KR20240138989A - Triarylmethane dye, coloring composition containing the dye, coloring agent for color filter, and color filter - Google Patents

Abstract

[식 (1) 중, R¹, R² 는 각각 독립적으로 ―H, 알킬기, 아실기, 방향족 탄화수소기를 나타내고, R³, R⁴ 는 각각 독립적으로 ―H, 할로겐 원자, ―OH, 알킬기, 알콕시기를 나타내고, R⁵ ∼ R⁸ 은 각각 독립적으로 ―H, 할로겐 원자, ―OH, ―NO₂, ―CN, 알킬기, 알콕시기, 방향족 탄화수소기를 나타내고, R⁹, R¹⁰ 은 각각 독립적으로 ―H, 알킬기, 아실기, 방향족 탄화수소기, 복소 고리기를 나타내고, R⁵ ∼ R¹⁰ 은 고리를 형성하고 있어도 된다. An 은 할로겐화물 이온을 제외한 아니온을 나타내고, m 은 자연수를 나타낸다.](Task) To provide a triarylmethane pigment having excellent heat resistance. To provide a colorant for a color filter having good color characteristics (color gamut, brightness, contrast ratio, etc.) by a coloring composition using the pigment.
(Solution) A triarylmethane pigment represented by the following general formula (1).

[In formula (1), R ¹ and R ² each independently represent —H, an alkyl group, an acyl group, and an aromatic hydrocarbon group, R ³ and R ⁴ each independently represent —H, a halogen atom, —OH, an alkyl group, and an alkoxy group, R ⁵ to R ⁸ each independently represent —H, a halogen atom, —OH, —NO ₂ , —CN, an alkyl group, an alkoxy group, and an aromatic hydrocarbon group, R ⁹ and R ¹⁰ each independently represent —H, an alkyl group, an acyl group, an aromatic hydrocarbon group, and a heterocyclic group, and R ⁵ to R ¹⁰ may form a ring. An represents an anion other than a halide ion, and m represents a natural number.]

Description

Triarylmethane dye, coloring composition containing the dye, coloring agent for color filter, and color filter

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

Liquid crystal displays, organic electroluminescence (OLED) displays, and solid-state imaging elements such as CCDs and CMOS sensors use color filters, and have red pixels (R), green pixels (G), and blue pixels (B). Pigments and dyes are used as colorants for color filters, but when manufacturing color filters, pigments that have better heat resistance and light resistance than dyes are generally used, since they are exposed to conditions such as high temperatures of 200°C or higher or ultraviolet irradiation. For example, as a blue pigment for forming a blue pixel portion, an ε-type copper phthalocyanine pigment (C. I. Pigment Blue 15:6) is generally used, and if necessary, a small amount of a purple dioxazine violet pigment (C. I. Pigment Violet 23) is used together with this for coloring.

As a recent trend, power saving of display devices is required, and high brightness of color filters is required to improve the utilization efficiency of backlights. In particular, the utilization efficiency of backlights in blue pixel areas is relatively low compared to red or green pixel areas, and thus improvement is desired.

Since pigments are generally insoluble in solvents, they exist in the form of fine particles in color filters that include resins, etc. Therefore, it is known that color filters using pigments have their brightness reduced or their color purity affected by the reflection and scattering of transmitted light on the surface of the pigment particles, and also that the contrast ratio of color display devices is reduced due to the fragmentation effect caused by reflection.

In order to improve the problem of lowering brightness or contrast ratio, methods such as using only dye as a coloring agent or using a method of using dye and pigment in combination have been proposed. Since dye is soluble in solvent, color filters using dye have suppressed scattering effect compared to cases where pigment is used only as a coloring agent, and thus have excellent spectral characteristics, and improvements in brightness, contrast, etc. are expected. For this reason, the use of dyes with superior solubility than pigments in general is attracting attention, especially for color filters of blue pixel portions.

In particular, triarylmethane pigments have excellent spectral characteristics, and for example, patent documents 1 and 2 attempt to use triarylmethane pigments as colorants for color filters. In addition, patent document 3 attracts attention because a triarylmethane pigment having a specific structure exhibits high stability under alkaline conditions.

Japanese Patent Publication No. 2008-304766 International Publication No. 2012/128318 Specification of United States Patent Application Publication No. 2008/0108817 Japanese Patent Publication No. 2012-83652

Horiguchi Hiroshi, "Synthetic Dyes", Sankyo Publishing Co., Ltd., July 15, 1969, p. 79-109

However, when a conventionally known triarylmethane pigment, such as that described in Patent Document 1 or 2, was used in the preparation of a color filter, there was a problem that the color was easily changed due to heat history, etc. in the manufacturing process. There is no description regarding heat resistance in the triarylmethane pigment described in Patent Document 3. A dye having high heat resistance is a characteristic required in the manufacturing process of a color filter. Therefore, there is always a demand for a dye having high heat resistance and also expressing good color characteristics.

The present invention aims to provide a triarylmethane pigment having excellent heat resistance, and to provide a colorant for a color filter having good color characteristics (color gamut, brightness, contrast ratio, etc.) by a coloring composition using the pigment.

The present invention has been obtained as a result of careful examination to solve the above problems, and its summary is as follows.

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

[Chemical Formula 1]

[In formula (1), R ¹ and R ² are each independently -H,

A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent;

An aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, or

It represents an acyl group having 1 to 12 carbon atoms that may have a substituent,

R ³ and R ⁴ are, each independently, ―H, a halogen atom, ―OH,

A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or

It represents a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent.

R ⁵ ∼ R ⁸ are each independently -H, a halogen atom, -OH, -NO ₂ , -CN,

A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent.

An aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, or

It represents a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent.

R ⁹ and R ¹⁰ are, each independently, ―H,

A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent.

An aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent.

A heterocyclic group having 2 to 20 carbon atoms, which may have a substituent, or

It represents an acyl group having 1 to 12 carbon atoms that may have a substituent,

R ⁵ to R ¹⁰ may be bonded to each other via a single bond, a substituted or unsubstituted methylene group or vinylene group, a nitrogen atom, an oxygen atom or a sulfur atom to form a ring.

An represents an anion other than a halide ion,

m represents a natural number.]

2. A triarylmethane pigment, wherein in the general formula (1) above, R ¹ and R ² are a linear, branched or cyclic alkyl group having 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.

3. A triarylmethane pigment, wherein in the general formula (1) above, R ³ and R ⁴ are linear alkyl groups having 1 to 3 carbon atoms which may have a substituent.

4. In the above general formula (1), An

Perfluoroalkylsulfonic acid anion having 1 to 24 carbon atoms,

A perfluoroalkylsulfonimide anion having 1 to 24 carbon atoms,

tris(trifluoromethanesulfonyl)methide anion, or

(PW ₁₂ O ₄₀ ) ^3- , (P ₂ W ₁₈ O ₆₂ ) ^6- ,

(SiW ₁₂ O ₄₀ ) ^4- , (PMo ₁₂ O ₄₀ ) ^3- ,

(SiMo ₁₂ O ₄₀ ) ^3- , (PW _12-x Mo _x O ₄₀ ) ^3- ,

A triarylmethane pigment which is a heteropolyacid anion represented by (P ₂ W _18-y Mo _y O ₄₀ ) ^6- , or (SiW _12-x Mo _x O ₄₀ ) ^4- (wherein x represents an integer from 1 to 11 and y represents an integer from 1 to 17).

5. A triarylmethane dye having a maximum absorption wavelength in an absorption band in an ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether acetate (PGMEA) solution of the above triarylmethane dye, the absorption wavelength being in a wavelength range of 590 nm to 670 nm.

6. A coloring composition containing a triarylmethane pigment (as described in any one of 1. to 3.)

7. A coloring composition containing the above-mentioned (4.) triarylmethane pigment.

8. A colorant for a color filter containing the above coloring composition.

9. A color filter using a colorant for the above color filter.

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

Hereinafter, embodiments of the present invention will be described in detail. In addition, the present invention is not limited to the embodiments below, and can be implemented by various modifications within the scope of the gist thereof. First, the triarylmethane pigment represented by the general formula (1) will be described.

In the general formula (1), the "linear, branched or cyclic alkyl group having 1 to 12 carbon atoms ^{" in the "linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent" represented by R 1 to} R 10 includes, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group; Branched alkyl groups such as an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylpropyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1-ethyl-1-methylpropyl group, an isooctyl group, and a 2-ethylhexyl group; Examples thereof include cyclic alkyl groups (cycloalkyl groups) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl; norbornyl, 1-adamantyl, 2-adamantyl, and bicyclo[4.3.0]nonyl. Here, for a branched or cyclic alkyl group, it will be understood by those skilled in the art that the lower limit of the carbon number is the carbon number that can form a branched or cyclic structure (i.e., carbon number 3).

In the general formula (1), 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 , R ² , R ⁵ to ^R 10 specifically includes 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 general formula (1), the "acyl group having 1 to 12 carbon atoms" in the "acyl group having 1 to 12 carbon atoms which may have a substituent" represented by R ¹ , R ² , R ⁹ , and R ¹⁰ specifically includes acyl groups such as a formyl group, an acetyl group, a propionyl group, an acryloyl group, and a benzoyl group.

In general formula (1), examples of the "halogen atom" represented by R ³ to R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. As the "halogen atom", a fluorine atom or a chlorine atom is preferable.

In the general formula (1), the "linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms" in the "linear, branched or cyclic alkoxy group which may have a substituent and having 1 to ¹² carbon atoms" represented by ^R 3 to R 8 specifically includes linear alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group; branched alkoxy groups such as an isopropoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, and an 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, 2-adamantyloxy group, etc.

In general formula (1), the "heterocyclic group having 2 to 20 carbon atoms" in the "heterocyclic group having 2 to 20 carbon atoms which may have a substituent" represented by R ⁹ and R ¹⁰ specifically includes 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, an imidazopyridyl group, an oxazolopyridyl group, an oxazolopyrazyl group, a purinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolyl group, a cinnolinyl group, a pteridinyl group, a phenanthridinyl group, a perimidinyl group, an antiridinyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, Tetrazolyl group, dihydropyrrolopyrrolyl group, indolyl group, isoindolyl group, indolizinyl group, indazolyl group, benzoimidazolyl group, benzotriazolyl group, carbazolyl group, azaindoleyl group, azaindazolyl group, pyrazolopyrimidinyl group, adenyl group, guanidinyl group, phenazinyl group, furyl group, thienyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothiophenyl group, dibenzofuranyl group, dibenzothienyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, furopyrrolyl group, thienopyrrolyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, Examples of heterocyclic groups include benzoisothiazolyl group, benzothiadiazolyl group, phenoxathiinyl group, benzo[1,2-b:4,5-b']dithiophenyl group, and bipyridinyl group (or heteroaromatic hydrocarbon group).

In general formula (1), whichever of R ¹ to R ¹⁰ is represented,

"A straight-chain, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent"

"Aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent"

"A straight, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent"

"A heterocyclic group having 2 to 20 carbon atoms which may have a substituent", or,

Specifically, as for the “substituent” in the “acyl group having 1 to 12 carbon atoms which may have a substituent”,

Deuterium atom, hydroxyl group (―OH), thiol group (―SH), cyano group (―CN), nitro group (―NO ₂ ), trifluoromethyl group (―CF ₃ ), carbonyl group (―(C=O)―);

Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms;

A straight-chain or branched alkyl group having 1 to 20 carbon atoms;

Cycloalkyl group having 3 to 20 carbon atoms;

A straight or branched alkenyl group having 2 to 20 carbon atoms;

A straight-chain or branched alkynyl group having 2 to 20 carbon atoms;

A straight-chain or branched alkoxy group having 1 to 20 carbon atoms;

A cycloalkoxy group having 3 to 20 carbon atoms, or a 1-adamantyloxy group, a 2-adamantyloxy group;

Acyl group having 1 to 20 carbon atoms;

Aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 20 carbon atoms;

A heterocyclic group having 2 to 20 carbon atoms;

Aryloxy group having 6 to 20 carbon atoms;

Unsubstituted amino group; Monosubstituted or disubstituted amino group having 1 to 20 carbon atoms;

―COO ^- , ―COOH, ―COOM, a carbonyl group, ester group or amide group having 1 to 20 carbon atoms which may have a substituent,

―SO ₃ ^- , ―SO ₃ H, ―SO ₃ M, or a sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent (wherein M represents an inorganic cation or organic cation);

These "substituents" may include only one or may include multiple ones, and in the case where they are included multiple ones, they may be the same or different. In addition, in the group having these "substituents", if the position to which the "substituents" are bonded is plural, for example, any of the four carbons in an n-butyl group, the para position, the meta position, or the ortho position in a phenyl group, the substituted position may be at any of the positions, and if the position to which the "substituents" are bonded is plural, such as a pyridyl group or a naphthyl group, the bond may be at any of the positions. In addition, these "substituents" may additionally have the substituents exemplified above. Therefore, these "substituents" are, for example, "a linear or branched unsubstituted or substituted alkyl group having 1 to 20 carbon atoms", "an unsubstituted or substituted cycloalkyl group having 3 to 20 carbon atoms", "a linear or branched unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms", "a linear or branched alkynyl group having 2 to 20 carbon atoms", "an unsubstituted or substituted cycloalkoxy group having 3 to 20 carbon atoms", "an unsubstituted or substituted aryloxy group having 6 to 20 carbon atoms", "an unsubstituted or substituted amino group having 0 to 20 carbon atoms", "an unsubstituted or substituted amide group having 1 to 20 carbon atoms", "an amide group having 0 to 20 carbon atoms". It can also be expressed as "unsubstituted or substituted ammonium group", "unsubstituted or substituted phenyl group having 6 to 20 carbon atoms", "unsubstituted or substituted phenoxy group having 6 to 20 carbon atoms", "phenyl group having 6 to 20 carbon atoms substituted with a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a halogen atom", etc. In addition, when the "substituent" contains a carbon atom, the carbon atom is included in the total number of carbon atoms in the description of the group specifying the number of carbon atoms, such as "1 to 12 carbon atoms", "6 to 20 carbon atoms", and "2 to 20 carbon atoms". In addition, these substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

In the general formula (1), when a “monosubstituted or disubstituted amino group having 1 to 20 carbon atoms” is present, it includes an “amino group having substituents R ¹¹ and R ¹² ” represented by “—NR ¹¹ R ¹² ”, and examples thereof include a monosubstituted amino group, a disubstituted amino group, and the like.

The "substituent" in "an amino group having substituents R ¹¹ and R ¹² " is the same as the "substituent" in each group represented by R ¹ to R ^10. Examples of the monosubstituted amino group include an ethylamino group, a butylamino group, an isopropylamino group, an acetylamino group, a phenylamino group, a 1-naphthylamino group, and a 2-naphthylamino group. Examples of the disubstituted 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, a dihexylamino group, an ethylmethylamino group, a di(2-ethylhexyl) group, and a di-t-butylamino group; a dialkenylamino group having 4 to 20 carbon atoms, such as a diallylamino group; Examples thereof include a diphenylamino group, an N-phenyl-1-naphthylamino group, an N-methyl-phenylamino group, an N-acetyl-N-phenylamino group, and an N-(n-butyl)-phenylamino group.

In the general formula (1), when an "inorganic cation" or "organic cation" represented by "M" is present, the "organic cation" specifically includes an ammonium ion represented by the formula R ¹³ R ¹⁴ R ¹⁵ R ¹⁶ N ⁺ , and R ¹³ to R ¹⁶ each independently represent a hydrogen atom, a linear or branched 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, and they may be bonded to each other to form a ring. In addition, in the above formula, the details of the "substituent", "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" in R ¹³ to R ¹⁶ are the same as those for R ¹ to R ¹⁰ in the general formula (1). In addition, examples of the "inorganic cation" include alkali metal ions such as lithium ion and sodium ion, or alkaline earth metal ions such as magnesium ion, calcium ion and barium ion. As M, an alkali metal ion is preferable.

In the general formula (1), when a “carbonyl group, ester group or amide group having 1 to 20 carbon atoms which may have a substituent” is present, it means a group represented by “―(C=O)―R ¹⁷ ”, “―(C=O)―O―R ¹⁷ ” or “―(C=O)―NR ¹¹ R ¹² ”, respectively. R ¹⁷ and “―NR ¹¹ R ¹² ” are the same as the “substituent” in each group represented by R ¹ to R ¹⁰ .

In the general formula (1), when a “sulfonyl group or sulfonamide group having 0 to 20 carbon atoms which may have a substituent” is present, it means a group represented by “—SO ₂ —R ¹⁷ ” (or “—S(=O) ₂ —R ¹⁷ ”) or “—S(=O) ₂ —NR ¹¹ R ¹² ”. R ¹⁷ and “—NR ¹¹ R ¹² ” are the same as the “substituent” in each group represented by R ¹ to R ¹⁰ .

In addition, among the various "groups" having "substituents" represented by R ¹ to R ¹⁰ in general formula (1), those exemplified as "substituents" are:

"A straight-chain or branched alkyl group having 1 to 20 carbon atoms"

"Cycloalkyl group having 3 to 20 carbon atoms",

"A straight or branched alkenyl group having 2 to 20 carbon atoms"

"A straight or branched alkynyl group having 2 to 20 carbon atoms"

"A straight-chain or branched alkoxy group having 1 to 20 carbon atoms"

"Cycloalkoxy group having 3 to 20 carbon atoms",

"Acyl group having 1 to 20 carbon atoms",

"Aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 20 carbon atoms",

"Complex ring group with 2 to 20 carbon atoms",

"Aryloxy group having 6 to 20 carbon atoms", or

Specifically, as a "monosubstituted or disubstituted amino group having 1 to 20 carbon atoms",

A linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, an isooctyl group, a nonyl group, a decyl group, etc.;

Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group;

An alkenyl group such as a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group, an isobutenyl group, or a linear or branched alkenyl group in which multiple groups of these are bonded;

An alkynyl group such as an ethynyl group, a propargyl group, a butynyl group, or a linear or branched alkynyl group having multiple bonds thereof; a mixed group of an alkenyl group and an alkynyl group such as a penta-3-en-1-ynyl group, a hexa-2-en-4-ynyl group;

A linear or branched alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an isopropoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, an isooctyloxy group, etc.;

Cycloalkoxy groups having 3 to 20 carbon atoms, such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, and cyclodecyloxy group;

Acyl groups such as formyl, acetyl, propionyl, acryloyl, and benzoyl groups;

Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl (anthryl), tetracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and triphenylenyl;

Heterocyclic groups such as thienyl group, furyl group (furanyl group), pyrrolyl group, thiazolyl group, oxazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, benzothienyl group, benzofuranyl group, indolyl group, isoindolyl group, benzothiazolyl group, benzoxazolyl group, benzoimidazolyl group, benzotriazolyl group, purinyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidinyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group, and carbolinyl group;

Aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthryloxy group, and phenanthrenyloxy group;

Examples thereof include linear or branched alkyl groups such as a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an ethylmethylamino group, a dipropylamino group, an isopropylamino group, a butylamino group, a dibutylamino group, a dihexylamino group, a di(2-ethylhexyl) group, a di-t-butylamino group, a phenylamino group, a 1-naphthylamino group, a 2-naphthylamino group, a diphenylamino group, a diallylamino group, an acetylamino group, an N-phenyl-1-naphthylamino group, an N-methyl-phenylamino group, an N-(n-butyl)-phenylamino group, an N-acetyl-N-phenylamino group, or a monosubstituted or disubstituted amino group having an aromatic hydrocarbon group.

In the general formula (1), R ¹ and R ² are preferably “a linear, branched or cyclic alkyl group having 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”. Preferable examples of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a methylphenyl group, and a methoxyphenyl group. 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, from the viewpoint of heat resistance, preferably a “halogen atom” or a “linear or branched alkyl group having 1 to 12 carbon atoms which may have a substituent”, more preferably a “fluorine atom” or a “linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent”, and even more preferably a “linear alkyl group having 1 to 3 carbon atoms which may have a substituent”. Preferable examples of R ³ and R ⁴ include a fluorine atom, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. R ³ and R ⁴ may be the same or different. From the viewpoint of molecular design, it is preferable that R ³ and R ⁴ are the same group.

In general formula (1), R ⁵ to R ⁸ are preferably a “hydrogen atom,” a “halogen atom,” or a “linear alkyl group having 1 to 20 carbon atoms which may have a substituent,” and a hydrogen atom or a methyl group is more preferably. From the viewpoint of molecular design, it is preferable that R ⁵ to R ⁸ are all hydrogen atoms.

In the general formula (1), R ⁹ and R ¹⁰ are preferably a “hydrogen atom”, a “linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent”, an “aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent”, or a “heterocyclic group having 2 to 10 carbon atoms which may have a substituent”. Preferred examples of R ⁹ and R ¹⁰ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an i-butyl group, a cyclohexyl group, an adamantyl group, a phenyl group which may have a substituent, a naphthyl group, and a 2,2,6,6-tetramethylpiperidinyl group.

R ⁵ to R ¹⁰ may be bonded to each other to form a ring via a single bond, a substituted or unsubstituted methylene group or vinylene group, a nitrogen atom, an oxygen atom, or a sulfur atom. The combination of R ⁵ to R ¹⁰ when forming a ring can be, for example, R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁶ and R ⁹ or R ¹⁰ , R ⁷ and R ⁹ or R ¹⁰ , R ⁹ and R ¹⁰ .

In general formula (1), An is not particularly limited as long as it is not a halide ion, and examples thereof include inorganic anions such as heteropoly acid anions, or organic anions having 1 to 30 carbon atoms and having an alkyl group, a perfluoroalkyl group, a sulfonyl group, or a sulfonic acid group. Specifically,

(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 ^- ,

(C ₂ F ₅ ) ₃ F ₃ P ^- ,

(CN) ₂ N ^- , (CN) ₃ C ^- , NC―S ^- , ;

(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- , (P ₂ W ₁₈ O ₆₂ ) ^6- ,

(SiW ₁₂ O ₄₀ ) ^4- , (PMo ₁₂ O ₄₀ ) ^3- , (SiMo ₁₂ O ₄₀ ) ^3- ,

(PW _12-x Mo _x O ₄₀ ) ^3- , (SiW _12-x Mo _x O ₄₀ ) ^4- ,

Heteropoly acid anions such as (P ₂ W _18-y Mo _y O ₄₀ ) ^6- (x represents an integer from 1 to 11, and y represents an integer from 1 to 17), etc.;

Alternatively, anions represented by structural formulas (Z-1) to (Z-16) below may be mentioned.

[Chemical formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

In the general formula (1), An may be single or may be a combination of two or more different ones, and is preferably single or an arbitrary combination of two or three selected from the anions exemplified above, and is more preferably single or an arbitrary combination of two or three selected from any of a perfluoroalkylsulfonic acid anion (more preferably a perfluoroalkylsulfonic acid anion having 1 to 24 carbon atoms), a perfluoroalkylsulfonimide anion (more preferably a perfluoroalkylsulfonimide anion having 1 to 24 carbon atoms), a tris(trifluoromethanesulfonyl)methide anion, or a heteropolyacid anion. Therefore, "m" in the general formula (1) is preferably any natural number such that the formula (1) as a whole becomes electrically neutral, depending on the valence of the entire [An] in the formula (1) and the valence of the cation of the structure of the triarylmethane skeleton in [ ].

The method for producing a triarylmethane dye compound represented by the general formula (1) is not particularly limited, and can be produced by applying a known method (for example, Non-patent Document 1) and using a reagent having various corresponding groups of the general formula (1) or other appropriate reagents. Hereinafter, one embodiment of a method for producing the compound of the present invention will be described. However, the present invention is not limited to these.

The triarylmethane pigment represented by the general formula (1) is obtained by condensing an aromatic aldehyde having a corresponding substituent and a tetrahydroquinoline having a corresponding substituent in the presence of an acid catalyst, and then oxidizing using an oxidizing agent. In addition, the triarylmethane pigment represented by the 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 in the absence of a solvent.

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

Hereinafter, specific examples of compounds preferable as the triarylmethane dye of the present invention represented by the general formula (1) are shown, but the present invention is not limited to these compounds. The following formulas (B-1) to (B-62) represent a portion of the triarylmethane dye in the general formula (1), and the anion portion represented by [An] is omitted. In the structural formula below, some hydrogen atoms are omitted, and all stereoisomers and tautomers that may occur are included, and planar structural formulas are described.

[Chemical formula 6]

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical formula 20]

[Chemical Formula 21]

The triarylmethane pigment of the present invention may be used as one type or in combination of two or more types having different molecular structures (for example, mixed). When two or more types are used, the mass concentration ratio of the smallest type of triarylmethane pigment in the total mass concentration ratio of the triarylmethane pigment is 0.1 to 50 mass%. It is preferable that there are one or two types of triarylmethane pigments.

The triarylmethane dye of the present invention, the coloring composition containing the dye, and the colorant for color filters containing the dye or the coloring composition need to be well dissolved or dispersed in an organic solvent containing a resin or the like in the manufacturing process of the colorant and the color filter, and therefore, it is preferable that the organic solvent have high solubility or dispersibility in the organic solvent. The organic solvent is not particularly limited, and specific examples thereof include: aromatic hydrocarbons such as toluene and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, and 2-propanol; Esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA); amides such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO), etc., are exemplified, and PGME, PGMEA, cyclohexanone, or DAA are preferable, and PGME or PGMEA is particularly preferable from the viewpoint of achieving both the solubility of the resin and the solubility of the triarylmethane pigment. These solvents may be used alone or in combination of two or more.

The triarylmethane pigment of the present invention exhibits a maximum absorption wavelength, which is the maximum absorbance, in the visible light region (for example, a wavelength range of 350 to 800 nm) of an ultraviolet-visible absorption spectrum measured at around room temperature (for example, 23 to 27° C.) using a solution prepared by dissolving it in an organic solvent. In the present invention, it is preferable that the maximum absorption wavelength in the PGMEA solution is in a wavelength range of 590 to 670 nm. Furthermore, the pigment concentration is preferably 0.005 to 0.02 mmol/L. The solvent is not limited as long as it dissolves the pigment, but it is preferable that the absorption wavelength of the ultraviolet-visible absorption spectrum does not shift significantly depending on the dissolution conditions, and PGMEA is preferable.

The triarylmethane pigment of the present invention can be mixed with various resin solutions and applied onto a glass substrate to produce a coating film. The obtained coating film can be color-measured using a spectrophotometer to obtain the color value of the coating film, thereby enabling color evaluation. The color value is generally determined using the CIE L ^* a ^* b ^* colorimetric system. Specifically, the color values L ^* , a ^* , and b ^* of the film sample are measured, and the heat resistance can be judged by the color difference (ΔE ^* ab) of the color values 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 indicator of heat resistance. A smaller ΔE ^* ab value means less color discoloration due to thermal decomposition and higher heat resistance, and is preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less. In addition, as a method for comparing the heat resistance of pigments, it may be evaluated by thermogravimetry, and for example, the 5% mass reduction temperature is measured by thermogravimetry in an inert gas atmosphere such as nitrogen, and a higher decomposition temperature is preferable.

The colorant for a color filter of the present invention comprises a triarylmethane pigment represented by the general formula (1), or a coloring composition containing at least one of the triarylmethane pigments, and a component generally used in the production of a color filter. A general color filter is obtained, for example, in the case of a method using a photolithography process, by mixing a pigment such as a dye or pigment with a resin component (including a monomer and an oligomer) or a solvent, applying a liquid prepared by applying the mixture onto a substrate such as glass or a resin, photopolymerizing using a photomask, to produce a coloring pattern of a pigment-resin composite film soluble/insoluble in the solvent, and then washing and heating. In addition, in the case of an electrodeposition method or a printing method, a coloring pattern is produced using a pigment mixed with a resin or other component. Therefore, specific components in the colorant for a color filter of the present invention include at least one triarylmethane pigment represented by the general formula (1), other pigments such as dyes or pigments, resin components, organic solvents, and other additives such as a photopolymerization initiator. Also, you can choose from these ingredients and add other ingredients as needed.

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

The colorant for the color filter of the present invention may use one or more types of triarylmethane pigments alone, or may additionally mix other known pigments such as dyes or pigments as described below for adjusting color tone, i.e., for adjusting spectral characteristics.

When used as a colorant for a blue color filter, examples thereof include, but are not particularly limited to, basic dyes such as C. I. Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129, C. I. Basic Violet 10; acid dyes such as C. I. Acid Blue 9, 74, C. I. Acid Red 52, 289; disperse dyes such as Disperse Blue 3, 7, 377; Spilon dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, and xanthene-based pigments not belonging to the present invention; and other blue lake pigments, and blue or red dyes or pigments.

When used as a colorant for a green color filter, examples thereof include, but are not limited to, blue, yellow or green dyes or pigments, such as green pigments such as C. I. Pigment Green 7, 10, 36, 47, 58, 59, 62 and 63; yellow pigments such as C. I. Pigment Yellow 83, 138, 139, 150, 180 and 185; Spillon dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based, isoindoline-based and quinophthalone-based pigments not belonging to the present invention; and other lake pigments.

In the present invention, as a pigment mixed for adjusting the color tone, when used as a colorant for a blue color filter, a triarylmethane pigment not belonging to the present invention, such as C. I. Basic Blue 7, or a xanthene pigment such as C. I. Basic Violet 10, C. I. Acid Red 52, 289, is preferable. When used as a colorant for a green color filter, a quinophthalone pigment such as C. I. Pigment Yellow 138, an isoindoline pigment such as C. I. Pigment Yellow 139, or an azo pigment is preferable. By using these pigments and a triarylmethane pigment belonging to the present invention, a blue or green color filter excellent in brightness or contrast ratio can be obtained.

The pigment may be subjected to, if necessary, surface treatment using rosin treatment, a pigment derivative having an acidic or basic group introduced therein, grafting treatment on the pigment surface using a polymer compound, a particulate treatment using a sulfuric acid particle method, or a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, or the like. It is preferable that the particle size of the pigment be uniform.

The mixing ratio of other pigments in the colorant for color filters of the present invention is preferably 5 to 2000 mass%, more preferably 10 to 1000 mass%, with respect to the triarylmethane pigment (the total of two or more pigments). The mixing ratio of pigment components such as dyes in the liquid colorant for color filters is preferably 0.5 to 70 mass%, more preferably 1 to 50 mass%, with respect to the entire colorant.

As the resin component in the colorant for color filters of the present invention, any known resin can be used as long as it has the properties necessary for the manufacturing method or use of the color filter resin film formed using them. Specifically, examples thereof include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolac) resins, other transparent resins, photocurable resins, or thermocurable resins, and appropriate combinations of these monomer or oligomer components can be used. In addition, copolymers of these resins can also be combined and used. In the case of a liquid colorant, the content of the resin in these colorant for color filters is preferably 5 to 95 mass%, and more preferably 10 to 50 mass%.

The coloring composition of the present invention may contain, as other components of the compound, substances such as a surfactant, a dispersant, an anti-foaming agent, a leveling agent, an antioxidant, an ultraviolet absorber, and other additives mixed during the production of a colorant for color filters, in order to enhance its performance as a colorant for color filters. However, the content of these additives in the coloring composition is preferably an appropriate amount, and is preferably a content that does not reduce the solubility of the coloring composition of the present invention in a solvent or increase it more than necessary, or affect the effect of other similar additives used during the production of color filters. These additives can be added at any timing of the preparation of the coloring composition.

Other additives in the colorant for color filters of the present invention include components necessary for polymerization or curing of resins, such as photopolymerization initiators and crosslinking agents, and surfactants and dispersants necessary for stabilizing the properties of components in the liquid colorant for color filters. Any known additives for producing color filters can be used, and are not particularly limited. 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 mass%, and more preferably 10 to 40 mass%.

Example

Hereinafter, embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. Reagents described in the synthetic examples were those manufactured by Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich, Alfa Aesar, etc. In addition, all reactions in the synthetic examples were carried out using a reaction vessel equipped with a condenser, a stirring device, and a thermometer. In addition, the identification of the compounds in the following synthetic examples was carried out by ¹ H-NMR analysis (nuclear magnetic resonance device manufactured by Bruker, type: Ascend ^TM 400 MHz).

[Synthetic Example 1] Synthesis of compound (C-1)

The following reaction was carried out under a nitrogen stream. In a reaction vessel, 40.0 g (211 mmol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, 65.9 g (423 mmol) of iodoethane, 52.6 g (380 mmol) of potassium carbonate, and 160 mL of DMF were placed, and the mixture was stirred at 75 ° C. for 7 hours. After cooling, 200 mL of ethyl acetate and 200 mL of heptane were added to the reaction solution, and the mixture was stirred at room temperature (23 to 28 ° C.) and then filtered. 300 mL of water was added to the filtrate, the organic layer was extracted, and the organic layer was washed twice with 300 mL of water. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. After dissolving the residue in 350 mL of heptane, 45 g of silica gel was added, stirred at room temperature (23 to 28 °C) for 30 minutes, and then filtered. The filtrate was concentrated under reduced pressure to obtain the following (intermediate 100) (42.5 g, yield 92%).

[Chemical Formula 22]

Subsequently, the following reaction was carried out under a nitrogen atmosphere. 1.32 g (18.1 mmol) of DMF and 1.77 g (18.1 mmol) of concentrated sulfuric acid were placed in a reaction vessel, and the mixture was stirred at room temperature (23 to 28°C). 3.20 g (18.1 mmol) of 4-diethylaminobenzaldehyde and 8.04 g (37.0 mmol) of the above (intermediate 100) were added, and the mixture was stirred at 120°C for 46 hours. 15 mL of DMF was added to the reaction solution, and then 50 mL of water was added, and the precipitated solid was collected by filtration. The obtained solid was purified by column chromatography (carrier: silica gel, solvent: heptane/ethyl acetate = 100/1 to 50/1 (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 101) (2.18 g, yield 20%).

[Chemical Formula 23]

Subsequently, 2.15 g (3.62 mmol) of the above (Intermediate 101) and 32 mL of chloroform were added to the reaction vessel, stirred, and after the solid was dissolved, 1.78 g (7.24 mmol) of p-chloranil was added. After stirring at room temperature (23 to 28 ° C.) for 12 hours, 0.5 mL of concentrated hydrochloric acid was added, and stirred for an additional 30 minutes. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure, and 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 suspended and washed with heptane, the solid was filtered, and dried under reduced pressure at 60°C to obtain the following (intermediate 102) (2.21 g, yield 97%).

[Chemical Formula 24]

Subsequently, 1.70 g (2.71 mmol) of the above (Intermediate 102) and 17 mL of methanol were added to the reaction vessel, stirred, and after dissolving the solid, 0.78 g (2.71 mmol) of lithium bis(trifluoromethanesulfonyl)imide (LiN(SO ₂ CF ₃ ) ₂ ) was added. After stirring at 45 ° C. for 1 hour, cooling, 60 mL of water was added, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 80 ° C., to obtain the target compound (C-1) as a brown solid (1.97 g, yield 84%).

NMR measurement of the obtained brown solid was performed, and the following 58 hydrogen signals were detected, and the structure of the compound represented by the following formula (C-1) was identified.

[Chemical Formula 25]

[Synthetic Example 2] Synthesis of compound (C-2)

The following reaction was carried out under a nitrogen stream. 83 mL of DMF was placed in a reaction vessel, and after cooling to 5°C, 16.9 g (110 mmol) of phosphorus oxychloride was added dropwise over 30 minutes. After the addition, the temperature was raised to room temperature (23 to 28°C), and 15.0 g (91.9 mmol) of N,N-diethyl-3-methylaniline was added dropwise. The solution was stirred at 90°C for 3 hours. After cooling, the reaction solution was poured into 300 mL of ice water and added, and sodium carbonate was further added to adjust the pH to 9. 150 mL of ethyl acetate and 150 mL of heptane were added to the solution, filtered, and the organic layer of the filtrate was extracted. The organic layer was further washed twice with 300 mL of water, extracted, and anhydrous magnesium sulfate was added. After drying the organic layer, filtering, and concentrating the filtrate under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: heptane/ethyl acetate = 90/10 (volume ratio)), and the solvent was distilled off under reduced pressure to obtain the following (intermediate 103) (14.8 g, yield 84%).

[Chemical Formula 26]

Continuing, in the synthesis of (Intermediate 101) of Synthetic Example 1, except that 4-diethylaminobenzaldehyde was changed to (Intermediate 103), the following (Intermediate 104) was obtained by the same method (2.84 g, yield 30%).

[Chemical Formula 27]

Continuing, in the synthesis of (Intermediate 102) of Synthetic Example 1, except that (Intermediate 101) was changed to (Intermediate 104), the following (Intermediate 105) was obtained by the same method (2.41 g, yield 81%).

[Chemical formula 28]

Continuing, in the synthesis of compound (C-1) of Synthetic Example 1, except that (intermediate 102) was changed to (intermediate 105), the target compound (C-2) was obtained as a purple solid by the same method (2.17 g, yield 87%).

NMR measurement of the obtained purple solid was performed, and the following 60 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-2).

[Chemical Formula 29]

[Synthetic Example 3] Synthesis of compound (C-3)

The following reaction was carried out under a nitrogen stream. 10.9 g (149 mmol) of DMF and 4.88 g (49.8 mmol) of concentrated sulfuric acid were placed in a reaction vessel, and the mixture was stirred at room temperature (23 to 28°C). 7.00 g (49.8 mmol) of 4-chlorobenzaldehyde and 21.9 g (101 mmol) of the above (intermediate 100) were added, and the mixture was stirred at 120°C for 6 hours. 50 mL of DMF was added to the reaction solution, and then 400 mL of water was poured into the mixture, and the precipitated solid was filtered out. 150 mL of methanol and 50 mL of water were added to the obtained solid, and the mixture was washed by suspension, and the solid was filtered out. The obtained solid was dried under reduced pressure at 60°C to obtain the following (intermediate 106) (26.4 g, yield 95%).

[Chemical formula 30]

Subsequently, 26.0 g (46.7 mmol) of the above (Intermediate 106) and 300 mL of methanol were added to the reaction vessel, and the mixture was cooled to 5°C. A solution of 13.8 g (60.7 mmol) of 1,2-dichloro-5,6-dicyano-p-benzoquinone (DDQ) dissolved in 90 mL of methanol was added dropwise over 1 hour. After the addition, the mixture was heated to room temperature (23 to 28°C) and stirred for 2 hours. 220.1 g (70.0 mmol) of LiN(SO ₂ CF ₃ ) was added to the solution, and the mixture was stirred at room temperature (23 to 28°C) for 1 hour. The solution was poured into 1.6 L of water, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 400 mL of dichloromethane, washed with 300 mL of water, extracted the organic layer, and dried by adding magnesium sulfate. The solution was filtered, 40 g of silica gel was added to the filtrate, stirred at room temperature (23 to 28°C) for 1 hour, and then filtered. After the filtrate was concentrated under reduced pressure, the residue was dissolved in 200 mL of methanol, and further 500 mL of water was poured and added. The precipitated solid was collected by filtering and dried under reduced pressure at 80°C to obtain the following (intermediate 107) (29.6 g, yield 76%).

[Chemical Formula 31]

Subsequently, the following reaction was carried out under a nitrogen stream. In a reaction vessel, 3.00 g (3.59 mmol) of the above (intermediate 107), 1.74 g (14.4 mmol) of N-ethylaniline, and 24 mL of 1-butanol were placed, and the mixture was stirred at 120°C for 40 hours. After cooling the reaction solution, 50 mL of methanol was added, and this solution was dropwise added to 400 mL of 0.5 M hydrochloric acid aqueous solution. The precipitated solid was filtered, and the obtained solid was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/heptane = 70/30 → dichloromethane → dichloromethane/acetone = 50/1 (volume ratio)), and the solvent was distilled off under reduced pressure. After dissolving the residue in 30 mL of methanol, 90 mL of water was added, and the precipitated solid was filtered. The obtained solid was dried under reduced pressure at 60° C. to obtain the target compound (C-3) as a brown solid (2.85 g, yield 86%).

NMR measurement of the obtained brown solid was performed, and the following 58 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-3).

[Chemical formula 32]

[Synthetic Example 4] Synthesis of compound (C-4)

In the synthesis of (Intermediate 106) of Synthetic Example 3, except that 4-chlorobenzaldehyde was changed to 4-fluorobenzaldehyde, the following (Intermediate 108) was obtained by the same method (37.8 g, yield 72%).

[Chemical formula 33]

Continuing, in the synthesis of (Intermediate 107) of Synthetic Example 3, except that (Intermediate 106) was changed to (Intermediate 108), the following (Intermediate 109) was obtained by the same method (49.2 g, yield 87%).

[Chemical Formula 34]

Subsequently, the following reaction was carried out under a nitrogen stream. In a reaction vessel, 3.00 g (3.66 mmol) of the above (intermediate 109), 2.51 g (18.3 mmol) of N-methyl-p-anisidine, and 15 mL of 1-butanol were placed, and the mixture was stirred at 110 ° C. for 5 hours. After cooling the reaction solution, 30 mL of methanol was added, and this solution was dropwise added to 120 mL of 0.5 M aqueous hydrochloric acid solution. The precipitated solid was filtered, and the obtained solid was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/heptane = 70/30 → dichloromethane → dichloromethane/acetone = 50/1 (volume ratio)), and the solvent was distilled off under reduced pressure. After dissolving the residue in 30 mL of methanol, 90 mL of water was added, and the precipitated solid was filtered. The obtained solid was dried under reduced pressure at 80° C. to obtain the target compound (C-4) as a purple solid (2.65 g, yield 77%).

NMR measurement of the obtained purple solid was performed, and the following 58 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-4).

[Chemical Formula 35]

[Synthetic Example 5] Synthesis of compound (C-5)

In the synthesis of compound (C-3) of Synthetic Example 3, the target compound (C-5) was obtained as a brown solid (2.94 g, yield 92%) by the same method except that N-ethylaniline was changed to aniline.

NMR measurement of the obtained brown solid was performed, and the following 54 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-5).

[Chemical formula 36]

[Synthetic Example 6] Synthesis of compound (C-6)

The following reaction was carried out under a nitrogen stream. In a reaction vessel, 5.00 g (6.10 mmol) of the above (intermediate 109), 5.23 g (48.8 mmol) of o-toluidine, and 15 mL of 1-butanol were placed, and the mixture was stirred at 110°C for 5 hours. After cooling the reaction solution, 30 mL of methanol was added, and this solution was dropwise added to 150 mL of a 1 M hydrochloric acid aqueous solution. The precipitated solid was collected by filtration, and the obtained solid was dissolved in 50 mL of dichloromethane, followed by adding 10 g of silica gel, and the mixture was stirred at room temperature (23 to 28°C) for 1 hour. The solution was filtered, the filtrate was concentrated under reduced pressure, and the residue was dissolved in 25 mL of methanol. 100 mL of water was added, the precipitated solid was filtered off, and the obtained solid was dried under reduced pressure at 80° C. to obtain the target compound (C-6) as a brown solid (5.10 g, yield 92%).

NMR measurement of the obtained brown solid was performed, and the following 56 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-6).

[Chemical formula 37]

[Synthetic Example 7] Synthesis of compound (C-7)

In the synthesis of compound (C-3) of Synthetic Example 3, the target compound (C-7) was obtained as a brown solid (3.09 g, yield 92%) by the same method except that N-ethylaniline was changed to p-phenethidine.

NMR measurement of the obtained brown solid was performed, and the following 58 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-7).

[Chemical formula 38]

[Synthetic Example 8] Synthesis of compound (C-8)

In the synthesis of compound (C-4) of Synthetic Example 4, except that N-methyl-p-anisidine was changed to 3,4-dimethoxyaniline, the target compound (C-8) was obtained as a brown solid (3.03 g, yield 87%) by the same method.

NMR measurement of the obtained brown solid was performed, and the following 58 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-8).

[Chemical Formula 39]

[Synthetic Example 9] Synthesis of compound (C-9)

In the synthesis of compound (C-4) of Synthetic Example 4, except that N-methyl-p-anisidine was changed to 3,4,5-trimethoxyaniline, the target compound (C-9) was obtained as a brown solid (3.09 g, yield 86%) by the same method.

NMR measurement of the obtained brown solid was performed, and the following 60 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-9).

[Chemical formula 40]

[Synthetic Example 10] Synthesis of compound (C-10)

In the synthesis of compound (C-4) of Synthetic Example 4, except that N-methyl-p-anisidine was changed to 3,4-methylenedioxyaniline, the target compound (C-10) was obtained as a brown solid (2.92 g, yield 85%) by the same method.

NMR measurement of the obtained brown solid was performed, and the following 54 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-10).

[Chemical Formula 41]

[Synthetic Example 11] Synthesis of compound (C-11)

In the synthesis of compound (C-3) of Synthetic Example 3, the target compound (C-11) was obtained as a dark purple solid by the same method except that N-ethylaniline was changed to N,N-diethyl-1,4-phenylenediamine (2.77 g, yield 80%).

NMR measurement was performed on the obtained dark purple solid, and the following 63 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-11).

[Chemical formula 42]

[Synthetic Example 12] Synthesis of compound (C-12)

The following reaction was carried out under a nitrogen stream. In a reaction vessel, 3.00 g (3.66 mmol) of the above (Intermediate 109) and 8.84 g (54.9 mmol) of 4-aminobenzotrifluoride were placed and stirred at 110°C for 14 hours. After cooling the reaction solution, 15 mL of methanol was added, and this solution was dropped into 90 mL of a 0.5 M hydrochloric acid aqueous solution. The precipitated solid was filtered, and the obtained solid was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/heptane = 70/30 → dichloromethane → dichloromethane/acetone = 50/1 (volume ratio)), and the solvent was distilled off under reduced pressure. After dissolving the residue in 30 mL of methanol, 90 mL of water was added, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 80°C to obtain the target compound (C-12) as a brown solid (2.76 g, yield 78%).

NMR measurement of the obtained brown solid was performed, and the following 53 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-12).

[Chemical Formula 43]

[Synthetic Example 13] Synthesis of compound (C-13)

In Synthetic Example 12, the target compound (C-13) was obtained as a dark purple solid (2.40 g, yield 72%) by the same method except that 4-aminobenzotrifluoride was changed to 2-fluoroaniline.

NMR measurement of the obtained dark purple solid was performed, and the following 53 hydrogen signals were detected, and the structure of the compound represented by the following formula (C-13) was identified.

[Chemical Formula 44]

[Synthetic Example 14] Synthesis of compound (C-14)

In the synthesis of compound (C-3) of Synthetic Example 3, the target compound (C-14) was obtained as a purple solid by the same method except that N-ethylaniline was changed to 1-naphthylamine (1.73 g, yield 51%).

NMR measurement of the obtained purple solid was performed, and the following 56 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-14).

[Chemical Formula 45]

[Synthetic Example 15] Synthesis of compound (C-15)

In the synthesis of compound (C-3) of Synthetic Example 3, the target compound (C-15) was obtained as a brown solid (1.79 g, yield 56%) by the same method except that N-ethylaniline was changed to cyclohexanamine.

NMR measurement of the obtained brown solid was performed, and the following 60 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-15).

[Chemical Formula 46]

[Synthetic Example 16] Synthesis of compound (C-16)

In the synthesis of compound (C-3) of Synthetic Example 3, the target compound (C-16) was obtained as a purple solid by the same method except that N-ethylaniline was changed to 1-adamantane amine (0.44 g, yield 13%).

NMR measurement of the obtained purple solid was performed, and the following 64 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-16).

[Chemical Formula 47]

[Synthetic Example 17] Synthesis of compound (C-17)

In the synthesis of compound (C-3) of Synthetic Example 3, except that N-ethylaniline was changed to 4-amino-2,2,6,6-tetramethylpiperidine, the target compound (C-17) was obtained as a purple solid (3.16 g, yield 92%) by the same method.

NMR measurement of the obtained purple solid was performed, and the following 67 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-17).

[Chemical formula 48]

[Synthetic Example 18] Synthesis of compound (C-18)

In the synthesis of (Intermediate 100) of Synthetic Example 1, the following (Intermediate 110) was obtained by the same method except that iodoethane was changed to 1-iodo-2-methylpropane (4.34 g, yield 67%).

[Chemical Formula 49]

Continuing, in the synthesis of (Intermediate 108) of Synthetic Example 4, except that (Intermediate 100) was changed to the above (Intermediate 110), the following (Intermediate 111) was obtained by the same method (2.66 g, yield 85%).

[Chemical formula 50]

Continuing, in the synthesis of (Intermediate 109) of Synthetic Example 4, except that (Intermediate 108) was changed to the above (Intermediate 111), the following (Intermediate 112) was obtained by the same method (2.53 g, yield 65%).

[Chemical Formula 51]

Continuing, in the synthesis of compound (C-4) of Synthetic Example 4, by the same method except that N-methyl-p-anisidine was changed to p-phenethidine and (intermediate 109) was changed to the above (intermediate 112), the target compound (C-18) was obtained as a brown solid (2.57 g, yield 95%).

NMR measurement of the obtained brown solid was performed, and the following 67 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-18).

[Chemical formula 52]

[Synthetic Example 19] Synthesis of compound (C-19)

The following reaction was carried out under a nitrogen stream. In a reaction vessel, 25.0 g (132 mmol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, 24.9 g (145 mmol) of bromotoluene, 22.2 g (198 mmol) of potassium t-butoxide, 88 mL of toluene, 1.48 g (6.60 mmol) of palladium acetate, and 5.34 g (13.2 mmol) of tri-t-butylphosphine (50 wt% toluene solution) were placed and stirred under reflux for 72 hours. After cooling, the reaction solution was filtered, the filtrate was washed with 200 mL of water, and the organic layer was extracted. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. After dissolving the residue in 350 mL of heptane, 35 g of silica gel was added, stirred at room temperature (23 to 28 °C) for 30 minutes, and then filtered. The filtrate was concentrated under reduced pressure to obtain the following (intermediate 113) (34.6 g, yield 94%).

[Chemical formula 53]

Subsequently, the following reaction was carried out under a nitrogen stream. 44.2 g (604 mmol) of DMF and 11.9 g (121 mmol) of concentrated sulfuric acid were placed in a reaction vessel, and the mixture was stirred at room temperature (23 to 28°C). 7.50 g (60.4 mmol) of 4-fluorobenzaldehyde and 34.1 g (122 mmol) of the above (intermediate 113) were added, and the mixture was stirred at 120°C for 16 hours. After the reaction solution was cooled to 100°C, 100 mL of water was poured and added, and the precipitated solid was filtered out. 160 mL of methanol was added to the obtained solid, and after suspension washing at 60°C, the solid was filtered out. The obtained solid was dried under reduced pressure at 60°C to obtain the following (intermediate 114) (36.3 g, yield 90%).

[Chemical formula 54]

Subsequently, 36.0 g (54.1 mmol) of the intermediate (114) and 180 mL of THF were placed in the reaction vessel, and the mixture was stirred at room temperature (23 to 28°C). A solution of 16.0 g (70.4 mmol) of DDQ dissolved in 90 mL of THF was added dropwise to the solution over 30 minutes, and after the addition, the mixture was stirred at room temperature (23 to 28°C) for 3 hours. 23.3 g (81.2 mmol) of LiN(SO ₂ CF ₃ ) ₂ was added to the solution, and the mixture was stirred at room temperature (23 to 28°C) for 1 hour. After the reaction solution was concentrated under reduced pressure, the residue was dissolved in 200 mL of methanol, and filtered. 1.2 L of water was added to the filtrate, and the precipitated solid was collected by filtration. The obtained solid was dissolved in 200 mL of dichloromethane, 50 g of silica gel was added, the mixture was stirred at room temperature (23 to 28°C) for 1 hour, and then filtered. The filtrate was concentrated under reduced pressure, the residue was dissolved in 200 mL of methanol, and further 600 mL of water was poured and added. The precipitated solid was collected by filtration and dried under reduced pressure at 80°C to obtain the following (intermediate 115) (41.5 g, yield 81%).

[Chemical formula 55]

Continuing, in the synthesis of compound (C-4) of Synthetic Example 4, the target compound (C-19) was obtained as a purple solid (3.15 g, yield 93%) by the same method except that N-methyl-p-anisidine was changed to diisobutylamine and (Intermediate 109) was changed to the above (Intermediate 115).

NMR measurement of the obtained purple solid was performed, and the following 70 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-19).

[Chemical formula 56]

[Synthetic Example 20] Synthesis of compound (C-20)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-20) was obtained as a brown solid (1.00 g, yield 33%) by the same method except that diisobutylamine was changed to N-ethylaniline.

NMR measurement of the obtained brown solid was performed, and the following 62 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-20).

[Chemical formula 57]

[Synthetic Example 21] Synthesis of compound (C-21)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-21) was obtained as a purple solid by the same method except that diisobutylamine was changed to N-methyl-p-anisidine (5.92 g, yield 91%).

NMR measurement of the obtained purple solid was performed, and the following 62 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-21).

[Chemical formula 58]

[Synthetic Example 22] Synthesis of compound (C-22)

In the synthesis of (Intermediate 114) of Synthetic Example 19, the following (Intermediate 116) was obtained by the same method except that 4-fluorobenzaldehyde was changed to 4-(N,N-diphenylamino)benzaldehyde (5.65 g, yield 76%).

[Chemical formula 59]

In the synthesis of (Intermediate 115) of Synthetic Example 19, except that (Intermediate 114) was changed to (Intermediate 116), the target compound (C-22) was obtained as a purple solid (5.07 g, yield 67%) by the same method.

NMR measurement of the obtained purple solid was performed, and the following 62 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-22).

[Chemical formula 60]

[Synthetic Example 23] Synthesis of compound (C-23)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-23) was obtained as a purple solid (3.02 g, yield 93%) by the same method except that diisobutylamine was changed to aniline.

NMR measurement of the obtained purple solid was performed, and the following 58 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-23).

[Chemical formula 61]

[Synthetic Example 24] Synthesis of compound (C-24)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-24) was obtained as a purple solid (3.21 g, yield 98%) by the same method except that diisobutylamine was changed to o-toluidine.

NMR measurement of the obtained purple solid was performed, and the following 60 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-24).

[Chemical formula 62]

[Synthetic Example 25] Synthesis of compound (C-25)

The following reaction was carried out under a nitrogen stream. 3.00 g (3.18 mmol) of the above (intermediate 115) and 3.85 g (31.8 mmol) of 2,6-dimethylaniline were placed in a reaction vessel and stirred at 110°C for 6 hours. After cooling the reaction solution, 20 mL of methanol was added, and this solution was dropped into 100 mL of 0.5 M hydrochloric acid aqueous solution. The precipitated solid was filtered, and the obtained solid was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/heptane = 70/30 → dichloromethane → dichloromethane/acetone = 50/1 (volume ratio)), and the solvent was distilled off under reduced pressure. After dissolving the residue in 20 mL of methanol, 60 mL of water was added, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 80°C to obtain the target compound (C-25) as a purple solid (3.02 g, yield 91%).

NMR measurement of the obtained purple solid was performed, and the following 62 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-25).

[Chemical formula 63]

[Synthetic Example 26] Synthesis of compound (C-26)

In the synthesis of compound (C-25) of Synthetic Example 25, except that 2,6-dimethylaniline was changed to 2,4,6-trimethylaniline, the target compound (C-26) was obtained as a purple solid (3.04 g, yield 90%) by the same method.

NMR measurement of the obtained purple solid was performed, and the following 64 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-26).

[Chemical formula 64]

[Synthetic Example 27] Synthesis of compound (C-27)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-27) was obtained as a purple solid (5.24 g, yield 93%) by the same method except that diisobutylamine was changed to p-phenitidine.

NMR measurement of the obtained purple solid was performed, and the following 62 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-27).

[Chemical formula 65]

[Synthetic Example 28] Synthesis of compound (C-28)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-28) was obtained as a purple solid (3.24 g, yield 92%) by the same method except that diisobutylamine was changed to 4-phenoxyaniline.

NMR measurement of the obtained purple solid was performed, and the following 62 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-28).

[Chemical formula 66]

[Synthetic Example 29] Synthesis of compound (C-29)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-29) was obtained as a brown solid (3.13 g, yield 93%) by the same method except that diisobutylamine was changed to 4-(methylthio)aniline.

NMR measurement of the obtained brown solid was performed, and the following 60 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-29).

[Chemical formula 67]

[Synthetic Example 30] Synthesis of compound (C-30)

In the synthesis of compound (C-19) of Synthetic Example 19, the target compound (C-30) was obtained as a purple solid by the same method except that diisobutylamine was changed to 3-fluoro-4-methoxyaniline (2.84 g, yield 84%).

NMR measurement of the obtained purple solid was performed, and the following 59 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-30).

[Chemical formula 68]

[Synthetic Example 31] Synthesis of compound (C-31)

In the synthesis of compound (C-25) of Synthetic Example 25, the target compound (C-31) was obtained as a purple solid by the same method except that 2,6-dimethylaniline was changed to 2-fluoroaniline (2.85 g, yield 87%).

NMR measurement of the obtained purple solid was performed, and the following 57 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-31).

[Chemical formula 69]

[Synthetic Example 32] Synthesis of compound (C-32)

In the synthesis of compound (C-25) of Synthetic Example 25, except that 2,6-dimethylaniline was changed to 3-fluoroaniline, the target compound (C-32) was obtained as a purple solid (2.83 g, yield 86%) by the same method.

NMR measurement of the obtained purple solid was performed, and the following 57 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-32).

[Chemical formula 70]

[Synthetic Example 33] Synthesis of compound (C-33)

In the synthesis of compound (C-25) of Synthetic Example 25, the target compound (C-33) was obtained as a purple solid by the same method except that 2,6-dimethylaniline was changed to 4-fluoroaniline (2.95 g, yield 90%).

NMR measurement of the obtained purple solid was performed, and the following 57 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-33).

[Chemical formula 71]

[Synthetic Example 34] Synthesis of compound (C-34)

In a reaction vessel, 1.10 g (1.04 mmol) of compound (C-27) and 10 mL of methanol were placed, and stirred at room temperature. A solution of 0.35 g of phosphotungstic acid hydrate dissolved in 5 mL of methanol was added dropwise to the solution. After the addition, the mixture was stirred at room temperature (23 to 28°C) for 3 hours, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure at 80°C, and the target compound (C-34) was obtained as a blue solid (1.16 g, yield 89%).

NMR measurement of the obtained blue solid was performed, and the following 186 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-34).

[Chemical formula 72]

[Synthetic Example 35] Synthesis of compound (C-35)

In the synthesis of compound (C-34) of Synthetic Example 34, the target compound (C-35) was obtained as a blue solid (2.80 g, yield 70%) by the same method except that compound (C-27) was changed to compound (C-4).

NMR measurement of the obtained blue solid was performed, and the following 174 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-35).

[Chemical formula 73]

[Synthetic Example 36] Synthesis of compound (C-36)

In the synthesis of compound (C-34) of Synthetic Example 34, the target compound (C-36) was obtained as a blue solid by the same method except that compound (C-27) was changed to compound (C-29) (16.3 g, yield 89%).

NMR measurement of the obtained blue solid was performed, and the following 180 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-36).

[Chemical formula 74]

[Synthetic Example 37] Synthesis of compound (C-37)

In the synthesis of (Intermediate 114) of Synthetic Example 19, the following (Intermediate 117) was obtained by the same method except that 4-fluorobenzaldehyde was changed to N-(4-formylphenyl)acetamide (1.90 g, yield 22%).

[Chemical formula 75]

In the synthesis of (Intermediate 115) of Synthetic Example 19, except that (Intermediate 114) was changed to (Intermediate 117), the target compound (C-37) was obtained as a purple solid (1.50 g, yield 56%) by the same method.

NMR measurement of the obtained purple solid was performed, and the following 56 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-37).

[Chemical formula 76]

[Synthetic Example 38] Synthesis of compound (C-38)

In the synthesis of compound (C-4) of Synthetic Example 3, the target compound (C-38) was obtained as a brown solid (1.80 g, yield 88%) by the same method except that N-methyl-p-anisidine was changed to p-anisidine.

NMR measurement of the obtained brown solid was performed, and the following 56 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-38).

[Chemical formula 77]

[Synthetic Example 39] Synthesis of compound (C-39)

In the synthesis of compound (C-34) of Synthetic Example 34, the target compound (C-39) was obtained as a blue solid (1.40 g, yield 53%) by the same method except that compound (C-27) was changed to compound (C-38).

NMR measurement of the obtained brown solid was performed, and the following 168 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-39).

[Chemical formula 78]

[Synthetic Example 40] Synthesis of compound (C-40)

In the synthesis of (Intermediate 108) of Synthetic Example 4, except that (Intermediate 100) was changed to 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline, the following (Intermediate 118) was obtained by the same method (7.50 g, yield 77%).

[Chemical formula 79]

Continuing, in the synthesis of (Intermediate 107) of Synthetic Example 3, except that (Intermediate 106) was changed to (Intermediate 118), the following (Intermediate 119) was obtained by the same method (2.40 g, yield 34%).

[Chemical formula 80]

Continuing, in the synthesis of compound (C-27) of Synthetic Example 27, the target compound (C-40) was obtained as a purple solid (1.00 g, yield 67%) by the same method except that (intermediate 115) was changed to the above (intermediate 119).

NMR measurement of the obtained purple solid was performed, and the following 50 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-40).

[Chemical formula 81]

[Synthetic Example 41] Synthesis of compound (C-41)

In the synthesis of (Intermediate 113) of Synthetic Example 19, the following (Intermediate 120) was obtained by the same method except that 4-bromotoluene was changed to bromobenzene (27.3 g, yield 88%).

[Chemical formula 82]

Continuing, in the synthesis of (Intermediate 108) of Synthetic Example 4, except that (Intermediate 100) was changed to the above (Intermediate 120), the following (Intermediate 121) was obtained by the same method (8.96 g, yield 87%).

[Chemical formula 83]

Continuing, in the synthesis of (Intermediate 107) of Synthetic Example 3, except that (Intermediate 106) was changed to (Intermediate 121), the following (Intermediate 122) was obtained by the same method (10.9 g, yield 85%).

[Chemical formula 84]

Continuing, in the synthesis of compound (C-23) of Synthetic Example 23, the target compound (C-41) was obtained as a purple solid (2.88 g, yield 92%) by the same method except that (intermediate 115) was changed to the above (intermediate 122).

NMR measurement of the obtained purple solid was performed, and the following 54 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (C-41).

[Chemical formula 85]

[Synthesis of comparative compound (D-1)]

By the method described in Synthesis Example 1 in paragraph [0058] of Patent Document 4 (Japanese Patent Application Laid-Open No. 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, and the structure of the compound represented by the following formula (D-1) was identified.

[Chemical formula 86]

[Synthesis of comparative compound (D-2)]

The following reaction was carried out under a nitrogen stream. 20.0 g (150 mmol) of 1,2,3,4-tetrahydroquinoline, 33.7 g (180 mmol) of 1-iodobutane, 41.5 g (300 mmol) of potassium carbonate, and 100 mL of DMF were placed in a reaction vessel, and the mixture was stirred at 80°C for 15 hours. After cooling the reaction solution, 200 mL of ethyl acetate was added, the mixture was stirred at room temperature (23 to 28°C), and then filtered. 100 mL of heptane and 300 mL of water were added to the filtrate, the organic layer was extracted, and the organic layer was washed twice with 300 mL of water. Anhydrous magnesium sulfate was added, the organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure. After dissolving the residue in 300 mL of heptane, 30 g of silica gel was added, stirred at room temperature (23 to 28°C) for 30 minutes, and then filtered. The filtrate was concentrated under reduced pressure to obtain the following (intermediate 202) (23.9 g, yield 84%).

[Chemical formula 87]

Subsequently, the following reaction was carried out under a nitrogen atmosphere. In a reaction vessel, 3.00 g (16.9 mmol) of 4-diethylaminobenzaldehyde, 6.50 g (34.4 mmol) of the above (intermediate 202), 0.51 g (8.46 mmol) of urea, 2.8 mL (33.9 mmol) of concentrated hydrochloric acid, and 45 mL of ethyl cellosolve were placed, and the mixture was stirred at 90 ° C. for 4 hours. The reaction solution was poured into 250 mL of water and added, and 3.50 g of sodium carbonate was added, and the mixture was stirred at room temperature (23 to 28 ° C.). After removing the supernatant, the residue was dissolved in dichloromethane, and dried by adding magnesium sulfate. This solution was filtered, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/heptane = 60/40 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 following (intermediate 203) (5.12 g, yield 56%).

[Chemical formula 88]

Subsequently, 5.10 g (9.48 mmol) of the above (Intermediate 203) and 51 mL of dichloromethane were added to the reaction vessel, stirred, and after the solid was dissolved, 3.50 g (14.2 mmol) of p-chloranil was added. After stirring at room temperature (23 to 28 °C) for 1 hour, 1.0 mL of concentrated hydrochloric acid was added, and stirred for an additional 30 minutes. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure, and 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 suspended and washed with heptane, the solid was filtered, and dried under reduced pressure at 80° C. to obtain the following (intermediate 204) (4.53 g, yield 83%).

[Chemical formula 89]

Subsequently, 3.50 g (6.12 mmol) of the above (Intermediate 204), 42 mL of water, and 21 mL of methanol were placed in the reaction vessel, stirred at 60°C, and after the solid was dissolved, 1.76 g (6.12 mmol) of LiN( _{SO2CF3 ) 2} was added. After stirring at 60°C for 1 hour, cooling, and the precipitated solid was filtered out. 50 mL of water was added to the obtained solid, and after suspension washing at 50°C, the solid was filtered out. The obtained solid was dried under reduced pressure at 80°C, to obtain a comparative example compound (D-2) represented by the following formula as a blue solid (4.63 g, yield 93%).

NMR measurement of the obtained blue solid was performed, and the following 50 hydrogen signals were detected, and the structure of the compound was identified as represented by the following formula (D-2).

[Chemical formula 90]

[Example 1]

(Measurement of maximum absorption wavelength)

The compound (C-1) obtained in Synthetic Example 1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA), and a solution having a concentration of 0.01 mmol/L was prepared. Using an ultraviolet-visible spectrophotometer (manufactured by Nippon Bunko Co., Ltd., model: V-650), the ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) as a spectral characteristic was measured at room temperature (25°C), and the maximum absorption wavelength in the measurement wavelength range was measured. The measurement results are shown in Table 1.

(Measurement of 5% mass loss temperature)

For the compound (C-1) obtained in Synthetic Example 1, a thermogravimetric-differential thermal analysis device (TG-DTA2000S type manufactured by Mac Science Co., Ltd.) was used to perform TG-DTA measurement (sample mass: 5.0 to 6.0 mg, heating rate: 10°C/min) under a nitrogen stream, and the 5% mass loss temperature was measured. The measurement results are shown in Table 1.

(Evaluation of heat resistance)

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

[Examples 2 to 41]

In Example 1, except that compounds (C-2) to (C-41) obtained in Synthetic Examples 2 to 41 were used instead of compound (C-1), measurement of the maximum absorption wavelength, measurement of the 5% mass loss temperature, and evaluation of heat resistance were performed in the same manner as in Example 1. The results are summarized and shown in Table 1.

[Comparative Example 1 and Comparative Example 2]

For comparison, instead of the compound (C-1) of the example, the triarylmethane pigments not belonging to the present invention, and the comparative example compounds (D-1) and (D-2) were used, and the measurement of the maximum absorption wavelength, the measurement of the 5% mass loss temperature, and the evaluation of heat resistance were performed in the same manner as in Example 1, except that they were used. The results are summarized and shown in Table 1.

As shown in Table 1, the triarylmethane pigment, which is a compound of an example of the present invention, is superior to the triarylmethane pigment of a comparative example in that it has a high 5% mass loss temperature and heat resistance during film formation.

The coloring composition containing the triarylmethane pigment related to the present invention has high heat resistance and can be used as a coloring material for various purposes such as a colorant for color filters. In addition, by using the coloring composition as a colorant for color filters, it is possible to produce a color filter having excellent color characteristics (color gamut, brightness, contrast ratio, etc.).

Claims (9)

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

[In formula (1), R ¹ and R ² are each independently -H,
A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent;
An aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, or
It represents an acyl group having 1 to 12 carbon atoms that may have a substituent,
R ³ and R ⁴ are, each independently, ―H, a halogen atom, ―OH,
A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent, or
It represents a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent.
R ⁵ ∼ R ⁸ are each independently -H, a halogen atom, -OH, -NO ₂ , -CN,
A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent.
An aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, or
It represents a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms which may have a substituent.
R ⁹ and R ¹⁰ are, each independently, ―H,
A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, which may have a substituent.
An aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent.
A heterocyclic group having 2 to 20 carbon atoms, which may have a substituent, or
It represents an acyl group having 1 to 12 carbon atoms that may have a substituent,
R ⁵ to R ¹⁰ may be bonded to each other via a single bond, a substituted or unsubstituted methylene group or vinylene group, a nitrogen atom, an oxygen atom, or a sulfur atom to form a ring.
An represents an anion other than a halide ion,
m represents a natural number.] In the first paragraph,
A triarylmethane pigment, wherein in the general formula (1) above, R ¹ and R ² are a linear, branched or cyclic alkyl group having 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. In the first paragraph,
A triarylmethane pigment, wherein in the general formula (1) above, R ³ and R ⁴ are linear alkyl groups having 1 to 3 carbon atoms which may have a substituent. In any one of claims 1 to 3,
In the above general formula (1), An
Perfluoroalkylsulfonic acid anion having 1 to 24 carbon atoms,
A perfluoroalkylsulfonimide anion having 1 to 24 carbon atoms,
tris(trifluoromethanesulfonyl)methide anion, or
(PW ₁₂ O ₄₀ ) ^3- , (P ₂ W ₁₈ O ₆₂ ) ^6- ,
(SiW ₁₂ O ₄₀ ) ^4- , (PMo ₁₂ O ₄₀ ) ^3- ,
(SiMo ₁₂ O ₄₀ ) ^3- , (PW _12-x Mo _x O ₄₀ ) ^3- ,
A triarylmethane pigment, which is a heteropolyacid anion represented by (P ₂ W _18-y Mo _y O ₄₀ ) ^6- or (SiW _12-x Mo _x O ₄₀ ) ^4- (wherein x represents an integer from 1 to 11 and y represents an integer from 1 to 17). In the first paragraph,
A triarylmethane dye, the maximum absorption wavelength of the absorption band in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 800 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether acetate (PGMEA) solution of the above triarylmethane dye is in the wavelength range of 590 nm to 670 nm. A coloring composition containing a triarylmethane pigment according to any one of claims 1 to 3. A coloring composition containing the triarylmethane pigment described in claim 4. A colorant for a color filter containing the coloring composition described in claim 7. A color filter using the colorant for a color filter described in Article 8.