JP2024046614A - Triarylmethane dye, coloring composition containing the dye, colorant for color filter, and color filter - Google Patents

Abstract

The present invention provides a dye having superior solubility and heat resistance compared to conventional triarylmethane dyes. The present invention provides a triarylmethane dye represented by the following general formula (1): TIFF2024046614000055.tif71165 [Selected Figure] None

Description

The present invention relates to a triarylmethane dye, a coloring composition containing the dye, a coloring agent for a color filter containing the dye or the coloring composition, and a color filter using the colorant.

A color filter is used in a liquid crystal display device or an organic electroluminescence (organic EL) display device, and includes a red pixel (R), a green pixel (G), and a blue pixel (B). Coloring agents used in color filters include pigments and dyes, but because they are exposed to conditions such as high temperatures of 200°C or higher and ultraviolet irradiation during the production of color filters, they have better heat resistance and light resistance than dyes. Superior pigments have generally been used. For example, an ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15:6) is generally used as a blue pigment for forming a blue pixel portion, and if necessary, it may be added to this for toning. A small amount of purple dioxazine violet pigment (C.I. Pigment Violet 23) is also used.

In recent years, there has been a demand for lower power consumption in image display devices, and a demand for higher brightness in color filters in order to improve the utilization efficiency of backlights. In particular, the backlight usage efficiency of the blue pixel section is relatively low compared to the red and green pixel sections, and improvements are desired.

Pigments are generally insoluble in solvents, so they exist in the form of fine particles in color filters that contain resins, etc. For this reason, color filters that use pigments are known to reduce brightness and affect color purity due to the reflected and scattered light on the pigment particle surfaces, and to reduce the contrast ratio of color display devices due to the depolarizing effect caused by reflection.

To improve the problem of reduced brightness and contrast ratio, methods have been proposed that use only dyes as colorants or a combination of dyes and pigments. Since dyes are soluble in solvents, color filters that use dyes have less depolarizing effect and have superior spectral characteristics compared to when only pigments are used as colorants, and it is expected that they will improve brightness and contrast. For this reason, the use of dyes, which generally have better solubility than pigments, has attracted attention, especially for color filters in the blue pixel area.

In particular, triarylmethane dyes are good candidates for use as blue colorants due to their spectral characteristics, and examples of the use of triarylmethane dyes are proposed in Patent Documents 1 to 3, for example.

Japanese Patent Application Publication No. 2008-304766 International Publication No. 2012/128318 JP2015-28121A JP2017-83852A JP2012-83652A

However, the dyes described in Patent Documents 1 to 3 have insufficient solubility in organic solvents and heat resistance suitable for use as colorants for color filters. High heat resistance is a required characteristic in the manufacturing process of color filters, and high solubility is an important characteristic for forming a uniform system and providing a high-brightness color filter. For this reason, there is always a demand for dyes with high heat resistance and solubility. An object of the present invention is to provide a dye that has superior solubility and heat resistance compared to conventional triarylmethane dyes.

As a result of intensive research to solve the above problems, the present inventors have discovered a triarylmethane dye that is superior in solubility and heat resistance to conventional triarylmethane dyes. That is, the gist of the present invention is as follows.

1. A triarylmethane dye represented by the following general formula (1).

[In formula (1), R ¹ and R ² each independently represent
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
^R3 and ^R4 are each independently
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 20 ring atoms which may have a substituent,
R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group,
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an amino group having 0 to 20 carbon atoms which may have a substituent,
R ¹³ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom,
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent,
R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom,
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R ^{13 to} R ¹⁸ may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, a vinylene group, an oxygen atom, or a sulfur atom to form a ring;
An represents an anion.

2. A triarylmethane dye represented by the general formula (1), wherein R ³ and R ⁴ are aromatic hydrocarbon groups having 6 to 12 carbon atoms which may have a substituent.

3. A triarylmethane dye in which R ¹³ to R ¹⁶ in the general formula (1) are hydrogen atoms.

4. A triarylmethane dye in which An is a halide ion, a bis(trifluoromethanesulfonyl)imide anion, a sulfonylimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a sulfonate anion in the general formula (1).

5. A coloring composition containing the triarylmethane dye (described in any one of 1. to 3.).

6. A coloring composition containing the triarylmethane dye (described in 4.).

7. A colorant for a color filter containing the coloring composition.

8. A color filter using the colorant for color filters.

The triarylmethane dye of the present invention has excellent solubility and heat resistance, and the coloring composition containing the dye is useful as a colorant for color filters.

Embodiments of the present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist. First, the triarylmethane dye represented by the general formula (1) will be explained.

In the general formula (1), specific examples of the " ^straight - ^chain , branched or cyclic alkyl group having 1 to 20 carbon atoms" in the "straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R 1 to R 18 include straight-chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl ... branched alkyl groups such as ethyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-1-methylpropyl, isooctyl, and 2-ethylhexyl; cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl; norbornyl, 1-adamantyl, and 2-adamantyl. Here, it will be understood by those skilled in the art that the lower limit of the carbon number of a "branched or cyclic alkyl group" is the number of carbons that allows the group to have a branched or cyclic structure (i.e., 3 carbons).

In general formula (1), specific examples of the "aromatic hydrocarbon group having 6 to 20 carbon atoms" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁸ include aromatic hydrocarbon groups such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an azulenyl group, an anthryl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, and a triphenylenyl group (the "aromatic hydrocarbon group" in the present invention also includes an aryl group or a condensed polycyclic aromatic group).

In the general formula (1), specific examples of the "heterocyclic group having 5 to 20 ring atoms" in the "heterocyclic group having 5 to 20 ring atoms which may have a substituent" represented by R ³ and R ⁴ include a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a pyrazinyl group, a triazinyl group, a naphthyridinyl group, an acridinyl group, a phenanthrolinyl group, a carbolinyl group, a purinyl group, a naphthyridinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a phenanthridinyl group, a perimidinyl group, an anthyridinyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, a dihydropyrrolopyrrolyl group, an indolyl group, an isoindolyl group, an indolizinyl group, an indazolyl group, a benzimidazolyl group, a benzotriazolyl group, Examples of heterocyclic groups (or heteroaromatic hydrocarbon groups) include a carbazolyl group, an azaindolyl group, an azaindazolyl group, a pyrazolopyrimidinyl group, an adenyl group, a guanidinyl group, a phenazinyl group, a furyl group, a thienyl group, a benzofuranyl group, an isobenzofuranyl group, a benzothienyl group, an isobenzothiophenyl group, a dibenzofuranyl group, a dibenzothienyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an oxadiazolyl group, a thiadiazolyl group, a furopyrrolyl group, a thienopyrrolyl group, a benzoxazolyl group, a benzoisoxazolyl group, a benzothiazolyl group, a benzoisothiazolyl group, a benzothiadiazolyl group, a phenoxathiinyl group, a benzo[1,2-b:4,5-b']dithiophenyl group, and a bipyridinyl group.

In the general formula (1), the "halogen atom" represented by R ⁵ to R ¹⁶ includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. The "halogen atom" is preferably a fluorine atom or a chlorine atom.

In general formula (1), specific examples of the "straight ^- chain, branched or cyclic alkoxy group having 1 to 20 carbon atoms" in the "straight-chain, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have ^a substituent" represented by R 5 to R 16 include straight-chain alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group and decyloxy group; branched alkoxy groups such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group and isooctyloxy group; cyclic alkoxy groups (cycloalkoxy groups) such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group and cyclodecyloxy group; 1-adamantyloxy group and 2-adamantyloxy group.

In the general formula (1), the "amino group having 0 to 20 carbon atoms" in the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by R ⁵ to R ¹² may or may not have a substituent, and when it has a substituent, it includes an "amino group having substituents R ¹⁰⁰ and R ¹⁰¹ " represented as "-NR ¹⁰⁰ R ¹⁰¹ ", and examples thereof include an unsubstituted amino group (-NH ₂ ), a monosubstituted amino group (-NHR ¹⁰⁰ ), and a disubstituted amino group (-NR ¹⁰⁰ R ¹⁰¹ ). Thus, the groups R ¹⁰⁰ and R ¹⁰¹ are each independently selected from a hydrogen atom and a "substituent" described below. The number of carbon atoms in the monosubstituted amino group or disubstituted amino group is, for example, 1 to 20, and may be 1 to 10. The "amino group having 0 to 20 carbon atoms which may have a substituent" may be a group to which the above-mentioned "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms", "aromatic hydrocarbon group having 6 to 20 carbon atoms", or "heterocyclic group having 5 to 20 ring atoms" is bonded via -NH-, -N< or -N=CH-. Examples of the mono-substituted amino group include an ethylamino group, a butylamino group, an acetylamino group, and a phenylamino group. Examples of the di-substituted amino group include a dialkylamino group having 2 to 20 carbon atoms such as a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a dihexylamino group; a dialkenylamino group having 4 to 20 carbon atoms such as a diallylamino group; a diphenylamino group, an N-acetyl-N-phenylamino group, and an N-butyl-N-phenylamino group.

In the general formula (1), a "linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by any one of R ¹ to R ¹⁸ ,
"An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent",
"A heterocyclic group having 5 to 20 ring atoms which may be substituted",
"A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent," or
Specific examples of the "substituent" in the "amino group having 0 to 20 carbon atoms which may have a substituent" include a deuterium atom, a hydroxyl group, a thiol group, a cyano group, and a nitro group;
Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms;
An amino group having 0 to 20 carbon atoms;
A sulfonyl group having 0 to 20 carbon atoms;
A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms;
a linear, branched, or cyclic alkenyl group having 2 to 20 carbon atoms;
a linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms;
An acyl group having 1 to 20 carbon atoms;
an ether group having 1 to 20 carbon atoms;
an aromatic hydrocarbon group or a condensed polycyclic aromatic group having 6 to 20 carbon atoms;
Heterocyclic groups having 5 to 20 ring atoms; and the like. When the "substituent" contains a carbon atom, the carbon atom is not included in the above "0 to 20 carbon atoms", "1 to 20 carbon atoms", or "6 to 20 carbon atoms". Only one of these "substituents" may be contained, or multiple "substituents" may be contained, and when multiple "substituents" are contained, they may be the same or different. In addition, in groups having these "substituents", when the position at which the "substituent" is bonded is multiple, such as any of the four carbons in an n-butyl group, or the para, meta, or ortho positions in a phenyl group, the "substituent" may be substituted at any of the positions, or when the "substituent" has multiple positions as a bond such as a pyridyl group or naphthyl group, the "substituent" may be bonded at any of the positions. In addition, these "substituents" may further have the substituents exemplified above. In addition, these substituents may be bonded to each other via a single bond, a substituted or unsubstituted methylene group or vinylene group, an oxygen atom (-O-), or a sulfur atom (-S-) to form a ring. When the substituents form a ring, adjacent substituents may form a ring, for example, R ¹ and R ³ , or R ¹³ and R ¹⁴ , or different rings or substituents on nitrogen may be linked to form a ring, for example, R ¹ and R ⁸ , R ⁵ and R ⁹ , or R ¹³ and R ^17. From the viewpoint of molecular design, it is preferable that adjacent substituents form a ring, such as R ¹ and R ³ , R ⁷ and R ⁸ , or R ¹³ and R ¹⁷ , and/or R ¹⁶ and R ^18. However, the number of "substituents" in each group represented by R ¹ to R ¹⁸ is up to 10, and the maximum number of carbon atoms in each group is 100.

In addition, in the general formula (1), in each of the above groups having a "substituent" represented by any one of R ¹ to R ¹⁸ , the "substituent" is listed as,
"Amino group having 0 to 20 carbon atoms",
"Sulfonyl group having 0 to 20 carbon atoms",
"A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms",
"Light chain, branched or cyclic alkenyl group having 2 to 20 carbon atoms",
"Light chain, branched or cyclic alkoxy group having 1 to 20 carbon atoms",
"Acyl group having 1 to 20 carbon atoms",
"ether group having 1 to 20 carbon atoms",
"Aromatic hydrocarbon group or fused polycyclic aromatic group having 6 to 20 carbon atoms" or "heterocyclic group having 5 to 20 ring atoms" specifically includes:
Amino group: a straight chain or branched group having 1 to 20 carbon atoms, such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, di-t-butylamino group, diphenylamino group, etc. an alkyl group, or a mono- or di-substituted amino group having an aromatic hydrocarbon group having 6 to 20 carbon atoms;
A group having a sulfonyl group (-S(=O) ₂ -) having 0 to 20 carbon atoms, such as a sulfonamide group (-S(=O) ₂ -NH ₂ ), a mesyl group, and a tosyl group; -SO ₃ ^- , -SO ₃ H, -SO ₃ M (M is an alkali metal atom);
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, Straight-chain or branched alkyl groups having 1 to 20 carbon atoms such as heptyl group, octyl group, isooctyl group, nonyl group, decyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, A cyclic alkyl group having 3 to 20 carbon atoms (cycloalkyl group) such as a cyclodecyl group; norbornyl group, 1-adamantyl group, 2-adamantyl group;
Number of carbon atoms to which vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or multiple of these alkenyl groups are bonded A linear or branched alkenyl group having 2 to 20 carbon atoms; a cyclic alkenyl group having 2 to 20 carbon atoms (cycloalkenyl group) such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group;
Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group , a linear or branched alkoxy group having 1 to 20 carbon atoms such as isooctyloxy group; cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group, cyclodecyloxy group, etc. cyclic alkoxy group (cycloalkoxy group) having 3 to 20 carbon atoms; 1-adamantyloxy group, 2-adamantyloxy group;
Acyl groups having 1 to 20 carbon atoms such as formyl group, acetyl group, propionyl group, acrylyl group, benzoyl group;
Ether group (-O-), aminooxy group, ester group represented by "-O-(C=O)-R" (R is any alkyl group or aromatic hydrocarbon group, etc.), phosphoric acid group, A group containing an ether group (-O-) having 0 to 20 carbon atoms, such as a phosphoric acid ester group;
Aromatic hydrocarbons having 6 to 20 carbon atoms such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group group or fused polycyclic aromatic group;
Pyridyl group, pyrimidilinyl group, triazinyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group, benzofuranyl group, benzothienyl group oxazolyl group, indolyl group, carbazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, carbon atom number 2 or more 20 heterocyclic groups;
Examples include aryloxy groups having 6 to 19 carbon atoms, such as phenyloxy, tolyloxy, biphenylyloxy, naphthyloxy, anthracenyloxy, and phenanthrenyloxy groups.

In the general formula (1), R ¹ and R ² are linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms which may have a substituent, or have a substituent. An aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred. Preferred examples of R ¹ and R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, cyclohexyl group, phenyl group, methylphenyl group, and methoxyphenyl group. In addition, when the "substituents" in R ¹ and R ² contain carbon atoms, they are not included in the "number of carbon atoms 1 to 8" and "number of carbon atoms 6 to 10", and the number of "substituents" is at most 5. The maximum number of carbon atoms in each group is preferably "20" and more preferably "12". R ¹ and R ² may be the same or different. From the viewpoint of molecular design, it is preferable that R ¹ and R ² are the same group.

In the general formula (1), R ³ and R ⁴ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms which may have a substituent, or a linear, branched or cyclic alkyl group which may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms or a heterocyclic group having 5 to 10 ring atoms which may have a substituent is preferable, and a carbon atom which may have a substituent. A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent is more preferable. Preferred examples of R ³ and R ⁴ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, tert-butyl group, cyclohexyl group, phenyl group, methylphenyl group, methoxyphenyl group. , fluorophenyl group, naphthyl group, pyridyl group, thienyl group, and thiazolyl group. In addition, when the "substituent" in R ³ and R ⁴ contains a carbon atom, the above "number of carbon atoms 1 to 20", "number of carbon atoms 1 to 6", "number of carbon atoms 6 to 20" and "carbon atom The number of "substituents" is preferably 5 at most, and the maximum number of carbon atoms in each group is preferably "20", more preferably "12". R ³ and R ⁴ may be the same or different. From the viewpoint of molecular design, R ³ and R ⁴ are preferably the same group.

In the general formula (1), R ⁵ to R ¹² are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a linear, branched or cyclic group having 1 to 20 carbon atoms which may have a substituent. Alkyl group, aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, linear, branched or cyclic having 1 to 20 carbon atoms which may have a substituent An alkoxy group, or an amino group having 0 to 20 carbon atoms which may have a substituent is preferable, such as a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a carbon atom which may have a substituent. A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. More preferred are linear, branched or cyclic alkoxy groups having numbers 1 to 10. Preferred examples of R ⁵ to R ¹² other than a hydrogen atom include a fluorine atom, a chlorine atom, a nitro group, a cyano group, a methoxy group, an ethoxy group, a dimethylamino group, a diethylamino group, a methyl group, an ethyl group, and a phenyl group. It will be done. In addition, when the "substituent" in R ⁵ to R ¹² contains a carbon atom, the above "number of carbon atoms 1 to 20", "number of carbon atoms 1 to 10", "number of carbon atoms 6 to 20" and "carbon atom The number of "substituents" is preferably 5 at most, and the maximum number of carbon atoms in each group is preferably "20", more preferably "12". There is no particular restriction as to which group among R ⁵ to R ¹² is a group other than a hydrogen atom, and R ⁵ to R ¹² may be the same or different. From the viewpoint of molecular design, groups that have a positional relationship such that the molecule is symmetrical, that is, the set of R ⁵ and R ⁹ , the set of R ⁶ and R ¹⁰ , the set of R ⁷ and R ¹¹ , and the set of R ⁸ and R ¹² are preferably the same group.

In the general formula (1), R ¹³ to R ¹⁶ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent. A linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a hydrogen atom, a straight chain having 1 to 6 carbon atoms which may have a substituent, More preferred are branched or cyclic alkyl groups, or linear, branched or cyclic alkoxy groups having 1 to 6 carbon atoms which may have a substituent. In addition, when the "substituent" in R ¹³ to R ¹⁶ contains a carbon atom, the above-mentioned "number of carbon atoms 1 to 20", "number of carbon atoms 1 to 6", "number of carbon atoms 6 to 20" and "carbon atom The number of "substituents" is preferably 5 at most, and the maximum number of carbon atoms in each group is preferably "20", more preferably "12". Further, R ¹³ to R ¹⁶ may form a ring with an adjacent group or with R ¹⁷ or R ¹⁸ described below.

In the general formula (1), R ¹⁷ and R ¹⁸ are preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, which may have a substituent, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have a substituent. Preferred examples of R ¹⁷ and R ¹⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, and a methoxyphenyl group. In addition, a pair of R ¹³ and R ¹⁷ and/or a pair of R ¹⁶ and R ¹⁸ may bond together to form a ring such as quinoline or tetrahydroquinoline, but it is preferable that R ¹⁷ and R ¹⁸ do not bond together to form a ring. In addition, when the "substituents" in R ¹⁷ and R ¹⁸ contain carbon atoms, they are not included in the above-mentioned "1 to 8 carbon atoms" and "6 to 10 carbon atoms", and the maximum number of the "substituents" is preferably 5, and the maximum number of carbon atoms in each group is preferably "20", and more preferably "12".

In general formula (1), "An" is not particularly limited, and examples include inorganic anions such as halide ions, or organic anions. in particular,
Cl ⁻ , Br ⁻ , I ⁻ ; (CF ₃ SO ₂ ) ₂ N ⁻ (or N ⁻ Tf ₂ ),
(CF ₃ SO ₂ ) ₃ C ^- (or C ^- Tf ₃ ),
(C ₂ F ₅ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^- , (C ₆ F ₅ SO ₂ ) ₂ N ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S-, (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
C ₆ H ₄ (C ₁₂ H ₂₅ ) (SO ₃ ^- ), PF ₆ ^- , BF ₄ ^- , (PW ₁₂ O ₄₀ ) ₃ ^- ,
Alternatively, examples include anions represented by the structural formulas (Z-1) to (Z-16) below.

In the general formula (1), An may be a single anion or a combination of two or more different anions, and is preferably a single anion or an arbitrary combination of two or three selected from the above-mentioned anions, including halide ions, bis(trifluoride), More preferably, it is a single or any combination of two or three selected from the group consisting of lomethanesulfonyl)imide anion, sulfonylimide anion, tris(trifluoromethanesulfonyl)methide anion, and sulfonic acid anion.

The compound which is a triarylmethane dye represented by the general formula (1) can be produced by applying a known method and using a reagent having various corresponding groups of the general formula (1) or other appropriate reagents. One embodiment of the method for producing the compound of the present invention is described below, but the production method of the present invention is not limited to this.

The triarylmethane dye represented by general formula (1) can be obtained by condensing an aromatic aldehyde having a corresponding substituent with an indole having a corresponding substituent in the presence of an acid catalyst, followed by oxidation using an oxidizing agent. Furthermore, the triarylmethane dye represented by general formula (1) can be produced by salt exchange with a salt having a corresponding structure, if necessary. The chemical reaction in this production may be carried out in the presence of an organic solvent or without a solvent.

In the method for producing a triarylmethane dye of the present invention, the indole compound used in the condensation reaction is preferably 1 mol or more and 5 mol or less, more preferably 1.5 mol or more and 3 mol or less, per 1 mol of aromatic aldehyde. In addition, in the method for producing a triarylmethane dye of the present invention, examples of the acid catalyst used in the condensation reaction include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, and organic acids such as acetic acid, trifluoroacetic acid, paratoluenesulfonic acid, and methanesulfonic acid. The amount of the acid catalyst used is preferably 0.01 mol or more and 10 mol or less, more preferably 0.1 mol or more and 5 mol or less, per 1 mol of aromatic aldehyde.

In the method for producing a triarylmethane dye of the present invention, examples of the oxidizing agent used in the oxidation reaction include hydrogen peroxide, iron trichloride, manganese dioxide, lead dioxide, chromium trioxide, ammonium persulfate, and cerium (IV) nitrate. Examples include ammonium, chloranil (2,3,5,6-tetrachloro-p-benzoquinone), and DDQ (2,3-dichloro-5,6-dicyano-p-benzoquinone). The amount of the oxidizing agent used is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol or more and 10 mol or less, per 1 mol of the condensate obtained in the previous step.

The isolation and purification of each product in the manufacturing method of the present invention can be carried out by appropriately combining known methods used in ordinary organic synthesis, such as purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and recrystallization or crystallization using a solvent. In addition, nuclear magnetic resonance analysis (NMR), absorbance measurement using a spectrophotometer, ultraviolet-visible absorption spectrum (UV-Vis) measurement, thermogravimetry-differential thermal analysis (TG-DTA), etc. can be used to identify, analyze, and evaluate the optical properties, thermal properties, and other physical properties of these compounds. These analytical methods can also be used to evaluate the solubility, color, and heat resistance of the obtained compounds.

Specific examples of compounds that are preferred as the triarylmethane dye of the present invention represented by general formula (1) are shown in the following formulas (B-1) to (B-38), but the present invention is not limited to these compounds. Note that in the general formula (1), the triarylmethane dye portion is shown, and the anion portion represented by An is omitted. In the structural formula below, some hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included, and a planar structural formula is shown.

The triarylmethane dyes of the present invention may be used alone or in combination (for example, mixed) of two or more with different molecular structures. When two or more of these types are used, the mass concentration ratio of the least triarylmethane dye to the total weight of the triarylmethane dye is 0.1 to 50% by weight. The number of types of triarylmethane dyes is preferably one or two types.

The triarylmethane dye of the present invention, the coloring composition containing the dye, and the coloring agent for color filters containing the dye or the coloring composition are used in the manufacturing process of the colorant and the color filter. Since it is necessary to dissolve or disperse well in a solvent, it is preferable that the solubility and dispersibility in an organic solvent are high. The organic solvent is not particularly limited, but specifically, aromatic hydrocarbons such as toluene and xylene; propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether (PGME) ethers such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 3-heptanone; alcohols such as methanol, ethanol, 2-propanol; methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, lactic acid Esters such as ethyl, ethyl acetate, butyl acetate, methyl 3-methoxypropionate; diacetone alcohol (DAA), etc.; amides such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP); dimethyl Examples include sulfoxide (DMSO); etherlum (trichloromethane), etc., PGME, PGMEA, cyclohexanone or DAA are preferred, and PGME or PGMEA is particularly preferred from the viewpoint of achieving both solubility of the resin and solubility of the triarylmethane dye. . These solvents may be used alone or in combination of two or more.

The solubility of the triarylmethane dye of the present invention in an organic solvent can be measured, for example, as follows. Solubility can be evaluated by mixing a triarylmethane dye and an organic solvent in an appropriate ratio, treating the mixture with ultrasonic waves, and then visually checking the presence or absence of insoluble matter at room temperature (25° C.). The organic solvent used for measuring solubility is not particularly limited and any of the organic solvents described above can be used, but PGME, PGMEA, cyclohexanone, or DAA is preferable, and PGME or PGMEA is more preferable.

The triarylmethane dye of the present invention has excellent solubility in organic solvents, particularly in PGMEA, and the solubility in PGMEA is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. When considering application to color filters with a high contrast ratio, the higher the solubility, the more preferable.

The triarylmethane dye of the present invention can be used in the visible light region of the ultraviolet-visible absorption spectrum (for example, wavelengths of 350 to 800 nm) measured at around room temperature (for example, 23 to 27°C) using a solution prepared by dissolving it in an organic solvent. The maximum absorption wavelength is observed, which shows the maximum absorbance in the range). In the present invention, the maximum absorption wavelength in the PGME solution is preferably in the wavelength range of 550 to 650 nm. Note that the dye concentration is preferably 0.005 to 0.02 mmol/L. The solvent is not limited as long as it dissolves the dye, but it is preferable that the absorption wavelength of the ultraviolet-visible absorption spectrum does not shift significantly depending on the dissolution conditions, and PGME is preferable.

The triarylmethane dye of the present invention can be mixed with various resin solutions and applied onto a glass substrate to prepare a coating film. The obtained coating film can be measured using a spectrophotometer to obtain the color value of the coating film, thereby performing color evaluation. The CIE L ^* a ^* b ^* color system is generally used for the color value. Specifically, the color values L ^* , a ^* , and b ^* of a film sample are measured, and the heat resistance can be judged from the color difference (ΔE ^* _ab ) of the color value before and after heating at an appropriate temperature. When applied to a color filter, the color difference at a temperature of about 230° C. can be used as an index of heat resistance. The smaller the value of ΔE ^* _ab , the less the color discoloration due to thermal decomposition and the higher the heat resistance, and 10 or less is preferable, and 5 or less is more preferable.

The colorant for color filters of the present invention includes a triarylmethane dye represented by general formula (1) or a coloring composition containing at least one of the triarylmethane dyes, and components commonly used in the manufacture of color filters. In the case of a method using a photolithography process, for example, a liquid prepared by mixing a dye such as a dye or pigment with a resin component (including a monomer and an oligomer) and a solvent is applied onto a substrate such as glass or resin, photopolymerized using a photomask, a colored pattern of a dye-resin composite film soluble/insoluble in the solvent is produced, and the resulting product is heated after washing. In the electrodeposition method and printing method, a colored pattern is produced using a mixture of a dye with a resin and other components. Thus, specific components in the colorant for color filters of the present invention include at least one triarylmethane dye represented by general formula (1), other dyes such as dyes and pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. In addition, these components may be selected from among them, and other components may be added as necessary.

When the triarylmethane dye of the present invention or a coloring composition containing the triarylmethane dye is used as a colorant for a color filter, it may be used for a color filter of each color, but is preferably used as a colorant for a blue or green color filter.

The colorant for color filters of the present invention may be one or more triarylmethane dyes used alone, or may further be mixed with other known dyes such as other dyes or pigments as described below in order to adjust the color tone, i.e., to adjust the spectral characteristics.

When used as a colorant for a blue color filter, C.I. I. Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129, C. I. Basic dyes such as Basic Violet 10; C.I. I. Acid Blue 9, 74, C. I. Acidic dyes such as Acid Red 52 and 289; Disperse dyes such as Disperse Blue 3, 7, and 377; Spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based which does not belong to the present invention , indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based dyes; and other blue-based lake pigments.
When used as a colorant for a green color filter, although not particularly limited, C.I. I. Pigment Green 7, 10, 36, 47, 58, 59, 62, 63 and other green pigments; C.I. I. Yellow pigments such as Pigment Yellow 83, 138, 139, 150, 180, and 185; Spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, which do not belong to the present invention , oxazine-based, dioxazine-based, azo-based, xanthene-based, isoindoline-based, and quinophthalone-based dyes; other lake pigments; and other blue, yellow, or green dyes or pigments.

In the present invention, when used as a coloring agent for a blue color filter, as a pigment to be mixed for color tone adjustment, C.I. I. Triarylmethane dyes that do not belong to the present invention, such as Basic Blue 7, or C.I. I. Basic Violet 10, C. I. Xanthene dyes such as Acid Red 52 and 289 are preferred. When used as a colorant for green color filters, C.I. I. Quinophthalone pigments such as Pigment Yellow 138, C.I. I. Isoindoline dyes such as Pigment Yellow 139, or azo dyes are preferred. By using these dyes and the triarylmethane dye belonging to the present invention, a blue or green color filter with excellent brightness and contrast ratio can be obtained.

The mixing ratio of the other dyes in the colorant for color filters of the present invention is preferably 5 to 2000% by mass, more preferably 10 to 1000% by mass, based on the triarylmethane dye (the total of the triarylmethane dyes when two or more types are used). The mixing ratio of the dye or other dye components in the liquid colorant for color filters is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, based on the total colorant.

The resin component in the coloring agent for color filters of the present invention may be any known resin component (for example, Patent Document 4 (Japanese Unexamined Patent Publication No. 2017-83852), "binder resin (B1)" described in paragraph [0229] Synthesis Example 23, etc.) can be used. Specifically, for example, acrylic resin, olefin resin, styrene resin, polyimide resin, urethane resin, polyester resin, epoxy resin, vinyl ether resin, phenol (novolak) resin, other transparent resin, photocurable resin, or thermosetting resin. Examples include resins, and these monomers or oligomer components can be used in appropriate combinations. Moreover, copolymers of these resins can also be used in combination. The resin content in these color filter colorants is preferably 5 to 95% by mass, more preferably 10 to 50% by mass in the case of liquid colorants.

In order to improve the performance as a coloring agent for color filters, the coloring composition of the present invention contains surfactants, dispersants, antifoaming agents, leveling agents, antioxidants, ultraviolet absorbers, Other substances such as additives mixed during the production of colorants for color filters can be added. However, it is preferable that the content of these additives in the coloring composition is in an appropriate amount. The content is preferably within a range that does not affect the effects of other similar additives used during production. These additives can be added at any timing during the preparation of the coloring composition.

Other additives in the coloring agent for color filters of the present invention include components necessary for polymerization and curing of the resin, such as photopolymerization initiators and crosslinking agents, and components in the liquid coloring agent for color filters. Examples include surfactants and dispersants that are necessary to stabilize the properties of For any of these, known ones for producing color filters can be used, and there are no particular limitations. The mixing ratio of the total amount of these additives in the entire solid content of the colorant for color filters is preferably 5 to 60% by mass, more preferably 10 to 40% by mass.

Hereinafter, embodiments of the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The reagents described in the synthesis examples were those manufactured by Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich, Alfa Aesar, etc. Furthermore, all reactions in the synthesis examples were carried out using a reaction vessel equipped with a cooling tube, a stirring device, and a thermometer. The compounds in the following synthesis examples were identified by ¹ H-NMR analysis (Bruker nuclear magnetic resonance apparatus, model: Ascend ^TM 400 MHz).

[Synthesis Example 1] Synthesis of Compound (C-1) The following reaction was carried out under a nitrogen stream. 5.00 g (28.2 mmol) of 4-diethylaminobenzaldehyde, 12.5 g (64.9 mmol) of 2-phenylindole, 55 mL of methanol, 5.5 mL of tetrahydrofuran (THF), and 5.0 mL of concentrated hydrochloric acid were placed in a reaction vessel and stirred at room temperature (23-28°C) for 5 hours. The reaction liquid was added to 150 mL of water and filtered under reduced pressure. 150 mL of 5% aqueous sodium hydrogen carbonate solution and 100 mL of ethyl acetate were added to the obtained solid, stirred at room temperature (23-28°C), and then filtered. The organic layer of the filtrate was extracted and washed twice with 200 mL of water, and the organic layer was extracted again. After drying with anhydrous magnesium sulfate, it was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. 150 mL of methanol was added to the residue, stirred at room temperature (23-28°C) for 1 hour, and then filtered. The obtained solid was dried under reduced pressure at 60° C. to obtain the following (Intermediate 100) (14.9 g, yield 97%).

The following reaction was then carried out under a nitrogen atmosphere. 5.00 g (9.16 mmol) of the above (intermediate 100), 2.57 g (27.5 mmol) of potassium hydroxide, and 25 mL of N,N-dimethylformamide (DMF) were placed in a reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. 3.77 g (27.5 mmol) of 1-bromobutane was added dropwise to this solution, and the mixture was stirred at the same temperature for 4 hours. 100 mL of ethyl acetate and 50 mL of heptane were added to the reaction solution, which was then filtered under reduced pressure, and the filtrate was washed three times with 100 mL of water. The organic layer was extracted and dried over anhydrous magnesium sulfate, then filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was dissolved in 100 mL of dichloromethane, and 2.50 g (11.0 mmol) of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) was added and the mixture was stirred at room temperature (23-28°C) for 1 hour. To this solution, 2 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature (23-28°C) for 1 hour, and then filtered under reduced pressure. The filtrate was washed with 100 mL of water and 100 mL of saturated saline solution in that order, and the organic layer was extracted. After drying over anhydrous magnesium sulfate, the mixture was filtered under reduced pressure, and the solvent in the filtrate was distilled off under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 100/1 to 10/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60°C, and the following (Intermediate 101) was obtained (3.12 g, yield 52%).

Next, 3.00 g (4.33 mmol) of the (intermediate 101), 1.24 g (4.33 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SO ₂ CF ₃ ) ₂ ), and 30 mL of methanol were placed in a reaction vessel and stirred at 50° C. for 1 hour. 20 mL of the solvent was removed by vacuum distillation, and then the mixture was filtered under reduced pressure. 30 mL of water was added to the obtained solid, and the mixture was stirred at 60° C. for 1 hour, and then filtered under reduced pressure. The obtained solid was dried under reduced pressure at 80° C. to obtain the target compound (C-1) as a brown solid (3.3 g, yield 82%).

The obtained brown solid was subjected to NMR measurement, and the following 50 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (C-1).

^1H -NMR (400 MHz, DMSO- _d6 ): δ (ppm) = 8.30-6.14 (22H), 4.16 (4H), 3.54 (4H), 1.61 (4H), 1.16 (10H), 0.74 (6H).

[Synthesis Example 2] Synthesis of Compound (C-2) The following reaction was carried out under a nitrogen stream. 20.0 g (104 mmol) of 2-phenylindole, 19.4 g (207 mmol) of potassium hydroxide, and 100 mL of N,N-dimethylformamide (DMF) were placed in a reaction container, and the mixture was stirred at room temperature (23 to 28°C) for 30 minutes. . 15.6 g (114 mmol) of 1-bromobutane was added dropwise to this solution, and the mixture was stirred at the same temperature for 4 hours. 100 mL of ethyl acetate and 100 mL of heptane were added to the reaction solution, which was filtered under reduced pressure, and the filtrate was washed three times with 200 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was dissolved in heptane, 50 g of silica gel was added, and the mixture was stirred at room temperature for 30 minutes. This solution was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure to obtain the following (intermediate 102) (17.3 g, yield 67%).

The following reaction was carried out under a nitrogen atmosphere. 9.16 g (50.0 mmol) of 4-methyldiphenylamine, 8.42 g (150.0 mmol) of potassium hydroxide, and 50 mL of dimethyl sulfoxide (DMSO) were placed in a reaction vessel and stirred at room temperature (23-28°C) for 30 minutes. 23.4 g (150 mmol) of iodoethane was added dropwise to this solution, and the mixture was stirred at the same temperature for 24 hours. 150 mL of ethyl acetate and 50 mL of heptane were added to the reaction solution, which was then filtered under reduced pressure. The filtrate was washed three times with 100 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent in the filtrate was distilled off under reduced pressure. The residue was dissolved in heptane, 20 g of silica gel was added, and the mixture was stirred at room temperature for 30 minutes. This solution was filtered under reduced pressure, and the solvent in the filtrate was distilled off under reduced pressure to obtain the following (intermediate 103) (3.10 g, yield 29%).

Subsequently, the following reactions were performed under a nitrogen atmosphere. 10 mL of DMF was placed in a reaction vessel, and 3.33 g (21.8 mmol) of phosphorus oxychloride was added dropwise while stirring at room temperature (23 to 28°C). A solution of 3.06 g (14.5 mmol) of the above (Intermediate 103) and 4.5 mL of DMF was added dropwise to this solution. After stirring at the same room temperature for 3 hours, 100 mL of water was added to the reaction solution. After neutralizing this solution by adding sodium hydroxide, 75 mL of ethyl acetate and 25 mL of heptane were added. The organic layer was extracted, washed three times with 100 mL of water, and the organic layer was extracted again and dried by adding anhydrous magnesium sulfate. This solution was filtered under reduced pressure, the solvent was distilled off under reduced pressure, and then dried under reduced pressure at 80°C to obtain the following (intermediate 104) (3.20 g, yield 92%).

Subsequently, the following reactions were performed under a nitrogen stream. Into a reaction container, put 3.20 g (13.4 mmol) of the above (Intermediate 104), 8.35 g (33.5 mmol) of the above (Intermediate 102), 27 mL of methanol, and 6.70 g (67.0 mmol) of concentrated hydrochloric acid, Stirred at room temperature (23-28°C) for 16 hours. 100 mL of dichloromethane and 100 mL of water were added to the reaction solution, and the organic layer was extracted. After washing twice with 100 mL of water, the organic layer was extracted again and dried over anhydrous magnesium sulfate. This solution was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. After adding and dissolving 54 mL of chloroform to the residue, 6.59 g (26.8 mmol) of 2,3,5,6-tetrachloro-p-benzoquinone (p-chloranil) was added and stirred at 60° C. for 3 hours. After cooling the reaction solution, it was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 100/1 to 10/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60°C to obtain the following (intermediate 105) (7.29 g, yield 72%).

Subsequently, 7.20 g (9.54 mmol) of the above (intermediate 105), 2.74 g (9.54 mmol) of LiN(SO ₂ CF ₃ ) ₂ and 72 mL of methanol were placed in a reaction container, and the mixture was heated to room temperature (23 to 28°C). ) for 1 hour. After 35 mL of the solvent in the reaction solution was distilled off under reduced pressure, 300 mL of water was added, the mixture was stirred at room temperature (23 to 28° C.) for 1 hour, and then filtered under reduced pressure. The obtained solid was dried under reduced pressure at 80° C. to obtain the target compound (C-2) as a purple solid (8.71 g, yield 91%).

The obtained purple solid was subjected to NMR measurement, and the following 52 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (C-2).

^1H -NMR (400MHz, DMSO- _d6 ): δ(ppm) = 8.24-5.86 (26H), 4.68-3.99 (4H), 3.98-3.42 (2H), 2.35 (3H), 1.87-1.37 (4H), 1.37-0.95 (7H), 0.74 (6H).

[Synthesis Example 3] Synthesis of Compound (C-3) The following reaction was carried out under a nitrogen stream. 4.96 g (40.0 mmol) of 4-fluorobenzaldehyde, 19.5 g (88.0 mmol) of 1-ethyl-2-phenylindole, 80 mL of methanol, 80 mL of THF, and 20.0 g (200 mmol) of concentrated hydrochloric acid were placed in a reaction vessel and stirred at room temperature (23 to 28°C) for 16 hours. The solvent of the reaction solution was distilled off under reduced pressure, and the residue was dissolved in 20 mL of dichloromethane. 200 mL of methanol was added to this solution and filtered under reduced pressure. 100 mL of methanol was added to the obtained solid, and the mixture was stirred at room temperature (23 to 28°C) for 1 hour, and then filtered under reduced pressure. The obtained solid was dried under reduced pressure at 60°C to obtain the following (intermediate 106) (21.5 g, yield 98%).

Next, 21.5 g (39.2 mmol) of the intermediate (106), 128 mL of chloroform, and 14.2 g (62.7 mmol) of DDQ were added to the reaction vessel, and the mixture was stirred at room temperature (23 to 28°C) for 1 hour, and then filtered under reduced pressure. 100 mL of 1% aqueous ascorbic acid solution was added to the filtrate, and the mixture was stirred at room temperature (23 to 28°C) for 30 minutes, and the organic layer was extracted. After washing twice with 100 mL of water, the organic layer was extracted again and dried over anhydrous magnesium sulfate. This solution was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 100/1 to 10/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60°C to obtain the following (intermediate 107) (6.58 g, yield 29%).

The following reaction was then carried out under a nitrogen stream. 1.98 g (3.40 mmol) of the above (intermediate 107) and 30 mL of 1-butanol were placed in a reaction vessel and stirred at room temperature (23-28°C). 0.93 g (6.80 mmol) of p-phenetidine was added dropwise to this solution, and the solution was stirred at 105°C for 3 hours. After cooling the reaction solution, 100 mL of ethyl acetate and 100 mL of 1M aqueous hydrochloric acid were added to extract the organic layer. After washing with 100 mL of 1M aqueous hydrochloric acid and 100 mL of saturated saline in sequence, the organic layer was extracted again and dried over anhydrous magnesium sulfate. This solution was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was dissolved in 100 mL of methanol, and then 300 mL of 1M aqueous hydrochloric acid was added, stirred at room temperature (23-28°C) for 1 hour, and then filtered under reduced pressure. The resulting solid was dissolved in 30 mL of diethyl ether, then 30 mL of heptane was added and stirred at room temperature (23-28°C) for 1 hour, after which the supernatant was removed. The residue was dried under reduced pressure at 60°C to obtain the following (Intermediate 108) (1.63 g, yield 68%).

Subsequently, 1.60 g (2.28 mmol) of the above (intermediate 108), 0.66 g (2.28 mmol) of LiN(SO ₂ CF ₃ ) ₂ and 16 mL of methanol were placed in a reaction vessel, and the mixture was heated to room temperature (23 to 28°C). ) for 1 hour. 200 mL of water was added to the reaction solution, stirred at room temperature (23-28°C) for 1 hour, and then filtered under reduced pressure. The obtained solid was dried under reduced pressure at 80° C. to obtain the target compound (C-3) as a brown solid (2.01 g, yield 93%).

NMR measurement of the obtained brown solid was performed, and the following 42 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-3).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 8.34-6.11 (27H), 4.59-3.80 (6H), 1.64-1.02 (9H) .

[Synthesis Example 4] Synthesis of Compound (C-4) The following reaction was carried out under a nitrogen stream. 19.3 g (100 mmol) of 2-phenylindole, 20.5 g (120 mmol) of 4-bromotoluene, 42.5 g (200 mmol) of tripotassium phosphate, 1.90 g (10.0 mmol) of copper (I) iodide, 2.28 g (20.0 mmol) of trans-1,2-diaminocyclohexane, and 100 mL of toluene were placed in a reaction vessel and stirred at 110°C for 40 hours. 100 mL of 0.5 M aqueous hydrochloric acid solution and 100 mL of ethyl acetate were added to the reaction solution, and the organic layer was extracted. After drying with anhydrous magnesium sulfate, the solution was filtered, and the filtrate was concentrated under reduced pressure. A mixed solution of 165 mL of dichloromethane and 335 mL of heptane was added to the residue, and the mixture was stirred at room temperature (23 to 28°C) for 30 minutes, and then filtered under reduced pressure. The solvent in the filtrate was distilled off under reduced pressure, and the residue was dried under reduced pressure at 80° C. to obtain the following (Intermediate 109) (22.7 g, yield 80%).

Then, the following reaction was carried out under a nitrogen stream. 0.62 g (5.00 mmol) of 4-fluorobenzaldehyde, 2.83 g (10.0 mmol) of the above (Intermediate 109), 6.7 mL of methanol, 3.3 mL of tetrahydrofuran (THF), and 2.00 g (20.0 mmol) of concentrated hydrochloric acid were placed in a reaction vessel and stirred at room temperature (23-28°C) for 2 hours. After the reaction solution was filtered under reduced pressure, the obtained solid was dispersed and washed with 100 mL of methanol. This solution was filtered under reduced pressure, and the obtained solid was dried under reduced pressure at 60°C to obtain the following (Intermediate 110) (2.89 g, yield 86%).

Next, 2.89 g (4.30 mmol) of the (Intermediate 110) and 10.3 mL of chloroform were placed in a reaction vessel and dissolved, after which 1.17 g (5.16 mmol) of DDQ was added and stirred at room temperature (23-28°C) for 1 hour. The reaction solution was filtered under reduced pressure, and 100 mL of water was added to the filtrate and stirred at room temperature (23-28°C) for 30 minutes. The organic layer was extracted, dried with anhydrous magnesium sulfate, and filtered under reduced pressure. The solvent in the filtrate was distilled off under reduced pressure, and then dried at 60°C under reduced pressure to obtain the following (Intermediate 111) (3.50 g, yield 99%).

Subsequently, the following reactions were performed under a nitrogen stream. 3.54 g (5.00 mmol) of the above (Intermediate 111), 1.37 g (10.0 mmol) of p-phenetidine, and 50.0 mL of 1-butanol were placed in a reaction container, and the mixture was stirred at 105° C. for 16 hours. After cooling the reaction solution to room temperature (23 to 28°C), 100 mL of ethyl acetate and 2.87 g (10.0 mmol) of LiN(SO ₂ CF ₃ ) ₂ were added and stirred for 20 minutes. 100 mL of water was added to this solution, and the organic layer was extracted. It was dried with anhydrous magnesium sulfate. This solution was filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 100/0 to 99/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C. to obtain the target compound (C-4) as a brown solid (1.64 g, yield 31%).

NMR measurement of the obtained brown solid was performed, and the following 46 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-4).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 10.57 (1H), 7.67-6.10 (34H), 4.08 (2H), 2.35 (6H), 1.35 (3H).

[Synthesis Example 5] Synthesis of Compound (C-5) The following reaction was carried out under a nitrogen stream. 1.17 g (10.0 mmol) of 4-diethylaminobenzaldehyde, 5.67 g (20.0 mmol) of the above (Intermediate 109), 0.30 g (5.00 mmol) of urea, and 20.0 mL of ethyl cellosolve were placed in a reaction vessel and stirred. 5.00 g (50.0 mmol) of concentrated hydrochloric acid was added to this solution, and this solution was stirred at 105°C for 16 hours. After cooling the reaction solution to room temperature (23 to 28°C), 100 mL of ethyl acetate was added, and the solution was washed twice with 100 mL of water and once with 100 mL of saturated saline. The organic layer was extracted, dried by adding anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure and then dried under reduced pressure at 60°C to obtain the following (Intermediate 112) (7.20 g, yield 100%).

Subsequently, the following reactions were performed under a nitrogen stream. 7.20 g (10.0 mmol) of the above (intermediate 112) and 20.0 mL of chloroform were placed in a reaction container and dissolved therein, and 2.27 g (10.0 mmol) of DDQ was added thereto, followed by stirring at 60° C. for 3 hours. After cooling the reaction solution to room temperature (23-28°C), the reaction solution was filtered under reduced pressure, and the filtrate was concentrated under reduced pressure. The residue was dissolved in 100 mL of methanol and filtered under reduced pressure. 5.74 g (20.0 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added to the filtrate, and the mixture was stirred at room temperature (23 to 28° C.) for 20 minutes. 200 mL of water was added to this solution and filtered under reduced pressure. The obtained solid was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/heptane = 50/50 to 100/0 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C. to obtain the target compound (C-5) as a blue-purple solid (3.60 g, yield 35.8%).

NMR measurement of the obtained blue-purple solid was performed, and the following 46 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-5).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 8.25-6.62 (30H), 4.04-3.37 (4H), 2.34 (6H), 1.57-0.65 (6H).

[Synthesis Example 6] Synthesis of Compound (C-6) The following reaction was carried out under a nitrogen stream. 10.6 g (15.0 mmol) of the above (intermediate 111), 4.83 g (30.0 mmol) of 4-aminobenzotrifluoride, and 150 mL of 1-butanol were placed in a reaction vessel, and the mixture was stirred at 105° C. for 16 hours. After the reaction solution was concentrated under reduced pressure, 200 mL of dichloromethane and 200 mL of water were added to the residue to extract the organic layer. After concentrating the organic layer under reduced pressure, the residue was dissolved in 100 mL of methanol, 8.61 g (30.0 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added, and the mixture was stirred at room temperature (23 to 28° C.) for 20 minutes. This solution was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/dichloromethane = 25/75 to 100/0 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C. to obtain the target compound (C-6) as a brown solid (3.60 g, yield 22%).

NMR measurement of the obtained brown solid was performed, and the following 41 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-6).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 10.14 (1H), 8.60-5.96 (34H), 2.36 (6H).

[Synthesis Example 7] Synthesis of Compound (C-7) The following reaction was carried out under a nitrogen stream. 10.6 g (15.0 mmol) of the (intermediate 111), 3.54 g (33.0 mmol) of N-methylaniline, and 150 mL of 1-butanol were placed in a reaction vessel and stirred at 105° C. for 16 hours. The reaction solution was concentrated under reduced pressure, and then 200 mL of dichloromethane and 200 mL of water were added to the residue to extract the organic layer. The organic layer was concentrated under reduced pressure, and then the residue was dissolved in 100 mL of methanol, and 8.61 g (30.0 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added, and the mixture was stirred at room temperature (23 to 28° C.) for 20 minutes. The solution was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/dichloromethane=50/50 to 100/0 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C. to obtain the desired compound (C-7) as a brown solid (6.00 g, yield 38%).

The obtained brown solid was subjected to NMR measurement, and the following 44 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (C-7).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 8.29-5.77 (35H), 3.69 (3H), 2.35 (6H).

[Synthesis Example 8] Synthesis of Compound (C-8) The following reaction was carried out under a nitrogen stream. 17.0 g (24.0 mmol) of the above (Intermediate 111), 4.94 g (36.0 mmol) of N-methyl-p-anisidine, and 240 mL of 1-butanol were placed in a reaction vessel, and the mixture was stirred at 105° C. for 16 hours. After the reaction solution was concentrated under reduced pressure, 200 mL of dichloromethane and 200 mL of water were added to the residue to extract the organic layer. After concentrating the organic layer under reduced pressure, the residue was dissolved in 100 mL of methanol, 10.3 g (36.0 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added, and the mixture was stirred at room temperature (23 to 28° C.) for 20 minutes. This solution was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/dichloromethane = 50/50 to 100/0 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C. to obtain the target compound (C-8) as a brown solid (7.00 g, yield 27%).

The obtained brown solid was subjected to NMR measurement, and the following 46 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (C-8).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 8.36-5.73 (34H), 3.85 (3H), 3.51 (3H), 2.35 (6H).

[Synthesis Example 9] Synthesis of Compound (C-9) The following reaction was carried out under a nitrogen stream. 12.8 g (136 mmol) of phenol, 46.9 g (339 mmol) of potassium carbonate, and 113 mL of DMF were placed in a reaction vessel and stirred at room temperature (23 to 28°C) for 10 minutes. 25.3 g (113 mmol) of 2-chloro-4-fluorobenzyl bromide was added to the reaction solution and stirred at room temperature (23 to 28°C) for 18 hours. 150 mL of ethyl acetate was added to the reaction solution, and the solution was washed with 200 mL of water, 200 mL of 0.5 M aqueous potassium carbonate solution, and 200 mL of saturated saline solution in that order. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and 100 mL of dichloromethane, 100 mL of heptane, and 30 g of activated clay were added to the residue, and the mixture was stirred at room temperature (23 to 28°C) for 20 minutes and then filtered. The solvent in the filtrate was distilled off under reduced pressure to obtain the following (Intermediate 113) (25.8 g, yield 96%).

Subsequently, the following reactions were performed under a nitrogen stream. 25.8 g (109 mmol) of the above (Intermediate 113), 24.6 g (136 mmol) of benzylidene aniline, 30.4 g (271 mmol) of potassium t-butoxide, and 110 mL of DMF were placed in a reaction vessel and stirred at 60° C. for 16 hours. After cooling the reaction solution to room temperature, 200 mL of ethyl acetate was added, and this solution was washed successively with 200 mL of water, 200 mL of 0.5M aqueous potassium carbonate, 200 mL of 1M aqueous hydrochloric acid, and 200 mL of saturated brine. After extracting the organic layer, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/dichloromethane = 85/15 (volume ratio)). By distilling off the solvent under reduced pressure, the following (intermediate 114) was obtained (16.8 g, yield 54%).

The following reaction was then carried out under a nitrogen stream. 16.8 g (58.5 mmol) of the above (intermediate 114), 3.63 g (29.3 mmol) of 4-fluorobenzaldehyde, 0.88 g (14.6 mmol) of urea, 292 mL of ethyl cellosolve, and 5.85 g (58.5 mmol) of concentrated hydrochloric acid were placed in a reaction vessel and stirred at 135°C for 16 hours. After cooling the reaction solution to room temperature, 200 mL of ethyl acetate was added, and the solution was washed successively with 400 mL of water, 400 mL of 1M aqueous hydrochloric acid, and 100 mL of saturated saline. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and 100 mL of dichloromethane and 100 mL of methanol were added to the residue to dissolve it. The solution was concentrated under reduced pressure, dichloromethane was distilled off, and the precipitated solid was collected by filtration. The obtained solid was dispersed and washed with 100 mL of methanol. This solution was filtered, and the resulting solid was dried under reduced pressure at 60°C to obtain the following (Intermediate 115) (15.0 g, yield 75%).

Next, 15.0 g (22.0 mmol) of the (intermediate 115), 80 mL of dichloromethane, and 8.99 g (39.6 mmol) of DDQ were added to a reaction vessel, stirred at room temperature (23-28°C) for 18 hours, and then filtered. 100 mL of 0.5 M potassium carbonate aqueous solution was added to the filtrate, and stirred at room temperature (23-28°C) for 30 minutes. 1 M hydrochloric acid aqueous solution was added to this solution to adjust the pH to 1, and the organic layer was extracted. The organic layer was washed twice with 100 mL of 1 M hydrochloric acid aqueous solution, and then the organic layer was extracted again and dried with anhydrous magnesium sulfate. This solution was filtered, 200 mL of heptane was added to the filtrate, and the precipitated solid was filtered. A mixed solvent of 180 mL of heptane and 20 mL of dichloromethane was added to the obtained solid, dispersed and washed at room temperature (23-28°C), and then filtered. The resulting solid was dried under reduced pressure at 60°C to obtain the following (Intermediate 116) (9.60 g, yield 61%).

The following reaction was carried out under a nitrogen stream. 1.43 g (2.00 mmol) of the above (intermediate 116), 1.71 g (16.0 mmol) of N-methylaniline, and 20 mL of 1-butanol were placed in a reaction vessel and stirred at 105° C. for 2 hours. The reaction solution was concentrated under reduced pressure, and 50 mL of dichloromethane was added to the residue and dissolved. 200 mL of heptane was added to this solution, and dichloromethane was distilled off by vacuum concentration. After discarding the supernatant, 50 mL of dichloromethane and 50 mL of methanol were added to the residue and dissolved, and then 0.86 g (3.00 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added and stirred for 30 minutes. After concentrating this solution under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C., and the target compound (C-9) was obtained as a brown solid (0.50 g, yield 24%).

NMR measurement of the obtained brown solid was performed, and the following 38 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-9).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 8.00-6.48 (35H), 3.58 (3H).

[Synthesis Example 10] Synthesis of Compound (C-10) The following reaction was carried out under a nitrogen stream. 23.7 g (252 mmol) of phenol, 87.1 g (630 mmol) of potassium carbonate, and 210 mL of DMF were placed in a reaction vessel and stirred at room temperature (23 to 28°C) for 10 minutes. 50.4 g (210 mmol) of 2,5-dichlorobenzyl bromide was added to the reaction solution and stirred at room temperature (23 to 28°C) for 18 hours. 500 mL of dichloromethane was added to the reaction solution, and the solution was washed three times with 500 mL of water. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was transferred to a reaction vessel, and 45.7 g (252 mmol) of benzylideneaniline, 56.6 g (504 mmol) of potassium t-butoxide, and 210 mL of DMF were placed in the reaction vessel and stirred at 80°C for 16 hours. After cooling the reaction solution to room temperature, 600 mL of dichloromethane was added, and the solution was washed successively with 500 mL of water, 500 mL of 1M aqueous hydrochloric acid, and 500 mL of saturated saline. The organic layer was extracted, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/dichloromethane = 90/10 (volume ratio)). The solvent was distilled off under reduced pressure to obtain the following (intermediate 117) (14.3 g, yield 22%).

The following reaction was then carried out under a nitrogen stream. 12.2 g (40.0 mmol) of the above (intermediate 117), 2.48 g (20.0 mmol) of 4-fluorobenzaldehyde, 0.60 g (10.0 mmol) of urea, 200 mL of ethyl cellosolve, and 4.00 g (40.0 mmol) of concentrated hydrochloric acid were placed in a reaction vessel and stirred at 135°C for 16 hours. After cooling the reaction solution to room temperature, 200 mL of ethyl acetate was added, and the solution was washed with 300 mL of water to extract the organic layer. Anhydrous magnesium sulfate was added, dried, and then filtered. The filtrate was concentrated under reduced pressure, and the residue was transferred to a reaction vessel, and 56 mL of dichloromethane and 6.36 g (28.0 mmol) of DDQ were added, stirred at room temperature (23-28°C) for 18 hours, and then filtered. 50 mL of 0.5 M potassium carbonate aqueous solution was added to the filtrate and stirred at room temperature (23-28°C) for 30 minutes. After extracting the organic layer, the organic layer was washed with 250 mL of 1M aqueous hydrochloric acid. The organic layer was extracted again and dried over anhydrous magnesium sulfate. This solution was filtered, and 200 mL of dichloromethane and 200 mL of heptane were added to the filtrate, followed by filtration. The filtrate was concentrated under reduced pressure to remove the dichloromethane, and the supernatant was removed. The residue was dissolved in 80 mL of dichloromethane, and 400 mL of diethyl ether was added, and the precipitated solid was filtered. The obtained solid was dried under reduced pressure at 60°C to obtain the following (Intermediate 118) (6.60 g, yield 44%).

Subsequently, the following reactions were performed under a nitrogen stream. 4.94 g (6.60 mmol) of the above (intermediate 118), 1.81 g (13.2 mmol) of N-methyl-p-anisidine, and 66 mL of 1-butanol were placed in a reaction vessel, and the mixture was stirred at 105° C. for 2 hours. After cooling the reaction solution, 200 mL of dichloromethane was added, and further 400 mL of heptane was added. The precipitated solid was collected by filtration. 100 mL of dichloromethane and 100 mL of methanol were added to the obtained solid, and after dissolving it, 2.84 g (9.90 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added and stirred for 30 minutes. After concentrating this solution under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 0/100 to 85/15 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 60° C. to obtain the target compound (C-10) as a brown solid (0.80 g, yield 11%).

NMR measurement of the obtained brown solid was performed, and the following 40 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-10).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 7.62-6.47 (34H), 3.85 (3H), 3.49 (3H).

[Synthesis Example 11] Synthesis of Compound (C-11) The following reaction was carried out under a nitrogen stream. In a reaction vessel, 70.5 g (365 mmol) of 2-phenylindole, 81.9 g (438 mmol) of 4-bromoanisole, 155 g (730 mmol) of tripotassium phosphate, 6.95 g (36.5 mmol) of copper(I) iodide, 8.34 g (73.0 mmol) of trans-1,2-diaminocyclohexane and 365 mL of toluene were added, and the mixture was stirred at 110° C. for 24 hours. After cooling the reaction solution to room temperature (23-28°C), 300 mL of ethyl acetate was added, and the mixture was washed three times with 300 mL of 0.5M aqueous hydrochloric acid. The organic layer was extracted, dried over anhydrous magnesium sulfate, and then filtered. The filtrate was concentrated under reduced pressure. After dissolving the residue in 300 mL of dichloromethane, 400 mL of methanol was added. This solution was concentrated under reduced pressure to remove dichloromethane, and the precipitated solid was collected by filtration. 300 mL of methanol was added to the obtained solid, and the mixture was dispersed and washed at room temperature (23 to 28°C). This solution was filtered and the obtained solid was dried under reduced pressure at 60°C to obtain the following (intermediate 119) (63.0 g, yield 58%).

Subsequently, the following reactions were performed under a nitrogen stream. In a reaction vessel, 3.72 g (30.0 mmol) of 4-fluorobenzaldehyde, 18.0 g (60.0 mmol) of the above (intermediate 119), 0.90 g (15.0 mmol) of urea, 60 mL of ethyl cellosolve, and 6.0 g of concentrated hydrochloric acid. 00g (60.0 mmol) was added thereto, and the mixture was stirred at room temperature (23 to 28°C) for 3 hours. 100 mL of methanol was added to the reaction solution, stirred for 30 minutes, and then filtered. The obtained solid was dispersed and washed with 100 mL of methanol. This solution was filtered and the obtained solid was dried under reduced pressure at 60°C to obtain the following (intermediate 120) (20.8 g, yield 98%).

Subsequently, 20.8 g (29.5 mmol) of the above (intermediate 120), 80 mL of dichloromethane, and 8.71 g (38.4 mmol) of DDQ were added to the reaction container, and after stirring at room temperature (23 to 28 ° C.) for 16 hours, Filtered. The filtrate was washed four times with 100 mL of a 0.5M aqueous potassium carbonate solution, and then washed with 100 mL of a 1M aqueous hydrochloric acid solution. The organic layer was extracted and dried over anhydrous magnesium sulfate. After filtering this solution and concentrating the filtrate under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/ethyl acetate = 50/50 to 0/100 (volume ratio)), and the solvent was removed under reduced pressure. Distilled away. The obtained solid was dried under reduced pressure at 60° C. to obtain the following (intermediate 121) (4.80 g, yield 22%).

Subsequently, the following reactions were performed under a nitrogen stream. 1.48 g (2.00 mmol) of the above (intermediate 121), 1.29 g (10.0 mmol) of dibutylaniline, and 20 mL of 1-butanol were placed in a reaction vessel, and the mixture was stirred at 105° C. for 24 hours. After cooling the reaction solution, 50 mL of ethyl acetate was added. This solution was washed three times with 100 mL of 1M aqueous hydrochloric acid solution, and the organic layer was extracted. After concentrating the organic layer under reduced pressure, the residue was dissolved in 60 mL of methanol, and 0.86 g (3.00 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added to this solution and stirred for 30 minutes. 40 mL of water was added to this solution and stirred at room temperature (23 to 28°C), and the precipitated solid was collected by filtration. The obtained solid was purified by column chromatography (carrier: silica gel, solvent: heptane/ethyl acetate = 70/30 to 50/50 (volume ratio)), and the solvent was distilled off under reduced pressure. The obtained solid was dried under reduced pressure at 60° C. to obtain the target compound (C-11) as a brown solid (0.58 g, yield 27%).

The brown solid obtained was subjected to NMR measurement, and the following 54 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (C-11).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 7.67-6.35 (34H), 3.71 (6H), 1.82 (4H), 1.52 (4H), 1.02 (6H).

[Synthesis Example 12] Synthesis of Compound (C-12) The following reaction was carried out under a nitrogen stream. 1.48 g (2.00 mmol) of the above (Intermediate 121), 0.43 g (4.00 mmol) of N-methylaniline, and 20 mL of 1-butanol were placed in a reaction vessel, and the mixture was stirred at 105° C. for 16 hours. The reaction solution was concentrated under reduced pressure, the residue was dissolved in 50 mL of methanol, 0.86 g (3.00 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added to this solution, and the mixture was stirred at room temperature (23 to 28° C.) for 30 minutes. After concentrating this solution under reduced pressure, the residue was purified by column chromatography (carrier: silica gel, solvent: heptane/dichloromethane = 50/50 (volume ratio)), and the solvent was distilled off under reduced pressure. The obtained solid was dried under reduced pressure at 60° C. to obtain the target compound (C-12) as a brown solid (0.30 g, yield 18%).

The obtained brown solid was subjected to NMR measurement, and the following 44 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (C-12).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ (ppm) = 7.61-6.30 (35H), 3.80 (6H), 3.72 (3H).

[Synthesis of Comparative Example Compound (D-1)]
According to the method described in paragraph [0058] Synthesis Example 1 of Patent Document 4 (JP-A-2012-83652), a comparative compound (D-1) represented by the following formula was obtained as a brown solid.

NMR measurement of the obtained brown solid was performed, and the following 39 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-1).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 8.01 (1H), 7.54-7.18 (7H), 6.90-6.62 (5H), 6.18 (1H) ), 3.62-3.51 (10H), 1.47 (3H), 1.30 (12H).

[Synthesis of Comparative Example Compound (D-2)]
According to the method described in paragraphs [0320] to [0322] of Patent Document 2, a comparative compound (D-2) represented by the following formula was obtained as a brown solid.

The obtained brown solid was subjected to NMR measurement, and the following 40 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-2).

^1H -NMR (400 MHz, _CDCl3 ): δ (ppm) = 7.80 (1H), 7.48-7.17 (11H), 6.93 (1H), 6.90-6.66 (4H), 3.85 (3H), 3.55 (8H), 1.15 (12H).

[Synthesis of Comparative Example Compound (D-3)]
Comparative Example Compound (D-3) represented by the following formula was obtained as a blue-purple solid by the method described in paragraphs [0208] to [0209] Example 1) of Patent Document 3.

The obtained blue-purple solid was subjected to NMR measurement, and the following 45 hydrogen signals were detected, identifying the structure as the compound represented by the following formula (D-3).

¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 7.56-7.41 (4H), 7.40-7.23 (6H), 7.21-7.11 (3H), 6 .84-6.72 (4H), 4.31 (1H), 3.91 (1H), 3.50 (8H), 2.31 (3H), 1.29 (3H), 1.11 (12H) ).

[Example 1]
(Measurement of maximum absorption wavelength)
Compound (C-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a solution with a concentration of 0.01 mmol/L. The ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) was measured at room temperature (25° C.) as a spectral property using a spectrometer (Model: V-650), and the maximum absorption wavelength in the measurement wavelength range was measured. The measurement results are shown in Table 1.

(Evaluation of solubility)
The solubility of compound (C-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA) was measured as follows. A mixed solution was prepared by weighing and placing 20 mg of Compound (C-1) as a dye and PGMEA in a sample bottle so that the dye concentration was 1 to 10% by mass. The sample bottle was tightly stoppered, subjected to ultrasonic treatment for 20 minutes, and then left at room temperature (25° C.) for 24 hours. The dye solutions of each concentration at room temperature (25° C.) were visually observed, and the highest dye concentration (mass %) without any insoluble matter was taken as the solubility. In addition, the solubility in propylene glycol monomethyl ether (PGME) was also measured in a similar manner. The measurement results are shown in Table 1.

(Evaluation of heat resistance)
20 mg of the compound (C-1) obtained in Synthesis Example 1 and 5 g of a 25% by mass DMF-PGMEA mixed solution of a copolymer of methacrylic acid, acrylic acid ester and styrene were placed in a sample bottle and mixed by stirring for 30 minutes. The obtained colored resin solution was filtered with a syringe filter, and 1 g of the filtrate was applied to a glass substrate (spin coating method, 1000 rpm-6 seconds), and heated and dried at 100 ° C for 2 minutes to prepare a thin film. The color value of the obtained film was measured using a spectrophotometer (CM-5, manufactured by Konica Minolta, Inc.). Then, the film was heated at 230 ° C for 20 minutes, and the color value was measured in the same manner. The color difference (ΔE ^* _ab ) of the color value before and after heating at 230 ° C was used as an index of heat resistance, and the results are shown in Table 1.

[Examples 2 to 12]
Except for using the compounds (C-2) to (C-12) obtained in Synthesis Examples 2 to 12 instead of the compound (C-1) in Example 1, the measurement of the maximum absorption wavelength, the evaluation of the solubility, and the evaluation of the heat resistance were carried out in the same manner as in Example 1. The results are summarized in Table 1.

[Comparative Examples 1 to 3]
For comparison, the solubility and heat resistance were evaluated in the same manner as in Example 1, except that the comparative compounds (D-1) to (D-3), which are triarylmethane dyes not belonging to the present invention, were used instead of the compound (C-1) in the example. The results are summarized in Table 1.

As shown in Table 1, the compounds of the examples of the present invention exhibit high solubility in PGMEA and PGME and high heat resistance during film formation, and the colored compositions containing the compounds of the present invention have a color There is no practical problem as a coloring agent for filters. In addition, it has higher heat resistance than the comparative example during film formation, and is excellent as a coloring agent for color filters.

The coloring composition containing the triarylmethane dye of the present invention has excellent solubility in organic solvents (PGMEA, PGME, etc.) and excellent heat resistance during film formation, making it useful as a dye material for various applications such as colorants for color filters.

Claims (8)

A triarylmethane dye represented by the following general formula (1):

[In formula (1), R ¹ and R ² each independently represent
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
^R3 and ^R4 are each independently
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 5 to 20 ring atoms which may have a substituent,
R ⁵ to R ¹² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group,
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, or an amino group having 0 to 20 carbon atoms which may have a substituent,
R ¹³ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom,
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent,
R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom,
represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R ¹³ to R ¹⁸ may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, a vinylene group, an oxygen atom, or a sulfur atom to form a ring;
An represents an anion. 2. The triarylmethane dye according to claim 1, wherein in the general formula (1), R ³ and R ⁴ are aromatic hydrocarbon groups having 6 to 12 carbon atoms which may have a substituent. The triarylmethane dye according to claim 1, wherein in the general formula (1), R ¹³ to R ¹⁶ are hydrogen atoms. The triarylmethane dye according to any one of claims 1 to 3, wherein in the general formula (1), An is a halide ion, a bis(trifluoromethanesulfonyl)imide anion, a sulfonylimide anion, a tris(trifluoromethanesulfonyl)methide anion, or a sulfonate anion. A coloring composition containing the triarylmethane dye according to any one of claims 1 to 3. A coloring composition containing the triarylmethane dye according to claim 4. A colorant for color filters containing the coloring composition according to claim 6. A color filter using the colorant for color filters according to claim 7.