JP7425576B2 - Xanthene pigments, coloring compositions containing the pigments, coloring agents for color filters, and color filters - Google Patents

Description

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

Color filters are used in liquid crystal, electroluminescent (EL) display devices, and CCD and CMOS image sensors. Color filters are made by laminating a colored layer such as a thin pigment film or a pigment-resin composite film on a light-transmitting substrate such as glass or transparent resin using a dyeing method, pigment dispersion method, printing method, electrodeposition method, etc. Manufactured by.
Xanthene dyes are compounds that are used as colorants for color filters because of their vividness (Patent Documents 1, 2, etc.). For example, C. I. Acid Red 289 and C.I. I. By using a xanthene dye such as Acid Red 52 in combination with an azopyridone dye, an excellent red color tone can be obtained (Patent Document 1). Here, C. I. means color index.

Japanese Patent Application Publication No. 2002-265834 JP2012-207224A Patent No. 6118213 Patent No. 5703630

"Chemical Communications", (UK), 2017, Volume 53, p. 1064-1067, Supporting Information

In the development of current display devices, higher performance (high definition, wide color gamut, low voltage) is required year by year, and demands are also placed on the performance of the color filters used (color characteristics such as high transmittance and high color purity). is also getting higher every year. As for dyes used in color filters, for example, xanthene dyes, those whose maximum absorption wavelength of the ultraviolet-visible absorption spectrum of the solution is in the range of 520 to 560 nm have been used in conventional red color filters (Patent Document 1, 2), but currently there is a demand for dyes having maximum absorption wavelengths on the longer wavelength side. However, with the molecular structure of conventional xanthene dyes, it has been difficult to synthesize a dye having a maximum absorption wavelength of 560 to 600 nm.

The present invention has been made to solve the above problems, and is a xanthene dye whose maximum absorption wavelength in the ultraviolet-visible absorption spectrum of a solution of the xanthene dye is on the long wavelength side of 560 nm or more. The object of the present invention is to provide a xanthene dye that has excellent heat resistance (range, brightness, contrast ratio, etc.), a coloring composition containing the compound, and a color filter containing the coloring composition.

As a result of intensive studies to solve the above problems and achieve the above objects, the present inventors found that the maximum in the wavelength range of 350 to 700 nm of the ultraviolet-visible absorption spectrum of a solution (solvent: propylene glycol monomethyl ether (PGME), etc.) We have completed the xanthene dye of the present invention, which has an absorption wavelength in the range of 560 nm or more, which is on the longer wavelength side than conventional xanthene dyes. That is, the present invention has the following gist.

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

[In the formula, R ¹ to R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form a ring via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom. .
R ⁵ and R ⁶ each independently represent -H, a halogen atom, -NO ₂ , or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent.
X represents -O-, -S- or -Se-.
Q represents a heterocyclic group having 2 to 30 carbon atoms which may have a substituent.
An represents an anion, a represents an integer of 1 to 3, and b represents an integer of 0 to 3.
However, general formula (1) is assumed to be charge neutral as a whole. ]

2. A xanthene dye in which Q in the general formula (1) is a heterocyclic group represented by the following general formula (Q1).

[In the formula, R ⁷ is -H, halogen atom, -OH, -CN, -OCH ₃ , -NO ₂ ,
-SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, -CO ₂ M,
A linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 28 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent, or an amino group having 0 to 28 carbon atoms which may have a substituent.
Z ¹ represents -O-, -S-, -N=, -NR ⁸ - or -CR ⁸ =,
Z ² represents -O-, -S-, -N=, -NR ⁹ - or -CR ⁹ =,
Z ³ represents -O-, -S-, -N=, -NR ¹⁰ - or -CR ¹⁰ =,
R ⁸ to R ¹⁰ are each independently, -H,
A linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 28 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent,
Adjacent groups of R ⁷ to R ¹⁰ may be bonded to each other via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom, or sulfur atom to form a ring.
M represents an organic cation or an inorganic cation, and when a plurality of them exist, they may be the same or different. ]

3. A xanthene dye in which Q in the general formula (1) is a heterocyclic group represented by the following general formula (Q11).

[In the formula, R ¹¹ to R ¹⁵ are each independently -H, a halogen atom, -OH,
-CN, _-OCH3 , _-NO2 ,
-SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, -CO ₂ M,
A linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent, or an amino group having 0 to 21 carbon atoms which may have a substituent,
R ¹⁶ and R ¹⁷ are each independently -H,
A linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent,
R ¹¹ to R ¹⁵ , R ¹⁶ and R ¹⁷ are adjacent groups that are bonded to each other via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom to form a ring. You may do so.
M represents an organic cation or an inorganic cation, and when a plurality of them exist, they may be the same or different. ]

4. A xanthene dye in which Q in the general formula (1) is a heterocyclic group represented by the following general formula (Q12).

[In the formula, R ¹⁸ to R ²¹ are each independently -H, a halogen atom, -OH,
-CN, _-OCH3 , _-NO2 ,
-SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, -CO ₂ M,
A linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent,
Adjacent groups may be bonded to each other via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom, or sulfur atom to form a ring.
^R22 is -H, halogen atom, -OH, -CN, _-OCH3 , _-NO2 ,
-SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, -CO ₂ M,
A linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent.
^R23 is -H,
A linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent,
Or represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent.
M represents an organic cation or an inorganic cation, and when a plurality of them exist, they may be the same or different. ]

5. A xanthene dye in the general formula (Q1), (Q11) or (Q12), wherein M is an alkali metal ion.

6. A xanthene dye in which, in the general formula (1), X is -O-.

7. In the general formula (1),
An is Cl ⁻ , Br ⁻ , I ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
A xanthene dye which is C ₆ H ₄ (C ₁₂ H ₂₅ )(SO ₃ ⁻ ), PF ₆ ⁻ , BF ₄ ⁻ or (PW ₁₂ O ₄₀ ) ^3- , and b is an integer from 1 to 3.

8. Using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye with a concentration of 0.005 to 0.02 mmol/L,
In the ultraviolet-visible absorption spectrum (wavelength range of 350-700 nm) measured at 23-27°C,
A xanthene pigment with maximum absorption wavelength in the wavelength range of 560 to 600 nm.

9. A colored composition containing the xanthene pigment.

10. A coloring agent for color filters containing the above-mentioned coloring composition.

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

The xanthene dye of the present invention has a maximum absorption wavelength of 560 nm or more in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) of a solution (solvent: propylene glycol monomethyl ether (PGME), etc.), and is similar to conventional xanthene dyes. Since it is on the longer wavelength side than the dye, it is useful as a coloring agent for color filters with excellent color properties (color gamut, brightness, contrast ratio, etc.) and heat resistance.

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

In the general formula (1), in the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁶ , -20 straight-chain or branched alkyl groups" specifically include:
Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group;
Examples include branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group, and 2-ethylhexyl group.

In the general formula (1), the "aromatic hydrocarbon group" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ⁴ is, Examples of "aromatic hydrocarbon groups having 6 to 20 carbon atoms" including aryl groups and fused polycyclic aromatic groups include phenyl groups, biphenylyl groups, terphenylyl groups, naphthyl groups, anthracenyl groups (anthryl groups) ), phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, and other aromatic hydrocarbon groups.

In general formula (1), the "halogen atom" represented by R ⁵ and R ⁶ includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a chlorine atom or a bromine atom being preferred.

In the general formula (1), "a linear or branched alkyl group having a substituent and ^having 1 to 20 carbon atoms" represented by R ¹ to R ⁶ and ^a "substituted Specifically, the "substituent" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms" or "methylene group having a substituent" is,
Deuterium atom, -OH, -CN, -CF ₃ , -NO ₂ ;
A sulfonic acid group represented by -SO ₃ ^- , -SO ₃ H, -SO ₃ M, or a carboxylic acid group represented by -CO ₂ ^- , -CO ₂ H, -CO ₂ M (where M is an organic Represents a cation or an inorganic cation);
Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms;
Straight chain or branched alkyl group having 1 to 20 carbon atoms;
Cycloalkyl group having 3 to 20 carbon atoms;
Straight chain or branched alkenyl group having 2 to 20 carbon atoms;
Straight chain or branched alkoxy group having 1 to 20 carbon atoms;
Cycloalkoxy group or 1-adamantyloxy group, 2-adamantyloxy group having 3 to 20 carbon atoms;
Acyl group having 1 to 20 carbon atoms;
Aromatic hydrocarbon group or fused 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 groups; mono- or di-substituted amino groups having 1 to 20 carbon atoms, and the like. One or more of these "substituents" may be included, and if more than one is included, they may be the same or different from each other. Moreover, these "substituents" may further have the above-mentioned substituents. In addition, when the "substituent" contains a carbon atom, the carbon atom is included in the above-mentioned "number of carbon atoms 1 to 20" and "number of carbon atoms 6 to 20". Further, 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 general formula (1), when an "inorganic cation" or "organic cation" represented by "M" exists, the "organic cation" specifically includes R ²⁴ R ²⁵ R ²⁶ R ²⁷ N ⁺ R ²⁴ to R ²⁷ are each independently -H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or It represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and may be bonded to each other to form a ring. In addition, in the formula, "substituent" in R ²⁴ to R ²⁷ , "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" For details, the same ones as R ¹ to R ⁴ in the general formula (1) above apply. Examples of the "inorganic cation" include alkali metal ions such as lithium ions and sodium ions, and alkaline earth metal ions such as magnesium ions, calcium ions, and barium ions. As M, an alkali metal ion is preferable.

In addition, in the above various "groups" having "substituents" represented by R ¹ to R ⁶ in general formula (1), the "substituents" are listed as
"Light chain or branched alkyl group having 1 to 20 carbon atoms",
"Cycloalkyl group having 3 to 20 carbon atoms",
"Light chain or branched alkenyl group having 2 to 20 carbon atoms",
"Light 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 fused polycyclic aromatic group having 6 to 20 carbon atoms",
"Heterocyclic group having 2 to 20 carbon atoms",
Specifically, "aryloxy group having 6 to 20 carbon atoms" or "monosubstituted or disubstituted amino group having 1 to 20 carbon atoms" includes:
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, Straight chain or branched alkyl groups such as heptyl group, octyl group, isooctyl group, nonyl group, decyl group;
Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group;
Alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or a straight chain in which multiple of these are bonded or branched alkenyl group;
Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group , a linear or branched alkoxy group such as an isooctyloxy group;
Cycloalkoxy groups having 3 to 20 carbon atoms such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group, cyclodecyloxy group;
Acyl groups such as formyl group, acetyl group, propionyl group, acrylyl group, benzoyl group;
Aromatic hydrocarbons such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group group or fused polycyclic aromatic group;
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, Benzimidazolyl group, benzotriazolyl group, purinyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidilinyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group , a naphthyridinyl group, a heterocyclic group such as a carbolinyl group;
Aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group, phenanthrenyloxy group;
Straight-chain or Examples include a branched alkyl group or a mono- or di-substituted amino group having an aromatic hydrocarbon group.

In general formula (1), R ¹ and R ² or R ³ and R ⁴ are bonded to each other via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom, or sulfur atom to form a ring. When forming a ring, it is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring.

In general formula (1), X represents an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), preferably -O- or -S-, and -O- More preferred.

In general formula (1), the "heterocyclic group having 2 to 30 carbon atoms" in the "heterocyclic group having 2 to 30 carbon atoms which may have a substituent" represented by "Q" is ,
Thienyl 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, benzimidazolyl group, benzo triazolyl group, purinyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidilinyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, acridinyl group, phenanthrolinyl group, naphthyridinyl group, Examples include carbolinyl group. In addition, as the "substituent" in the "heterocyclic group having 2 to 30 carbon atoms having a substituent", in general formula (1), the above-mentioned "substituent" having a "substituent" represented by R ¹ to R ⁶ may be used. The same things listed as "substituents" in various "groups" can be mentioned. In addition, when the "substituent" contains a carbon atom, the carbon atom is included in the "number of carbon atoms 2 to 30" in "Q" in the above general formula (1).

In the general formula (1), "a" represents the number of moieties of the compound (xanthene dye) represented by the following general formula (1-C) in the general formula (1). "An" represents an anion, and "b" represents the number of An. In general formula (1), when the molecule of the following formula (1-C) is a cation with a valence of more than one in the total charge of the entire molecule, that is, when b is an integer from 1 to 3, as a counter ion, It can be used by forming a complex with any anion represented by "An". However, in the compound represented by the general formula (1), a and b are selected so as to be charge neutral as a whole. a represents an integer of 1 to 3, preferably 1 or 2. b represents an integer of 0 to 3, preferably an integer of 1 to 3.

[In the formula, R ¹ to R ⁶ and X have the same definition as in the general formula (1). ]

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

In general formula (1), R ¹ to R ⁴ are -H,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent is preferred. .

In general formula (1), R ⁵ and R ⁶ are preferably -H, a chlorine atom, or a bromine atom.

In the general formula (1), Q represents a monovalent heterocyclic group having 2 to 30 carbon atoms which may have a substituent, and is a heterocyclic group represented by the above general formula (Q1). It is preferable. That is, the general formula (1) is preferably the following general formula (1-Q1).

[Wherein, R ¹ to R ⁶ , X, An, a, and b have the same definitions as in the general formula (1), and R ⁷ and Z ¹ to Z ³ have the same definitions as in the general formula (Q1). It has the same definition as the definition. ]

In general formula (Q1), the "halogen atom" represented by R ⁷ includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom or a chlorine atom being preferred.

In general formula (Q1), R ⁷ ,
R ⁸ in "-NR ⁸ - or -CR ⁸ =" in Z ¹ ,
R ⁹ in "-NR ⁹ - or -CR ⁹ =" in Z ² , and
Represented by R ¹⁰ in "-NR ¹⁰ - or -CR ¹⁰ =" in Z ³ ,
"A straight-chain or branched alkyl group having 1 to 28 carbon atoms" in "a straight-chain or branched alkyl group having 1 to 28 carbon atoms which may have a substituent,"
"A linear or branched alkenyl group having 2 to 28 carbon atoms" in "a straight chain or branched alkenyl group having 2 to 28 carbon atoms which may have a substituent,"
"Aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent" or "Aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent" Specifically, the "amino group having 0 to 28 carbon atoms" in "amino group having 0 to 28 carbon atoms" is
Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group;
Branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group, 2-ethylhexyl group;
Alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, or a straight chain in which multiple of these are bonded or branched alkenyl group;
Aromatic hydrocarbons such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group groups (including aryl groups and fused polycyclic aromatic groups);
Methylamino group, ethylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group, diphenylamino group, ethyl Examples include phenylamino group.

In general formula (Q1), "a linear or branched alkyl group having a substituent and having 1 to 28 carbon atoms" represented by R ⁷ to R ¹⁰ ,
"A linear or branched alkenyl group having 2 to 28 carbon atoms having a substituent,
As a "substituent" in "an aromatic hydrocarbon group having a substituent having 6 to 28 carbon atoms" or "an amino group having a substituent having 0 to 28 carbon atoms",
In the general formula (1), "a linear or branched alkyl group having a substituent and ^having 1 to 20 carbon atoms" represented by ^{R 1 to} R ⁶ or " Examples of the "substituent" in "Aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent" include the same ones as those listed above. One or more of these "substituents" may be included, and if more than one is included, they may be the same or different from each other. Moreover, these "substituents" may further have the above-mentioned substituents. In addition, when the "substituent" contains a carbon atom, the carbon atom is included in the "number of carbon atoms 2 to 30" in "Q" in the above general formula (1). Further, 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 general formula (Q1), R ⁷ to R ¹⁰ are adjacent groups that are bonded to each other via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom, or sulfur atom to form a ring. Specifically, it is preferable that adjacent groups R ⁸ and R ⁹ , R ⁹ and R ⁷ , R ⁷ and R ¹⁰ form a ring, and further adjacent groups to these rings The groups may be bonded to form a ring. Moreover, it is preferable that the ring formed is a 5-membered ring or a 6-membered ring.

In general formula (Q1), the "organic cation" or "inorganic cation" represented by "M" includes the above-mentioned "organic cation" or "inorganic cation" when "M" is present in general formula (1). Examples include "inorganic cations". That is, an ammonium ion represented by R ²⁴ R ²⁵ R ²⁶ R ²⁷ N ⁺ is mentioned, and R ²⁴ to R ²⁷ each independently contain a hydrogen atom or a carbon atom number of 1 to 1 which may have a substituent. It represents a 20 straight-chain or branched alkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and may be bonded to each other to form a ring. In addition, in the formula, "substituent" in R ²⁴ to R ²⁷ , "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" The same details as R ¹ to R ⁴ apply. Examples of the "inorganic cation" include alkali metal ions and alkaline earth metal ions, with lithium ions, sodium ions, and potassium ions being preferred.

Q in general formula (1) is preferably a heterocyclic group represented by the above general formula (Q1), more preferably a heterocyclic group represented by the above general formula (Q11) or (Q12). preferable. That is, general formula (1) is preferably the following general formula (1-Q11) or the following general formula (1-Q12).

[In the formula, R ¹ to R ⁶ , X, An, a, and b have the same definitions as in the above general formula (1), and R ¹¹ to R ¹⁷ have the same definitions as in the above general formula (Q11) has. ]

[In the formula, R ¹ to R ⁶ , X, An, a, and b have the same definitions as in the general formula (1), and R ¹⁸ to R ²² have the same definitions as in the general formula (Q12). has. ]

In the general formula (Q11), the "halogen atom" represented by R ¹¹ to R ¹⁵ includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom or a chlorine atom being preferred.

In general formula (Q11), "a linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent" represented by R ¹¹ to R ¹⁷ ;
"A linear or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent" represented by R ¹¹ to R ¹⁵ ;
"Aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent" represented by R ¹¹ to R ¹⁷ , or "Aromatic hydrocarbon group having a substituent and not having a substituent" represented by R ¹¹ to R ¹⁵ Various "groups" in "an optional amino group having 0 to 21 carbon atoms" include:
In the general formula (Q1), "a linear or branched alkyl group having a substituent and having 1 to 28 carbon atoms" represented by R ⁷ ;
"A linear or branched alkenyl group having 2 to 28 carbon atoms that may have a substituent",
Various "groups" in "aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent" or "amino group having 0 to 28 carbon atoms which may have a substituent" Examples include groups similar to those listed above, and each group has a maximum of 21 carbon atoms.
The “substituents” that these “groups” may have are the same as the “substituents” that various “groups” represented by R ⁷ in general formula (Q1) may have. may be included, and may be included in one or more than one, and if more than one is included, they may be the same or different from each other. Moreover, these "substituents" may further have the above-mentioned substituents. In addition, when the "substituent" contains a carbon atom, the carbon atom is included in the "number of carbon atoms 2 to 30" in "Q" in the above general formula (1). Further, 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 general formula (Q11), R ¹¹ to R ¹⁵ or R ¹⁶ and R ¹⁷ are adjacent groups that are bonded to each other through a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom, or sulfur atom. , may be bonded to each other to form a ring, and the formed ring is preferably a 5-membered ring or a 6-membered ring.

R ¹¹ to R ¹⁵ in general formula (Q11) are:
-H, -CN, halogen atom, -NO ₂ ,
"A straight chain or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" or "A straight chain or branched alkyl group having 2 to 10 carbon atoms which may have a substituent ``alkenyl group'' is preferable. Moreover, as R ¹⁶ and R ¹⁷ , -H,
"A linear or branched alkyl group having 1 to 10 carbon atoms that may have a substituent",
"Aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent" is preferred.

In the general formula (Q11), the "organic cation" or "inorganic cation" represented by "M" is the "organic cation" or "inorganic cation" represented by "M" in the general formula (Q1) described above. cations” can be mentioned.

Examples of the "halogen atom" represented by R ¹⁸ to R ²¹ in general formula (Q12) include fluorine atom, chlorine atom, bromine atom, and iodine atom, with fluorine atom or chlorine atom being preferred.

In general formula (Q12), "a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent" represented by R ¹⁸ to R ²³ ,
"Aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent", or
As the "amino group having 0 to 22 carbon atoms which may have a substituent" represented by R ¹⁸ to R ²² ,
In the general formula (Q1), "a linear or branched alkyl group having a substituent and having 1 to 28 carbon atoms" represented by R ⁷ ;
"A linear or branched alkenyl group having 2 to 28 carbon atoms that may have a substituent",
Various "groups" in "aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent" or "amino group having 0 to 28 carbon atoms which may have a substituent" Examples include groups similar to those listed above, and each group has a maximum of 22 carbon atoms.
The “substituents” that these “groups” may have are the same as the “substituents” that various “groups” represented by R ⁷ in general formula (Q1) may have. may be included, and may be included in one or more than one, and if more than one is included, they may be the same or different from each other. Moreover, these "substituents" may further have the above-mentioned substituents. In addition, when the "substituent" contains a carbon atom, the carbon atom is included in the "number of carbon atoms 2 to 30" in "Q" in the above general formula (1). Further, 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 general formula (Q12), R ¹⁸ to R ²¹ are adjacent groups that are bonded to each other via a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom, or sulfur atom to form a ring. The ring formed is preferably a 5-membered ring or a 6-membered ring.

R ¹⁸ to R ²¹ in general formula (Q12) are preferably -H, a halogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent.
Moreover, as R ²² , -H,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
an aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent;
An amino group having 0 to 10 carbon atoms which may have a substituent is preferred.
Moreover, as ^R23 ,
A linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent,
An aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent is preferred.

In the general formula (Q12), the "organic cation" or "inorganic cation" represented by "M" includes the above-mentioned "organic cation" or "inorganic cation" represented by "M" in the general formula (Q1). cations” can be mentioned.

The xanthene dye represented by the general formula (1) can be synthesized as follows by applying a known method (for example, Patent Documents 3 and 4, Non-Patent Document 1). dialkylaminoxanthone having a corresponding group in general formula (1), such as 3,6-bis(diethylamino)xanthone, and N-ethyl-N,4-diphenyl-1,3-thiazol-2-amine, A heterocyclic compound having a group corresponding to the general formula (1) is subjected to a condensation reaction using phosphorus oxychloride in a toluene solvent under appropriate heating conditions, and the reaction mixture is filtered. ) is obtained.

Specific examples of compounds preferable as the xanthene dye of the present invention represented by general formula (1) are shown in the following formulas (A-1) to (A-42), but the present invention is not limited to these compounds. . Note that the cation portion represented by the general formula (1-C) is shown, and the anion portion represented by An is omitted. In the structural formula below, some hydrogen atoms are omitted. Furthermore, even when stereoisomers exist, their planar structural formulas are described.

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

During the synthesis of the xanthene pigment of the present invention, methods for purifying the product include purification by column chromatography; purification by adsorption with silica gel, activated carbon, activated clay, etc.; known methods such as recrystallization with a solvent and crystallization method. can be given. If necessary, these compounds can be identified and analyzed using nuclear magnetic resonance analysis (NMR), absorbance measurement using a spectrophotometer, ultraviolet-visible absorption spectrum (UV-Vis) measurement, thermogravimetry-differential thermal analysis ( TG-DTA), etc. Furthermore, these methods can also be used to evaluate the solubility, color, heat resistance, etc. of the obtained compound.

A coating film can be prepared by mixing the xanthene dye of the present invention with various resin solutions and applying the mixture onto a glass substrate. Color evaluation can be performed by measuring the color of the obtained coating film using a spectrophotometer and obtaining the color value of the coating film. The CIE L ^* a ^* b ^* color system is generally used for color values. Specifically, the color values L ^* , a ^* , b ^* of the film sample are measured, and the heat resistance can be determined from the difference in color values (ΔE ^* _ab ) before and after heating at an appropriate temperature. When applied to color filters, the color difference at a temperature of around 230° C. can be used as an index of heat resistance. A smaller value of ΔE ^* _ab means less discoloration due to thermal decomposition, and ΔE*ab is preferably 10 or less, more preferably 3 or less.

The xanthene dye of the present invention, the coloring composition containing the dye, and the coloring agent for color filters containing the coloring composition are used in the coloring agent for color filters and the organic solvent containing resin etc. in the manufacturing process of the color filter. Since it is necessary to dissolve or disperse it well in organic solvents, it is preferable that the solubility and dispersibility in organic solvents be high. The organic solvent is not particularly limited, but specifically includes esters such as ethyl acetate and n-butyl acetate; diethyl ether, propylene glycol monomethyl ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve). Ethers; Ether esters such as propylene glycol monomethyl ether acetate (PGMEA); Ketones such as acetone and cyclohexanone; Alcohols such as methanol, ethanol, and 2-propanol; Diacetone alcohol (DAA), etc.; benzene, toluene, xylene Aromatic hydrocarbons such as; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); and chloroform (trichloromethane). These solvents may be used alone or in combination of two or more.

The xanthene dye represented by the general formula (1) is used in the visible light region of the ultraviolet-visible absorption spectrum (for example, A maximum absorption wavelength is observed that exhibits maximum absorbance in the wavelength range of 350 to 700 nm). In the present invention, this maximum absorption wavelength is preferably in the range of 560 nm to 610 nm, more preferably in the range of 570 nm to 600 nm. Note that the dye concentration is preferably 0.005 to 0.02 mmol/L. The solvent is not limited as long as it dissolves the dye, but it is preferably one that does not cause a large shift in the absorption wavelength of the ultraviolet-visible absorption spectrum depending on the dissolution conditions, and propylene glycol monomethyl ether (PGME) is preferable.

The coloring agent for color filters of the present invention includes a coloring composition containing at least one xanthene dye represented by general formula (1), and components commonly used in the production of color filters. For example, in the case of a method using a photolithography process, a general color filter is made by mixing a liquid such as a dye or pigment with a resin component (including monomers and oligomers) and a solvent, and then using a liquid such as glass or resin. It can be obtained by applying the dye onto a substrate, photopolymerizing it using a photomask, creating a colored pattern of a dye-resin composite film that is soluble/insoluble in a solvent, washing it, and then heating it. Furthermore, in the electrodeposition method and the printing method, a colored pattern is created using a mixture of pigments and resins and other components. Therefore, specific components in the coloring agent for color filters of the present invention include at least one xanthene dye represented by the general formula (1), other dyes and pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Further, these components may be selected or selected, and other components may be added as necessary.

When the coloring composition containing the xanthene dye of the present invention is used as a coloring agent for color filters, it may be used for color filters for each color, but it is preferably used as a coloring agent for red color filters.

The coloring agent for color filters containing the xanthene dye of the present invention may use one or more xanthene dyes alone, or may contain other known dyes or pigments to adjust the color tone. dyes may be mixed. When used as a colorant for a red color filter, although not particularly limited, C.I. I. Pigment Red 177, 209, 242, 254, 255, 264, 269, C. I. Pigment Orange 38, 43, 71 and other red pigments; other red lake pigments; C.I. I. Pigment Yellow 138, 139, 150 and other yellow pigments; C.I. I. Acid Red 88, C. I. Examples include red dyes such as Basic Violet 10. When used as a colorant for a blue color filter, C.I. I. Basic dyes such as Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129; C.I. I. Acidic dyes such as Acid Blue 9 and 74; Disperse dyes such as Disperse Blue 3, 7, and 377; Spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based , oxazine-based, dioxazine-based, azo-based, xanthene-based which does not belong to the present invention; and other blue-based lake pigments.

The mixing ratio of other pigments in the coloring agent for color filters containing the xanthene pigment of the present invention is 5 to 2000% by weight relative to the xanthene pigment (in the case of two or more types, the total thereof). The content is preferably 10 to 1000% by weight. The mixing ratio of pigment components such as dyes in the liquid coloring agent for color filters is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight based on the total coloring agent.

As the resin component in the coloring agent for color filters of the present invention, any known resin component may be used as long as it has the properties necessary for the manufacturing method and use of the color filter resin film formed using these components. can. Examples 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, and thermosetting resins. These monomers or oligomer components can be used in appropriate combinations. Moreover, copolymers of these resins can also be used in combination. In the case of liquid colorants, the content of resin in these coloring agents for color filters is preferably 5 to 95% by weight, more preferably 10 to 50% by weight.

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

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

Hereinafter, embodiments of the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The compounds obtained in the synthesis examples were identified by ¹ H-NMR analysis (Bruker nuclear magnetic resonance apparatus, model number: Magnet System 300MHz/54mm UltraShield).

[Synthesis Example 1] Synthesis of Compound (D-1) The following chemical reaction was carried out under a nitrogen stream. In a 100 mL four-neck flask equipped with a cooling tube, a stirring device, and a thermometer, 3.00 g of an intermediate represented by the following formula (100) synthesized with reference to a known method (Non-Patent Document 1, Supporting Information). (8.28 mmol), 2.51 g (8.52 mmol) of an intermediate represented by the following formula (Q-100) synthesized with reference to a known method (Patent Document 3), and 40 mL of toluene were added and dissolved. 3.94 g (25.7 mmol) of phosphorus oxychloride was added. The reaction solution was stirred at 50°C for 19.5 hours and then at 80°C for 3.5 hours. After the reaction solution was allowed to cool to 30° C. or lower and filtered under reduced pressure, the solid was dissolved in 150 mL of dichloromethane and washed with water. The aqueous layer was re-extracted with 150 mL of dichloromethane, and the organic layers were mixed, dried over anhydrous magnesium sulfate, and filtered under reduced pressure. The solvent of the filtrate was distilled off under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 5/1 (volume ratio)). After purification, the black-purple solid obtained by drying was washed with ethyl acetate and dried under reduced pressure at 80°C to obtain the target compound (D-1) as a black-purple solid (4.43 g, yield 79%). ).

The obtained black-purple solid was subjected to NMR measurement, and the following 43 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (D-1).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.56-7.45 (5H), 7.44-7.36 (3H), 7.30-7.22 (5H) , 7.04 (2H), 3.77-3.63 (8H), 3.56 (2H), 2.33 (3H), 1.76-1.50 (12H), 1.31 (3H) .

[Synthesis Example 2] Synthesis of Compound (D-2) The following chemical reaction was carried out under a nitrogen stream. In a 100 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, 2.00 g (2.96 mmol) of the compound (D-1) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, Li ⁺ (CF 0.93 g (3.34 mmol) of ₃ SO ₂ ) ₂ N ⁻ ) and 45 mL of DMF were added, and the mixture was stirred at 50° C. for 3.5 hours. The reaction solution was allowed to cool to below 30°C, poured into 300 mL of water, stirred at room temperature (25°C) for 30 minutes, and then filtered under reduced pressure. The residue was washed with 150 mL of water, filtered under reduced pressure, and then dried under reduced pressure at 80° C. to obtain the target compound (D-2) as a dark blue-purple solid (2.29 g, yield 84%).

The obtained dark blue-purple solid was subjected to NMR measurement, and the following 43 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-2).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.55-7.44 (6H), 7.43-7.36 (2H), 7.29-7.21 (5H) , 7.04 (2H), 3.78-3.66 (10H), 2.33 (3H), 1.76-1.54 (12H), 1.31 (3H).

[Synthesis Example 3] Synthesis of Compound (D-3) In Synthesis Example 1, 3.00 g (8.86 mmol) of the following formula intermediate (101) and the intermediate (Q -100), 3.06 g (9.80 mmol) of the following formula intermediate (Q-101) and 4.22 g (27.5 mmol) of phosphorus oxychloride were used at 60°C for 4 hours and at 80°C for 14 hours. The target compound (D-3) was obtained as a black-blue solid (4.87 g, yield 82%) by the same method except that the mixture was stirred at 100° C. for 24 hours.

The obtained black-blue solid was subjected to NMR measurement, and the following 42 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (D-3).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.69-7.61 (1H), 7.60-7.46 (4H), 7.45-7.27 (3H) , 7.26-7.15 (1H), 7.13-6.98 (3H), 6.87-6.77 (2H), 4.30-3.79 (2H), 3.72-3 .52 (8H), 2.35 (3H), 1.29 (3H), 1.16 (12H).

[Synthesis Example 4] Synthesis of Compound (D-4) In Synthesis Example 2, 1.00 g (1.49 mmol) of the compound (D-3) and lithium bis(trifluoromethane) were used instead of compound (D-1). The target compound (D-4) was obtained as a dark purple solid (1.28, yield 94%) in the same manner except that 0.47 g (1.6 mmol) of sulfonyl)imide was used.

The obtained dark purple solid was subjected to NMR measurement, and the following 42 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-4).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.69-7.61 (1H), 7.60-7.46 (4H), 7.45-7.37 (2H) , 7.36-7.26 (1H), 7.25-7.15 (1H), 7.13-6.98 (3H), 6.87-6.77 (2H), 4.30-3 .79 (2H), 3.72-3.52 (8H), 2.35 (3H), 1.29 (3H), 1.16 (12H).

[Synthesis Example 5] Synthesis of Compound (D-5) In Synthesis Example 1, 4.50 g (13.3 mmol) of the above intermediate (101) and intermediate (Q-100) were used instead of intermediate (100). The same method was used, except that 4.58 g (13.3 mmol) of the intermediate (Q-102) of the following formula and 6.32 g (41.2 mmol) of phosphorus oxychloride were used instead of, and the mixture was stirred at 70° C. for 24 hours. The target compound (D-5) was obtained as a dark reddish-purple solid (4.87 g, yield 82%).

The obtained dark reddish-purple solid was subjected to NMR measurement, and the following 45 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (D-5).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.15 (1H), 7.85-7.59 (5H), 7.55-7.30 (7H), 6.93-6 .71 (4H), 4.52-4.28 (1H), 4.12-3.89 (1H), 3.77-3.45 (8H), 2.41 (3H), 1.56- 1.12 (15H).

[Synthesis Example 6] Synthesis of Compound (D-6) In Synthesis Example 2, 6.00 g (8.55 mmol) of the compound (D-5) and lithium bis(trifluoromethane) were used instead of compound (D-1). The target compound (D-6) was obtained as a dark reddish-purple solid (7.50 g, yield 93%) in the same manner except that 2.70 g (9.40 mmol) of sulfonyl)imide was used.

The obtained dark reddish-purple solid was subjected to NMR measurement, and the following 45 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-6).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.16 (1H), 7.83-7.61 (5H), 7.52-7.34 (7H), 6.83-6 .68 (4H), 4.52-4.28 (1H), 4.15-3.89 (1H), 3.70-3.49 (8H), 2.42 (3H), 1.56- 1.15 (15H).

[Synthesis Example 7] Synthesis of Compound (D-7) In Synthesis Example 1, 3.00 g (8.86 mmol) of the above intermediate (101) and intermediate (Q-100) were used instead of intermediate (100). The same method was used, except that 3.37 g (9.78 mmol) of the intermediate (Q-103) of the following formula and 4.23 g (27.6 mmol) of phosphorus oxychloride were used instead of, and stirring was performed at 100 ° C. for 3.5 hours. The target compound (D-7) was obtained as a purple solid (5.81 g, yield 101%).

The obtained purple solid was subjected to NMR measurement, and the following 49 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (D-7).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.62-7.55 (2H), 7.48-7.42 (2H), 7.27-7.19 (3H) , 7.11-7.04 (2H), 6.93-6.87 (2H), 3.72-3.49 (12H), 1.70 (4H), 1.38 (4H), 1. 19 (12H), 0.96 (6H).

[Synthesis Example 8] Synthesis of Compound (D-8) In Synthesis Example 2, 5.50 g (8.0 g) of the compound (D-7) was used instead of 2.00 g (2.96 mmol) of Compound (D-1). The target compound (D-8) was obtained as a dark green solid (7.22 g, yield rate 95%).

The obtained black-green solid was subjected to NMR measurement, and the following 49 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-8).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.62-7.54 (2H), 7.49-7.41 (2H), 7.28-7.20 (3H) , 7.11-7.03 (2H), 6.93-6.87 (2H), 3.72-3.49 (12H), 1.70 (4H), 1.38 (4H), 1. 19 (12H), 0.96 (6H).

[Synthesis Example 9] Synthesis of Compound (D-9) In Synthesis Example 1, 4.00 g (8.65 mmol) of intermediate (102) of the following formula and intermediate (Q-100) were used instead of intermediate (100). ), 2.61 g (9.51 mmol) of the following formula intermediate (Q-104) and 4.11 g (26.8 mmol) of phosphorus oxychloride were used, and the mixture was stirred at 105° C. under reflux for 144 hours. By the same method, the target compound (D-9) was obtained as a black-purple solid (5.04 g, yield 77%).

The obtained black-purple solid was subjected to NMR measurement, and the following 51 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-9).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.73-7.66 (1H), 7.58-7.21 (13H), 6.38-6.24 (1H) , 5.93-5.82 (1H), 4.08-3.80 (2H), 3.56-340 (6H), 2.30-1.98 (15H), 1.32-1.01 (12H).

[Synthesis Example 10] Synthesis of Compound (D-10) In Synthesis Example 2, 4.00 g (5.29 mmol) of the compound (D-9) and lithium bis(trifluoromethane) were used instead of compound (D-1). The target compound (D-10) was obtained as a purple solid (4.68 g, yield 79%) in the same manner except that 1.70 g (5.92 mmol) of sulfonyl)imide was used.

The obtained purple solid was subjected to NMR measurement, and the following 51 hydrogen signals were detected, which were identified as the structure of a compound represented by the following formula (D-10).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.73-7.66 (1H), 7.58-7.21 (13H), 6.38-6.24 (1H) , 5.93-5.82 (1H), 4.08-3.80 (2H), 3.56-340 (6H), 2.30-1.98 (15H), 1.32-1.01 (12H).

[Synthesis Example 11] Synthesis of Compound (D-11) The following chemical reaction was carried out under a nitrogen stream. 1.63 g (67.0 mmol) of magnesium powder, 1 grain of iodine, and 50 mL of dry tetrahydrofuran (THF) were placed in a 100 mL four-neck flask equipped with a cooling tube, a stirrer, and a thermometer, and the mixture was stirred at room temperature for 10 minutes. 9.00 g (55.2 mmol) of 2-bromothiophene was added over 15 minutes to prepare a Grignard reagent.
The following chemical reactions were performed under a nitrogen stream. 4.00 g (11.0 mmol) of the intermediate represented by the above formula (100) and 80 mL of dry THF were placed in a 250 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, and the mixture was heated in methanol/dry ice refrigerant. Cooled to 0°C. The previously prepared Grignard reagent (total amount) was added dropwise over 15 minutes together with 5 mL of dry THF, then the mixture was heated to room temperature and stirred for 17 hours. After adding 10 mL of concentrated hydrochloric acid to the reaction solution to stop the reaction, 150 mL of water was added, and the mixture was extracted twice with 300 mL of dichloromethane. The organic layer was washed successively with water and saturated brine, mixed, and dried over anhydrous sodium sulfate. The mixture was filtered under reduced pressure, the solvent of the filtrate was distilled off under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 5/1 (volume ratio)), and the solvent was distilled off under reduced pressure. did. The residue was dried under reduced pressure at 80° C. overnight to obtain the target compound (D-11) as a dark green solid (4.89 g, yield 95%).

The obtained dark green solid was subjected to NMR measurement, and the following 29 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-11).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 8.20-8.13 (1H), 7.62-7.54 (3H), 7.49-7.43 (1H) , 7.42-7.34 (2H), 7.17-7.12 (2H), 3.83-3.73 (8H), 1.77-1.59 (12H).

[Synthesis Example 12] Synthesis of Compound (D-12) In Synthesis Example 2, 2.00 g (4.30 mmol) of the compound (D-11) and lithium bis(trifluoromethane) were used instead of compound (D-1). The target compound (D-12) was obtained as a blue-purple solid (2.78 g, yield 91%) in the same manner except that 1.33 g (4.78 mmol) of sulfonyl)imide was used.

The obtained blue-violet solid was subjected to NMR measurement, and the following 29 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-12).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 8.20-8.13 (1H), 7.62-7.54 (3H), 7.48-7.43 (1H) , 7.42-7.34 (2H), 7.17-7.12 (2H), 3.83-3.73 (8H), 1.79-1.58 (12H).

[Synthesis Example 13] Synthesis of Compound (D-13) The following chemical reaction was carried out under a nitrogen stream. 2.46 g (11.5 mmol) of 3-bromobenzo[b]thiophene and 30 mL of THF were placed in a 100 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, and after cooling to -50°C, n-butyl 7.20 mL (11.5 mmol) of lithium (n-BuLi) (1.6 M n-hexane solution) was added over 5 minutes. After stirring at −50° C. for 30 minutes, 3.00 g (8.86 mmol) of the intermediate (101) was dissolved in 15 mL of THF and added over 5 minutes. The reaction solution was stirred at -50°C for 1.5 hours, then warmed to room temperature over 2 hours, and stirred at room temperature for 18 hours. The reaction solution was cooled to 0° C., 20 mL of water was added to stop the reaction, and 20 mL of concentrated hydrochloric acid was added to make the reaction solution acidic, followed by stirring at room temperature for 30 minutes. The reaction solution was diluted with 100 mL of water, extracted twice with 150 mL of dichloromethane, and then the organic layer was washed successively with water and saturated brine. The organic layers were mixed, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. After adsorbing the residue on 10 g of silica gel, it was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 5/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 80° C. overnight to obtain the target compound (D-13) as a black solid (0.80 g, yield 18%).

The obtained black solid was subjected to NMR measurement, and the following 31 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-13).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 8.32-7.88 (3H), 7.77-7.52 (3H), 7.42-7.32 (1H) , 7.25-7.12 (2H), 7.10-6.96 (2H), 3.69 (8H), 1.23 (12H).

[Synthesis Example 14] Synthesis of Compound (D-14) In Synthesis Example 2, 0.70 g (1.0 g) of the compound (D-13) was used instead of 2.00 g (2.96 mmol) of Compound (D-1). The target compound (D-14) was obtained as a dark green solid (0.74 g, yield rate 76%).

The obtained dark green solid was subjected to NMR measurement, and the following 31 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-14).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 8.32-7.88 (3H), 7.77-7.52 (3H), 7.42-7.32 (1H) , 7.25-7.12 (2H), 7.10-6.95 (2H), 3.68 (8H), 1.23 (12H).

[Synthesis Example 15] Synthesis of Compound (D-15) In Synthesis Example 1, 3.50 g (10.3 mmol) of the intermediate (101) and the intermediate (Q-100) were used instead of the intermediate (100). ), 2.14 g (10.3 mmol) of 1-methyl-2-phenylindole and 4.92 g (32.1 mmol) of phosphorus oxychloride were used, and the same method was used except that the mixture was stirred at 70° C. for 24 hours. The target compound (D-15) was obtained as a dark reddish-purple solid (4.50 g, yield 77%).

The obtained dark reddish-purple solid was subjected to NMR measurement, and the following 38 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-15).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.67-7.30 (8H), 7.27-7.18 (3H), 6.90-6.54 (4H), 3 .92 (3H), 3.81-3.42 (8H), 1.57-1.17 (12H).

[Synthesis Example 16] Synthesis of Compound (D-16) In Synthesis Example 2, 4.50 g (7.98 mmol) of the compound (D-15) and lithium bis(trifluoromethane) were used instead of compound (D-1). The target compound (D-16) was obtained as a reddish-purple solid (5.30 g, yield 82%) in the same manner except that 2.52 g (8.78 mmol) of sulfonyl)imide was used.

The obtained reddish-purple solid was subjected to NMR measurement, and the following 38 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-16).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.62-7.56 (1H), 7.55-7.47 (2H), 7.45-7.38 (1H), 7 .36-7.30 (4H), 7.27-7.18 (3H), 6.83-6.78 (2H), 6.72-6.63 (2H), 3.92 (3H), 3.80 (8H), 1.30 (12H).

[Synthesis Example 17] Synthesis of compound (D-17) In the same manner as in Synthesis Example 13, except that 1.14 g (10.6 mmol) of benzothiazole was used instead of 3-bromobenzo[b]thiophene. The target compound (D-17) was obtained as a black-purple solid (4.01 g, yield 92%).

The obtained black-purple solid was subjected to NMR measurement, and the following 30 hydrogen signals were detected, and the structure was identified as that of a compound represented by the following formula (D-17).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 8.38 (1H), 8.30 (1H), 7.79-7.64 (2H), 7.64-7.57 (2H), 7.24-7.14 (2H), 7.08-7.00 (2H), 3.70 (8H), 1.23 (12H).

[Synthesis Example 18] Synthesis of Compound (D-18) In Synthesis Example 2, 3.90 g (7.93 mmol) of the compound (D-17) and lithium bis(trifluoromethane) were used instead of compound (D-1). The target compound (D-16) was obtained as a dark green solid (5.29 g, yield 90.6%) in the same manner except that 2.52 g (8.78 mmol) of sulfonyl)imide was used.

The obtained black-green solid was subjected to NMR measurement, and the following 30 hydrogen signals were detected and identified as the structure of a compound represented by the following formula (D-18).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 8.37 (1H), 8.30 (1H), 7.79-7.57 (4H), 7.24-7.14 (2H), 7.08-7.00 (2H), 3.70 (8H), 1.23 (12H).

[Example 1]
Compound (D-2) obtained in Synthesis Example 2 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a solution with a concentration of 0.02 mmol/L. The ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) was measured at room temperature (25° C.) using a spectrometer (model number: V-650), and the maximum absorption wavelength in the measurement wavelength range was measured. The measurement results are shown in Table 1. Further, 5.0 g of a 2% by weight DMF solution of methacrylic acid-acrylic acid ester copolymer and 20 mg of the compound (D-2) were placed in a 20 mL sample bottle, and the mixture was stirred for 30 minutes. The obtained colored resin solution was filtered with a syringe filter, and the filtrate was applied onto a glass substrate (film forming method: drop 1 g of the filtrate onto glass and form a film at 300 rpm for 10 seconds using a spin coater), A film was formed by heating at 100° C. for 2 minutes. The color value of the produced film was measured using a spectrophotometer (manufactured by Konica Minolta, Inc., model number: CM-5) using transmitted light. Thereafter, it was heated at 230° C. for 20 minutes, and the color value was measured in the same manner. The color difference (ΔE ^* _ab ) between the color values before and after heating at 230° C. was used as an index of heat resistance, and the results of evaluation in the following three stages are shown in Table 1.
"○": ΔE ^* _ab ≦3.0
“△”: 3.0<ΔE ^* _ab ≦10.0
"×": ΔE ^* _ab > 10.0

[Comparative Example 1 to Comparative Example 3]
For comparison, instead of Compound (D-1) of Example, a xanthene dye compound that does not belong to the present invention,
C.I. represented by the above formulas (B-1) and (B-2). I. Acid Red 289, C. I. Acid Red 52 or C.I. I. Same as Example 1 except that Basic Violet 10 was used, and the maximum absorption wavelength of the PGME solution in the wavelength range of 350 to 700 nm and the color difference in the color value of the prepared film before and after heating (230 ° C. - 20 minutes) (ΔE ^* _ab ) was measured and evaluated. The results are summarized in Table 1.

As shown in Table 1, the xanthene dyes, which are the compounds of the examples of the present invention, have higher UV-visible absorption spectra (wavelength range of 350 to 700 nm) of solutions than the conventional xanthene dyes such as the comparative examples. It has a maximum absorption wavelength on the long wavelength side. Moreover, the colored composition containing the xanthene dye of the example has good heat resistance during film formation, and there is no problem in practical use as a coloring agent for color filters. Furthermore, the heat resistance of the colored compositions of Examples during film formation is equal to or higher than that of Comparative Examples, and is useful as a coloring agent for color filters.

The coloring composition containing the xanthene dye according to the present invention has excellent heat resistance and is useful as a coloring agent for color filters, and can produce color filters with excellent color characteristics (color gamut, brightness, contrast ratio, etc.) Is possible.

Claims (10)

A xanthene dye represented by the following general formula (1),
In the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye at a concentration of 0.005 to 0.02 mmol/L, the maximum A xanthene pigment with an absorption wavelength in the wavelength range of 560 to 600 nm.

[In the formula, R ¹ to R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
When R ¹ and R ² or R ³ and R ⁴ are the alkyl groups, they may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring .
R ⁵ and R ⁶ each represent -H .
X represents -O- .
Q is

or

represents.
a represents an integer from 1 to 3.
An is (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
C ₆ H ₄ (C ₁₂ H ₂₅ ) (SO ₃ ⁻ ), PF ₆ ⁻ , BF ₄ ⁻ or
(PW ₁₂ O ₄₀ ) ^3- , and b is an integer from 1 to 3 .
However, general formula (1) is assumed to be charge neutral as a whole. ] A xanthene dye represented by the following general formula (1),
In the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye at a concentration of 0.005 to 0.02 mmol/L, the maximum A xanthene pigment with an absorption wavelength in the wavelength range of 560 to 600 nm.

[In the formula, R ¹ to R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R ⁵ and R ⁶ each represent -H .
X represents -O- .
Q is a heterocyclic group represented by the following general formula (Q11).
a represents an integer from 1 to 3.
An is (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
C ₆ H ₄ (C ₁₂ H ₂₅ ) (SO ₃ ⁻ ), PF ₆ ⁻ , BF ₄ ⁻ or
(PW ₁₂ O ₄₀ ) ^3- , and b is an integer from 1 to 3.
However, general formula (1) is assumed to be charge neutral as a whole. ]

[In the formula, R ¹¹ to R ¹⁵ are each independently -H, a halogen atom, -OH, -CN, -OCH ₃ , -NO ₂ ,
-SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, -CO ₂ M,
A linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent, or an amino group having 0 to 21 carbon atoms which may have a substituent,
R ¹⁶ and R ¹⁷ are each independently -H,
A linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent,
When R ¹¹ to R ¹⁵ , R ¹⁶ and R ¹⁷ are the alkyl groups, adjacent groups may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring. good.
M represents an organic cation or an inorganic cation, and when a plurality of them exist, they may be the same or different. ] A xanthene dye represented by the following general formula (1),
In the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye at a concentration of 0.005 to 0.02 mmol/L, the maximum A xanthene pigment with an absorption wavelength in the wavelength range of 560 to 600 nm.

[In the formula, R ¹ to R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
When R ¹ and R ² or R ³ and R ⁴ are the alkyl groups, they may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring .
R ⁵ and R ⁶ each represent -H .
X represents -O- .
Q is a heterocyclic group represented by the following general formula (Q11).
a represents an integer from 1 to 3.
An is (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
C ₆ H ₄ (C ₁₂ H ₂₅ ) (SO ₃ ⁻ ), PF ₆ ⁻ , BF ₄ ⁻ or
(PW ₁₂ O ₄₀ ) ^3- , and b is an integer from 1 to 3.
However, general formula (1) is assumed to be charge neutral as a whole. ]

[In the formula, R ¹¹ to R ¹⁵ are each independently -H, -OH, -CN, -OCH ₃ , -NO ₂ ,
-SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, -CO ₂ M,
A linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent, or an amino group having 0 to 21 carbon atoms which may have a substituent,
R ¹⁶ and R ¹⁷ are each independently -H,
A linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent,
When R ¹¹ to R ¹⁵ , R ¹⁶ and R ¹⁷ are the alkyl groups, adjacent groups may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring. good.
M represents an organic cation or an inorganic cation, and when a plurality of them exist, they may be the same or different. ] A xanthene dye represented by the following general formula (1),
In the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye at a concentration of 0.005 to 0.02 mmol/L, the maximum A xanthene pigment with an absorption wavelength in the wavelength range of 560 to 600 nm.

[In the formula, R ¹ to R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
When R ¹ and R ² or R ³ and R ⁴ are the alkyl groups, they may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring .
R ⁵ and R ⁶ each represent -H .
X represents -O- .
Q is a heterocyclic group represented by the following general formula (Q12).
a represents an integer from 1 to 3.
An is (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
C ₆ H ₄ (C ₁₂ H ₂₅ ) (SO ₃ ⁻ ), PF ₆ ⁻ , BF ₄ ⁻ or
(PW ₁₂ O ₄₀ ) ^3- , and b is an integer from 1 to 3.
However, general formula (1) is assumed to be charge neutral as a whole. ]

[In the formula, R ¹⁸ to R ²¹ are each independently -H, a halogen atom, -OH, -CN, -OCH ₃ , -NO ₂ ,
_-CO2- ^, _-CO2H , _-CO2M ,
A linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent,
When the alkyl group is mentioned above, adjacent groups may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring .
R ²² is -H, halogen atom, -OH, -CN, -OCH ₃ , -NO ₂ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ ^- , -CO ₂ H, - _CO2M ,
A linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent,
Represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent.
^R23 is -H,
A linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent,
Or represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent.
M represents an organic cation or an inorganic cation, and when a plurality of them exist, they may be the same or different. ] A xanthene dye represented by the following general formula (1),
In the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye at a concentration of 0.005 to 0.02 mmol/L, the maximum A xanthene pigment with an absorption wavelength in the wavelength range of 560 to 600 nm.

[In the formula, R ¹ to R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
When R ¹ and R ² or R ³ and R ⁴ are the alkyl groups, they may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring .
R ⁵ and R ⁶ each represent -H .
X represents -O- .
Q is a heterocyclic group represented by the following general formula (Q1).
a represents an integer from 1 to 3.
An is (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ SO ₃ ⁻ )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ⁻ )),
C ₆ H ₄ (C ₁₂ H ₂₅ ) (SO ₃ ⁻ ), PF ₆ ⁻ , BF ₄ ⁻ , or
(PW ₁₂ O ₄₀ ) ^3- , and b is an integer from 1 to 3 .
However, general formula (1) is assumed to be charge neutral as a whole. ]

[In the formula, Z ¹ represents -CR ⁸ =,
Z ² represents -CR ⁹ =,
Z ³ represents -S-,
R ⁷ , R ⁸ and R ⁹ each independently represent -H, a linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent, or a substituent. represents an aromatic hydrocarbon group having 6 to 28 carbon atoms, which may be
When R ⁷ and R ⁹ and R ⁸ and R ⁹ are the alkyl groups, adjacent groups may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring. good. ] The xanthene dye according to any one of claims 2 to 4, wherein in the general formula (Q11) or (Q12), M is an alkali metal ion. A colored composition containing the xanthene pigment according to any one of claims 1 to 6. A xanthene dye represented by the following general formula (1),
In the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) measured at 23 to 27°C using a propylene glycol monomethyl ether (PGME) solution of the xanthene dye at a concentration of 0.005 to 0.02 mmol/L, the maximum A colored composition containing a xanthene dye having an absorption wavelength in the wavelength range of 560 to 600 nm.

[In the formula, R ¹ ～R ⁴ are each independently, -H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R ¹ and R ² , or R ³ and R ⁴ When these are the alkyl groups, they may be bonded to each other via a single bond to form a 5-membered ring or a 6-membered ring.
R ⁵ and R ⁶ represent -H, respectively.
X represents -O-.
Q is

represents.
a represents an integer from 1 to 3.
An is (CF ₃ S.O. ₂ ) ₂ N ^- , (CF ₃ S.O. ₂ ) ₃ C ^- ,
(CN) ₂ N ^- , (CN) ₃ C ^- ,NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,
(C ₆ H ₄ S.O. ₃ ^- )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(S.O. ₃ ^- )),
C ₆ H ₄ (C ₁₂ H ₂₅ )(S.O. ₃ ^- ), P.F. ₆ ^- , B.F. ₄ ^- ,or,
(P.W. ₁₂ O ₄₀ ) ^3- and b is an integer from 1 to 3.
However, general formula (1) is assumed to be charge neutral as a whole. ] A coloring agent for color filters, comprising the coloring composition according to claim 7 or 8. A color filter using the colorant for color filters according to claim 9.