyl group which may have a substituent group having the group represented by the formula (II), and may be, for example, the group represented by the formula (II). The basic body may be a group having a group represented by the above formula (II) bonded to an alkylene group which may have a substituent. Among them, the basic body represented by the above-mentioned formula (II) is preferable from the viewpoint of making a large space around the nitrogen atom. That is, since this substituent is suppressed from becoming light The cause of decomposition comes from the attack of other molecules, so there is a tendency to contribute to the improvement of various physical properties.

Examples of the α and β alkyl groups include a linear, branched, or cyclic alkyl group. Regarding the number of carbons, α and β are included in the number of carbons, preferably 30 or less, more preferably 12 or less, still more preferably 8 or less, most preferably 6 or less, and usually 1 or more. By setting it to be equal to or less than the above upper limit value, the solubility of the formula (I-1) in the solvent can be adjusted to be appropriate in the colored resin composition, and association of the molecules represented by the formula (I-1) can be generated. The effective interaction of a combination or cation with an anion tends to increase heat resistance and light resistance.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, third butyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl. , 3-methylbutyl and the like. Among these, a linear alkyl group is preferred from the viewpoint of the association of molecules represented by formula (I-1) with each other or electrostatic interaction with anions.

Specific examples of the alkyl group having a substituent include phenethyl and 2-ethoxyethyl.

Examples of the α and β aromatic ring groups include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, even more preferably 6 or less, and usually 4 or more. By setting it below the above upper limit value, the solubility of the formula (I-1) in the solvent can be adjusted to be appropriate, and the association of the molecules represented by the formula (I-1) or the effectiveness of the cations and anions can be achieved. Because of interaction, there is a tendency that heat resistance and light resistance are improved.

The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, and a fluorene ring having one free atomic valence. , Benzopyrene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring having one free atomic valence, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyridine. Azole ring, imidazole ring, Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thieno Furan ring, benzoiso Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine Ring Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinine Phenoline ring, morphine ring, benzimidazole ring, Pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

α and β may be linked to form a ring, and the ring may have a substituent.

The ring may be a ring crosslinked with a hetero atom. The carbon number of the ring (including C atoms bonded to α and β, α and β) is preferably 30 or less, more preferably 12 or less, even more preferably 8 or less, and usually 3 or more. By setting it below the above upper limit value, the solubility of the formula (I-1) in the solvent can be adjusted to be appropriate, and the association of the molecules represented by the formula (I-1) or the effectiveness of the cations and anions can be achieved. Because of interaction, there is a tendency that heat resistance and light resistance are improved.

When 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 of α and β may have include the following substituent group W1. Examples of the substituent which the aromatic ring group may have include, for example, the following substituent group W2. Furthermore, as a substituent which the ring formed by mutual connection may have, for example, one of the following substituent groups W3 is mentioned.

As α and β, it is preferable that α and β are included in the carbon number, and each is independently a linear alkyl group having 1 to 12 carbon atoms which may have a substituent, or α and β are connected to each other to form a ring. More preferably, it may have an alkyl group having 2 to 6 carbon atoms or a neighboring α and β having 3 to 10 carbon atoms which may have a substituent. When they are connected to form a ring. If these substituents are used, the compounds represented by the formula (I-1) may be associated with each other or an effective interaction between a cation and an anion, and therefore, heat resistance and light resistance tend to be improved.

The total number of carbon atoms of the alkyl group having a secondary carbon of R ³ and R ⁴ is preferably 30 or less, more preferably 12 or less, still more preferably 8 or less, and most preferably 6 or less. It is usually 3 or more, preferably 4 or more, and further preferably 5 or more. By setting it within the above range, in the colored resin composition, the interaction between the molecules represented by the formula (I-1) or the intramolecular cation and anion in the compound represented by the formula (I-1) The electrostatic interaction becomes appropriate, and the durability tends to be improved.

Specific examples of the alkyl group having a secondary carbon include isopropyl, second butyl, 1-methylpropyl, 1-ethylpropyl, 1-methylbutyl, cyclopentyl, 1-methylpentyl, 1-ethylbutyl, 1-propylbutyl, 1-ethylpentyl, 1-propylpentyl, 1-butylpentyl, 1-methylhexyl, 1- Ethylhexyl, 1-propylhexyl, 1-butylhexyl, 1-propylhexyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-propylcyclohexyl, 2-isopropyl Cyclohexyl, 2-cyclopropylcyclohexyl, 2-butylcyclohexyl, 2-second butylcyclohexyl, 2-third butylcyclohexyl, 2-isobutylcyclohexyl, 2-cyclobutyl Cyclohexyl, 2-pentylcyclohexyl, 2-cyclopentylcyclohexyl, 2-cyclohexylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,6-dimethylcyclohexyl, 2 , 4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl , 4-third butylcyclohexyl, 1-ethylheptyl, 1-methylheptyl, 1-propylheptyl, 1-butylheptyl, 1-pentylheptyl, 1-hexylheptyl, cyclo Heptyl, 2-methylcycloheptyl, 3-methyl Heptyl, 4-methylcycloheptyl, 2,7-dimethylcycloheptyl, 1-cyclohexylethyl, 1-methyloctyl, 1-ethyloctyl, 1-propyloctyl, 1-butyloctyl, 1-pentyloctyl, 1-hexyloctyl, 1-heptyloctyl, cyclooctyl, 1-methylcyclooctyl, 2-methylcyclooctyl, 3-methyl Cyclooctyl, 4-methylcyclooctyl, 2-adamantyl and the like.

Among these, the molecules represented by formula (I-1) are associated with each other or electrostatically with anions. From the viewpoint of durability improvement due to the interaction, isopropyl, second butyl, 1-methylpropyl, 1-ethylpropyl, 1-methylbutyl, and 1-ethyl are preferred. Butyl, 1-propylbutyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, cyclopentyl, or cyclooctyl base.

On the other hand, when any one of R ³ and R ⁴ is an alkyl group having a second carbon which may have a substituent, and the other is a group other than the alkyl group, this is taken as Examples of the group other than an alkyl group (a group other than an alkyl group having a secondary carbon group which may have a substituent) include, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a third butyl group, and a pentyl group. Alkyl groups of 1 to 5 carbons, hydroxyalkyls of 1 to 5 carbons such as ethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, ethoxypropyl, butoxy Alkoxyalkyl groups with 1 to 5 carbons such as ethyl, 2-hydroxyethoxy groups with 1 to 5 carbons such as 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy Equal to 1 to 5 carbon alkoxy (1 to 5 carbon) alkoxy, 2-sulfoethyl, carboxyethyl, cyanoethyl, etc.

Examples of the substituent which the alkyl group of R ¹ to R ⁴ may have include the following substituent group W1. Examples of the substituent which the aromatic ring group may have include one of the following substituent group W2. Furthermore, as a substituent which the ring formed by mutual connection may have, for example, one of the following substituent groups W3 is mentioned.

(Substituent group W1)

Fluorine atom, chlorine atom, alkenyl group with 2 to 8 carbon atoms, alkoxy group with 1 to 8 carbon atoms, phenyl group, Alkyl, tolyl, naphthyl, cyano, ethoxyl, alkylcarbonyloxy with 2-9 carbons, sulfamoyl, alkylaminesulfonyl with 2-9 carbons, 2 ~ carbon 9 alkylcarbonyl, phenethyl, hydroxyethyl, acetamido, dialkylaminoethyl bonded to an alkyl group having 1 to 4 carbons, trifluoromethyl, 1 to 8 carbons Trialkylsilyl group, nitro group, alkylthio group with 1 to 8 carbon atoms.

Among them, an alkoxy group having 1 to 8 carbon atoms, a cyano group, an ethoxyl group, an alkyl carboxy group having 2 to 8 carbon atoms, an sulfamolenyl group, and an alkylamine sulfonyl group having 2 to 9 carbon atoms are preferred. , And 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, alkoxy group having 1 to 8 carbon atoms, phenyl group, Alkyl, tolyl, naphthyl, cyano, ethoxyl, alkylcarbonyloxy with 2-9 carbons, sulfamoyl, alkylaminesulfonyl with 2-9 carbons, 2 ~ carbon 9 alkylcarbonyl, hydroxyethyl, acetamido, dialkylaminoethyl bonded to an alkyl group having 1 to 4 carbons, trifluoromethyl, trialkyl having 1 to 8 carbon groups Silyl, nitro, and alkylthio groups with 1 to 8 carbon atoms.

Among them, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 8 carbons, cyano, ethoxyl, alkyl carboxy group having 2 to 8 carbons, sulfamoyl group, and carbon number 2 are preferred ~ 9 alkylaminesulfonyl and 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, alkoxy group having 1 to 8 carbon atoms, phenyl group, Alkyl, tolyl, naphthyl, cyano, ethoxyl, alkylcarbonyloxy with 2-9 carbons, sulfamoyl, alkylaminesulfonyl with 2-9 carbons, 2 ~ carbon 9 alkylcarbonyl, phenethyl, hydroxyethyl, acetamido, dialkylaminoethyl bonded to an alkyl group having 1 to 4 carbons, trifluoromethyl, 1 to 8 carbons Trialkylsilyl group, nitro group, alkylthio group with 1 to 8 carbon atoms.

Among them, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 8 carbons, cyano, ethoxyl, alkyl carboxy group having 2 to 8 carbons, sulfamoyl group, and carbon number 2 are preferred ~ 9 alkylaminesulfonyl and fluorine atom.

(R ⁵ and R ⁶ )

R ⁵ and R ⁶ each independently represent an aromatic ring group which may have a substituent. The triarylmethane-based compound represented by the general formula (I-1) used in the colored resin composition of the present invention is considered to be a cation conjugate because R ⁵ and R ⁶ are each independently an aromatic ring group which may have a substituent. The system is expanded, the charge is stable, and the heat resistance and light resistance are improved.

Examples of the aromatic ring group of 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. By setting it below the above upper limit value, the solubility of the formula (I-1) in the solvent can be adjusted to be appropriate, and the association of the molecules represented by the formula (I-1) or the effectiveness of the cations and anions can be achieved. Because of interaction, there is a tendency that heat resistance and light resistance are improved.

The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, and a fluorene ring having one free atomic valence. , Benzopyrene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring having one free atomic valence, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyridine. Azole ring, imidazole ring, Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thieno Furan ring, benzoiso Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine Ring Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinine Phenoline ring, morphine ring, benzimidazole ring, Pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

R ⁵ and R ⁶ may be connected to R ¹ and R ² to form a ring, and the ring may have a substituent. The ring may be a ring crosslinked with a hetero atom. 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 which the ring formed by mutual connection may have include the above-mentioned substituent group W3. If these substituents are used, the compounds represented by the formula (I-1) may have associations with each other or effective interactions between cations and anions between the molecules, so there is a tendency to improve heat resistance and light resistance.

Among these, from the viewpoint of steepness of the absorption waveform near 500 nm, that is, high brightness, an aromatic hydrocarbon ring group having one free atomic valence is preferable, and a monocyclic or bicyclic aromatic ring is more preferable. The hydrocarbon ring group is more preferably a benzene ring.

Examples of the substituent which the aromatic cyclic group of R ⁵ and R ⁶ may have include the substituent group W2 described above. In particular, from the viewpoint of the steepness of the absorption waveform near 500 nm, that is, high brightness, or the viewpoint of improving heat resistance or light resistance by stabilizing cations due to charge dispersion in cations caused by superconjugation, It is preferred that the aromatic ring groups of R ⁵ and R ^{6 are} unsubstituted, or have an alkyl group as a substituent, or have an alkoxy group as a substituent, more preferably unsubstituted or have an alkyl group as a substituent. The number of carbon atoms of the alkyl group and the alkoxy group which the aromatic ring group may have is not particularly limited. From the viewpoint of heat resistance, it is preferably 8 or less, more preferably 4 or less, and still more preferably 2 or less. 1 or more.

(Combination of R ¹ ~ R ⁶ )

R ¹ to R ⁶ may be appropriately selected from the above. Specific examples of the combination include those described in Table 1. In addition, the alkyl group, aromatic hydrocarbon ring group, and aromatic heterocyclic group listed in the following table may further contain arbitrary substituents. In addition, C in the table means a carbon number.

As a combination of R ¹ to R ⁶ , from the viewpoint of heat resistance, since the compounds represented by the formula (I-1) are easily associated with each other, the thermal decomposition of the compounds represented by the formula (I-1) can be suppressed. The reason comes from the attack of other molecules, and does not reduce the electrostatic interaction of cations and anions due to the steric hindrance of the substituents, so it is preferred that R ³ is a hydrogen atom and R ⁴ is a carbon number that may have a substituent 1 ~ The alkyl group of 12 can inhibit the attack of other molecules on the carbon atoms of the two benzene rings and the naphthalene ring bonded to the triarylmethane skeleton. Therefore, it is preferable that R ¹ and R ² are each independently a carbon that may have a substituent. An alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon ring group having 4 to 12 carbon atoms which may have a substituent, or an aromatic heterocyclic group having 4 to 12 carbon atoms which may have a substituent.

On the other hand, from the viewpoint of the steepness of the absorption waveform near 500 nm, that is, high brightness, since the π conjugate system is prevented from expanding and the shape of the absorption spectrum becomes steep, it is preferable that R ¹ and R ² are respectively It is independently an alkyl group having 1 to 12 carbons which may have a substituent and R ³ is a hydrogen atom and R ⁴ is an alkyl group having 1 to 12 carbons which may have a substituent. In addition, there is no charge of a π conjugated system Due to the deviation, the shape of the absorption spectrum becomes steep. Therefore, it is further preferred that R ⁵ and R ⁶ are each independently an aromatic hydrocarbon ring having 4 to 12 carbon atoms which may have a substituent.

The triarylmethane compound represented by formula (I-1) is a symmetric molecule having a nitrogen atom bonded to the para position of two benzene rings forming a triarylmethane skeleton and a hydrogen atom bonded to the ortho and meta positions. Structure, it is considered that the structure is better and the brightness is higher than other structures having substituents in the ortho or meta positions. In addition, it is considered that the heat resistance is better because the torsion of the molecule due to steric hindrance is reduced as compared with the case where there is a substituent at the ortho or meta position. From the viewpoint of making the molecular structure symmetrical, 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-1), [A ^n- ] represents an n-valent halogenated alkylsulfonimide anion which may have a substituent, or an n-valent halogenated alkylsulfonimide methylate which may have a substituent. Anion, n represents an integer of 1 to 4. Here, A represents an atomic group constituting an anion.

From the viewpoint of interaction with a cation, n is 4 or less, preferably 2 or less, and more preferably 1. When the anion and the cation are arranged close to each other, the physical properties such as heat resistance and light resistance tend to be improved by setting the anion and the cation to be close to each other.

From the viewpoint that the charge of the counter anion is easily delocalized, the counter anion of the triarylmethane cation is a compound containing a sulfonium imide or a methylate anion. That is, by delocalizing the charge of the anion, it is possible to prevent the counter anion from reacting with the triarylmethane cation due to heat and light, and therefore the durability tends to be improved.

In particular, when the anion is a halogenated alkylsulfonimide anion or a halogenated alkylsulfonylmethylide anion, the interaction with the cation is enhanced due to the delocalization of the charge of the anion, which is considered to be heat-resistant. Increasing sexual tendency.

The number of carbon atoms of the halogenated alkyl group in the halogenated alkylsulfonimide anion or the halogenated alkylsulfonylmethylide anion is preferably 12 or less, more preferably 10 or less, still more preferably 6 or less, and usually 1 or more. . By setting it to be above the lower limit value, the charge of the anions is dispersed and the anion tends to be stabilized. By setting it to be less than the above upper limit value, the effect of the steric barrier with the cation is reduced, and it becomes possible to realize The tendency to interact more strongly with cations.

The type of the halogen atom in the halogenated alkyl group 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 the halogen atom to the above, the charge of the anion is further delocalized, and the heat resistance of the color material tends to be improved.

The number of halogen atoms in the halogenated alkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, even more preferably 6 or less, and usually 3 or more. By setting it above the lower limit value, the charge of the anions is dispersed, and there is a tendency for the anion to stabilize, and by setting it below the upper limit value, the solubility is moderate, and the effect on the steric energy barrier of the cation is reduced. Small, and there is a tendency to make it possible to achieve stronger interactions with cations.

Specific examples of the halogenated alkylsulfonimide anion include bistrifluoromethanesulfonimide anion, dipentafluoroethanesulfonimide anion, bisnonafluorosulfonimide anion, and the like. From the viewpoint of heat resistance, a bistrifluoromethanesulfinimide anion or a dipentafluoroethanesulfonimide anion is more preferable, and a bistrifluoromethanesulfinimide anion is more preferable.

Specific examples of the halogenated alkylsulfonylmethylide anion include tris (trifluoromethanesulfonyl) imine anion, tris (pentafluoroethanesulfonyl) imine anion, and tris (nonafluorobutane). From the viewpoint of having a small effect on the steric energy barrier of the cation, the tris (trifluoromethanesulfonyl) imine anion, or tris (pentafluoroethanesulfonyl) imine, is preferred. An anion, more preferably a bistrifluoromethanesulfonylimide anion.

The substituents that the halogenated alkylsulfonimide anion or the halogenated alkylsulfonylmethylate anion can have are not particularly limited, and examples of the substituent group W3 can be used. From the viewpoint of the stability of the charge distribution, an aromatic ring group which may have a substituent is preferred.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is not particularly limited, but is preferably 30 or less, more preferably 12 or less, and usually 4 or more. Preferably it is 6 or more. When it is at most the above upper limit value, there is a tendency that steric hindrance with cations is suppressed and anions are stabilized.

The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, and a fluorene ring having one free atomic valence. , Benzopyrene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring having one free atomic valence, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyridine. Azole ring, imidazole ring, Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thieno Furan ring, benzoiso Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine Ring Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinine Phenoline ring, morphine ring, benzimidazole ring, Pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

Among these, from the viewpoint of suppressing steric hindrance with a cation, a benzene ring, a naphthalene ring, a thiophene ring, or a triphenylene ring is preferred. Ring, more preferably benzene ring, or three Ring, further preferably three ring. three Because the ring has high planarity, it is considered that there is a tendency that the interaction with the aromatic part of the dye cation or the anion part existing in the same system is enhanced. In addition, since it has a sulfoimide skeleton or a sulfomethylidene skeleton, it is considered that the steric energy barrier with the cation is small, and it is easy to form a stronger ion pair. As a result, since the cation and the anion are difficult to separate, the heat resistance is good, and it is easy to suppress the reduction of the interaction between the cation and the anion even in an electric field, and the voltage retention rate of the pixel thus obtained tends to be high.

The number of substituents that the halogenated alkylsulfonimide anion or halogenated alkylsulfonylmethylide anion may have is not particularly limited. From the viewpoint of suppressing steric hindrance, it is preferably one to three. , More preferably one.

(Anion represented by formula (A-1) and formula (A-2))

Among these, from the viewpoint of anion stabilization, the above-mentioned substituent is preferably located at the terminal of the anion, more preferably an anion represented by the following formula (A-1), or an anion represented by the following formula (A-2) Representing an anion.

In the 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 halogenated alkyl group.

X ¹ to X ³ each independently represent at least one group selected from the group consisting of a direct bond,-(CH ₂ )-, -NH-, -O-, and -S-, or two or more of these Bonded base.

In the 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 represent a halogenated alkyl group.

X ⁴ to X ⁶ each independently represent at least one group selected from the group consisting of a direct bond,-(CH ₂ )-, -NH-, -O-, and -S-, or two or more of these Bonded base.

(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 which may have a substituent, or an aromatic ring group which may have a substituent.

Among these, examples of the alkyl group include a linear, branched, or cyclic alkyl group. In terms of solubility in a solvent, the number of carbons is preferably 8 or less, more preferably 5 or less, and in terms of solubility in a solvent, 2 or more is preferable.

Specific examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, third butyl, 2-ethylhexyl, cyclohexyl, cyclohexylmethyl, and cyclo Hexylethyl, 3-methylbutyl and the like. Among these, from the viewpoint of the balance between the crystallinity and solubility of the formed salt, a linear or branched alkyl group is preferred, and a linear alkyl group is more preferred.

Examples of the substituent that the alkyl group may have include the substituent group W1 described above.

Among these, examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. From the viewpoint of suppressing steric hindrance, the number of carbons is preferably 30 or less, more preferably 12 or less, and from the viewpoint of the balance between crystallinity and solubility, it is preferably 4 or more, more preferably 6 or more.

The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fused tetraphenyl ring, and a fluorene ring having one free atomic valence. , Benzopyrene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring having one free atomic valence, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyridine. Azole ring, imidazole ring, Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanofuran ring, thieno Furan ring, benzoiso Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine Ring Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinine Phenoline ring, morphine ring, benzimidazole ring, Pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

Among these aromatic ring groups, an aromatic hydrocarbon ring group is preferred in terms of ease of production.

Examples of the substituent which the aromatic cyclic group may have include those in the above-mentioned substituent group W2.

Among these, from the viewpoint of the stability of the colored resin composition, R ^1a and R ^2a are each preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.

R ^1a and R ^2a may be the same or different. For example, R ^1a and R ^2a may be each independently an alkyl group which may have a substituent, R ^1a and R ^2a may be each independently an aromatic ring group which may have a substituent, or R ^1a may be an alkyl group which may have a substituent And R ^2a is an aromatic cyclic 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 be each independently an alkyl group which may have a substituent, R ^5a and R ^6a may be each independently an aromatic ring group which may have a substituent, or R ^5a may be an alkyl group which may have a substituent And R ^6a is an aromatic cyclic group which may have a substituent.

(R ^3a , R ^7a )

R ^3a and R ^7a represent 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. Suppress the deviation of charge From a viewpoint, the number of carbons is preferably 8 or less, more preferably 5 or less, and usually 1 or more.

Specific examples include methylene, ethylene, and propyl. Among these, a methylene group is preferable from a viewpoint of suppressing the variation of a charge.

Examples of the substituent that the alkylene group may have include the substituent group W1 described above.

Among these, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. From the viewpoint of the rigidity and heat resistance of the anion, the number of carbons is preferably 30 or less, more preferably 12 or less, usually 4 or more, and preferably 6 or more.

The divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, and a fused tetraphenyl ring having two free atomic valences. , Pyrene ring, benzopyrene ring, Ring, bitriphenylene ring, fluorene ring, fluoranthene ring, fluorene ring and other groups.

The aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include a furan ring having two free atomic valences, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyridine. Azole ring, imidazole ring, Diazole ring, indene ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furofuran ring, thieno Furan ring, benzoiso Azole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine Ring Ring, pyrimidine ring, three Ring, quinoline ring, isoquinoline ring, Porphyrin ring, quinine Phenoline ring, morphine ring, benzimidazole ring, Pyrimidine ring, quinazoline ring, quinazolinone ring, fluorene ring and the like.

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 variation in electric charge.

Examples of the substituent which the divalent aromatic ring group may have include the substituent group W2 described above.

(R ^4a , R ^8a , R ^9a )

R ^4a , R ^8a , and R ^9a each independently represent a halogenated alkyl group.

The kind of halogen atom in the halogenated alkyl group is not particularly limited, but fluorine, Chlorine, bromine, or iodine is more preferably fluorine or chlorine, and still more preferably fluorine. By setting the type of the halogen atom to the above, the charge of the anion is further delocalized, and the heat resistance of the color material tends to be improved.

The number of halogen atoms in the halogenated alkyl group is not particularly limited, but is preferably 27 or less, more preferably 12 or less, even more preferably 6 or less, and usually 3 or more. By setting it above the lower limit value, the charge of the anions is dispersed, and there is a tendency for the anion to stabilize, and by setting it below the upper limit value, the solubility is moderate, and the effect on the steric energy barrier of the cation is reduced. Small, and there is a tendency to make it possible to achieve stronger interactions with cations.

The number of carbon atoms of the halogenated alkyl group is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and usually 1 or more. By setting it to be above the lower limit value, the charge of the anions is dispersed and the anion tends to be stabilized. By setting it to be less than the above upper limit value, the effect of the steric barrier with the cation is reduced, and it becomes possible to realize The tendency to interact more strongly with cations.

Specific examples include trifluoromethyl, pentafluoroethyl, 1,1,1-trifluoroethyl, and the like. From the viewpoint of suppressing variation in electric charge, trifluoromethyl is preferred.

(X ¹ ~ X ⁶ )

X ¹ to X ⁶ each independently represent at least one group selected from the group consisting of a direct bond,-(CH ₂ )-, -NH-, -O-, and -S-, or two or more of these Bonded base.

That is, X ¹ to X ⁶ are each independent, and may be obtained by bonding two or more divalent radicals selected from the above-mentioned groups, or may be obtained by bonding two or more radicals of one kind. . The number at the time of bonding is usually 2 or more, and usually 15 or less, preferably 12 or less, and more preferably 10 or less.

Among these, from the viewpoint of ease of synthesis,-(CH ₂ )-or -NH- is preferred, and -NH- is more preferred.

Among these, from the viewpoints that the heat resistance is high and the effect of the steric barrier with the cation is small, the interaction between the anion and the cation is reduced, and the counter ion is stabilized to improve the heat resistance of the dye, preferably Bistrifluoromethanesulfonylimide anion, tris (trifluoromethanesulfonyl) methylate anion, or containing 2,6-diphenylamino-4-butylamino-1,3,5-tris Trifluoromethanesulfonimide anion.

In addition, the existence form of the triarylmethane-based compound represented by the above formula (I-1) in the colored resin composition is not particularly limited, and may be a dye and / or a pigment. From the viewpoint of brightness and contrast, it is preferred. It exists as a dye.

(Molecular weight)

In the triarylmethane-based compound represented by the general formula (I-1), the molecular weight of the triarylmethane cation is preferably 270 or more, more preferably 470 or more, and usually 1970 or less. If it is in the said range, it is preferable that the solubility in a colored resin composition is sufficient, and since the content in a colored resin composition can be reduced, hardenability can be fully ensured.

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. If it is in the said range, it is preferable that the solubility in a colored resin composition is sufficient, and since the content in a colored resin composition can be reduced, hardenability can be fully ensured.

(Specific example of the compound represented by formula (I-1))

As the compound represented by the formula (I-1), for example, those listed below can be used.

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

(Synthesis method of compound represented by formula (I-1))

The triarylmethane compound represented by the above formula (I-1) can be based on, for example, "Review of Synthetic Dyes" (by Higuchi Hiroshi, Sankyo Publishing Co., 1968), and "Theoretical Manufacturing of Dye Chemistry" (by Hosoda Toyoda, Kyododo, 1957 ), Synthesized by the method described in International Publication No. 2009/107734, but it is not limited to this method.

(Content ratio of the compound represented by the formula (I-1) in the colored resin composition)

In the colored resin composition of the present invention, the color material (A) may contain only one type of the compound represented by the formula (I-1), or may contain two or more types. The compound represented by the formula (I-1) can be preferably 0.01 mass% or more, more preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 5 masses in the total solid content. % Or more, particularly preferably 8% by mass or more, more preferably 70% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass It is contained in a proportion of not more than mass%, particularly preferably not more than 20% by mass.

If it is below the said upper limit, it is difficult to reduce the hardenability of a coating film, and there exists a tendency for film strength to be sufficient, and it is preferable. Moreover, if it is more than the said lower limit value, since the tinting power is sufficient, it becomes easy to obtain the chromaticity of a desired density | concentration, and since film thickness is hard to become thick, it is preferable.

(Content ratio of the compound represented by the formula (I-1) in the color material)

The content ratio of the compound represented by formula (I-1) in the color material (A) is not particularly limited, and is preferably 0.01% by mass or more, and more preferably 1% by mass or more, with respect to the (A) color material. , More preferably 5 mass% or more. If it is more than the said lower limit, since the tinting power is sufficient, it is easy to obtain a desired brightness, and it is preferable. It is usually 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

On the other hand, the colored resin composition of the present invention in the second aspect is characterized by containing (A) a color material, (B) a solvent, and (C) a binder resin, and (A) the color material contains the following formula ( The triarylmethane compound represented by I-2). Furthermore, it is preferable to contain at least one of (D) a polymerizable monomer, (E) a photopolymerization starting component, and (E ') a thermal polymerization starting component, and may contain other components as needed.

(Compound represented by general formula (I-2))

The color material (A) contained in the colored resin composition of the present invention in the second aspect contains a triarylmethane-based compound represented by the following general formula (I-2).

The colored resin composition of the present invention in the second aspect contains a specific triarylmethane-based compound represented by the following general formula (I-2), and has high color purity, which can meet the long-term reliability requirements of a color display. Light resistance and voltage retention.

[Chemical 22]

(In the above formula (I-2), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent; R ⁵ and R ⁶ each independently represent An aromatic ring group which may have a substituent; adjacent R ¹ to R ⁶ may be connected to each other to form a ring, and the ring may also have a substituent; specifically, R ¹ and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ can also be connected to each other to form a ring; M ⁺ represents a monovalent cation; m represents an integer of 0 to 4)

In addition, in the formula (I-2), the -SO ₃ ^- group and-(SO ₃ ^- M ⁺ ) group shown outside [] represent an aromatic ring group, R ¹ to R ⁶ , or The substituents R ¹ to R ^{6 each} have are substituted with a -SO ₃ ^- group or a-(SO ₃ ^- M ⁺ ) _m group.

As R ¹ to R ⁶ in the above formula (I-2), those exemplified as R ¹ to R ⁶ in the above formula (I-1) can be preferably used.

(Combination of R ¹ ~ R ⁶ )

R ¹ to R ⁶ in the formula (I-2) may be appropriately selected from the above. Specific examples of the combination include those described in Table 2. In addition, the alkyl group, aromatic hydrocarbon ring group, and aromatic heterocyclic group listed in the following table may further include arbitrary substituents. In addition, C in the table means a carbon number.

As a combination of R ¹ to R ⁶ , from the viewpoint of heat resistance, the triarylmethane-based compounds represented by the formula (I-2) are easily associated with each other, and the triaryl group represented by the formula (I-2) can be suppressed. The cause of the thermal decomposition of the methane-based compound comes from the attack of other molecules, and does not reduce the intermolecular cation and anion of the triarylmethane-based compound represented by formula (I-2) due to the steric hindrance of the substituent. Electrostatic interaction, so it is preferred that R ³ is a hydrogen atom and R ⁴ is an alkyl group having 1 to 12 carbon atoms which may have a substituent. Since it can inhibit other molecules from bonding to the two benzene rings with a triarylmethane skeleton, Attack of the carbon atom of the naphthalene ring, so it is preferred that R ¹ and R ² are each independently an alkyl group having 1 to 12 carbons which may have a substituent, and an aromatic hydrocarbon ring group having 4 to 12 carbons which may have a substituent. Or, it may have an aromatic heterocyclic group having 4 to 12 carbon atoms as a substituent.

On the other hand, from the viewpoint of the steepness of the absorption waveform near 500 nm, that is, high brightness, since the π conjugate system is prevented from expanding and the shape of the absorption spectrum becomes steep, it is preferable that R ¹ and R ² are respectively It is independently an alkyl group having 1 to 12 carbons which may have a substituent and R ³ is a hydrogen atom and R ⁴ is an alkyl group having 1 to 12 carbons which may have a substituent. In addition, there is no charge of a π conjugated system Due to the deviation, the shape of the absorption spectrum becomes steep. Therefore, it is further preferred that R ⁵ and R ⁶ are each independently an aromatic hydrocarbon ring having 4 to 12 carbon atoms which may have a substituent.

The triarylmethane compound represented by formula (I-2) is a symmetrical molecule having a nitrogen atom bonded to the para position of two benzene rings forming a triarylmethane skeleton and a hydrogen atom bonded to the ortho and meta positions. Structure, it is considered that compared with other structures with substituents in the ortho or meta position, the molecules caused by steric hindrance are less twisted, the spectral shape is better, and the brightness is higher. From the viewpoint of making the molecular structure symmetrical, it is preferable that R ¹ and R ^{2 are the} same group and / or R ⁵ and R ^{6 are the} same group.

(M ⁺ and m)

M ⁺ represents a monovalent cation, and examples include hydrogen ion, alkali metal cation, alkaline earth metal cation, tertiary ammonium cation, and tertiary ammonium cation.

Examples of the alkali metal cation include lithium, sodium, and potassium. Examples of the alkaline earth metal of the alkaline earth metal cation include magnesium, calcium, and barium.

The tertiary ammonium cation is represented by N ⁺ HR ₃ (R represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent; furthermore, R may include the same or different R) .

Examples of the preferable carbon number of the R alkyl group and the substituents which the alkyl group may have are the same as those exemplified as the R ¹ to R ⁴ alkyl group described above. Examples of the preferable carbon number of the aromatic ring group and the substituents that the aromatic ring group may have are the same as those exemplified as the aromatic ring group of R ¹ to R ⁴ described above. Specific examples include lower alkylammonium cations having 1 to 6 carbon atoms (for example, methylammonium cation, ethylammonium cation, diethylammonium cation, triethylammonium cation, etc.), and carbon numbers substituted with hydroxyl groups. 1 to 6 alkylammonium cations (e.g., ethanol ammonium cation, diethanolammonium cation, triethanolammonium cation, etc.), 1 to 6 alkylammonium cations (e.g., carboxymethylammonium cation, carboxyethyl) Ammonium cations, carboxypropylammonium cations, dicarboxymethylammonium cations, etc.), ammonium cations (for example, N, N-diethylphenylammonium cations) substituted with aromatic ring groups and alkyl groups, and the like.

The quaternary ammonium cation is represented by N ⁺ R ₄ , and R represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. In addition, R including a plurality may be the same or different. Examples of the preferable carbon number of the alkyl group and the substituents that the alkyl group may have are the same as those exemplified as the alkyl group of R ¹ to R ⁴ described above. Examples of the preferable carbon number of the aromatic ring group and the substituents that the aromatic ring group may have are the same as those exemplified in the case of the aromatic ring group of R ¹ to R ⁴ described above.

Specifically, a 4th order alkylammonium cation (for example, a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, etc.) having a carbon number of 1 to 6 can be mentioned.

The type of cations of M ⁺ is not limited to one type, and plural types may be mixed. Moreover, you may mix multiple types in one molecule of a compound, and you may mix multiple types in a colored resin composition. From the viewpoint of solubility in an organic solvent used for the colored resin composition, M ⁺ is preferred, and hydrogen ions, alkali metal cations, tertiary ammonium cations, and tertiary ammonium cations are further preferred. Preferred are lithium cation, sodium cation, unsubstituted ammonium cation, and tetrabutylammonium cation.

In addition, m represents an integer of 0 to 4.

The larger m is, the more triarylmethane compounds represented by formula (I-2) tend to be: by replacing a large amount of hydrophilic sulfo groups, heat resistance and light resistance are improved, and in hydrophobic liquid crystals The solubility is also reduced, so the voltage holding rate is also improved. Coloring resin group In terms of higher solubility in the organic solvent used in the composition, m is preferably 0 to 2.

(Substitution position of -SO ₃ ^- group and-(SO ₃ ^- M ⁺ ) _m group)

In the triarylmethane compound represented by the formula (I-2), the -SO ₃ ^- group and the-(SO ₃ ^- M ⁺ ) _m group are substituted for the aromatic ring group, R ¹ to R ⁶ , Or a hydrogen atom of a substituent of R ¹ to R ⁶ . Preferred substitution positions of the -SO ₃ ^- group and the-(SO ₃ ^- M ⁺ ) _m group are a hydrogen atom on a naphthalene ring forming a triarylmethane skeleton, a hydrogen atom on a R ³ or R ⁴ group, or R ⁵ or A hydrogen atom on the aromatic ring group of R ⁶ .

The reason why the -SO ₃ ^- group or-(SO ₃ ^- M ⁺ ) _m group is preferably substituted to form a hydrogen atom on the naphthalene ring of the triarylmethane skeleton is as follows. In the case where a triarylmethane compound represented by the formula (I-2) is substituted with a -SO ₃ ^- group by a hydrogen atom on a naphthalene ring, the -SO ₃ ^- group of one molecule and the nitrogen of another molecule A cation existing on an atom or a central carbon atom forms an ionic bond, but at this time, by placing the -SO ₃ ^- group of the triarylmethane compound represented by formula (I-2) on a naphthalene ring, the compound (I- 2) The distance between the naphthalene ring of another molecule and the aromatic ring forming the triarylmethane skeleton of another molecule becomes closer. Therefore, in addition to ionic bonds, π-π interactions also occur between the two molecules, so the intermolecular force becomes stronger, and the heat resistance and the voltage retention rate become higher. In addition, by positioning the -SO ₃ ^- group on the naphthalene ring, the position of the central carbon of the same molecule and the -SO ₃ ^- group become closer, and a strong salt-forming effect in the molecule can also be expected. Furthermore, especially when the -SO ₃ ^- group is substituted on the unsubstituted nitrogen ring of the naphthalene ring, the benefit to the conjugated system of the triarylmethane skeleton is small, and the effect on color development is small. , And also better in terms of brightness.

Secondly, the reason why the -SO ₃ ^- or-(SO ₃ ^- M ⁺ ) _m group is preferable to replace the hydrogen atom on the R ³ or R ⁴ group is as follows. The introduction of the -SO ₃ ^- group to the R ³ or R ⁴ group has fewer restrictions on the synthesis, and is relatively easy to synthesize, compared to the case of introduction to the substituents of R ¹ , R ² , R ⁵ , or R ⁶ . The -SO ₃ ^- group on the R ³ or R ⁴ group is based on the formation of ionic bonds within or between molecules, which can take a relatively free position, and is easily arranged at a position where a strong ionic bond can be formed. Especially when the R ³ or R ⁴ group to which the -SO ₃ ^- group is to be introduced is an alkyl group, since the degree of freedom of the substituent is high, it is easy to form a preferable position for forming an ionic bond within and between molecules. It replaces the -SO ₃ ^- group and thus forms a strong ionic bond, and is therefore superior in heat resistance and electrical reliability. In addition, the conjugated system of the triarylmethane skeleton has a small benefit, has a small effect on color development, and is also better in the brightness of the obtained pixels.

Secondly, the reason why a -SO ₃ ^- group or a-(SO ₃ ^- M ⁺ ) _m group is preferable to substitute a hydrogen atom on the aromatic ring group of R ⁵ or R ⁶ is as follows. When the -SO ₃ ^- group is located on the aromatic ring group of R ⁵ or R ⁶ , when a triarylmethane compound represented by formula (I-2) forms an intermolecular salt, -SO of one molecule ₃ ^- present on the base of the system and the central carbon atom or a nitrogen atom of another molecule of the ionic bond-forming cation, but this time, of formula (I-2) represented by the bonded triaryl methane-based compound has the -SO ₃ ^- The distance between the aromatic ring group of the radical and the aromatic ring possessed by another molecule becomes closer. Therefore, in addition to the ionic bond between the two molecules, a π-π interaction also occurs, so the intermolecular force becomes stronger, and the heat resistance and electrical reliability become higher. In addition, by placing the -SO ₃ ^- group on the aromatic ring of R ⁵ or R ⁶ , the position of the central carbon of the same molecule and the position of the -SO ₃ ^- group become closer, and a strong salt-forming effect in the molecule can be expected.

Among these, from the viewpoint of brightness, hydrogen substituted on a naphthalene ring of a triarylmethane skeleton and a substituent of R ³ or R ⁴ is more preferably -SO ₃ ^- group or-(SO ₃ ^- M ⁺ ) _m group. atom.

Furthermore, in the formula (I-2), the expression that the bond of the -SO ₃ ^- group or the -SO ₃ ^- M ⁺ group passes through the bracket ([]) of the triarylmethane skeleton means that the substitution position is plural, Or it can be obtained synthetically as a mixture of compounds with different positions.

In addition, the existence form of the triarylmethane-based compound represented by the above formula (I-2) in the colored resin composition is not particularly limited, and may be a dye and / or a pigment. From the viewpoint of brightness and contrast, it is preferred. It exists as a dye.

(Molecular weight)

The molecular weight of the triarylmethane-based compound represented by the general formula (I-2) is preferably 270 or more, more preferably 470 or more, and usually 1970 or less. If it is in the said range, it is preferable that the solubility in a coloring resin composition is sufficient, and since the content in a coloring resin composition can be reduced, the hardenability is fully ensured.

(Specific example of triarylmethane-based compound represented by formula (I-2))

As the triarylmethane-based compound represented by the formula (I-2), for example, those listed below can be used.

[Chemical 25]

[Chemical 26]

(Synthesis method of triarylmethane compound represented by formula (I-2))

The triarylmethane-based compound represented by the above formula (I-2) can be based on, for example, "Review of Synthetic Dyes" (by Higuchi Hiroshi, Sankyo Publishing Co., 1968), and "Theoretical Manufacturing of Dye Chemistry" (by Hosoda Toyoda, Kyododo, 1957). ), Synthesized by the method described in International Publication No. 2009/107734, but it is not limited to this method.

(Content ratio of the triarylmethane-based compound represented by formula (I-2) in the colored resin composition)

The colored resin composition of the present invention may contain only one triarylmethane-based compound represented by formula (I-2) in the color material (A), or may include two or more kinds. The triarylmethane-based compound represented by the formula (I-2) may be contained in an amount of preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, in all solid components. Good for 5 quality It is preferably contained in an amount of not less than 8% by mass, more preferably not less than 8% by mass, more preferably not more than 70% by mass, more preferably not more than 40% by mass, still more preferably not more than 30% by mass, particularly preferably not more than 20% by mass.

If it is less than the said upper limit, since the hardenability of a coating film is hard to fall, there exists a tendency for film strength to be sufficient. Moreover, if it is more than the said lower limit, since tinting power is sufficient, it becomes easy to obtain the chromaticity of a desired density | concentration, and since film thickness is hard to become thick, it is preferable.

(Content ratio of triarylmethane-based compound represented by formula (I-2) in color material)

The content ratio of the compound represented by the formula (I-2) in the color material (A) is not particularly limited, and is preferably 1% by mass or more, and more preferably 5% by mass or more, with respect to the (A) color material. It is more preferably 10% by mass or more. If it is more than the said lower limit, since the tinting power is sufficient, it is easy to obtain a desired brightness, and it is preferable. It is usually 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

(Other color materials)

The (A) coloring material contained in the colored resin composition of the present invention contains a triarylmethane-based compound represented by the formula (I-1) or (I-2), but may further contain as long as the effect of the present invention is not impaired. Other color materials. Examples of the color material include dyes and pigments.

(Content ratio of colored resin composition and other color materials in color materials)

The colored resin composition of the present invention may also contain a coloring material other than the triarylmethane-based compound represented by the formula (I-1) or (I-2), and the content ratio is not particularly limited. It is preferably 70% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. The content ratio to the color material (A) is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less. By setting it as the said range, it is preferable in the point which does not have a big influence on the absorption waveform and brightness in a coloring resin composition, and the hue, heat resistance, and light resistance of the obtained pixel become easy to become more favorable.

(Other dyes)

Examples of other dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. Dyes, cyanine dyes, triarylmethane dyes, dipyrrole methylene dyes, Department of dyes and so on.

Examples of the azo dye include: CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Active Yellow 2, CI Active Red 17, CI Active Red 120, CI Active Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Medium Red 7, CI Medium Yellow 5, CI Medium Black 7, etc.

Examples of the anthraquinone dye include CI reduction blue 4, CI acid blue 25, CI acid blue 40, CI acid blue 80, CI acid green 25, CI active blue 19, CI active blue 49, CI disperse red 60, CI Disperse Blue 56, CI Disperse Blue 60, etc.

Examples of the phthalocyanine dye include CI Direct Blue 86, CI Direct Blue 199, CI Reductive Blue 5, Japanese Patent Laid-Open No. 2002-14222, Japanese Patent Laid-Open No. 2005-134759, and Japanese Patent Laid-Open No. As disclosed in 2010-191358 and Japanese Patent Laid-Open No. 2011-148950, examples of the quinimine-based dyes include CI Basic Blue 3 and CI Basic Blue 9. As quinoline dyes, for example, Examples include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, and the like. Examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42 and the like.

Examples of the triarylmethane-based dye include those described in C.I. Acid Blue 86, C.I. Acid Blue 88, C.I. Acid Blue 108, International Publication No. 2009/107734, and International Publication No. 2011/162217.

Furthermore, examples of the cyanine-based dye include those described in International Publication No. 2011/162217, and preferred embodiments are also the same.

Examples of the dipyrromethene dye include Japanese Patent Laid-Open No. 2008-292970, Japanese Patent Laid-Open No. 2010-84009, Japanese Patent Laid-Open No. 2010-84141, and Japanese Patent Laid-Open No. 2010-85454. Japanese Patent Laid-Open No. 2011-158654, Japanese Patent Laid-Open No. 2012-158739, Japanese Patent Laid-Open No. 2012-224852, Japanese Patent Laid-Open No. 2012-224849, Japanese Patent Laid-Open No. 2012-224847 It is described in Japanese Patent Publication No. 2012-224846 and the like.

As Examples of the dyes include CI Acid Red 50, CI Acid Red 52, CI Acid Red 289, Japanese Patent No. 3387541, Japanese Patent Laid-Open No. 2010-32999, Japanese Patent No. 4492760, and "Synthetic Dye Review "(By Higuchi Hiroshi, Sankyo Publishing House, 1968), pages 326 to 348, etc.

Especially when forming blue pixels, it is preferable Based dyes, triarylmethane based dyes, anthraquinone based dyes, azo based dyes, dipyrromethene based dyes, cyanine based dyes, and phthalocyanine based dyes are more preferred from the viewpoint of durability. Dyes or dipyrromethene dyes.

In the colored resin composition of the present invention, as the (A) coloring material, only one kind of the compound represented by the general formula (I-1) or (I-2) may be contained, or two or more kinds may be contained.

Similarly, other dyes may contain only one kind, and may contain two or more kinds.

(Other pigments)

As a pigment, when forming a pixel of a color filter, etc., pigments of various colors, such as blue and purple, can be used. Examples of the chemical structure include phthalocyanine-based, quinacridone-based, benzimidazolone-based, and Series, Yin Dan Shilin series, 苝 series of organic pigments. In addition, various inorganic pigments can be used. Hereinafter, specific examples of pigments that can be used are disclosed by pigment numbers.

Examples of the blue pigment include CI 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 so on.

Among these, from the viewpoint of heat resistance and light resistance, a phthalocyanine pigment having a central metal is preferred, and a blue copper phthalocyanine pigment is particularly preferred. Examples of the copper phthalocyanine pigment include C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and the like, and C.I. Pigment Blue 15: 6 is preferable.

Therefore, when the colored resin composition of the present invention contains a blue pigment, it is preferably 80% by mass or more, particularly 90% by mass or more, and particularly 95 to 100% by mass relative to the total content of the blue pigment. % Is CI Pigment Blue 15: 6.

Examples of the purple pigment include CI 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, etc.

Of these, purple two is preferred Pigment as the two Examples of the pigment include CI Pigment Violet 19 and 23, and more preferably CI Pigment Violet 23.

Therefore, when the colored resin composition of the present invention contains a purple pigment, it is preferably 80% by mass or more, particularly 90% by mass or more, and particularly 95 to 100% by mass relative to the total content of the purple pigment. CI Pigment Violet 23.

These may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and ratios.

Regarding the pigment that can be used in the colored resin composition of the present invention, in terms of forming a pixel with a high contrast, the average primary particle diameter is preferably smaller, and specifically, the average primary particle diameter is preferably 40 nm or less. , More preferably 35 nm or less.

In particular, the same is true of blue copper phthalocyanine pigments. The average primary particle diameter is preferably 40 nm or less, more preferably 35 nm or less, and even more preferably 20 to 30 nm.

Again, about two The average primary particle diameter of the pigment is preferably 40 nm or less, and more preferably 25 to 35 nm. In terms of difficulty in agglomerating the pigment in the colored resin composition, the average primary particle diameter is preferably 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 was dispersed in chloroform and dropped onto a sieve with a cotton-wool film attached, dried, and observed with a transmission electron microscope (TEM) to obtain a primary particle image of the pigment. . Based on this image, the particle diameter of each pigment particle was set as the area circle equivalent diameter converted to the diameter of a circle having the same area, and the particle diameter was obtained for a plurality of (usually about 200 to 300) pigment particles.

Using the value of the obtained primary particle diameter, the number average was calculated according to the calculation formula of the following formula, and the average particle diameter was obtained.

Particle size of each pigment particle: X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m (m is the number of particles)

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

[(B) Solvent]

The solvent (B) contained in the colored resin composition of the present invention has a function of dissolving or dispersing each component contained in the colored resin composition to adjust viscosity.

As the solvent (B), any component that can dissolve or disperse the colored resin composition may be used, and it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.

Examples of such a solvent 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 third butyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methyl Glycol monoalkyl ethers such as oxybutanol, tripropylene glycol monomethyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Glycol dialkyl ethers such as alcohol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ether ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid Methoxypentyl ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxy acetate Glycol alkyl ether acetates such as butyl esters; two Ethers such as methyl ether, dipropyl ether, diisopropyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl ether Isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl Ketones such as hexyl ketone, methyl nonyl ketone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, monoglycerol such as glycerol or Polyols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane , Cycloaliphatic hydrocarbons such as methylcyclohexene, bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate Ester, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, 3-ethoxypropionate Of ethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Chain or cyclic esters; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride; Ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; these solvents can be used alone or in combination of two or more.

Among the above solvents, from the standpoint of the adhesiveness between the substrate and the coating film and the uniform thickness of the coating film, it is preferable to contain a glycol monoalkyl ether. Among these, propylene glycol monomethyl ether is particularly preferred in terms of the solubility of various constituent components in the colored resin composition.

In addition, for example, when the pigment is contained as an optional component, the balance between coating properties and surface tension is good, and it is more preferable that the component is further mixed in terms of the relatively high solubility of the constituent components in the colored resin composition. Glycol alkyl ether acetates were used as solvents. Furthermore, in a colored resin composition containing a pigment, glycol monoalkyl ethers have high polarity and tend to agglomerate the pigment, while the viscosity of the colored resin composition may be increased, which may reduce storage stability. Therefore, the amount of glycol monoalkyl ethers is preferably not too much, and the ratio of glycol monoalkyl ethers in the solvent (B) is preferably 5 to 50% by mass, and more preferably 5 to 30% by mass. .

From the viewpoint of adaptability to a recent sandwich coating method corresponding to a large substrate or the like, it is preferable to also use a solvent having a boiling point of 150 ° C. or more in combination. In this case, the content of such a high-boiling-point solvent is preferably 3 to 50 masses relative to the entire amount of (B) the solvent. %, More preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass. If the amount of the high-boiling-point solvent is too small, for example, there is a possibility that the dye component is equal to the precipitation and solidification of the tip of the slit nozzle, which may cause foreign body defects, and if it is too large, the drying speed of the composition may be slowed down, which may cause the following color filter There may be a problem of poor contact in the vacuum drying process in the manufacturing process of the device, or a problem of pre-baking pore marks.

In addition, the solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to include a solvent having a boiling point of 150 ° C or higher. .

The colored resin composition of the present invention can also be used for the manufacture of color filters by the inkjet method. In the manufacture of color filters by the inkjet method, the number of inks ejected from the nozzles is several. pL to tens of pL are very small, so there is a tendency for the solvent to evaporate before being sprayed on the periphery of the nozzle opening or in the pixel bank, resulting in ink concentration and evaporation. To avoid this, the boiling point of the solvent is preferably high, and specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C or higher. It is particularly preferred to contain a solvent having a boiling point of 200 ° C or higher, especially a boiling point of 220 ° C or higher. The high-boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more in the (B) solvent. When the ratio of such a high-boiling-point solvent is less than 50% by mass, the effect of preventing the solvent from evaporating from ink droplets cannot be sufficiently exerted.

In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited, and the upper limit thereof is usually 99% by mass based on the total amount of the composition. When the content of the (B) solvent in the composition exceeds 99% by mass, the concentration of each component other than the (B) solvent may become too small, and it may become difficult to form a coating film. On the other hand, regarding the lower limit of the content of the (B) solvent, in consideration of the viscosity suitable for coating, etc., it is usually 70% by mass, preferably 75% by mass, and even more preferably 80% by mass.

[(C) Adhesive resin]

(C) The preferable binder resin varies depending on the curing method of the colored resin composition.

When the colored resin composition of the present invention is a photopolymerizable resin composition, as the (C) binder resin, for example, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2003-233179, etc. Among the polymer compounds described in various publications, the following resins (C-1) to (C-5) and the like are preferred.

(C-1): a resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group in a copolymer of an epoxy-containing (meth) acrylate and another radical polymerizable monomer, or An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction (hereinafter, sometimes referred to as "resin (C-1)")

(C-2): Linear alkali-soluble resin (C-2) containing a carboxyl group (hereinafter referred to as "resin (C-2)")

(C-3): A resin obtained by adding an epoxy-containing unsaturated compound to the carboxyl portion of the resin (C-2) (hereinafter, referred to as "resin (C-3)")

(C-4): (meth) acrylic resin (hereinafter referred to as "resin (C-4)")

(C-5): epoxy acrylate resin having a carboxyl group (hereinafter referred to as "resin (C-5)")

Among these, the resin (C-1) is particularly preferred, and the resin will be described below.

In addition, the resins (C-2) to (C-5) may be any resin as long as it is soluble in an alkaline developing solution and has a degree of solubility capable of being subjected to a target development process, and is separately disclosed in Japanese Patent Laid-Open 2009-025813 is the same as that described in the same item. The same applies to the preferred aspect.

(C-1): A resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group in a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, or An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction

As one of the particularly preferable resins of the resin (C-1), 5 to 90 mol% of the epoxy group-containing (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomers can be cited. The copolymer is obtained by adding 10 to 100 mol% of an epoxy group to an unsaturated monobasic acid, or adding 10 to 100 mol% of a hydroxyl group generated by the addition reaction to a polybasic acid anhydride. The obtained alkali-soluble resin.

Examples of the epoxy-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and (3,4) (meth) acrylic acid. -Epoxycyclohexyl) methyl ester, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among these, glycidyl (meth) acrylate is preferable. These (meth) acrylates containing an epoxy group may be used individually by 1 type, and may use 2 or more types together.

The other radically polymerizable monomer copolymerized with the epoxy-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include vinyl aromatics, dienes, (Meth) acrylic acid esters, (meth) acrylamide, vinyl compounds, unsaturated dicarboxylic acid diesters, monocis butylene diimines, etc., preferably having the following formula ( Mono (meth) acrylate of the structure represented by III).

The repeating unit derived from a mono (meth) acrylate having a structure represented by the following formula (III) preferably contains 5 to 90 mol% of the repeating unit derived from "other radical polymerizable monomer". In addition, it is more preferable to contain 10 to 70 mol%, and even more preferable to contain 15 to 50 mol%.

In the 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. Furthermore, 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, which may be either saturated or unsaturated, and further preferably has a carbon number of 5 to 6.

Among them, the structure represented by the formula (IV) is particularly preferably represented by the following structural formula (IVa), (IVb), or (IVc).

The mono (meth) acrylate having the structure represented by the formula (IV) may be used alone. One type may be used, or two or more types may be used in combination.

As "other radically polymerizable monomers" other than the mono (meth) acrylate having a structure represented by the above formula (IV), in terms of improving the heat resistance and strength excellent in a colored resin composition, Examples include: styrene, n-butyl (meth) acrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, isopropyl (meth) acrylate Esters, adamantyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylcis butylene diimide, N-cyclohexylcis butene Dihydrazone.

The content of the repeating unit derived from at least one monomer selected from the above-mentioned monomer group is preferably 1 to 70 mole%, and more preferably 3 to 50 mole%.

The copolymerization reaction of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer is a known solution polymerization method.

In the present invention, as the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, it is preferable to include a repeat derived from the epoxy group-containing (meth) acrylate Units of 5 to 90 mol% and repeating units of 10 to 95 mol% derived from other free-radically polymerizable monomers, further preferably including the former 20 to 80 mol% and the latter to 80 to 20 mol% It is particularly preferable to include the former 30 ~ 70 mole% and the latter 70 ~ 30 mole%.

If it is in the said range, the addition amount of the following polymerizable component and alkali-soluble component is sufficient, and since heat resistance or the strength of a film is sufficient, it is preferable.

The epoxy group portion of the epoxy group-containing copolymer synthesized by the above method is reacted with an unsaturated monoacid (polymerizable component), and a polybasic acid anhydride (alkali-soluble component) is reacted therewith.

Here, as the unsaturated monobasic acid added to the epoxy group, a known one can be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

As specific examples, (meth) acrylic acid, butene acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid, α-position halogenated alkyl group, alkoxy group, halogen atom, Monocarboxylic acids such as (meth) acrylic acid substituted with nitro or cyano. among them, (Meth) acrylic acid is preferred. These may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, polymerizability can be imparted to the binder resin used in the present invention.

The unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. If it is in the said range, since a colored resin composition is excellent in stability over time, it is preferable. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the polybasic acid anhydride added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, a known one can be used.

Examples include dibasic anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridged anhydride; trimellitic acid Acid anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride and the like. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used singly or in combination of two or more kinds.

By adding such a component, it is possible to impart alkali solubility to the binder resin used in the present invention.

These polybasic acid anhydrides usually add 10 to 100 mole% of the hydroxyl group generated by the addition of an unsaturated monobasic acid to the epoxy group of the above copolymer, preferably 20 to 90 mole%, and more preferably 30 ~ 80 mole%.

If it is in the said range, since the residual film rate and solubility at the time of image development are sufficient, it is preferable.

As a method for adding a polybasic acid anhydride to the hydroxyl group, a known method can be adopted.

Furthermore, in order to improve the light sensitivity, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to a part of the generated carboxyl group after the above-mentioned polybasic acid anhydride is added. The structure of this resin is described, for example, in Japan Japanese Patent Laid-Open No. 8-297366 or Japanese Patent Laid-Open No. 2001-89533.

The polystyrene-equivalent weight average molecular weight (Mw) of the above-mentioned adhesive resin (C) measured by GPC (gel permeation chromatography) is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. If it is in the said range, since heat resistance or film strength, and also solubility in a developing solution are favorable, it is preferable.

In addition, as a standard for the 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 the binder resin (C) is usually 10 to 200 mg-KOH / g, preferably 15 to 150 mg-KOH / g, and more preferably 25 to 100 mg-KOH / g. If the acid value becomes too low, the solubility in the developer may decrease. On the contrary, if it is too high, the film may be roughened.

The content ratio of the (C) binder resin in the colored resin composition is usually 0.1 to 80% by mass, and preferably 1 to 60% by mass, based on the total solid content.

If it is within the above range, the adhesion to the substrate is good, and the permeability of the developer to the exposed portion is moderate, and the surface smoothness or sensitivity of the pixel is good, which is preferable in this respect.

[(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, and is preferably a compound capable of addition polymerization having at least one ethylenic double bond (hereinafter, referred to as "ethenic" Compounds ").

The ethylenic compound is a compound having an ethylenic double bond which is subjected to addition polymerization and hardened by the action of a photopolymerization starting component when the colored resin composition of the present invention is irradiated with active light. In addition, the (D) polymerizable monomer of the present invention means a concept opposite to a so-called high molecular substance, and includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.

Examples of the ethylenic compound of the (D) polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxylation Esters of compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and polyhydroxy compounds such as unsaturated polycarboxylic acids and polycarboxylic acids and the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds An ester obtained by an esterification reaction; an ethylenic compound having a urethane skeleton and the like obtained by reacting a polyisocyanate compound with a (meth) acrylfluorenyl-containing hydroxyl compound.

Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and trimethylolpropane tri (methyl). Acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (methyl) ) (Meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate and the like. In addition, examples include changing the (meth) acrylic acid part of these (meth) acrylic acid esters to the iconic acid part of the iconic acid part, the butenoic acid part of the butenoic acid part, or the maleic acid part. Maleic acid esters of the oxalic acid portion.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcinol di (meth) acrylate, and pyrogallol tri (methyl) Acrylate, etc.

The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxy compound may be a single substance or a mixture. As a representative example, a condensate of (meth) acrylic acid, phthalic acid, and ethylene glycol; a condensate of (meth) acrylic acid, maleic acid, and diethylene glycol; (methyl ) Condensates of acrylic acid, terephthalic acid, and pentaerythritol; condensates of (meth) acrylic acid, adipic acid, butanediol, and glycerol.

Examples of the ethylenic compound having a urethane skeleton produced by reacting a polyisocyanate compound with a (meth) acrylfluorene-containing hydroxy compound include 1,6-hexanediisocyanate, trimethylhexamethylene Aliphatic diisocyanates such as methyl diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; toluene diisocyanate Aromatic diisocyanates such as esters, diphenylmethane diisocyanates, and the like containing 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloxymethyl] propane, etc. Reactant of (meth) acrylfluorenyl hydroxy compound.

Examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide, and allyl esters such as diallyl phthalate. Class; vinyl-containing compounds such as divinyl phthalate.

Among these, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, a (meth) acrylate of pentaerythritol or dipentaerythritol is 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 it is preferred that an unreacted hydroxyl group of the aliphatic polyhydroxy compound react with a non-aromatic carboxylic acid anhydride to have an acid. Polyfunctional monomers are particularly preferred in that the aliphatic polyhydroxy compound in the ester is at least one of pentaerythritol and dipentaerythritol.

These monomers may be used alone, but it is difficult to obtain a single compound in production, so a mixture of two or more monomers may also be used.

If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the (D) polymerizable monomer.

The preferred 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.

If it is in the said range, it will become difficult to reduce a developing dissolution characteristic, and it will become easy to manufacture or handle. Furthermore, it is difficult to reduce the photopolymerization performance, and the hardenability such as the surface smoothness of the pixel is good, so it is preferable.

In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate as a main component. This polyfunctional monomer can also be combined with other polyfunctional monomers Use in combination.

In the colored resin composition of the present invention, the content ratio of the (D) polymerizable monomers is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass of the total solid content. Above, and generally, it is 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, and even more preferably 20% by mass. %the following.

The content ratio of the (D) polymerizable monomer to 100 parts by mass of the color material (A) is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and usually 200 parts by mass or less, preferably 100 parts by mass or less, and still more preferably 80 parts by mass or less.

If it is within the above range, light curing is moderate, and it is difficult to cause poor adhesion during development, and it is difficult to form an inverted tapered cross-section after development, and further, it is difficult to cause peeling and defective peeling due to reduced solubility, which is preferable.

[(E) Photopolymerization starting component and (E ') Thermal polymerization starting component]

The colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization starting component and (E ') a thermal polymerization starting component in order to harden the coating film. Among them, the hardening method may be a method other than the method using these initiators.

In particular, when the colored resin composition of the present invention contains a resin having an ethylenic double bond as the component (C), or when it contains an ethylenic compound as the (D) component, it is preferable to contain a resin having direct absorption of light or light. At least one of a photopolymerization starting component which functions as a function of generating a polymerization-active radical by a decomposition reaction or a hydrogen abstraction reaction which is sensitized, and a thermal polymerization-starting component which generates a polymerization-active radical by heat. Furthermore, in the present invention, the so-called (E) component as the photopolymerization starting component means that a polymerization accelerator (hereinafter, also referred to as "(E1) component") is used in combination with a photopolymerization initiator (hereinafter, It is also arbitrarily called "(E2) component"), and a mixture of adjuvants, such as a sensitizing dye (henceforth, it is also called an "(E3) component" arbitrarily).

[(E) Photopolymerization starting component]

The (E) photopolymerization initiating component of the present invention is generally used in the form of a mixture of (E1) a photopolymerization initiator and (E2) a polymerization accelerator and (E3) a sensitizing dye and the like, which are added if necessary. It is a component that has the function of directly absorbing light or performing photosensitization to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization-active radical.

Examples of the (E1) photopolymerization initiator constituting the photopolymerization starter include the titanocene derivatives described in Japanese Patent Laid-Open No. 59-152396, Japanese Patent Laid-Open No. 61-151197, and the like. Types; hexaarylbiimidazole derivatives described in Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, and the like; Japanese Patent Laid-Open No. 10 -Methylation described in Japanese Patent No. 39503 Diazole derivatives, halomethyl Derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, etc. Base active agents, α-amino alkyl phenone derivatives; oxime ester derivatives described in Japanese Patent Laid-Open No. 2000-80068 and the like.

Specifically, for example, a photopolymerization initiator described in International Publication No. 2009/107734 and the like can be cited.

Among these photopolymerization initiators, α-aminoalkyl phenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and 9-oxysulfur are more preferable. Derivatives.

Examples of the oxime ester derivatives include 2- (benzyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone and O-acetamidine Group-1- [6- (2-methylbenzylidene) -9-ethyl-9H-carbazol-3-yl] ethanone oxime, a compound represented by the following formula (V), and the like.

[Chemical 30]

(In the 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. Alkyl, which may each have a substituent; or, R ¹⁰¹ may be bonded to X or Z to form a ring;

R ¹⁰² represents an alkanoyl group having 2 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an arylene group having 7 to 20 carbon atoms, and 2 to 10 carbon atoms. Alkoxycarbonyl, aryloxycarbonyl with 7-20 carbons, heteroaryl with 2-20 carbons, heteroarylfluorenyl with 3-20 carbons or alkylaminocarbonyl with 2-20 carbons, Etc. may have substituents;

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic heterocyclic group which may be obtained by condensing two or more rings having a substituent;

(Z represents an aromatic ring group which may have a substituent)

Furthermore, among the compounds represented by the above formula (V), compounds in which X is a carbazole ring which may have a substituent are preferable, and specifically, compounds represented by the following formula (VI), etc. are particularly preferred It is a compound represented by a following formula (VII).

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

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

In the formula (VIIa), R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, a phenyl group, or an N-ethenyl-N-ethenyloxyamino group. * Indicates a bonding site.

R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents ^a 3,6-carbazolyl group in which ^a nitrogen atom is substituted with an 1-4 alkyl group. Z ^a represents an alkyl-substituted phenyl group or a morpholinyl-substituted naphthyl group.

As the oxime-based initiator, a commercially available product may be used. Examples of commercially available products include: OXE-01, OXE-02 (manufactured by BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Changzhou Power Electronics) (Manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).

Examples of the photopolymerization initiator include benzoin alkyl ethers and anthraquinone derivatives; benzenes such as 2-methyl- (4'-methylthienyl) -2-morpholinyl-1-acetone Ethyl ketone derivatives, 2-ethyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur 9-oxysulfur Derivatives, benzoate derivatives, acridine derivatives, brown Derivatives and anthrone derivatives. As such an initiator, a commercially available product may be used.

Examples of commercially available products include: IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784 (all manufactured by BASF, "IRGACURE" "Are registered trademarks).

Of these photopolymerization initiators, α-aminoalkyl phenone derivatives and 9-oxysulfur are more preferred. Derivatives, oxime ester derivatives. Especially preferred are oxime ester derivatives.

Examples of the (E2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as ethyl N, N-dimethylaminobenzoate; 2-mercaptobenzene Benzothiazole, 2-mercaptobenzo Thiol compounds such as azoles, 2-mercaptobenzimidazoles and the like having heterocycles; mercapto compounds such as aliphatic polyfunctional mercapto compounds; and the like.

These (E1) photopolymerization initiators and (E2) polymerization accelerators may be used individually by 1 type, and may use 2 or more types together.

Moreover, (E3) a sensitizing dye is used as needed in order to improve a sensitivity. The sensitizing pigment is appropriately used according to the wavelength of the image exposure light source, and examples thereof include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756. Pigments; coumarin pigments with heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, etc .; Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open 3-ketocoumarin pigments described in Japanese Patent Publication No. 5-289335, etc .; pyrromethene pigments described in Japanese Patent Publication No. 6-19240, etc .; Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58- 15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open Pigments having a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application Laid-Open No. 4-288818, and the like.

(E3) A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

In the colored resin composition of the present invention, the content ratio of these (E) photopolymerization starting components is usually 0.1% by mass or more, preferably 0.2% by mass or more, and more preferably 0.5% by mass of the total solid content. Above, further preferably 1% by mass or more, further 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, and further preferably 20% by mass. The range is below mass%.

If it is within the above range, the sensitivity to the exposure light is good, and the solubility of the unexposed portion in the developing solution is also good, and it is difficult to cause development failure, etc., which is preferable in this respect.

[(E ') Thermal polymerization starting component]

Specific examples of the (E ') thermal polymerization initiating component that can be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Among these, an azo-based compound is suitably used. More specifically, for example, a thermal polymerization starting component described in International Publication No. 2009/107734 or the like can be used.

These thermal polymerization starting components may be used individually by 1 type, and may use 2 or more types together.

[Other optional ingredients]

The colored resin composition of the present invention may contain, 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 protection agent, adhesion promoter, development improver, etc. As these arbitrary components, various compounds described in, for example, Japanese Patent Laid-Open No. 2007-113000 can be used. When a pigment is contained, a dispersant or a dispersing aid may be contained.

[Dispersant]

When the coloring resin composition of this invention contains a pigment, it is preferable to further contain a dispersing agent.

The type of the dispersant of the present invention is not particularly limited as long as it disperses the pigment and remains stable.

For example, a cationic, anionic, nonionic, or amphoteric dispersant can be used, and a polymer dispersant is preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate salts of polymer copolymers, cationic comb-type graft polymers, and the like. Among these dispersants, block copolymers, polyurethanes, and cationic comb-type graft polymers are preferred. Particularly preferred is a block copolymer, of which a block copolymer including an A-block having a lipophilic property and a B-block having a functional group containing a nitrogen atom is preferred.

Specifically, examples of the B block having a functional group containing a nitrogen atom include a unit structure having at least one of a quaternary ammonium salt group and an amine group in a side chain. Examples of the A block include a unit structure having no quaternary ammonium salt group and amine group.

The B block system constituting the acrylic block copolymer has a unit structure including at least one of a quaternary ammonium salt group and an amine group and has a pigment adsorption function.

When the B block has a quaternary ammonium salt group, the quaternary ammonium salt group may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.

Examples of such a block copolymer include those described in Japanese Patent Laid-Open No. 2009-025813.

The colored resin composition of the present invention may contain a dispersant other than the above. Examples of other dispersants include those described in Japanese Patent Application Laid-Open No. 2006-343648.

When the colored resin composition of the present invention contains a pigment, the content ratio of the dispersant in the total solid content is preferably 2 to 1000 parts by mass, especially 5 to 100 parts by mass relative to the total content of the pigment. 500 parts by mass, especially 10 to 250 parts by mass Use in a range manner.

By setting it within the above range, it is possible to ensure good pigment dispersibility without affecting the heat resistance of the triarylmethane-based compound represented by the formula (I-1) or (I-2), and the pigment The dispersion stability is better, and it is better in this respect.

[Dispersion aid]

The colored resin composition of the present invention may contain a dispersing aid. Here, the so-called dispersion aid may be a pigment derivative. As the pigment derivative, for example, Japanese Patent Laid-Open No. 2001-220520, Japanese Patent Laid-Open No. 2001-271004, and Japanese Patent Laid-Open No. 2002-179976 may be used. , Various compounds described in Japanese Patent Laid-Open No. 2007-113000, and Japanese Patent Laid-Open No. 2007-186681.

In addition, the content ratio of the dispersing assistant in the colored resin composition of the present invention is usually 0.1% by mass or more, and usually 30% by mass or less, and preferably 20% by mass relative to the total amount of the solid components of the pigment. Hereinafter, it is more preferably 10% by mass or less, and still more preferably 5% by mass or less. By controlling the amount to be added in the above range, it is preferable in terms of exhibiting the effect as a dispersing aid and having better dispersibility and dispersion stability.

[Dispersion resin]

The colored resin composition of the present invention may contain a part or all of the resin selected from the above-mentioned (C) binder resin or other binder resins as the following dispersion resin.

Specifically, in the following [preparation method of a colored resin composition], by including the above-mentioned components such as a dispersant and (C) a binder resin, the (C) binder resin has a synergistic effect with the dispersant It helps the dispersion stability of pigment. As a result, there is a possibility of reducing the amount of the dispersant added, so it is preferable. In addition, it also exhibits the effect of improving the developability, and does not leave undissolved matter on the non-pixel portion of the substrate, and improves the adhesion of the pixel to the substrate, which is preferable.

As such, 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, and more preferably used in an amount of about 10 to 100% by mass, relative to 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, by combining the (A) color material and (C) binder resin containing the compound (I-1) or (I-2) with ( B) It is prepared by mixing a solvent and any components used as necessary.

In addition, a color material containing liquid containing the (A) color material and the (B) solvent containing the compound (I-1) or (I-2) may be prepared, and the (C) binder resin and optional ingredient.

In addition, as a preparation method in the case where a pigment is contained, it is used in a solvent containing a pigment, and in the presence of a dispersant and a dispersing aid added as necessary, together with a part of the (C) binder resin as the case may be, for example A paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. are pulverized, mixed, and dispersed to prepare a pigment dispersion liquid. Examples include adding to the pigment dispersion (A) a color material containing the compound (I-1) or (I-2), (C) a binder resin, (D) a polymerizable monomer as needed, ( E) A method of preparing at least one of a photopolymerization starting component, a thermal polymerization starting component, and the like, and mixing them.

On the other hand, in the case where no pigment is used, for example, when a dye is used as the coloring material, the preparation method does not require a dispersant or a dispersing aid, and does not require complicated pigment dispersion steps, so it can be inexpensive. The colored resin composition is manufactured.

[Application of colored resin composition]

The colored resin composition of the present invention is generally in a state in which all constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form constituent members 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, applications of pixels as color filters, and the use of such liquid crystal display devices (panels) and organic EL display devices will be described.

<Color filter>

The color filter of the present invention has a coloring resin composition of the present invention. Of pixels.

Hereinafter, a method for forming the color filter of the present invention will be described.

The pixels of the color filter can be formed by various methods. Here, a case where a photopolymerizable colored resin composition is used and formed by a photolithography method is described as an example, but the production method is not limited to this.

First, a black matrix is formed on the surface of the substrate as needed to divide the pixel-forming portions, and the colored resin composition of the present invention is coated on the substrate, followed by pre-baking to evaporate the solvent to form a coating film. Next, after exposing the coating film through a light-shielding mask, it was developed using an alkaline developer to dissolve and remove the unexposed portion of the coating film, and then red, green, and blue pixels were formed by post-baking. Pattern to make a color filter.

In the present invention, it is particularly preferred that the pixel formed by using the colored resin composition of the present invention is a blue pixel.

The substrate used when forming a pixel is not particularly limited as long as it is transparent and has a moderate strength, and examples thereof include polyester resins, polyolefin resins, polycarbonate resins, acrylic resins, and thermoplastic resins. Sheets, epoxy resins, thermosetting resins, various glasses, etc.

In addition, for these substrates, if necessary, a pretreatment such as a thin film formation treatment using a silane coupling agent or a urethane resin, a surface treatment such as a corona discharge treatment, or an ozone treatment may be appropriately performed.

When the colored resin composition is applied to a substrate, a spin coating method, a bar coating method, a flow coating method, a nip rotation coating method, a mold coating method, a roll coating method, a spray coating method, and the like can be cited. Among these, a nip rotation coating method and a die coating method are preferred.

The thickness of the coating film is the film thickness after drying, and is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and particularly preferably 0.8 to 5.0 μm.

Within the above range, it is easy to adjust in the pattern development or liquid crystal cellization step Gap is also better in terms of easier color presentation.

As the radiation used in the exposure, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. can be used, and preferably radiation having a wavelength in the range of 190 to 450 nm.

The light source used for image exposure to use radiation with a wavelength of 190 to 450 nm is not particularly limited. Examples include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, and medium-pressure mercury lamps. , Low-pressure mercury lamp, carbon arc, fluorescent lamp and other lamp light sources; argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, semiconductor laser and other laser light sources. In the case of using light with a specific wavelength, an optical filter may be used.

The radiation exposure is preferably 10 to 10,000 J / m ² .

The alkaline developer is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, or metasilicon. Sodium, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic basic compounds; monoethanolamine, diethanolamine, triethanolamine, monomethylamine, Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diiso Aqueous solutions of organic basic compounds such as propanolamine, triisopropanolamine, ethyleneimine, ethyleneimine, tetramethylammonium hydroxide (TMAH), and choline.

To the above-mentioned alkaline developing solution, for example, isopropyl alcohol, benzyl alcohol, ethyl cellolysin, butyl cellolysin, phenyl cellolysin, propylene glycol, diacetone alcohol, and other water-soluble organic solvents or surfactants can be appropriately added. Furthermore, after alkaline development, washing with water is usually performed.

As the development processing method, any method such as a dip development method, a jet development method, a brush development method, and an ultrasonic development method can be adopted. The developing conditions are preferably room temperature (23 ° C) and 5 to 300 seconds.

The conditions for the development treatment are not particularly limited, and the development temperature is preferably usually 10 ° C or higher. It is usually in the range of 15 ° C. or higher, and further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, and further 40 ° C. or lower.

As the development method, any method such as a dip development method, a jet development method, a brush development method, and an ultrasonic development method can be adopted.

When a color filter manufactured in this way is used in a liquid crystal display device, a transparent electrode such as ITO is formed on an image in this state and used as a part of a color display or a liquid crystal display device. To improve the smoothness or durability of the surface, a top coat such as polyimide or polyimide may be provided on the image as required. In applications such as a planar alignment drive method (IPS mode), a transparent electrode may not be formed in a part. Moreover, in a vertical alignment type driving method (MVA mode), a barrier wall may be formed. In addition, a pillar structure (photosensitive spacer) may be formed by a photolithography method instead of the bead-dispersed spacer.

<Liquid crystal display device>

The liquid crystal display device of the present invention is the one using the color filter of the present invention. The type and structure of the liquid crystal display device of the present invention are not particularly limited, and the color filter of the present invention can be used for assembly according to a conventional method.

For example, the liquid crystal display device of the present invention can be formed by a method described in "Liquid Crystal Device Handbook" (published by Nikkan Kogyo Shimbun, published on September 29, 1989, by the 142nd Committee of the Japan Society for the Promotion of Science).

<Organic EL Display Device>

When manufacturing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a blue filter of a pixel 20 is formed on a transparent support substrate 10 by using the colored resin composition of the present invention. On the device, the organic light-emitting body 500 is laminated via the organic protective layer 30 and the inorganic oxide film 40 to produce a multi-color organic EL element.

As a method for stacking the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, and an electric current are sequentially formed on the upper surface of the color filter. The method of the sub-injection layer 54 and the cathode 55; or the method of bonding the organic light emitting body 500 formed on another substrate to the inorganic oxide film 40, and the like. The organic EL element 100 manufactured in this way can be applied to an organic EL display device of a passive driving method, and can also be applied to an organic EL display device of an active driving method.

Examples

Next, the present invention will be described more specifically by citing synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples as long as they do not exceed the gist thereof.

{Embodiment of the first aspect}

<Synthesis of Dyes>

(Synthesis Example 1-1: Synthesis of Dye 1-A)

Under a nitrogen environment, 1-iodonaphthalene (5.1g, 20mmol), 2-methylcyclohexylamine (4.7g, 41mmol), sodium tert-butoxide (2.4g, 25mmol), and tris (dibenzylideneacetone) ) (Chloroform) dipalladium (0) (52mg, 0.050mmol), 2,2 '-(diphenylphosphino) -1,1'-binaphthalene (96mg, 0.15mmol), toluene (50mL) in a mixture Stir at 100 ° C for 2.5 hours. After cooling to room temperature, filtration and separation were performed, and the filtrate was washed with a saturated ammonium chloride aqueous solution and a saturated sodium chloride aqueous solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification was performed by silica gel column chromatography (hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) to obtain compound 1-1 (3.6 g, yield 75%).

[Chemical 35]

Phosphorus chloride (1.28 g, 8.35 mmol) was added to a mixture of compound 1-2 (1.51 g, 3.34 mmol), compound 1-1 (0.84 g, 3.34 mmol) and toluene (30 mL) under a nitrogen atmosphere, and heated To 95 ° C. After heating and stirring for 12 hours, it was left to cool to room temperature, and water (10 mL) was added and stirred for 1 hour. After the toluene layer was removed by decantation, chloroform (50 mL) was added and extraction was performed, 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 ~ 95/5 (volume ratio)) to obtain compound 1-3 (2.00 g as a blue solid). , 74% yield).

Under a nitrogen atmosphere, compound 1-3 (2.16 g, 3.06 mmol) was dissolved in methanol (50 mL) at room temperature, and lithium bis (trifluoromethanesulfonyl) 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 left to cool to room temperature. The solvent was concentrated by an evaporator, and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 100/0 to 91/9 (volume ratio)) to obtain dye 1 as a blue solid. -A (2.00 g, yield 69%).

Dye 1-A was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 639 nm, and the gram absorption coefficient (g) was 87.9 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 670 (M ⁺ C ₄₈ H ₅₂ N ₃ )

(Synthesis example 1-2: Synthesis of dye 1-B)

In a nitrogen environment, N, N-dimethylformamide (DMF) (60 mL) was added to N-ethyl-o-toluidine (21.6 g, 160 mmol), and the mixture was cooled to 5 ° C or lower. While maintaining the temperature below 5 ° C., potassium tert-butoxide (18.0 g, 160 mmol) was added in several portions. Next, keep the N, N-dimethylformamide (DMF) solution (35mL) of 4,4-difluorobenzophenone (8.73g, 40.0mmol) in a temperature of 15 ° C or below while maintaining it for 30 minutes. Dropwise. After completion of the dropwise addition, 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, it was left to cool to room temperature, and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed three times with water (20 mL), and then the solvent was distilled off by an evaporator. The obtained solid was purified by silica gel column chromatography (hexane / ethyl acetate = 100/0 ~ 66/34 (volume ratio)) to obtain compound 1-4 (3.08 g, yield 17%). ).

[Chemical 38]

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

Under a nitrogen environment, a mixed solution of compound 1-5 (0.59 g, 0.84 mmol), methanol (5 mL), and lithium bis (trifluoromethanesulfonium) imide (0.24 g, 0.84 mmol) at an external temperature of 50 ° C Heat and stir for 1.5 hours. It was left to cool to room temperature, and the solvent was distilled off by an evaporator, and then washed with a methanol / water = 2/1 (volume ratio) mixed solution (30 mL). Get the solid The body was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 94/6 to 87/13 (volume ratio)) to obtain dye 1-B (0.50 as a blue solid). g, yield 62%).

Dye 1-B was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 575 nm, and the gram absorption coefficient (g) was 81.8 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 670 (M ⁺ C ₄₈ H ₅₂ N ₃ )

(Synthesis example 1-3: Synthesis of dye 1-C)

Under a nitrogen environment, a mixed solution of N-ethyl m-toluidine (7.65 g, 49.9 mmol) of N, N-dimethylformamide, N, N-dimethylformamide (DMF) (24 mL) After cooling to 5 ° C or lower, potassium tert-butoxide (6.73 g, 60 mmol) was maintained at 5 ° C or lower, and added in portions. A DMF solution (13 mL) of 4,4'-difluorobenzophenone (3.27 g, 15.0 mmol) was added dropwise over 30 minutes while maintaining the temperature at 15 ° C or lower. After completion of the dropwise addition, 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 three times with water (20 mL), and then the solvent was distilled off by an evaporator. The obtained solid was purified by silica gel column chromatography (hexane / ethyl acetate = 92/8 ~ 71/29 (volume ratio)) to obtain compound 1-6 (0.39 g, yield 6%). ).

Phosphorus chloride was added dropwise to a mixture of compound 1-6 (1.35 g, 3.00 mmol), compound 1-1 (0.72 g, 3.00 mmol) and toluene (22 mL) under a nitrogen atmosphere at room temperature over 5 minutes. (0.69 g, 4.50 mmol). After the dropwise addition, the mixture was heated to 80 to 85 ° C, and the mixture was heated and stirred for 8 hours in this state. Phosphorus chloride (0.46 g, 3.00 mmol) was further added dropwise, and after heating and stirring for 4 hours in this state, it was left to cool to room temperature. Water (30 mL) was added, and after stirring at room temperature, chloroform (30 mL) was added, and the mixture was stirred and left 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 to 81/19 (volume ratio)) to obtain Compound 1 as a blue solid. -7 (1.19 g, 56% yield).

Under a nitrogen environment, a mixed solution of compound 1-7 (1.12 g, 1.58 mmol), methanol (10 mL) and lithium bis (trifluoromethanesulfonium) imine (1.12 g, 1.58 mmol) was used at an external temperature of 50 ° C. Heat and stir for 1.5 hours. It was left to cool to room temperature, and the solvent was distilled off by 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 gel chromatography (developing solvent: chloroform / methanol = 94/6 to 87/13 (volume ratio)) to obtain dye 1 as a blue solid. -C (0.50 g, 62% yield).

Dye 1-C was dissolved at 10 mass ppm in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 638 nm, and the gram absorption coefficient (g) was 80.1 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 670 (M ⁺ C ₄₈ H ₅₂ N ₃ )

(Synthesis Example 1-4: Synthesis of Dye 1-D)

Under nitrogen, add N-ethylaniline (10.02g, 82.5mmol), difluorobenzophenone (4.50g, 20mmol), potassium tert-butoxide (9.26g, 82.5mmol) and DMF (40mL). The mixture was heated to 50 ° C, and heated in this state 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 three times with water (20 mL), and then the solvent was distilled off by an evaporator. The obtained oil was purified by silica gel column chromatography (hexane / ethyl acetate = 86/14 ~ 65/35 (volume ratio)) to obtain compound 1-8 (2.34 g, yield 28%).

[Chemical 44]

Phosphorus chloride (2.13 g, 13.9 mmol) was added to a mixture of compound 1-8 (2.34 g, 5.56 mmol), compound 1-1 (1.33 g, 5.56 mmol) and toluene (30 mL) under a nitrogen atmosphere. It heated to 100 degreeC, and stirred for 12.5 hours in this state. After leaving to cool to room temperature, water (10 mL) was added and stirred for 1 hour. After the toluene layer was removed by decantation, chloroform (50 mL) was added and extraction was performed, and the organic layer was washed three times with saturated brine (20 mL). After removing the solvent by distillation with an evaporator, the obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 100/0 ~ 95/5 (volume ratio)). Compounds 1-9 (3.00 g, yield 81%) were obtained as a blue solid.

Compound 1-9 (1.90 g, 2.80 mmol) was dissolved in methanol (50 mL) under a nitrogen atmosphere at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. The solvent was distilled off by an evaporator, and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 100/0 ~ 95/5 (volume ratio)) to obtain dye 1 as a blue solid. -D (3.00g, Yield: 81%).

Dye 1-D was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 638 nm, and the gram absorption coefficient (g) was 75.6 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 642 (M ⁺ C ₄₆ H ₄₈ N ₃ )

(Synthesis example 1-5: Synthesis of dye 1-E)

Under a nitrogen environment, compound 1-2 (synthesized by the method described in International Publication No. 2011/162217) (2.01 g, 4.45 mmol), compound 1-10 (1.12 g, 4.45 mmol), and toluene (30 mL) Phosphonium chloride (1.70 g, 11.1 mmol) was added to the mixture), and the mixture was heated to 100 ° C and stirred in this state for 9 hours. After leaving to cool to room temperature, water (10 mL) was added and stirred for 1 hour. After the toluene layer was removed by decantation, chloroform (50 mL) was added and extraction was performed, and the organic layer was washed three times with saturated brine (20 mL). After the solvent was removed by distillation using an evaporator, the obtained solid was dissolved in chloroform (10 mL) and subjected to silica gel chromatography (developing solvent: hexane / ethyl acetate = 70/30, chloroform / methanol = 100/0 ~ 95/5 (volume ratio)) was purified to obtain compound 1-11 (2.13 g, yield 66%) as a blue solid.

[Chemical 47]

Under a nitrogen atmosphere, compound 1-11 (2.13 g, 2.96 mmol) was dissolved in methanol (50 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. The solvent was distilled off by an evaporator, and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 99/1 to 92/8 (volume ratio)) to obtain dye 1 as a blue solid. -E (2.00 g, yield 70%).

Dye 1-E was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 600 nm, and the gram absorption coefficient (g) was 81.2 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 684 (M ⁺ C ₄₅ H ₄₅ F ₃ N ₃ )

(Synthesis example 1-6: Synthesis of dye 1-F)

Under a nitrogen environment, p-methoxyaniline (12.3g, 0.10mol), bromopropane (12.29 g, 0.10 mol), a mixture of 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. After leaving to cool to room temperature, it was poured into water (100 mL), and extracted twice with toluene (50 mL). The organic layer was washed three times with water (20 mL), and then the solvent was distilled off with an evaporator. The concentrate was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 100/0 to 82/18 (volume ratio)) to obtain compound 1-12 (8.58 g as a pale yellow oil). , 52% yield).

Under a nitrogen atmosphere, compound 1-12 (8.50 g, 51.4 mmol), dichlorobenzophenone (2.80 g, 12.8 mmol), palladium acetate (277 mg, 1.28 mmol), and third butyl phosphine (517 mg, 2.56 mmol), sodium tert-butoxide (4.33 g, 51.4 mmol), and toluene (50 mL) were heated to 90 ° C. and heated with stirring for 5 hours. After leaving to cool to room temperature, water (10 mL) was added to stop the reaction, and insoluble matter was removed by filtration through celite. After performing toluene extraction, the solvent was removed by distillation using an evaporator. The concentrate was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 82/18 ~ 61/39 (volume ratio)) to obtain compound 1-13 (1.79 g, product Rate of 27%).

Phosphorus chloride (1.35 g, 8.80 mmol) was added to a mixture of compound 1-13 (1.79 g, 3.52 mmol), compound 1-1 (0.84 g, 3.52 mmol) and toluene (30 mL) under a nitrogen atmosphere. It heated to 100 degreeC, and stirred in this state for 11.5 hours. After leaving to cool to room temperature, water (5 mL) was added and stirred for 1 hour. After the toluene layer was removed by decantation, chloroform (50 mL) was added and extraction was performed, and the organic layer was washed three times with water (20 mL). After the solvent was removed by distillation using an evaporator, the obtained solid was dissolved in chloroform (10 mL) and subjected to silica gel chromatography (developing solvent: hexane / ethyl acetate = 70/30, chloroform / methanol = 100/0 ~ 85/15 (volume ratio)), and the compound 1-14 (2.00 g, yield 74%) was obtained as a blue solid.

In a nitrogen atmosphere, compound 1-14 (2.00 g, 2.61 mmol) was dissolved in methanol (50 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. The solvent was concentrated by an evaporator, and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 100/0 to 85/15 (volume ratio)) to obtain dye 1 as a blue solid. -F (1.70 g, 64% yield).

The dye 1-F was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 639 nm, and the gram absorption coefficient (g) was 88.8 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 730 (M ⁺ C ₅₀ H ₅₆ N ₃ O ₂ )

(Synthesis example 1-7: Synthesis of dye 1-G)

Compound 1-9 (1.03 g, 1.5 mmol) was dissolved in methanol (50 mL) under a nitrogen atmosphere at room temperature, and compound 1-15 (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 by an evaporator, and then washed three times with water (20 mL). The obtained solid was dissolved in chloroform (5 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 100/0 to 93/7 (volume ratio) to obtain dye 1 as a blue solid. -G (1.15 g, 74% yield).

The dye 1-G was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 639.5 nm, and the gram absorption coefficient (g) was 70.9 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 642 (M ⁺ C ₄₆ H ₄₈ N ₃ )

(Synthesis example 1-8: Synthesis of dye 1-H)

Under a nitrogen environment, add N-ethyl-1-naphthylamine (12.9g, 75.2mmol) and DMF (34mL) and cool in an ice bath. Add a third butanol at an internal temperature of 5 ° C or lower while stirring. Potassium (9.1 g, 81.0 mmol). Thereafter, difluorobenzophenone (4.5 g, 20.8 mmol) and DMF (20 mL) were added, and the mixture was heated and stirred at 50 ° C for 6.5 hours. After leaving to cool to room temperature, toluene (10 mL) and water were added to stop the reaction. After extraction with toluene, the organic layer was washed with water (50 mL) twice. After the solvent was distilled off by an evaporator, crystallization was performed using methanol in an ice bath, and after methanol suspension washing, ethyl acetate suspension washing was performed for purification, thereby obtaining compounds 1-16 (2.1 g, yield, pale yellow solid). 20%).

Under a nitrogen atmosphere, phosphoric acid chloride (0.824 g, 5.37 mmol) was added to a mixture of compound 1-16 (1.12 g, 2.15 mmol), compound 1-1 (0.51 g, 2.15 mmol) and toluene (30 mL), and then heated. The temperature was increased to 100 ° C, and the mixture was stirred for 12 hours. After leaving to cool to room temperature, water (20 mL) was added and stirred for 1 hour. Add chloroform (50 mL) and perform extraction The organic layer was washed three times with water (20 mL). After the solvent was removed by distillation using an evaporator, the obtained solid was dissolved in chloroform (5 mL) and subjected to silica gel chromatography (developing solvent: hexane / ethyl acetate = 70/30, chloroform / methanol = 100/0 ~ 80/20 (volume ratio)) was purified to obtain compound 1-17 (1.92 g) as a blue solid.

Under a nitrogen atmosphere, compound 1-17 (1.92 g, 2.15 mmol) was dissolved in methanol (50 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. The solvent was concentrated and removed by an evaporator, and then washed with water (100 mL). The obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 96/4 ~ 80/20 (volume ratio)) to obtain dye 1 as a blue solid. -H (1.87 g, yield 85%).

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

(Synthesis example 1-9: Synthesis of dye 1-I)

[Chemical 56]

Under nitrogen, aniline (9.4g, 0.1mol), 2-bromoethylethyl ether (15.5g, 0.1mol), potassium carbonate (15.6g, 0.11mol) and N-methyl-2-pyrrolidine A mixture of ketone (NMP) (80 mL) was heated to 80 ° C and stirred for 4 hours, and then stirred at room temperature for 9 hours. Then, water (100 mL) was poured, and extraction was performed with toluene (100 mL). The organic layer was washed twice with saturated saline (100 mL), and then the solvent was distilled off by an evaporator. The concentrate was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 95/5 to 74/26 (volume ratio)) to obtain compound 1-18 (7.08 g as a pale yellow oil). , Yield 43%).

Under nitrogen, add compound 1-18 (7.0g, 42.3mmol) and DMF (16mL) and cool in an ice bath. While stirring, add potassium tert-butoxide (4.7g, 42.0) at an internal temperature of 5 ° C or lower. mmol). 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 leaving to cool to room temperature, toluene (10 mL) and water were added to stop the reaction, and toluene extraction was performed. After that, the organic layer was washed twice with water (30 mL). The solvent was distilled off by an evaporator, and then crystallized in an ice bath. After methanol was suspended and washed, it was dissolved in toluene and purified by crystallization in methanol to obtain a pale yellow solid Compound 1-19 (2.3g , 46% yield).

Phosphonium chloride (1.01 g, 6.6 mmol) was added to a mixture of compound 1-19 (1.31 g, 2.6 mmol), compound 1-1 (0.64 g, 2.7 mmol) and toluene (20 mL) under a nitrogen atmosphere. It heated to 100 degreeC, and stirred in this state for 28.5 hours. After leaving to cool to room temperature, water (5 mL) was added and stirred for 1 hour. Chloroform (50 mL) was added and extraction was performed, and the organic layer was washed with saturated brine (50 mL). After the solvent was removed by distillation using an evaporator, the obtained solid was dissolved in chloroform (10 mL) and subjected to silica gel chromatography (developing solvent: (first time) only ethyl acetate, (second time) chloroform / methanol = 100/0 ~ 90/10 (volume ratio)), and the compound 1-20 (1.60 g, yield 81%) was obtained as a blue solid.

[Chemical 59]

In a nitrogen atmosphere, compound 1-20 (1.60 g, 2.1 mmol) was dissolved in methanol (20 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. Water (20 mL) was added and stirred, and then filtered. The obtained solid was dissolved in ethyl acetate and washed with water. The solvent was distilled off, and then dissolved in chloroform (10 mL). : Chloroform / methanol = 100/0 ~ 86/14 (volume ratio)), and the dye 1-I (0.54 g, yield 26%) was obtained as a blue solid.

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

(Synthesis example 1-10: Synthesis of dye 1-J)

Under a nitrogen environment, 1-naphthylamine (0.5 g, 3.5 mmol) and 3-pentanone (0.3 g, 3.5 mmol) were dissolved in acetic acid (4 mL) and chloroform (4 mL) at room temperature, and gradually added in small amounts. Sodium triacetoxyborohydride (0.74 g, 3.5 mmol) was stirred at room temperature for 12 hours in this state. 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 separated by filtration, and the solvent was distilled off to obtain Compound 1-21 as an oil.

Under a nitrogen environment, phosphorophosphonium chloride (1.57 g, 10.3 mmol) was added to a mixture of compound 1-4 (1.54 g, 3.43 mmol), compound 1-21 and toluene (23 mL), and then heated to 100 ° C. Stir for 2 hours. After the reaction liquid 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 and extraction was performed, and the organic layer was washed 3 times with saturated brine (20 mL). After removing the solvent by distillation, 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)), and Compound 1-22 (1.85 g, 79%) was obtained as a blue solid.

Under a nitrogen atmosphere, compound 1-22 (1.85 g, 2.72 mmol) was dissolved in methanol (27 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. After the solvent was concentrated by an evaporator, the solvent was 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 to 86/14 (volume ratio)) to obtain dye 1 as a blue solid. -J (1.98 g, 79% yield).

The dye 1-J was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 575 nm, and the gram absorption coefficient (g) was 79.2 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 644 (M ⁺ C ₄₆ H ₅₀ N ₃ )

(Synthesis example 1-11: Synthesis of dye 1-K)

Under a nitrogen environment, 1-naphthylamine (0.5 g, 3.5 mmol) and 2-heptanone (0.4 g, 3.5 mmol) were dissolved in acetic acid (4 mL) and chloroform (4 mL) at room temperature, and gradually added in small amounts. Sodium triacetoxyborohydride (0.74 g, 3.5 mmol) was stirred at room temperature for 12 hours in this state. 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 separated by filtration, and the solvent was distilled off to obtain oily compounds 1-23.

Under a nitrogen environment, phosphorochlorine (1.57 g, 10.3 mmol) was added to a mixture of compound 1-4 (1.54 g, 3.43 mmol), compound 1-23 and toluene (23 mL), and then heated to 100 ° C. Stir for 3.5 hours. After the reaction liquid was cooled to room temperature, water (10 mL) was added and stirred for 1 hour. After the toluene layer was removed by decantation, chloroform (30 mL) was added to perform extraction, and the organic layer was washed three times with saturated saline (20 mL). After removing the solvent by distillation, the obtained solid was dissolved in chloroform (10 mL) and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 ~ 90/10 (volume ratio)), and Compounds 1-24 (1.88 g, 76%) were obtained as a blue solid.

Under a nitrogen atmosphere, compound 1-24 (1.88 g, 2.60 mmol) was dissolved in methanol (26 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to a room. temperature. After the solvent was concentrated by an evaporator, the solvent was 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 to 85/15 (volume ratio)) to obtain dye 1 as a blue solid. -K (2.07 g, 84% yield).

The dye 1-K was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 576 nm, and the gram absorption coefficient (g) was 79.9 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 672 (M ⁺ C ₄₈ H ₅₄ N ₃ )

(Synthesis example 1-12: Synthesis of dye 1-L)

Compound 1-25 was synthesized by the method described in Japanese Patent Laid-Open No. 2013-087248.

Compound 1-9 (0.20 g, 0.30 mmol) was dissolved in methanol (3 mL) under a nitrogen atmosphere at room temperature, and compound 1-25 (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 left 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 to 82/18 (volume ratio)) to obtain dye 1 as a blue solid. -L (0.30 g, 87% yield).

The dye 1-L was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 640 nm, and the gram absorption coefficient (g) was 58.0 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 642 (M ⁺ C ₄₆ H ₄₈ N ₃ )

(Synthesis example 1-13: Synthesis of dye 1-M)

In a nitrogen atmosphere, compound 1-5 (0.53 g, 0.8 mmol) was dissolved in methanol (20 ml) at room temperature, and compound 1-25 (0.75 g, 1.3 mmol) was added. This mixed solution was stirred at an external temperature of 70 ° C. for 5.5 hours, and then left to cool to room temperature. After adding water (100 mL) and stirring, filtration was performed. The obtained solid was washed with water, dissolved in chloroform (10 mL), and subjected to silica gel chromatography (developing solvent: chloroform / methanol = 100/0 ~ 93 / 7 (volume ratio)) was purified to obtain dye 1-M (0.55 g, yield 60%) as a blue solid.

The dye 1-M was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 635 nm, and the gram absorption coefficient (g) was 57.0 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 670 (M ⁺ C ₄₈ H ₅₂ N ₃ )

(Synthesis example 1-14: Synthesis of dye 1-N)

The solution of compound 1-26 was synthesized by the method described in Japanese Patent Laid-Open No. 2013-087248.

Water (17 mL) was added to the solution of compound 1-26 (2.72 mmol), and a solution prepared by suspending cyanuric chloride (0.5 g, 2.72 mmol) in acetone (2 mL) was added at a pH of 4 to 6 Add while maintaining at 0 to 5 ° C, and stir for 1.5 hours. Then, a liquid obtained by dissolving a mixture of aniline (0.25 g, 2.72 mmol) and hydrochloric acid (0.28 mL) in water (1 ml) was added at room temperature at pH = 6 to 7, and stirred for 0.5 hours. Thereafter, a liquid 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 pH was set to 8 to 9 at an external temperature of 70 ° C. and stirred for 8 hours . The obtained reaction solution was cooled to room temperature, and then filtered to obtain compound 1-27 (1.22 g, yield 76%).

Compound 1-9 (0.20 g, 0.30 mmol) was dissolved in methanol (3 mL) under a nitrogen atmosphere at room temperature, and compound 1-27 (0.19 g, 0.33 mmol) was added. The mixed solution After stirring at an external temperature of 50 ° C for 1.5 hours, it was left 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 to 94/6 (volume ratio)) to obtain dye 1 as a blue solid. -N (0.18 g, 51% yield).

The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 642 (M ⁺ C ₄₆ H ₄₈ N ₃ )

(Synthesis Example 1-15: Synthesis of Dye 1-O)

Water (17 mL) was added to the solution of compound 1-26 (2.72 mmol), and a solution prepared by suspending cyanuric chloride (0.5 g, 2.72 mmol) in acetone (2 mL) was added at a pH of 4 to 6 Add while maintaining at 0 to 5 ° C, and stir for 1.5 hours. Then, a liquid obtained by dissolving a mixture of 2-ethylhexylamine (0.35 g, 2.72 mmol) and hydrochloric acid (0.28 mL) in water (1 mL) was added at room temperature at pH = 6 to 7, and further Stir for 0.5 hours. Then, a liquid obtained 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 set to 8 at an external temperature of 70 ° C. 9 and stir for 10 hours. The obtained reaction solution was cooled to room temperature, and then subjected to salting out with sodium chloride, thereby obtaining Compound 1-28 (1.78 g, yield 99%).

[Chemical 71]

In a nitrogen atmosphere, compound 1-9 (0.20 g, 0.30 mmol) was dissolved in methanol (3 mL) at room temperature, and compound 1-28 (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 left 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 gel chromatography (developing solvent: chloroform / methanol = 100/0 to 94/6 (volume ratio)) to obtain dye 1 as a blue solid. -O (0.19 g, yield 49%).

The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 642 (M ⁺ C ₄₆ H ₄₈ N ₃ )

(Synthesis Example 1-16: Synthesis of Comparative Dye 1-1)

Compound 1-29 (2.00 g, 3.40 mmol, synthesized by the method described in International Publication No. 2011/158794) was dissolved in methanol (20 mL) under a nitrogen atmosphere at room temperature, and bis (trifluoro) was added. Lithium mesylate) (0.99 g, 3.40 mmol). This mixed solution After the solution was stirred at an external temperature of 50 ° C for 1.5 hours, it was left to cool to room temperature. After the solvent was concentrated by an evaporator, the solvent was 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 gel chromatography (developing solvent: chloroform / methanol = 10/1 to 5/1 (volume ratio)) to obtain a comparative dye as a blue solid. 1-1 (1.80 g, 63% yield).

Comparative dye 1-1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 628 nm, and the gram absorption coefficient (g) was 111 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 546 (M ⁺ C ₃₈ H ₄₈ N ₃ )

(Synthesis Example 1-17: Synthesis of Comparative Dye 1-2)

The following comparative dyes 1-2 were synthesized by the method described in International Publication No. 2011/162217.

(Synthesis Example 1-18: Synthesis of Comparative Dye 1-3)

Under a nitrogen atmosphere, p-iodotoluene (5.00 g, 33.9 mmol) and N-butyl-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 added to a nitrogen-substituted container, and tri-third butyl was added dropwise thereto. A solution in which phosphine (0.370 g, 1.83 mmol) was dissolved in toluene (2 mL) was heated to 40 ° C. When the red color disappears and becomes transparent, it is added to the toluene solution prepared previously. Furthermore, after adding sodium tert-butoxide (4.84 g, 50.4 mmol), it heated up to toluene reflux and reacted for 2 hours. After leaving to cool to room temperature, it was poured into water (100 mL), and extracted twice with toluene (50 mL). After drying with anhydrous magnesium sulfate, filtration was performed, and the filtrate was concentrated with an evaporator. The concentrate was purified by silica gel chromatography (developing solvent: hexane / toluene = 10/1 (volume ratio)) to obtain an oily compound 1-30 (5.0 g, yield 97%).

Under a nitrogen environment, the mixture of anhydrous aluminum chloride (3.55g, 26.6mmol) and 1,2-dichloroethane (5mL) was cooled in an ice bath to below 0 ° C, and 4-bromobenzidine was added dropwise over 20 minutes. Chlorine (4.85 g, 22.1 mmol). Next, compound 1- was added dropwise between -2 and 2 ° C over 25 minutes. 30 (4.82 g, 22.1 mmol), and stirred in this state for 1 hour. Next, stirring was continued for 2.5 hours while warming to room temperature. After completion of the reaction, the reaction solution was poured into ice water (200 mL). Chloroform (50 mL) was added and extraction was performed. After washing 3 times with a 1 N aqueous sodium hydroxide solution (10 mL), the mixture was dried with anhydrous sodium sulfate. After filtering, the filtrate was concentrated by an evaporator, and the concentrate was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 15/1 to 10/1 (volume ratio)) to obtain an oily substance. Compound 1-31 (5.3 g, yield 59%).

Under a nitrogen atmosphere, compound 1-31 (5.3 g, 13.0 mmol) was dissolved in toluene (55 mL), and N-ethyltoluidine (4.99 g, 37.9 mmol) and sodium tert-butoxide (2.49 g) were added thereto. , 26.0 mmol), palladium acetate (0.175 g, 0.778 mmol), tri-t-butylphosphine (0.315 g, 1.56 mmol), heated to 100 ° C. and reacted for 3 hours. After leaving to cool to room temperature, water (10 mL) was added and the mixture was filtered through celite. Toluene was added to the filtrate and extraction was performed, followed by drying with anhydrous sodium sulfate. After filtering, the filtrate was concentrated by an evaporator, and the concentrate was purified by silica gel chromatography (developing solvent: hexane / ethyl acetate = 10/1 (volume ratio)) to obtain an oily compound 1 -32 (4.5 g, 66% yield).

[Chemical 77]

Phosphonium chloride (2.93 g, 19.4 mmol) was added to a mixture of compound 1-32 (4.5 g, 9.72 mmol), compound 1-10 (2.46 g, 9.72 mmol) and toluene (50 mL) under a nitrogen atmosphere. The mixture was heated under reflux and stirred for 5 hours in this state. After leaving to cool to room temperature, water (10 mL) was added and stirred for 1 hour. Chloroform (50 mL) was added and extraction was performed, and the organic layer was washed twice with saturated brine (10 mL). After the solvent was removed by distillation using an evaporator, the obtained solid was dissolved in chloroform (10 mL) and purified by silica gel chromatography (developing solvent: chloroform / methanol = 100 / 0-20 / 1 (volume ratio)). Compound 1-33 (1.32 g, yield 19%) was obtained as a tar.

Under a nitrogen atmosphere, Compound 1-33 (1.30 g, 1.77 mmol) was dissolved in methanol (33 mL) at room temperature, and lithium bis (trifluoromethylsulfonium) 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 left to cool to room temperature. After the solvent was concentrated by an evaporator, the solvent was washed with methanol / water = 1/3 to 1/2 (volume ratio) and filtered. Vacuum drying at 40 ° C to obtain a comparative dye of blue-violet solid 1-3 (1.40 g, 81% yield).

Comparative dyes 1-3 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 637 nm, and the gram absorption coefficient (g) was 77.2 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 698 (M ⁺ C ₄₆ H ₄₇ F ₃ N ₃ )

(Synthesis Example 1-19: Synthesis of Comparative Dye 1-4)

In a nitrogen atmosphere, compound 1-9 (0.65 g, 0.96 mmol) was dissolved in methanol (20 mL) at room temperature, 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 left 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 1-4 (0.38 g, yield 59%, LC purity 93%) as a blue solid.

Comparative dyes 1-4 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 638.5 nm, and the gram absorption coefficient (g) was 89.9 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 642 (M ⁺ C ₄₆ H ₄₈ N ₃ )

(Synthesis example 1-20: Synthesis of resin 1-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. To this, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto over 3 hours, and 2,2 ' -8.47 parts by mass of a mixed solution of azobis (2-methylbutyronitrile), and further stirred at 90 ° C for 2 hours. Next, the inside of the reaction vessel was replaced with air, 1.1 parts by mass of tris (dimethylamino) methylphenol 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 the mixture was reacted at 100 ° C for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw of the resin solution obtained in this manner was about 9,000, and the acid value was 25 mg-KOH / g. To this resin solution, propylene glycol monomethyl ether acetate was added so that the solid content became 40% by mass, and was used as resin 1-A.

(Synthesis Example 1-21: Synthesis of Resin 1-B)

400 parts by mass of "NC3000H" (epoxy equivalent 288, softening point 69 ° C) (manufactured by Nippon Kayaku Co., Ltd.), 102 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, 264 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was charged into a reaction vessel, and stirred at 95 ° C. until the acid value became 3 mg-KOH / g or less. It takes 9 hours to reach the target acid value (acid value 2.2 mg-KOH / g). Then, 151 parts by mass of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain an acid value of 102 mg-KOH / g and a weight average molecular weight in terms of polystyrene measured by GPC ( Mw) is a resin solution of 3900. To this resin solution, propylene glycol monomethyl ether acetate was added so that solid content became 44 mass%, and it was used as resin 1-B.

(Synthesis Example 1-22: Synthesis of Resin 1-G)

Based on the method described in Example 1 of Japanese Patent Laid-Open No. 2008-248142 Synthetic resin. Propylene glycol monomethyl ether acetate was added so that the solid content of the resin became 38.2% by mass, and was used as resin 1-G.

(Synthesis example 1-23: Synthesis of initiator)

3- (2-Ethyloxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl was synthesized by the method described in International Publication No. 2009/131189. -6- (o-toluenyl) -9H-carbazole.

[Preparation of colored resin composition 1]

The dyes 1-A to 1-O obtained in the above Synthesis Examples 1-1 to 1-15, the comparative dyes 1-1 to 1-4 obtained in the Synthesis Examples 1-16 to 1-19, and the Synthesis Example 1- The resins 1-A and 1-B obtained in 20 and 1-21 were mixed with other components so as to have a composition described in Tables 3 and 4 below to prepare a colored resin composition.

In addition, the numerical values in the upper stages of Tables 3 and 4 indicate the content ratio (mass%) of each component added to the colored resin composition, and the numerical values in () in the lower stage indicate the contents of each component in all solid components. Ratio (% by mass).

When mixing, stir each component for more than 1 hour until it is fully mixed, and finally filter the pawn-type filter with a 5 μm to remove foreign matter.

The coloring resin composition of Examples 1-1 to 1-15 uses dyes 1-A to 1-O, and the coloring resin composition of Comparative Examples 1-1 to 1-4 uses comparative dyes 1-1 to 1-4. .

The compounds in Tables 3 and 4 are as follows.

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

F559: oligomer containing perfluoroalkyl group

Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

JPP-100: Tetraphenyldipropylene glycol diphosphite

[Preparation of colored resin composition 2]

<Preparation of Pigment Dispersion>

(Preparation of blue pigment dispersion (1))

15: 6 11.36 parts by mass of CI Pigment Blue as a blue pigment, 57.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and "Disperbyk 2000" (manufactured by BYK-Chemie) as a dispersant were used as solid components 215.7 parts by mass of zirconia beads having a conversion of 3.02 parts by mass and a diameter of 0.5 mm were filled into a stainless steel container, and dispersed with a paint shaker for 6 hours to prepare a blue pigment dispersion liquid (1).

(Preparation of blue pigment dispersion (2))

11.36 parts by mass of CI Pigment Blue 15: 6 and Violet 23 as a blue pigment at a mass ratio of 9.20: 3.81, 57.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and "Disperbyk 2000" as a dispersant (Manufactured by BYK-Chemie) A stainless steel container was filled with 215.7 parts by mass of 3.02 parts by mass of zirconia beads having a diameter of 0.5 mm in terms of solid content, and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion (2).

<Preparation of colored resin composition>

They were mixed at the ratios shown in Table 5 below to prepare a colored resin composition.

When mixing, stir each component for more than 1 hour until it is fully mixed, and finally filter the pawn-type filter with a 5 μm to remove foreign matter.

In addition, the numerical values in the upper stage in Table 5 indicate that each component added in the colored resin group The content ratio (mass%) in the compound, and the numerical values in () in the lower paragraph indicate the content ratio (mass%) of each component in all solid components. The (E) photopolymerization starting component, other components, and (B) solvent system in Table 5 are the same as those in Tables 3 and 4.

[Manufacture of colored resin film and evaluation of heat resistance]

The above-mentioned [Preparation of colored resin composition 1] and [Preparation of colored resin composition 2] were applied on a glass substrate cut to a size of 5 cm square by a spin coating method so that the y value after firing became 0.120 as described below. Each of the colored resin compositions prepared in the above was dried under reduced pressure, and then pre-baked at 80 ° C. for 3 minutes using a hot plate. After that, the entire surface was exposed at an exposure amount of 60 mJ / cm ² , and then baked in a dust-free oven at 230 ° C. for 30 minutes. Regarding the spectral transmittance of the obtained film, the light transmittance was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and brightness of the XYZ color system were calculated.

At 230 ° C, after heating for 30 minutes, Examples 1-1 to 1-15 showed higher results than those of Comparative Example 1-3 using a dye having an o-methyl group and using a dye having an anion of PF _6- ^. The brightness of Examples 1-4 showed that the heat resistance was high.

[Manufacture of colored resin film and evaluation of light resistance]

Each colored resin composition prepared in the above-mentioned [Preparation of colored resin composition 1] was coated on a glass substrate cut to a size of 5 cm square by a spin coating method, dried under reduced pressure, and then heated on a hot plate at Pre-bake at 80 ° C for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ² , and then baked in a dust-free oven at 230 ° C. for 30 minutes. At this time, it adjusted so that the y value when it baked at 230 degreeC for 30 minutes in a dustless oven becomes 0.120. After that, the entire surface was exposed at an exposure amount of 60 mJ / cm ² and then baked at 230 ° C. for 30 minutes. Regarding the spectral transmittance of the obtained film, the light transmittance was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the brightness was calculated. A polarizing plate having a transmittance shown in FIG. 2 was placed on a Weather-Ometer Ci4000 (manufactured by Atlas), and simulated sunlight was irradiated for 20 hours. The color difference (ΔE * ab) before and after the irradiation was measured as light resistance, and the evaluation results are summarized in Table 7.

The color differences ΔE * ab of Examples 1-1 to 1-13 showed values smaller than those of Comparative Examples 1-1 and 1-2 in which R ⁵ and R ^{6 of} Formula (I-1) did not have an aromatic ring group. By using the colored resin composition of the present invention, even after long-term high-temperature baking performed in the manufacturing process of a color display, a color filter with small color difference, a liquid crystal display device using the same, and an organic EL display can be provided. Device.

According to Tables 6 and 7, it is known that the colored resin compositions of Examples 1-1 to 1-15 of the present invention satisfy both the light resistance required for the long-term reliability of a color display and the requirements for the manufacturing steps of a color display. Heat resistance at 230 ℃.

[Manufacture of colored resin film and measurement of contrast ratio]

Each colored resin composition prepared in the above-mentioned [Preparation 1 of colored resin composition] and [Preparation of colored resin composition 2] was applied on a glass substrate cut to a size of 5 cm square by a spin coating method, After drying under reduced pressure, it was pre-baked at 80 ° C for 3 minutes using a hot plate. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ² , and then fired at 230 ° C. for 60 minutes in a dust-free oven. The obtained substrates before and after heating were sandwiched between two polarizing plates, and light with a wavelength range of 380 to 780 nm was irradiated from the rear side and the polarizing plate on the front side was rotated, and measured with a luminance meter BM-5AS (manufactured by TOPCON) The maximum and minimum values of transmitted light intensity. Then, the maximum value is divided by the minimum value, and the obtained value is evaluated as a contrast ratio.

In Examples 1-1 to 1-4, the contrast was higher than 10,000 and higher, while in Comparative Examples 1-5, it was lower than 8000.

Accordingly, Examples 1-1 to 1-15 are colored resin compositions that show high brightness and contrast ratio and high light resistance and high heat resistance, and are therefore suitable for color filters and the use thereof. Liquid crystal display device, organic EL display device.

[Measurement of voltage holding ratio using 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 a voltage holding ratio.

‧ (A) Color material Dye 1-L 2.7 parts by mass

‧ (C) Binder Resin 1-G 18 parts by mass

‧ (D) Polymerizable monomer 6.9 parts by mass of dipentaerythritol hexaacrylate

‧ (E) Photopolymerization initiator 3- (2-Ethyloxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toluene Fluorenyl) -9H-carbazole 1.5 parts by mass

‧Other ingredients F559 (manufactured by DIC Corporation) 0.02 parts by mass

‧ (B) 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 a composition for forming a protective layer>

The following components were mixed to prepare a protective layer-forming composition.

‧Polymerizable monomer pentaerythritol hexaacrylate 7.1 parts by mass

‧Binder resin 7.1 parts by mass of ZAR1035 manufactured by Nippon Kayaku Co., Ltd.

‧Photopolymerization initiator 2- [4- (methylthio) benzylidene] -2- (4-morpholinyl) propane 0.75 parts by mass

‧Other ingredients F559 (manufactured by DIC) 0.04 parts by mass

‧Solvent PGMEA 85 parts by mass

<Measurement of voltage holding ratio>

The number of rotations was set so that the colored resin composition prepared in the above-mentioned "Preparation of the colored resin composition for measuring the voltage holding ratio" was used so that the thickness of the coating film was 2 to 3 µm (the film thickness after heat curing was about 2 µm) (300 rpm ~ 700 rpm) on a glass substrate (ITO glass MN entity MN-1392 for evaluation manufactured by EHC) coated on a glass substrate on which ITO (indium-tin oxide alloy) electrodes are vapor-deposited on a whole surface by a spin coater. After preheating the heating plate for 3 minutes, it was dried in a vacuum chamber for 1 minute.

Next, using a high-pressure mercury lamp, a mask was applied to the outer periphery of the electrode, and the coating film was exposed with an exposure amount of radiation of 32 mW and 60 mJ / cm ² including wavelengths of 303 nm, 313 nm, 334 nm, 365 nm, 405 nm, and 436 nm, and further Post-baking at 230 ° C. for 60 minutes to harden the coating film to obtain a blue pixel substrate.

The composition for forming a protective layer prepared in the above-mentioned "Preparation of the composition for forming a protective layer" is used to set the rotation so that the thickness of the coating film becomes 1.5 to 2.0 μm (the film thickness after heat curing is approximately 1.6 μm). (300-400 rpm) with a spin coater to coat the blue pixel substrate. After drying under reduced pressure, it is pre-baked on a hot plate at 100 ° C for 1 minute and 40 seconds.

Next, using a high-pressure mercury lamp, a mask was applied to the outer periphery of the electrode, and the coating film was exposed with an exposure amount of radiation of 32 mW and 60 mJ / cm ² including wavelengths of 303 nm, 313 nm, 334 nm, 365 nm, 405 nm, and 436 nm, and further Post-baking at 230 ° C for 30 minutes to harden the coating film to obtain a blue pixel substrate for liquid crystal evaluation.

The blue pixel substrate for liquid crystal evaluation and the electrode substrate (evaluation glass SZ-B11MIN (B) MN11396 manufactured by EHC) with a specific shape on which the ITO electrode was vapor-deposited were washed with water and 45 ° C warm water, and then the temperature was 105 ° C After drying in an oven, bonding with a sealant mixed with 5 μm glass beads (gap is 5 μm), annealing in an oven at 180 ° C. for 2 hours, and injecting liquid crystal MLC-7021-000 (Merck Company), and a liquid crystal cell having an electrode area of 1 cm ² was produced.

Then, the liquid crystal cell property evaluation system type 6254 (manufactured by Toyo Technology Co., Ltd.) was used to measure the voltage holding ratio of the liquid crystal cell at 25 ° C. The applied voltage at this time was a square wave of 5.0 V, and the measurement frequency was 60 Hz. Here, the so-called voltage holding ratio is generally known in two ways: the area ratio and the voltage ratio. However, in this specification, the area ratio value (the trace of the voltage between 0 ms and 16.7 ms and the voltage zero level is used). The ratio of the area to the area obtained by maintaining a voltage of 0 milliseconds for an observation time of 16.7 milliseconds).

As a result, the voltage holding ratio at 60 Hz showed a high value of 90%.

[Preparation of colored resin composition 3]

Each component was mixed at the ratio shown in Table 9 below to prepare a colored resin composition.

When mixing, stir the ingredients for more than 1 hour to fully mix, and finally use 5μm filter the pawn-type filter to remove foreign matter.

In addition, the numerical values in the upper stage in Table 9 indicate the content ratio (mass%) of each component added to the colored resin composition, and the numerical values in () in the lower stage indicate the content ratio of each component to all solid components. (quality%). The (E) photopolymerization starting component, other components, and (B) solvent in Table 9 are the same as those in Tables 3 and 4.

In addition, each compound in Table 9 is as follows.

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

F559: oligomer containing perfluoroalkyl group

Irganox 1010: Pentaerythritol tetra [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester]

JPP-100: Tetraphenyldipropylene glycol diphosphite

[Manufacture of colored resin film and evaluation of heat resistance]

The colored resin composition prepared in the above-mentioned [Preparation of colored resin composition 3] was applied on a glass substrate cut to a size of 5 cm square by a spin coating method so that the y value after firing became 0.120 as described below, After drying under reduced pressure, it was pre-baked at 80 ° C for 3 minutes using a hot plate. After that, the entire surface was exposed at an exposure amount of 60 mJ / cm ² , and then baked in a dust-free oven at 230 ° C. for 30 minutes. Regarding the spectral transmittance of the obtained film, the light transmittance was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and brightness of the XYZ color system were calculated. The measurement results of Examples 1-4 and 1-16 are also disclosed below.

In Example 1-16, although it was a dispersion system with a pigment, it showed the same brightness as that in the case of only the dye of Example 1-4, and it was found that high brightness can be maintained.

{Example of the second aspect}

<Synthesis of Dyes>

(Synthesis Example 2-1: Synthesis of Dye 2-A)

{Synthesis of Compound 2-1}

Under a nitrogen environment, N-ethylaniline (24.3 g, 200 mmol) was dissolved in N, N-dimethylformamide (80 mL), and cooled to 5 ° C or lower. To this was gradually added a small amount of potassium tert-butoxide (22.5 g, 200 mmol). Furthermore, a solution of 4,4'-difluorobenzophenone (10.9 g, 50 mmol) in N, N-dimethylformamide (40 mL) was added dropwise for 25 minutes while maintaining the temperature at 5 ° C or lower. After completion of the dropwise addition, the mixture was stirred at 50 ° C for 7 hours. After completion of the reaction, it was cooled to room temperature and mixed with water (100 mL). After extraction with toluene, the organic layer was washed with water and dried over anhydrous sodium sulfate. The desiccant was separated by filtration and the solvent was distilled off. The obtained solid was suspended and washed with n-hexane, and then toluene (30 mL) was added and heated to 60 ° C. to dissolve. The obtained solution was added dropwise to methanol (120 mL), and the precipitated solid was filtered and dried to obtain compound 2-1 (11.6 g, yield 55%).

{Synthesis of Compound 2-2}

Under a nitrogen atmosphere, compound 2-1 (0.90 g, 2.14 mmol) was dissolved in tetrahydrofuran (15 mL) at room temperature, and lithium borohydride (a 3 mol / L tetrahydrofuran solution, 0.3 mL) was added dropwise. After being stirred at room temperature in this state for 6.5 hours, it was heated to 50 ° C and stirred for 13 minutes. After cooling to room temperature, an aqueous sodium hydroxide solution (1 mol / L, 0.4 mL) was added to stop the reaction. After adding hydrochloric acid (1 mol / L) for neutralization, it was mixed with water (15 mL), and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The drying agent was separated by filtration, and the solvent was distilled off, thereby obtaining Compound 2-2 (0.82 g, yield 88%) as an oil.

{Synthesis of Compound 2-3}

Under a nitrogen atmosphere, 1,7-Cleve's acid (2.23 g, 10.0 mmol), 1,1,1-trifluoro-4-iodobutane (2.38 g, 10.0 mmol ), Potassium carbonate (2.76 g, 20 mmol) and N-methylpyrrolidone (22 mL) were mixed and stirred at 80 ° C. for 8.5 hours. Furthermore, 1,1,1-trifluoro-4-iodobutane (0.60 g, 2.0 mmol) was added, and it stirred for 1.75 hours. After the reaction solution was cooled to room temperature, it was mixed with water (150 mL), adjusted to pH 5.3 with concentrated hydrochloric acid, and then extracted with ethyl acetate (200 mL). After the organic layer was dried over anhydrous sodium sulfate, the desiccant was separated by filtration, and the solvent was distilled off. The obtained crystal was suspended and washed with diisopropyl ether, and was separated from the solvent by filtration under reduced pressure, and the obtained solid was vacuum-dried at 50 ° C to obtain compound 2-3 (a white solid) 2.79 g, yield 84%).

{Synthesis of Compound 2-4}

Dissolve compound 2-2 (0.82 g, 1.9 mmol) and compound 2-3 (0.7 g, 2.1 mmol) Dissolve in glacial acetic acid (20 mL) and stir at room temperature for 3.5 hours. The reaction solution was mixed with water to precipitate a solid. The obtained solid was separated by filtration, washed with water, and then dried at 50 ° C. under reduced pressure to obtain compound 2-4 (1.39 g, yield 97%) as a light blue solid.

{Synthesis of Dye 2-A}

Compound 2-4 (1.39 g, 1.9 mmol), tetrachlorobenzoquinone (0.47 g, 1.9 mmol) and methanol (30 mL) were mixed and stirred at 50 ° C for 5 hours. After the reaction solution was cooled to room temperature, insoluble matter was removed by filtration, and the solvent was distilled off. This crude product was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 to 95/5 (volume ratio)) to obtain a dye 2-A (0.23 g, 17% yield).

The dye 2-A was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 637 nm, and the gram absorption coefficient (g) was 91.5 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below.

LCMS (ESI, posi) m / z 736 (M ⁺ C ₄₃ H ₄₁ F ₃ N ₃ O ₃ S)

(Synthesis example 2-2: Synthesis of dye 2-B)

{Synthesis of Compound 2-5}

[Chemical 85]

Under a nitrogen environment, 1-iodonaphthalene (5.1g, 20mmol), 2-methylcyclohexylamine (4.7g, 41mmol), sodium tert-butoxide (2.4g, 25mmol), and tris (dibenzylideneacetone) ) (Chloroform) dipalladium (0) (52mg, 0.050mmol), 2,2 '-(diphenylphosphino) -1,1'-binaphthalene (96mg, 0.15mmol), toluene (50mL) in a mixture Stir at 100 ° C for 2.5 hours. The reaction solution was cooled to room temperature, and then filtered through filter paper. The filtrate was washed with a saturated aqueous ammonium chloride solution and a saturated sodium chloride aqueous solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification was performed by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 100/0 to 95/5 (volume ratio)) to obtain compound 2-5 (3.6 g, yield 75%).

{Synthesis of Compound 2-6}

Phosphorus chloride (2.13 g, 13.9 mmol) was added to a mixture of compound 2-1 (2.34 g, 5.56 mmol), compound 2-5 (1.33 g, 5.56 mmol) and toluene (30 mL) under a nitrogen atmosphere. It heated to 100 degreeC, and stirred for 12.5 hours in this state. After the reaction liquid was cooled to room temperature, water (10 mL) was added and stirred for 1 hour. Removal of the toluene layer by decantation Then, chloroform (50 mL) was added and extraction was performed, and the organic layer was washed 3 times with saturated brine (20 mL). After removing the solvent by distillation, the obtained solid was dissolved in chloroform (10 mL) and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 ~ 95/5 (volume ratio)), and Compound 2-6 (3.00 g, yield 81%) was obtained as a blue solid.

{Synthesis of Dye 2-B}

After adding concentrated sulfuric acid (10.0 g) to compound 2-6 (0.73 g, 1.07 mmol), it was heated to 50 ° C and stirred in this state for 2.5 hours. After the reaction solution was cooled to room temperature, it was mixed with ice water (10 mL), and the precipitated solid was filtered. The obtained solid was suspended in water (5 mL), and an aqueous sodium hydroxide solution (1 mo1 / L) was added to adjust the pH to 8. After filtration, the obtained solid was dissolved in chloroform (3 mL) and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 97/3 ~ 80/20 (volume ratio)) to obtain blue Dye 2-B (0.21 g, yield 27%) as a color solid.

Dye 2-B was dissolved at 10 mass ppm in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 640 nm, and the gram absorption coefficient (g) was 106 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below.

LCMS (ESI, posi) m / z 722 (M ⁺ C ₄₆ H ₄₇ N ₃ O ₃ S)

(Synthesis example 2-3: Synthesis of dye 2-C)

{Synthesis of Compound 2-7}

Add DMF (100 mL) to p-toluidine (17.4 g, 0.163 mol) and potassium carbonate (27 g, 0.195 mol), heat to 70 ° C and gradually add a small amount of ethoxyethyl bromide (25 g, 0.163 mol) in this state. Stir for 7 hours. After completion of the reaction, it was cooled to room temperature, and the reaction solution was poured into water (100 mL). Extraction was performed with toluene (100 mL), followed by washing with water (20 mL) three times, washing with 1 N hydrochloric acid (30 mL) once, washing with water (20 mL) three times, and concentration to obtain a yellow oily compound. This crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 100/0 to 79/21 (volume ratio)) to obtain compound 2-7 (10.0 g, product Rate of 34%).

{Synthesis of Compound 2-8}

Under a nitrogen atmosphere, compounds 2-7 (10.0 g, 55.8 mmol) and DMF (50 mL) were added, and the mixture was cooled to 5 ° C. To this, potassium tert-butoxide (6.26 g, 55.8 mmol) was gradually added in small amounts while maintaining the temperature below 10 ° C. Then, 4,4'-difluorobenzophenone (3.04 g, 13.9 mmol) in DMF (50 mL) was added dropwise, and then heated to 50 ° C and stirred for 3 hours. Reaction completed After that, it was cooled to room temperature and poured into water (100 mL). This was extracted twice with toluene (50 mL), washed three times with water (20 mL), and then evaporated under reduced pressure using an evaporator to obtain a brown oily compound. This crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 86/14 to 65/35 (volume ratio)) to obtain compound 2-8 (4.60 g, product Rate 62%).

{Synthesis of Compound 2-9}

Under a nitrogen environment, in a 100 mL four-necked flask, compound 2-8 (2.29 g, 4.3 mmol) was dissolved in tetrahydrofuran (30 mL), and lithium borohydride (3 mol / L hexane solution, 1.7 mL)). After the addition, the mixture was heated to 50 ° C and stirred in this state for 1 hour. After leaving to cool to room temperature, water (5 mL) was added to stop the reaction. After concentrating tetrahydrofuran under reduced pressure, ethyl acetate (40 mL) was added, and the mixture was washed three times with water (5 mL) and once with saturated brine (5 mL). The organic layer was dried over anhydrous magnesium sulfate, and then filtered and concentrated to remove the solvent to obtain compound 2-9 (2.38 g) as a pale yellow oily compound. Compounds 2-9 were used without further purification for subsequent reactions.

{Synthesis of Compound 2-10}

[Chemical 91]

Compound 2-9 (2.29 g, 4.3 mmol) and compound 2-3 (1.42 g, 4.3 mmol) were dissolved in acetic acid (15 mL), and stirred at room temperature for 1 hour. The reaction solution was poured into water (100 mL), and the pH was adjusted to 6.5 with a 20% NaOH aqueous solution to precipitate a solid. The obtained solid was separated by filtration, washed with water (100 mL), and then vacuum-dried at 40 ° C to obtain compound 2-10 (3.33 g). Compound 2-10 was used in the next reaction without purification.

{Synthesis of Dye 2-C}

Methanol (50 mL) was added to compound 2-10 (3.33 g, 3.8 mmol) and tetrachlorobenzoquinone (0.96 g, 3.8 mmol), and the mixture was stirred at 50 ° C for 1 hour. After the reaction solution was cooled, insoluble matter was removed by filtration, and the solvent was distilled off under reduced pressure. Pass the crude product through a silicone tube Purification was performed by column chromatography (developing solvent: chloroform / methanol = 100/0 to 94/6 (volume ratio)) to obtain dye 2-C (0.74 g, yield 20%).

Dye 2-C was dissolved at 10 mass ppm in propylene glycol monomethyl ether 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 absorption coefficient (g) was 82.4 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below.

LCMS (ESI, posi) m / z 853 (M + 1) ⁺ C ₄₉ H ₅₃ F ₃ N ₃ O ₅ S)

(Synthesis Example 2-4: Synthesis of Dye 2-D)

{Synthesis of Compound 2-11}

Under nitrogen, 1,7-clefic acid (1 g, 4.48 mmol) and 2-methylcyclohexanone (0.5 g, 4.48 mmol) were dissolved in acetic acid (5 mL) and N-methyl at room temperature. To pyrrolidone (5 mL), sodium triacetoxyborohydride (6.66 g, 31.4 mmol) was gradually added in small amounts, and the mixture was stirred at room temperature for 4 hours in this state. After completion of the reaction, it was mixed with water (10 mL). The aqueous layer was saturated with common salt and extracted with ethyl acetate, and then the organic layer was dried with anhydrous sodium sulfate. The desiccant was separated by filtration and the solvent was distilled off to obtain an oil. This crude product was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 to 84/16 (volume ratio)) to obtain compound 2-11 (0.98 g, yield 68%). ).

{Synthesis of Compound 2-12} [Chem 94]

Compound 2-2 (1.73 g, 4.1 mmol) and compound 2-11 (1.35 g, 4.2 mmol) were dissolved in glacial acetic acid (6 mL) and N-methylpyrrolidone (6 mL), and stirred at room temperature for 10 minutes. minute. The reaction solution was mixed with water to precipitate a solid. The obtained solid was separated by filtration, washed with water, and then dried at 50 ° C. under reduced pressure to obtain compound 2-12 (3.0 g, yield 97%) as a light blue solid.

{Synthesis of Dye 2-D}

Compound 2-12 (3.0 g, 4.1 mmol), tetrachlorobenzoquinone (2.0 g, 8.3 mmol) and N-methylpyrrolidone (51 mL) were mixed and stirred at 50 ° C for 2 hours. After the reaction solution was cooled to room temperature, the reaction solution was mixed with water to precipitate a solid. The obtained solid was separated by filtration, washed with water, and then dissolved in chloroform, and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 ~ 88/12 (volume ratio)). , And the dye 2-D (2.28 g, yield 77%) was obtained as a dark blue solid.

The dye 2-D was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 644 nm, and the gram absorption coefficient (g) was 91.9 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below.

LCMS (ESI, posi) m / z 722 (M + 1) ⁺ C ₄₆ H ₄₈ N ₃ O ₃ S)

(Synthesis example 2-5: Synthesis of dye 2-E)

{Synthesis of Dye 2-E}

Dye 2-D (2.6 g, 3.2 mmol) was added to concentrated sulfuric acid (20 mL), and the mixture was stirred at 50 ° C for 5 hours. After the reaction solution was cooled to room temperature, the reaction solution was added to ice-cooled water (100 mL) to precipitate a solid. The obtained solid was separated by filtration, washed with water, dissolved in methanol, and purified by silica gel column chromatography (developing solvent: chloroform / methanol = 100/0 ~ 75/25 (volume ratio)). , And the dye 2-E (1.0 g, yield 35%) was obtained as a dark blue solid.

The dye 2-E was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 641 nm, and the gram absorption coefficient (g) was 55.6 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below.

LCMS (ESI, posi) m / z 801 (M + 1) ⁺ C ₄₆ H ₄₈ N ₃ O ₆ S ₂ )

(Synthesis Example 2-6: Synthesis of Comparative Dye 2-1)

The following comparison was synthesized by the method described in International Publication No. 2013/147099. Dye 2-1.

(Synthesis Example 2-7: Synthesis of Comparative Dye 2-2)

The following comparative dye 2-2 was synthesized by the method described in International Publication No. 2013/147099.

(Synthesis Example 2-8: Synthesis of Comparative Dye 2-3)

Compound 2-13 (2.00 g, 3.40 mmol, synthesized by the method described in International Publication No. 2011/158794) was dissolved in methanol (20 mL) under a nitrogen atmosphere at room temperature, and bis (trifluoro) was added. Lithium mesylate) (0.99 g, 3.40 mmol). The mixed solution was stirred at an external temperature of 50 ° C for 1.5 hours, and then left to cool to room temperature. After the solvent was concentrated by an evaporator, the solvent was 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 gel chromatography (developing solvent: chloroform / methanol = 10/1 to 5/1 (volume ratio)) to obtain a comparative dye as a blue solid 2-3 (1.80 g, 63% yield).

Comparative dye 2-3 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) at 10 mass ppm. The maximum absorption wavelength (λmax) at this time was 628 nm, and the gram absorption coefficient (g) was 111 Lg ^-1 cm ^-1 . The results of liquid chromatography mass analysis of this compound are shown below. The mass at this time indicates the mass of the triarylmethane cation site.

LCMS (ESI, posi) m / z 546 (M ⁺ C ₃₆ H ₄₈ N ₃ )

(Synthesis Example 2-9: Synthesis of Resin 2-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. 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, monoacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto over 3 hours, and 2,2 ' -Azobis (2-methylbutane Nitrile) 8.47 parts by mass of the mixed solution, and further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 67.0 parts by mass of acrylic acid, 1.1 parts by mass of tris (dimethylamino) methylphenol, and 0.19 parts by mass of hydroquinone were added, 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 the mixture was reacted at 100 ° C for 3.5 hours. The polystyrene-equivalent weight average molecular weight (Mw) of the resin solution thus obtained, measured by GPC, was about 9,000, and the acid value was 25 mg-KOH / g. To this resin solution, propylene glycol monomethyl ether acetate was added so that the solid content became 40% by mass, and was used as resin 2-A.

(Synthesis Example 2-10: Synthesis of Resin 2-B)

400 parts by mass of "NC3000H" (epoxy equivalent 288, softening point 69 ° C) (manufactured by Nippon Kayaku Co., Ltd.), 102 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and 264 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was charged into a reaction vessel, and stirred at 95 ° C. until the acid value became 3 mg-KOH / g or less. It takes 9 hours to reach the target acid value (acid value 2.2mg-KOH / g). Then, 151 parts by mass of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain an acid value of 102 mg-KOH / g and a weight average molecular weight in terms of polystyrene measured by GPC ( Mw) is a resin solution of 3900. To this resin solution, propylene glycol monomethyl ether acetate was added so that solid content became 44 mass%, and it was used as resin 2-B.

(Synthesis example 2-11: Synthesis of initiator)

3- (2-Ethyloxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl was synthesized by the method described in International Publication No. 2009/131189. -6- (o-toluenyl) -9H-carbazole.

[Preparation of colored resin composition]

The dyes 2-A to 2-E obtained in the above Synthesis Examples 2-1 to 2-5, the comparative dyes 2-1 to 2-3 obtained in the Synthesis Examples 2-6 to 2-8, and the Synthesis Example 2- The resins 2-A and 2-B obtained in 9 and 2-10 are mixed with other components so as to have the composition described in Table 11 below, and A colored resin composition is prepared.

In addition, the numerical values in the upper stage of Table 11 indicate the content ratio (mass%) of each component added to the colored resin composition, and the numerical values in the lower stage indicate the content ratio (mass%) of each component in all solid matter components.

When mixing, stir each component for more than 1 hour to fully mix, and finally filter the pawn-type filter with 5 μm to remove foreign matter.

The colored resin compositions of Examples 2-1 to 2-5 used dyes 2-A to 2-E, and the colored resin compositions of Comparative Examples 2-1 to 2-3 used comparative dyes 2-1 to 2-3. .

The compounds in Table 11 are as follows.

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

F559: oligomer containing perfluoroalkyl group

Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

JPP-100: Tetraphenyldipropylene glycol diphosphite

[Manufacture of colored resin film and evaluation of heat resistance]

Each colored resin composition prepared in the above-mentioned [Preparation of colored resin composition] was applied on a glass substrate cut to a size of 5 cm square by a spin coating method so that the y value after firing became 0.120 as described below. After drying under reduced pressure, it was pre-baked at 80 ° C for 3 minutes using a hot plate. After that, the entire surface was exposed at an exposure amount of 60 mJ / cm ² and then baked in a dust-free oven. The firing temperature was set to 200 ° C in Examples 2-1 to 2-5, Comparative Examples 2-1 and 2-2, and 230 ° C in Comparative Example 2-3. Regarding the spectral transmittance of the obtained film, the light transmittance was measured using a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity (C light source) and brightness of the XYZ color system were calculated.

The brightness of Examples 2-1 to 2-5 was maintained at a high value equivalent to that of Comparative Examples 2-1 to 2-3.

[Manufacture of colored resin film and evaluation of light resistance]

Each colored resin composition prepared in the above-mentioned [Preparation of colored resin composition] was coated on a glass substrate cut to a size of 5 cm square by a spin coating method, dried under reduced pressure, and then heated at 80 with a hot plate. Pre-bake at 3 ° C for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ² , and then baked in a dust-free oven at 200 ° C. for 30 minutes. At this time, it adjusted so that the y value when it baked for 30 minutes in a dustless oven becomes 0.120. The firing temperature was set to 200 ° C in Examples 2-1 to 2-5, Comparative Examples 2-1 and 2-2, and 230 ° C in Comparative Example 2-3. Then, regarding the spectral transmittance of the obtained film, the light transmittance was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the brightness was calculated. A polarizing plate having a transmittance shown in FIG. 2 was placed in a Weather-Ometer Ci4000 (manufactured by Atlas), and simulated sunlight was irradiated 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 13.

The color differences ΔE * _{ab of} Examples 2-1 to 2-5 showed values smaller than those of Comparative Examples 2-1 to 2-3 in which R ⁵ and R ^{6 of} Formula (I-2) did not have an aromatic ring group. By using the colored resin composition of the present invention, it is possible to provide a color filter with good light resistance, a liquid crystal display device and an organic EL display device using the same.

[Measurement of voltage holding ratio using liquid crystal]

Each colored resin composition prepared in the above-mentioned [Preparation of colored resin composition] was set so that the thickness of the coating film became 2 to 3 μm (the film thickness after heat curing was about 2 μm). A spin coater with a fixed number of rotations (300 rpm to 700 rpm) was applied on a glass substrate (ITO-incorporated glass ITO entity MN-1392 for evaluation manufactured by EHC) on a glass substrate having ITO (indium-tin oxide alloy) electrodes vapor-deposited on the entire surface. After pre-baking the heating plate at 80 ° C for 3 minutes, it was dried in a vacuum chamber for 1 minute.

Next, using a high-pressure mercury lamp, a mask was applied to the outer periphery of the electrode, and the coating film was exposed with an exposure amount of radiation of 32 mW and 60 mJ / cm ² including wavelengths of 303 nm, 313 nm, 334 nm, 365 nm, 405 nm, and 436 nm, and further After 60 minutes of baking (hereinafter also referred to as "curing temperature"), the coating film is cured to obtain a blue pixel substrate (hereinafter, also referred to as "photoresist film") for liquid crystal evaluation. The hardening temperature of the post-baking was set to 200 ° C in Examples 2-1 to 2-5, Comparative Examples 2-1 and 2-2, and 230 ° C in Comparative Example 2-3.

The substrate on which the blue pixels were formed and the electrode substrate (the evaluation glass SZ-B11MIN (B) MN11396 manufactured by EHC) were evaporated to a specific shape, and then washed with water and 45 ° C warm water at 105 ° After drying in an oven, bonding with a sealant mixed with 5 μm glass beads (gap is 5 μm), annealing in an oven at 180 ° C. for 2 hours, and injecting liquid crystal MLC-7021-000 ( (Manufactured by Merck), and a liquid crystal cell having an electrode area of 1 cm ² was produced.

Then, the liquid crystal cell property evaluation system type 6254 (manufactured by Toyo Technology Co., Ltd.) was used to measure the voltage holding ratio of the liquid crystal cell at 25 ° C. The applied voltage at this time was a square wave of 5.0 V, and the measurement frequency was 60 Hz. Here, the so-called voltage holding ratio is generally known as two expressions of area ratio and voltage ratio. In this specification, the area ratio value (0 millisecond to 16.7 millisecond voltage trajectory and voltage zero level are enclosed. The ratio of the area to the area obtained by maintaining a voltage of 0 milliseconds for an observation time of 16.7 milliseconds).

The liquid crystal evaluation results are summarized in Table 14. In Table 14, the so-called "impossible measurement" refers to the fact that the voltage drops to less than 2V within a time shorter than the response speed of the liquid crystal, that is, within 1 millisecond immediately after the voltage is applied. Voltage In this case, it means that the electrical characteristics are significantly lower.

In Examples 2-1 to 2-5, the voltage retention rate at 60 Hz is high.

Based on this, Examples 2-1 to 2-5 are colored resin compositions with high brightness, good voltage retention, and high light resistance, so they are suitable for color filters and liquid crystal displays using them. Device, organic EL display device.

[Industrial availability]

According to the present invention, a colored composition having high brightness and satisfying light resistance can be provided. In addition, according to the present invention, a color filter having high brightness and satisfying light resistance, and a high-quality liquid crystal display device and an organic EL display device can be provided. Therefore, the present invention is useful for application to a color filter, a liquid crystal display device, an organic EL display device, and the like.

As mentioned above, although this invention was demonstrated in detail using the specific aspect, a practitioner understands that various changes and changes can be made without departing from the meaning and scope of this invention. Furthermore, this application is based on a Japanese patent application filed on November 29, 2013 (Japanese Patent Application No. 2013-248170) and a Japanese patent application filed on February 10, 2014 (Japanese Patent Application No. 2014-023414) ), Which is incorporated herein by reference in its entirety.

Claims (22)

A colored resin composition, comprising: (A) a color material, (B) a solvent, and (C) a binder resin; and (A) the color material contains a triarylmethane represented by the following formula (I-1) Department of compounds, (In the above formula (I-1), [A ^n- ] represents an n-valent halogenated alkylsulfonimide anion which may have a substituent, or an n-valent halogenated alkylsulfonylmethyl group which may have a substituent. Anions; 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; R ⁵ and R ⁶ each independently represent an aromatic group which may have a substituent A cyclic group; n represents an integer of 1 to 4; when n is 2 to 4, the plurality of cations represented by the following formula (I-1) _CA contained in one molecule may independently have the same structure or may have the same structure Are different structures; furthermore, R ¹ to R ^{6 in} _CA (I-1) have the same meaning as above) [化 2] The colored resin composition according to claim 1, wherein the halogenated alkyl group in the above anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms. The colored resin composition according to claim 1 or 2, wherein the above-mentioned anion is a bistrifluoromethanesulfonylimide anion and contains 2,6-diphenylamino-4-butylamino-1,3,5- three Ring trifluoromethanesulfonylimide anion, or tris (trifluoromethanesulfonyl) methylate anion. The colored resin composition according to claim 1 or 2, wherein each of R ¹ to R ^{4 in} the formula (I-1) is independently a hydrogen atom or an alkyl group which may have a substituent. The colored resin composition according to claim 1 or 2, wherein each of R ⁵ and R ^{6 in} the formula (I-1) is independently a phenyl group which may have a substituent. The colored resin composition according to claim 1 or 2, wherein the content ratio of the triarylmethane-based compound represented by the formula (I-1) is 0.01% by mass or more in the total solid content. A colored resin composition, comprising: (A) a color material, (B) a solvent, and (C) a binder resin; and (A) the color material contains a triarylmethane represented by the following formula (I-2) Compound, [化 3] (In the above formula (I-2), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent; R ⁵ and R ⁶ each independently represent An aromatic ring group which may have a substituent; adjacent R ¹ to R ⁶ may be connected to each other to form a ring, and the ring may also have a substituent; M ⁺ represents a monovalent cation; m represents an integer of 0 to 4). For example, the colored resin composition of claim 7, wherein each of R ¹ to R ^{4 in} the formula (I-2) is independently a hydrogen atom or an alkyl group which may have a substituent, and each of R ⁵ and R ^{6 is} independently Substituted phenyl. The colored resin composition according to claim 7 or 8, wherein the content ratio of the triarylmethane-based compound represented by the formula (I-2) is 0.01% by mass or more in the total solid content. The colored resin composition according to any one of claims 1, 2, 7, and 8, further comprising (D) a polymerizable monomer. The colored resin composition according to any one of claims 1, 2, 7, and 8, further comprising (E) a photopolymerization starting component and / or (E ') a thermal polymerization starting component. The colored resin composition according to any one of claims 1, 2, 7, and 8, wherein (A) the color material further contains a pigment. A color filter having a pixel formed using the colored resin composition according to any one of claims 1 to 12. A liquid crystal display device having a color filter as claimed in claim 13. An organic EL display device having a color filter as claimed in claim 13. A triarylmethane-based compound represented by the following formula (I-1), (In the above formula (I-1), [A ^n- ] represents an n-valent halogenated alkylsulfonimide anion which may have a substituent, or an n-valent halogenated alkylsulfonylmethyl group which may have a substituent. Anions; 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; R ⁵ and R ⁶ each independently represent an aromatic group which may have a substituent A cyclic group; n represents an integer of 1 to 4; when n is 2 to 4, the plurality of cations represented by the following formula (I-1) _CA contained in one molecule may independently have the same structure or may have the same structure Have different structures; furthermore, R ¹ to R ^{6 in} _CA (I-1) have the same meaning as above) [Chem. 5] For example, the triarylmethane compound according to claim 16, wherein the halogenated alkyl group in the above anion is an alkyl group having 1 to 10 carbon atoms substituted with 3 to 6 halogen atoms. The triarylmethane compound according to claim 16 or 17, wherein the above anion is a bistrifluoromethanesulfonylimide anion and contains 2,6-diphenylamino-4-butylamino-1,3,5 -three Ring trifluoromethanesulfonylimide anion, or tris (trifluoromethanesulfonyl) methylate anion. The triarylmethane compound according to any one of claims 16 or 17, wherein each of R ¹ to R ^{4 in} the formula (I-1) is independently a hydrogen atom or an alkyl group which may have a substituent. The triarylmethane compound according to any one of claims 16 or 17, wherein each of R ⁵ and R ^{6 in the} above formula (I-1) is independently a phenyl group which may have a substituent. A triarylmethane-based compound represented by the following formula (I-2), (In the above formula (I-2), 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; R ⁵ and R ^{6 each} may have a substituent Is an aromatic ring group; adjacent R ¹ to R ⁶ may be connected to each other to form a ring, and the ring may have a substituent; M ⁺ represents a monovalent cation; m represents an integer of 0 to 4). For example, the triarylmethane compound of claim 21, wherein each of R ¹ to R ^{4 of the} above formula (I-2) is independently a hydrogen atom or an alkyl group which may have a substituent, and each of R ⁵ and R ^{6 is} independently A phenyl group having a substituent.