KR20210096554A - Xantene pigment, coloring composition containing the pigment, coloring agent for color filter, and color filter - Google Patents

Abstract

An objective is to provide a xanthene pigment having excellent solubility and heat resistance, a coloring composition containing the pigment, a coloring agent for a color filter containing the pigment or the coloring composition, and a color filter using the coloring agent. The present invention includes a xanthene pigment represented by the following general formula (1). In the formula (1), R^1 to R^4 each independently represent -H, an alkyl group or an aromatic hydrocarbon group, and R^1 and R^2 or R^3 and R^4 can be bonded to each other to form a ring; R^5 and R^6 each independently represent -H, a halogen atom, -NO_2 or an alkyl group; X represents -O-, -S- or -Se-; Q represents a heterocyclic group having a six-membered ring containing nitrogen; An represents an anion; a represents an integer of 1 to 3; and b represents an integer of 0 to 3.

Description

Xanthene pigment, the coloring composition containing the pigment|dye, the colorant for color filters, and a color filter TECHNICAL FIELD

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

A color filter is used for a liquid crystal, an electroluminescent (EL) display apparatus, and the imaging element of CCD and CMOS. A color filter is manufactured by laminating|stacking a colored layer, such as a dye thin film or a dye-resin composite film, by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, etc. on a light-transmitting substrate, such as glass or a transparent resin. The xanthene dyes represented by the following formulas (B-1) to (B-3) and the like are compounds used as coloring agents for color filters and the like from their vividness (Patent Documents 1 to 3 and the like). For example, C.I. Acid Red 289 (Formula (B-1)) B. C.I. By using together a xanthene dye (C.I. is an abbreviation of a color index), such as Acid Red 52 (Formula (B-2)) with an azopyridone dye, the outstanding red color tone is obtained (patent document 1).

[Formula 1]

Japanese Laid-Open Patent Publication No. 2002-265834 Japanese Patent Laid-Open No. 2012-207224 Japanese Laid-Open Patent Publication No. 2018-076403

「Chemical Communications」, (UK), 2017, vol. 53, p.1064-1067, Supporting Information

In the development of the present display device, high performance (high definition, wide color gamut, low voltage) is demanded every year. The demand for the performance of color filters (color characteristics such as high transmittance and high color purity) has also increased, and high performance in terms of color development, solubility, and heat resistance is required for dyes currently used as colorants for color filters.

However, the conventional xanthene dye did not satisfy both solubility and heat resistance as a colorant for color filters. For example, although it is described in patent document 3 that the xanthene dye which has a heterocyclic substituent represented by a following formula (B-4) is useful for provision of the color filter excellent in contrast, it does not describe about fastness. .

[Formula 2]

The present invention has been made to solve the above problems, and uses a xanthene dye having excellent solubility and heat resistance, a coloring composition containing the compound, a colorant for color filters containing the dye or the coloring composition, and the colorant An object of the present invention is to provide a color filter that does

MEANS TO SOLVE THE PROBLEM The present inventors discovered the xanthene dye excellent in solubility and heat resistance, as a result of earnestly examining in order to solve the said subject and achieve the said objective. That is, this invention makes the following summary.

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

[Formula 3]

[In formula (1), 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 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 via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

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 a nitrogen-containing 6-membered ring having 3 to 30 carbon atoms which may have a substituent.

An represents an anion, a represents an integer of 1-3, and b represents an integer of 0-3.]

2. The xanthene dye in the general formula (1), wherein Q is a heterocyclic group having a nitrogen-containing 6-membered ring represented by the following general formula (Q1).

[Formula 4]

[In formula (Q1), Z ¹ to Z ⁵ each independently represent -N= or -CR ⁷ =.

However, one, two, or three of Z ¹ ~ Z ⁵ is assumed to be the -N =.

R ⁷ is, -H, halogen atom, -OH, -SH, -CN, -NO ₂ ,

sulfonic acid group, carboxyl group, sulfonamide group, amide group,

A linear or branched alkyl group having 1 to 27 carbon atoms which may have a substituent;

A linear or branched alkenyl group having 2 to 27 carbon atoms which may have a substituent;

A C6-C27 aromatic hydrocarbon group which may have a substituent;

an alkoxy group having 1 to 27 carbon atoms which may have a substituent;

a C1-C27 sulfanyl group which may have a substituent, or

an amino group having 0 to 27 carbon atoms which may have a substituent;

R ⁷ , when there are a plurality of them, may be the same as or different from each other,

In adjacent groups, a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom may be interposed between them to form a ring.]

3. In the said General formula (1), Q is a C4-C30 pyridyl group which may have a substituent, a pyrimidinyl group, a quinolyl group, or a xanthene dye which is an isoquinolyl group.

4. The xanthene dye in the general formula (1), wherein X is -O-.

5. 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 ^- )),

C ₆ H ₄ (C ₁₂ H ₂₅ )(SO ₃ ^- ), PF ₆ ^- , BF ₄ ^- or

(PW ₁₂ O ₄₀ ) It is ^3- , and b is an integer of 1-3.

6. The coloring composition containing a xanthene pigment|dye whose solubility with respect to propylene glycol monomethyl ether (PGME) in 25±2 degreeC (23-27 degreeC) is 1 mass % or more.

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

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

The xanthene dye of the present invention is useful as a colorant for color filters excellent in solubility and heat resistance.

EMBODIMENT OF THE INVENTION Embodiment of this invention is described in detail below. In addition, this invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary. First, the xanthene dye represented by the said General formula (1) is demonstrated.

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 in the general formula (1), "a straight chain having 1 to 20 carbon atoms" As a "chain or branched alkyl group", specifically,

linear alkyl groups 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, and a decyl group;

and 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 an aryl group or a condensed polycyclic aromatic group.} Including, the "aromatic hydrocarbon group having 6 to 20 carbon atoms" is specifically, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group Aromatic hydrocarbon groups, such as a perylenyl group, a fluoranthenyl group, and a triphenylenyl group, are mentioned.

In the 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, and a chlorine atom or a bromine atom is preferable.

In the general formula (1), represented by ^{R 1} to R ⁶

To "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" represented by ^{R 1} to R ⁴ As a "substituent" in, specifically,

deuterium atom, -OH, -CN, -CF ₃ , -NO ₂ ;

-SO ₃ ^- , -SO ₃ H, -SO ₃ M a sulfonic acid group, or

A carboxy group represented by -CO ₂ ^- , -CO ₂ H, -CO ₂ M, -CO ₂ -R (provided that M represents an organic cation or an inorganic cation. (R represents an arbitrary monovalent group.)) ;

a sulfonamide group represented by -SO ₂ NR _{2 , or}

an amide group represented by -CONR _{2 (R represents an arbitrary monovalent group);}

Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;

a C1-C20 linear or branched alkyl group;

a C3-C20 cycloalkyl group;

a linear or branched alkenyl group having 2 to 20 carbon atoms;

a linear or branched alkoxy group having 1 to 20 carbon atoms;

a C3-C20 cycloalkoxy group, 1-adamantyloxy group, 2-adamantyloxy group;

an acyl group having 1 to 20 carbon atoms;

A C6-C20 aromatic hydrocarbon group or a condensed polycyclic aromatic group;

a C2-C20 heterocyclic group;

an aryloxy group having 6 to 20 carbon atoms;

unsubstituted amino group; A C1-C20 monosubstituted or disubstituted amino group, etc. are mentioned. The number of these "substituents" may be one or plural, and when there are two or more, mutually same or different may be sufficient as them. Moreover, these "substituents" may further have the substituent illustrated above. In addition, when "substituent group" contains a carbon atom, the carbon atom is counted in "C1-C20" and "C6-C20" in the "group" represented by ^{R 1} to R ^{6 .} do. Moreover, these substituents may bond with each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom, and may form the ring.

When "inorganic cation" or "organic cation" represented by "M" in general formula (1) exists, or "nitrogen-containing 6" represented by "Q" or "Q1" in general formula (1) The "inorganic cation" or "organic cation" represented by "M" included in the "heterocyclic group having a ring" or the "heterocyclic group containing a nitrogen-containing 6-membered ring structure" will be described. Specific examples of the “organic cation” include an ammonium ion represented by ^{R 8} R ⁹ R ¹⁰ R ¹¹ N ^{+ , R 8} to R ¹¹ are each independently —H, carbon which may have a substituent A linear or branched alkyl group having 1 to 20 atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent may be shown, and may be bonded to each other to form a ring. In addition, the details of the "substituent group", "a linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" in ^{R 8} to R ^{11 are described above.} is equal to R ¹ ~ R ⁴ is applied in the formula (1). Moreover, as an "inorganic cation", alkali metal ions, such as a lithium ion and a sodium ion, or alkaline-earth metal ions, such as a magnesium ion, a calcium ion, and a barium ion, are mentioned. As M, an alkali metal ion is preferable.

In various "groups" having "substituents" represented by ^{R 1} to R ⁶ in the general formula (1), exemplified as "substituents",

"R" in or "-CONR _2", - "-CO ₂ -R ',' SO ₂ NR _2"

"A linear or branched alkyl group having 1 to 20 carbon atoms";

“Cycloalkyl group having 3 to 20 carbon atoms”;

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

"A linear 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”;

"A C6-C20 aromatic hydrocarbon group or condensed polycyclic aromatic group";

“a heterocyclic group having 2 to 20 carbon atoms”;

“an aryloxy group having 6 to 20 carbon atoms”, or

As "a C1-C20 monosubstituted or disubstituted amino group", the following groups are mentioned specifically,.

Methyl group, ethyl group (Et), 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 - A linear or branched alkyl group, such as an ethylhexyl group, a heptyl group, an octyl group, an isooctyl group, a nonyl group, and a decyl group;

Cycloalkyl groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, and a 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 direct combination thereof a chain 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 , a linear or branched alkoxy group such as a t-butoxy group or an isooctyloxy group;

C3-C20 cycloalkoxy groups, such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cyclononyloxy group, and a cyclodecyloxy group;

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

Aromatic hydrocarbons such as phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, tetracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group group or condensed polycyclic aromatic group;

Thienyl group, furyl 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, Heterocyclic groups, such as an isoquinolyl group, a naphthyridinyl group, an acridinyl group, a phenanthrolinyl group, and a carbolinyl group;

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

Linear or branched groups such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group, diphenylamino group A monosubstituted or disubstituted amino group having an alkyl group or an aromatic hydrocarbon group.

In the general formula (1), R ¹ and R ² , or R ³ and R ⁴ are 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 You may form, and when forming a ring, it is preferable that it is a 5-membered ring or a 6-membered ring.

In general formula (1), X represents an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), -O- or -S- is preferable, -O - is more preferable.

In the "C3-C30 heterocyclic group which contains a nitrogen-containing 6-membered ring structure and may have a substituent" represented by "Q" in the general formula (1), the "nitrogen-containing 6-membered ring structure" ", structures derived from pyridine, pyrimidine, pyrazine, triazine, and the like are exemplified.

In general formula (1), in the "heterocyclic group having a nitrogen-containing 6-membered ring having 3 to 30 carbon atoms which may have a substituent" represented by "Q", the "nitrogen containing 3 to 30 carbon atoms" In "heterocyclic group having a 6-membered ring" or "a heterocyclic group having 3 to 30 carbon atoms which contains a nitrogen-containing 6-membered ring structure and may have a substituent" Examples of the heterocyclic group include a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a pyrazinyl group, a triazinyl group, a naphthyridinyl group, an acridinyl group, a phenanthrolinyl group, a carbolinyl group, a purinyl group, an indole group. a rhizinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a phenanthridinyl group, a perimidinyl group, an antiridinyl group, etc. are mentioned.

Further, "a heterocyclic group having a nitrogen-containing 6-membered ring having 3 to 30 carbon atoms having a substituent" or "a heterocyclic group having 3 to 30 carbon atoms including a nitrogen-containing 6-membered ring structure and having a substituent" As a "substituent" in Formula (1), in the various "groups" having a "substituent" represented by ^{R 1} to R ^{6 in the general formula (1), "substituents" including the same ones exemplified as "substituents".} can be heard

In addition, when "substituent group" contains a carbon atom, the carbon atom is counted in "C3-30" in "Q" in General formula (1).

In the general formula (1), "a" represents the number of cation moieties in the compound (xanthene dye) represented by the following general formula (1-C). "An" represents an anion, and "b" represents the number of An. a represents the integer of 1-3, and 1 or 2 is preferable. b represents the integer of 0-3, and the integer of 1-3 is preferable.

[Formula 5]

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

In General formula (1), "An" is not specifically limited, For example, inorganic anions, such as a halide ion, or an organic anion is mentioned. Specifically,

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 ^- , (C ₆ F ₅ SO ₂ ) ₂ N ^- ,

(CN) ₂ N ^- , (CN) ₃ C ^- , NC-S ^- , (C ₂ F ₅ ) ₃ F ₃ P ^- ,

(C ₆ H ₄ SO ₃ ^- )O(C ₆ H ₃ (C ₁₂ H ₂₅ )(SO ₃ ^- )),

C ₆ H ₄ (C ₁₂ H ₂₅ )(SO ₃ ^- ), PF ₆ ^- , BF ₄ ^- , (PW ₁₂ O ₄₀ ) ^3- , or a structural formula of the following formulas (J-1) to (J-16) and anions represented by .

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the formula ^{(1), R 1 ~ R} 4 are, -H, carbon atoms which may have a substituent of 1 to 10 linear or branched alkyl group of, or number of carbon atoms which may contain a substituent group of 6 to The aromatic hydrocarbon group of 12 is preferable.

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

In the general formula (1), Q is a "heterocyclic group having a nitrogen-containing 6-membered ring" or "a heterocyclic group including a nitrogen-containing 6-membered ring structure" having 3 to 30 carbon atoms which may have a substituent. and is preferably a monovalent heterocyclic group represented by the general formula (Q1). That is, the general formula (1) is preferably the following general formula (1-Q1).

[Formula 11]

[In formula (1-Q1), R ¹ to R ⁶ , X, An, a and b have the same definitions as those in the general formula (1). Further, Z ¹ ~ Z ^5, and Z ¹ ~ R ⁷ contained in Z ⁵ is, has the same definition as defined in the general formula (Q1).]

^{Examples of the "halogen atom" represented by R 7} in the general formula (Q1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.

In the general formula (Q1),

Represented by ^{R 7} in ^{“-CR 7} =” in Z ¹ to Z ^{5 ,}

"sulfonic acid group", "carboxy group", "sulfonamide group", "amide group",

"C1-C27 linear or branched alkyl group" in "C1-C27 linear or branched alkyl group which may have a substituent";

"A linear or branched alkenyl group having 2 to 27 carbon atoms" in "a linear or branched alkenyl group having 2 to 27 carbon atoms which may have a substituent";

"C6-C27 aromatic hydrocarbon group" in "C6-C27 aromatic hydrocarbon group which may have a substituent";

"A C1-C27 alkoxy group" in "The C1-C27 alkoxy group which may have a substituent";

"C1-C27 sulfanyl group" in "C1-C27 sulfanyl group which may have a substituent" or

The following groups are specifically mentioned as "a C0-C27 amino group" in "the C0-C27 amino group which may have a substituent".

-SO ₃ ^- , -SO ₃ H, -SO ₃ M a sulfonic acid group, or

a carboxy group represented by -CO ₂ ^- , -CO ₂ H, -CO ₂ M, or -CO ₂ -R (provided that M represents an organic cation or an inorganic cation. R represents an arbitrary monovalent group);

a sulfonamide group represented by -SO ₂ NR _{2 , or}

an amide group represented by -CONR _{2 (R represents an arbitrary monovalent group);}

linear alkyl groups 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, and a decyl group;

branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group and 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 direct combination thereof a chain or branched alkenyl group;

Phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group (anthryl group), tetracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenyl group Aromatic hydrocarbon groups, such as a nyl group (An aryl group and a condensed polycyclic aromatic group are included.);

methylamino group, ethylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group, diphenylamino group, ethylphenylamino group.

In the general formula (Q1), represented by ^{R 7 ,}

"R" in or "-CONR _2", - "-CO ₂ -R ',' SO ₂ NR _2"

"A linear or branched alkyl group having 1 to 27 carbon atoms which may have a substituent";

"A linear or branched alkenyl group having 2 to 27 carbon atoms which may have a substituent";

"A C6-C27 aromatic hydrocarbon group which may have a substituent",

"A C1-C27 alkoxy group which may have a substituent",

"C1-C27 sulfanyl group which may have a substituent" or

As "substituent" in "amino group having 0 to 27 carbon atoms having a substituent",

In general formula (1), represented by ^{R 1} to R ⁶

“A linear or branched alkyl group having 1 to 20 carbon atoms having a substituent” or

Examples of the "substituent" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms" represented by R ¹ to R ^{4 can be exemplified.} Only one of these "substituents" may be contained, and two or more may be contained, and when two or more are contained, they may mutually be same or different. Moreover, these "substituents" may further have the substituent illustrated above.

In addition, when R<^7> or "substituent group" contains a carbon atom, the carbon atom is counted in "C3-30" in "Q" in General formula (1).

Moreover, these substituents may bond with each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom, and may form the ring.

In the general formula (Q1), when there ^{are a plurality of R 7} , between adjacent groups, a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom are bonded to each other to form a ring You may form, and it is preferable that the ring to form is a 5-membered ring or a 6-membered ring.

As "heterocyclic group having a nitrogen-containing 6-membered ring" or "heterocyclic group having a nitrogen-containing 6-membered ring structure" represented by Q in the general formula (1) or the general formula (Q1), a substituent is It is preferable that they are a pyridyl group, pyrimidinyl group, quinolyl group or isoquinolyl group having 4 to 30 carbon atoms which may have, and the "substituent" that these groups have is exemplified as a "substituent" in the general formula (Q1). It may be the same as what exists. As these "substituents", -H, -CN, a fluorine atom, a chlorine atom, -NO ₂ , "a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent", "even if it has a substituent" A linear or branched alkenyl group having 2 to 10 carbon atoms,” “an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent”, and “a C1-C10 linear or branched alkenyl group which may have a substituent” An alkoxy group", "a C1-C10 sulfanyl group which may have a substituent", or "A C0-C10 amino group which may have a substituent" is preferable.

The xanthene dye represented by the general formula (1) can be synthesized as follows by a known method (non-patent document 1, etc.) using a reagent having various corresponding groups of the general formula (1). . A xanthone derivative such as 3,6-bis(diethylamino)xanthone and a heterocyclic compound such as 2-bromopyridine are mixed with n-butyllithium in a suitable solvent such as tetrahydrofuran (THF). Then, the product containing the compound represented by the general formula (1) is obtained by carrying out a condensation reaction under appropriate cooling conditions and filtering the reaction mixture.

Although the specific example of the compound preferable as a xanthene dye of this invention represented by General formula (1) is shown to the following formulas (A-1) - (A-35), this invention is not limited to these compounds. In addition, the cation part represented by the said General formula (1-C) is shown, and the anion part represented by An is abbreviate|omitted and described. In the following structural formulas, hydrogen atoms are partially omitted. In addition, even when stereoisomers exist, their planar structural formulas are described.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

You may use (for example, mix) the xanthene dye of this invention in combination of 1 type or 2 or more types from which molecular structures differ. When using the said 2 or more types, in the whole xanthene pigment|dye, 1 type of xanthene pigment|dye with the fewest is 0.1-50 mass %. It is preferable that the kind of xanthene pigment|dye is 1 type or 2 types.

As a purification method related to the xanthene dye of the present invention, purification by column chromatography; adsorption purification by silica gel, activated carbon, activated clay, or the like; Well-known methods, such as recrystallization by a solvent and a crystallization method, are mentioned. In addition, the identification and analysis of the compounds of the present invention include nuclear magnetic resonance analysis (NMR), absorbance measurement with a spectrophotometer, ultraviolet and visible absorption spectrum (UV-Vis) measurement, thermogravimetry-differential thermal analysis (TG-DTA). ), etc., can be carried out. Moreover, these methods can be used also for solubility, color evaluation, heat resistance evaluation, etc. of the obtained compound.

The xanthene dye of the present invention can be mixed with various resin solutions and applied on a transparent substrate such as glass to prepare a coating film, and then color the coating film using a spectrophotometer to perform color evaluation. For color values, the CIE L ^* a ^* b ^* color space system is generally used. Specifically, the color values L ^* , a ^* , b ^* of the film sample are measured, and heat resistance can be judged from ^{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 around 230°C can be used as an index of heat resistance. ΔE ^* _ab means that there is little discoloration of color due to thermal decomposition as the value is smaller, preferably 10 or less, and more preferably 3 or less.

The xanthene dye of the present invention, the coloring composition containing the dye, and the colorant for color filters containing the dye or the coloring composition are favorably applied to an organic solvent containing a resin or the like in the process for producing a colorant and a color filter. Since it is necessary to melt|dissolve or disperse|distribute, a thing with high solubility and dispersibility with respect to an organic solvent is preferable. Although it does not specifically limit as an organic solvent, Specifically, Ester, such as ethyl acetate and acetate-n-butyl; ethers such as diethyl ether, propylene glycol monomethyl ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve); 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) and the like; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethylsulfoxide (DMSO); Chloroform (trichloromethane) etc. are mentioned, Propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, or diacetone alcohol (DAA) is preferable, and the solubility of resin and From a viewpoint of coexistence of the solubility of a xanthene dye, propylene glycol monomethyl ether (PGME) or cyclohexanone is especially preferable. You may use these solvents individually or in mixture of 2 or more types.

The xanthene dye of the present invention is excellent in solubility in organic solvents, particularly solubility in PGME, for example, the solubility in PGME is preferably 1 mass% or more, more preferably 3 mass% or more, 5 It is especially preferable that it is mass % or more. When application to a color filter having a high contrast ratio is considered, a higher solubility is more preferable.

Solubility can be evaluated by mixing the xanthene dye of the present invention and an organic solvent in an appropriate ratio, performing ultrasonic treatment, and then visually checking the presence or absence of insoluble content at room temperature (25°C). The organic solvent used for the measurement of solubility is not particularly limited, and any of the above organic solvents can be used, but propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, or diacetone Alcohol (DAA) is preferable, and propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, or diacetone alcohol (DAA) is especially preferable.

The coloring agent for color filters of this invention contains the coloring composition containing at least 1 type of xanthene dye represented by General formula (1), and the component normally used for manufacture of a color filter. In a general color filter, for example, in the case of a method using a photolithography process, a liquid prepared by mixing a dye such as a dye or a pigment with a resin component (including monomers and oligomers) or a solvent is applied to a substrate such as glass or resin. It is obtained by coating and photopolymerizing using a photomask to prepare a coloring pattern of a dye-resin composite film soluble/insoluble in a solvent, washing and heating. Moreover, also in the electrodeposition method and the printing method, the coloring pattern is manufactured using what mixed the pigment|dye with resin and another component. Therefore, as a specific component in the colorant for color filters of the present invention, at least one xanthene dye represented by the general formula (1), other dyes or pigments such as pigments, resin components, organic solvents, and photoinitiators and other additives. Moreover, you may select from these components, and you may add another component as needed.

When using the coloring composition containing the xanthene dye of this invention as a coloring agent for color filters, although you may use for the color filter for each color, using as a coloring agent for red color filters is preferable.

The coloring composition or colorant for a color filter containing a xanthene dye of the present invention may be one or two or more xanthene dyes alone, and for adjustment of color tone, other dyes or known dyes such as pigments may be mixed. Although it does not specifically limit when using for the colorant for red color filters, C.I. Pigment Red 177, 209, 242, 254, 255, 264, 269, C.I. red pigments such as pigment orange 38, 43, and 71; other red-based lake pigments; C.I. Yellow pigments, such as Pigment Yellow 138, 139, and 150; C.I. Acid Red 88, C.I. Red dyes, such as Basic Violet 10, etc. are mentioned. Although it does not specifically limit when using for the colorant for blue color filters, C.I. Basic dyes, such as Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129; C.I. acid dyes such as acid blue 9 and 74; Disperse dyes, such as Disperse Blue 3, 7, and 377; spilon dye; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, indanthrene, oxazine, dioxazine, azo, and xanthene that do not belong to the present invention; Other blue-based dyes or pigments, such as a blue-type lake pigment, are mentioned.

It is preferable that the mixing ratio of the other pigments in the coloring composition containing the xanthene pigment of the present invention or the colorant for a color filter is 5 to 2000 mass% with respect to the xanthene pigment (a total of them in the case of two or more types), It is more preferable to set it as 10-1000 mass %. It is preferable that it is 0.5-70 mass % with respect to the whole coloring agent, and, as for the mixing ratio of the dye component in the liquid colorant for color filters, it is more preferable that it is 1-50 mass %.

As a resin component in the coloring composition or coloring agent for color filters of this invention, a well-known thing can be used if it has the property required at the time of the manufacturing method and use of the color filter resin film formed using these. For example, acrylic resin, polyolefin resin, styrene resin, polyimide resin, polyurethane resin, polyester resin, epoxy resin, vinyl ether resin, phenol (novolac) resin, other transparent resin, photocurable resin or thermosetting resin These can be mentioned, combining these monomer or oligomer components suitably, and can be used. Moreover, it can also be used combining the copolymer of these resins. In the case of a liquid coloring agent, it is preferable that it is 5-95 mass %, and, as for content of resin in these colorants for color filters, it is more preferable that it is 10-50 mass %.

As a component of the coloring composition of this invention, surfactant, a dispersing agent, an antifoamer, a leveling agent, and another additive can be added according to a use. It is preferable that the content rate of the additive in a coloring composition is an appropriate amount, to reduce the solubility in the solvent of the coloring composition of this invention, or to improve more than necessary, and to use at the time of manufacture of products, such as a color filter. It is preferable that it is a content rate in the range which does not affect the effect of another same kind of additive. These additives can be injected|thrown-in at arbitrary timings of preparation of a coloring composition.

Other additives in the color filter colorant of the present invention include components necessary for polymerization and curing of resins such as photoinitiators and crosslinking agents, and to stabilize the properties of components in the liquid color filter colorant. and surfactants and dispersants necessary for this purpose. All of these can use the well-known thing for color filter manufacture, and are not specifically limited. 5-60 mass % is preferable and, as for the mixing ratio of the total amount of these additives in the whole solid content of the coloring agent for color filters, 10-40 mass % is more preferable.

Example

Although an Example demonstrates embodiment of this invention concretely, this invention is not limited to a following Example. In addition, the identification of the compound obtained in the synthesis example was performed by ^<1> H-NMR analysis (Nuclear magnetic resonance apparatus manufactured by Bruker, model number: Magnet System 300 MHz/54 mm UltraShield), and the measurement result and the identified structure were analyzed. It is shown in the following synthesis example.

[Synthesis Example 1] Synthesis of compound (D-1)

The following chemical reactions were performed under a nitrogen stream. Magnesium (Turnings) 2.15 g (88.6 mmol), one piece of iodine, and 40 mL of THF were put into a 100 mL capacity four-necked flask equipped with a cooling tube, a stirring device, and a thermometer, and at room temperature (23-28°C) for 30 minutes stirred. After adding 11.67 g (73.87 mmol) of 2-bromopyridine and 30 ml of THF dropwise, the reaction liquid was stirred at room temperature for 30 minutes, and the Grignard reagent was prepared.

5.00 g (14.7 mmol) of an intermediate represented by the following formula (100) synthesized by reference to a known method (Non-Patent Document 1, Supporting Information) in a 100 ml four-neck flask equipped with a cooling tube, a stirring device and a thermometer , THF 40 ml was added, and after cooling to 5° C. in a refrigerant bath, the total amount of the Grignard reagent and 10 ml of THF were added dropwise. The reaction solution was heated to room temperature and stirred for 14 hours. After cooling a reaction liquid at 5 degreeC, adding 20 ml of water and stopping reaction, it neutralized with 35-38% concentrated hydrochloric acid, and adjusted to pH 7. After 30 g of sodium chloride was added to the mixture and stirred at room temperature for 30 minutes, the mixture was extracted with 300 ml of dichloromethane, and the organic layer was washed with 100 ml of water and 100 ml of saturated brine. The aqueous layer was re-extracted with 300 ml of dichloromethane, 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 = 30/1 (volume ratio)). After purification, the black-purple solid obtained by drying was washed with 100 ml of ethyl acetate and filtered under reduced pressure. The residue was dried under reduced pressure at 80°C to obtain the following compound (D-1) as a target product as a black-purple solid (2.39 g, yield 37%).

[Formula 24]

[Formula 25]

[Synthesis Example 2] Synthesis of compound (D-2)

The following chemical reactions were performed under a nitrogen stream. 2.02 g (4.63 mmol) of the compound (D-1), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, Li ⁺ (CF ₃ SO ₂ ) ₂ N ⁻ ) 1.47 g (5.12 mmol) and DMF 45 ml were added, and the mixture was stirred at 50° C. for 3 hours. The reaction solution was allowed to cool to 30°C or lower, poured into 200 ml of water, stirred at room temperature for 10 minutes, and then filtered under reduced pressure. The residue was washed with 100 ml of water, filtered under reduced pressure, and then the residue was dried under reduced pressure at 80°C to obtain the target compound (D-2) as a dark green solid (2.72 g, yield 87%).

[Formula 26]

[Synthesis Example 3] Synthesis of compound (D-3)

The following chemical reactions were performed under a nitrogen stream. 2.80 g (17.7 mmol) of 3-bromopyridine and 50 ml of THF were put in a 250 ml 4-neck flask equipped with a cooling tube, a stirring device and a thermometer, and after cooling to -50 ° C. in a refrigerant bath, 1.6 12.0 ml (19.2 mmol) of M n-butyllithium/n-hexane solution was added, and it stirred at -50 degreeC for 30 minutes. To the reaction solution, a solution of 5.00 g (14.8 mmol) of Intermediate (100) in 20 mL of THF was added for 10 minutes, stirred at -50°C for 30 minutes, and then stirred for 1.5 hours while raising the temperature to 0°C as it was. After cooling the reaction liquid to -50 degreeC and adding 10 ml of water to stop reaction, 10 ml of concentrated hydrochloric acid was added and it was made acidic. The mixture was warmed to room temperature, neutralized to pH 7 with aqueous sodium hydroxide solution, and extracted with 100 ml of dichloromethane. The organic layer was washed with 100 ml of water and 100 ml of saturated brine, and then re-extracted from the aqueous layer with 100 ml of dichloromethane. The organic layers were mixed, dried over anhydrous sodium sulfate, filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol = 10/1 (volume ratio)), and the black-green solid obtained by drying was washed with 30 ml of ethyl acetate and filtered under reduced pressure. The residue was dried under reduced pressure at 80°C to obtain the target compound (D-3) as a black-green solid (0.42 g, yield 6%).

[Formula 27]

[Synthesis Example 4] Synthesis of compound (D-4)

In Synthesis Example 2, by the same method except that 0.40 g (0.92 mmol) of compound (D-3) and 0.29 g (1.0 mmol) of LiTFSI were used instead of compound (D-1), the target The following compound (D-4) was obtained as a green solid (0.47 g, yield 75%).

[Formula 28]

[Synthesis Example 5] Synthesis of compound (D-5)

In Synthesis Example 3, in place of 3-bromopyridine, 6.03 g (26.3 mmol) of the following intermediate (Q-100), 16.4 ml (26.2 mmol) of a 1.6 M n-butyllithium/n-hexane solution, and the intermediate (100) By the same method except that 4.45 g (13.1 mmol) was used, the target compound (D-5) below was obtained as a dark reddish purple solid (2.30 g, yield 34%).

[Formula 29]

[Formula 30]

[Synthesis Example 6] Synthesis of compound (D-6)

In Synthesis Example 2, the target compound (D-5) 1.80 g (3.55 mmol) and LiTFSI 1.12 g (3.90 mmol) was used instead of the compound (D-1) by the same method. The following compound (D-6) was obtained as a dark purple solid (2.00 g, yield 75%).

[Formula 31]

[Synthesis Example 7] Synthesis of compound (D-7)

In Synthesis Example 3, instead of 3-bromopyridine, 5.75 g (25.1 mmol) of the following intermediate (Q-101), 15.7 ml (25.1 mmol) of a 1.6 M n-butyllithium/n-hexane solution, and the intermediate (100) By the same method except that 4.25 g (12.6 mmol) was used, the target compound (D-7) below was obtained as a dark purple solid (5.60 g, yield 68%).

[Formula 32]

[Formula 33]

[Synthesis Example 8] Synthesis of compound (D-8)

In Synthesis Example 2, 5.20 g (10.3 mmol) of Compound (D-7) and 3.24 g (14.3 mmol) of LiTFSI were used in place of Compound (D-1) by the same method as the target. The following compound (D-8) was obtained as a red solid (7.20 g, yield 97%).

[Formula 34]

[Synthesis Example 9] Synthesis of compound (D-9)

In Synthesis Example 3, instead of 3-bromopyridine, 5.75 g (25.0 mmol) of the following intermediate (Q-102), 15.7 ml (25.1 mmol) of a 1.6 M n-butyllithium/n-hexane solution, and the intermediate (100) By the same method except having used 4.25 g (12.6 mmol), the following target compound (D-9) was obtained as a black solid (1.90 g, yield 30%).

[Formula 35]

[Formula 36]

[Synthesis Example 10] Synthesis of compound (D-10)

In Synthesis Example 2, by the same method except that 1.40 g (2.76 mmol) of compound (D-9) and 0.87 g (3.03 mmol) of LiTFSI were used instead of compound (D-1), the target The following compound (D-10) was obtained as a dark purple solid (1.70 g, yield 82%).

[Formula 37]

[Synthesis Example 11] Synthesis of compound (D-11)

In Synthesis Example 3, in place of 3-bromopyridine, 5.50 g (29.6 mmol) of the following intermediate (Q-103), 18.5 ml (29.6 mmol) of a 1.6 M n-butyllithium/n-hexane solution, and the intermediate (100) By the same method except that 5.00 g (14.8 mmol) was used, the target compound (D-11) below was obtained as a dark purple solid (2.30 g, yield 36%).

[Formula 38]

[Formula 39]

[Synthesis Example 12] Synthesis of compound (D-12)

In Synthesis Example 2, by the same method except that 1.80 g (3.88 mmol) of compound (D-11) and 1.22 g (4.25 mmol) of LiTFSI were used instead of compound (D-1), the target The following compound (D-12) was obtained as a dark purple solid (2.20 g, yield 80%).

[Formula 40]

[Example 1]

(Evaluation of solubility)

In a 10 ml capacity glass sample bottle, 20 mg of the compound (D-2) obtained in Synthesis Example 2 and propylene glycol monomethyl ether (PGME) were mixed with a dye concentration of 0.5 mass%, 1 mass%, 3 mass%, 5 mass%. % was weighed, and the mixture was prepared. After ultrasonication for 20 minutes, it was left at room temperature (25°C) for 24 hours. The dye solution of each density|concentration was observed visually, and the highest dye concentration in which an insoluble content was not seen was made into solubility. Table 1 shows the measurement results.

(Evaluation of heat resistance)

5.0 g of a 2 mass % DMF solution of the methacrylic acid-acrylic acid ester copolymer and 20 mg of the compound (D-2) were placed in a 20 ml capacity sample bottle, and the mixture was stirred at room temperature (25°C) for 30 minutes. The obtained colored resin solution is filtered with a syringe filter, and the filtrate is applied on a glass substrate (film forming method: 1 g of the filtrate is dripped onto the glass and formed into a film at 300 rpm for 10 seconds using a spin coater) and heated at 100°C for 2 minutes to form a film. With respect to the produced film, the color value by transmitted light was measured using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., model number: CM-5). Then, it heated at 230 degreeC for 20 minutes, and measured the color value similarly. ^{The color difference (ΔE*} _ab ) of 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 steps are shown in Table 1 together.

「○」: ΔE ^* _ab ≤ 3.0

"Δ": 3.0 < ΔE ^* _ab ≤ 10.0

「×」: ΔE ^* _ab > 10.0

[Example 2 to Example 6]

In Example 1, solubility and heat resistance were evaluated by the method similar to Example 1 except having used the compound shown in Table 1 instead of compound (D-2). A result is put together in Table 1, and is shown.

[Comparative Examples 1 to 3]

As a comparative example, instead of the compound (D-2) of Example 1, C.I. Acid Red 289, C.I. Acid Red 52 or C.I. Solubility and heat resistance were evaluated in the same manner as in Example 1 except that Basic Violet 10 was used. A result is put together in Table 1, and is shown.

As shown in Table 1, the xanthene dye which is a compound of the Example of this invention has higher solubility than the conventional xanthene dye of the comparative example. Moreover, the coloring composition containing the xanthene pigment|dye of an Example is equipped with favorable heat resistance at the time of film forming, and there is no problem practically as a coloring agent for color filters. Moreover, the heat resistance at the time of film forming of the coloring composition of an Example is equal to or more than a comparative example, and is useful as a coloring agent for color filters.

The coloring composition containing the xanthene dye which concerns on this invention is excellent in solubility and heat resistance, and can be utilized as a coloring material for various uses, such as a coloring agent for color filters. Moreover, it is possible to manufacture the color filter excellent in color characteristics (color gamut, luminance, contrast ratio, etc.) by using this coloring composition as a coloring agent for color filters.

Claims (8)

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

[In formula (1), 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 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 via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
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 C3-C30 heterocyclic group which contains a nitrogen-containing 6-membered ring structure and may have a substituent.
An represents an anion, a represents an integer of 1-3, and b represents an integer of 0-3.] The method of claim 1,
In the said general formula (1), Q is group represented by the following general formula (Q1), The xanthene dye.

[In formula (Q1), Z ¹ to Z ⁵ each independently represent -N= or -CR ⁷ =.
However, one, two, or three of Z ¹ ~ Z ⁵ is assumed to be the -N =.
R ⁷ is, -H, halogen atom, -OH, -SH, -CN, -NO ₂ ,
sulfonic acid group, carboxyl group, sulfonamide group, amide group,
A linear or branched alkyl group having 1 to 27 carbon atoms which may have a substituent;
A linear or branched alkenyl group having 2 to 27 carbon atoms which may have a substituent;
A C6-C27 aromatic hydrocarbon group which may have a substituent;
an alkoxy group having 1 to 27 carbon atoms which may have a substituent;
a C1-C27 sulfanyl group which may have a substituent, or
an amino group having 0 to 27 carbon atoms which may have a substituent;
R ⁷ , when there are a plurality of them, may be the same as or different from each other,
In adjacent groups, a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom may be interposed between them to form a ring.] 3. The method according to claim 1 or 2,
In the said General formula (1), Q is a C4-C30 pyridyl group which may have a substituent, a pyrimidinyl group, a quinolyl group, or an isoquinolyl group, The xanthene pigment|dye. 4. The method according to any one of claims 1 to 3,
In the said General formula (1), X is -O-, A xanthene dye. 5. The method according to any one of claims 1 to 4,
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 ^- )),
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 of 1-3. The coloring composition containing the xanthene dye in any one of Claims 1-5 whose solubility with respect to propylene glycol monomethyl ether (PGME) in 25±2 degreeC is 1 mass % or more. The coloring agent for color filters containing the xanthene pigment|dye as described in any one of Claims 1-5, or the coloring composition of Claim 6. A color filter using the colorant for color filters according to claim 7.