JP2019167488A - Salt-forming compound, and coloring composition and color filter colorant containing the same - Google Patents

Abstract

To provide a dye that is a novel coumarin salt-forming compound, having excellent solubility in an organic solvent such as propylene glycol monomethyl ether (PGME), generally used in the production of color filters and also having excellent heat resistance, and a coloring composition and a color filter colorant containing the same.SOLUTION: The present invention provides a salt-forming compound including a coumarin cationic dye represented by the formula and an organic anion, and a coloring composition and a color filter colorant containing the same.SELECTED DRAWING: None

Description

The present invention relates to a salt-forming compound comprising a coumarin-based cationic dye and an organic anion, a coloring composition containing the salt-forming compound, a colorant for a color filter using the composition, and a color filter using the coloring agent It is about.

A color filter may be used for a liquid crystal or an electroluminescence (EL) display device. A color filter is manufactured by laminating a colored layer on a light-transmitting substrate such as glass by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. Colorants used in the colored layer are broadly classified into pigments and dyes, and pigments that are generally excellent in heat resistance and light resistance are widely used (see, for example, Patent Documents 1 to 3). However, since pigments are generally insoluble in a solvent, they exist in the form of fine particles in a color filter containing a resin or the like. Therefore, color filters using pigments affect the transparency and color purity by reflecting and scattering the transmitted light on the surface of the pigment particles in the filter, and also have a depolarizing effect due to reflection, so that color liquid crystal displays It is known that the contrast ratio of the device is reduced.

In order to improve such a decrease in contrast ratio, a method using only a dye as a colorant or a method using a dye and a pigment in combination has been proposed. Since the dye is soluble in the solvent, the color filter using the dye has an excellent spectral characteristic as compared with the case where only the pigment is used as the colorant, and the debiasing action is suppressed. As dyes used for color filters, xanthene dyes and the like are known from the viewpoint of excellent color developability, heat resistance and light resistance (see Patent Documents 4 to 8). For example, Patent Document 4 discloses C.I. I. Acid Red 289 and C.I. I. It is described that an excellent red color tone can be obtained by using a xanthene dye such as Acid Red 52 in combination with an azopyridone dye. Here, C.I. I. Means a color index.

Further, it is known that a blue color filter having a high contrast ratio and high color purity can be produced by using these xanthene dyes or derivatives thereof together with a phthalocyanine dye (see, for example, Patent Documents 6 and 7). A color filter that uses both a dye and a pigment mixes with different colors to form an aggregate, so that charge transfer occurs immediately between the photoexcited dye molecule and the nearby pigment molecule. It is considered that there is also an effect of suppressing the decomposition of each other, and it is possible to maintain color development and improve light resistance as compared with a color filter prepared by using a dye alone.

However, although conventional dye pigments can secure a certain degree of solubility in alcohols such as water and methanol, the solubility in organic solvents used in the production of color filters is insufficient, further improving the solubility Is desired.

JP 2001-220520 A Japanese Published Patent Publication No. 2007-533802 JP2012-12498A JP 2002-265834 A JP 2012-207224 A JP 2010-254964 A JP 2014-12814 A JP 2014-59538 A JP 09-328482 A

The present invention has been made in order to solve the above-mentioned problems, and has excellent solubility in organic solvents such as propylene glycol monomethyl ether (PGME) generally used in the production of color filters, and is excellent. It is an object of the present invention to provide a dye, which is a novel coumarin salt-forming compound having heat resistance, a coloring composition containing the same, and a color filter colorant.

As a result of intensive studies to solve the above problems, the present inventors have improved the solubility of a salt-forming compound composed of a coumarin-based cationic dye and an organic anion in an organic solvent such as PGME while maintaining heat resistance. The present invention has been completed.

That is, the present invention has been obtained as a result of intensive studies to achieve the above object, and has the following gist.

The present invention is a salt-forming compound represented by the following general formula (1), which comprises a coumarin cationic dye and an organic anion.

（１）

(1)

In the general formula (1), R ^{1 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
An optionally substituted acyl group having 1 to 20 carbon atoms,
An amino group having 0 to 20 carbon atoms which may have a substituent;
Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
R ² and R ³ , R ^{4 to} R ⁷ may be bonded to each other at adjacent groups to form a ring,
X represents an organic anion,
Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ ;
R ⁸ and R ⁹ are each a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cyclohexane having 3 to 20 carbon atoms which may have a substituent. An alkyl group,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or
Represents a heterocyclic group having 2 to 20 carbon atoms which may have a substituent;
R ⁸ and R ⁹ may be bonded to each other to form a ring,
Z represents —NH—, —N (CH ₃ ) —, —N ⁺ (CH ₃ ) ₂ —, an oxygen atom, or a sulfur atom, and a and b represent integers of 1 to 6.

In the general formula (1), X is a salt-forming compound which is an organic anion having a sulfonic acid group.

Furthermore, the present invention is the in the general formula (1), Y ^is a -N ₊ (CH ³⁾ salt-forming compound is R 8 ^{R 9.}

Further, the present invention is in the formula (1), Z ^{_{is, -N + (CH 3) 2}} - is a salt-forming compound is.

In the present invention or the general formula (1), Y is —N ⁺ (CH ₃ ) R ⁸ R ⁹ and Z is —N ⁺ (CH ₃ ) ₂ —.

The present invention relates to a salt-forming compound having a decomposition initiation temperature measured by performing thermogravimetry-differential thermal analysis (TG-DTA) in a range of 250 to 400 ° C.

Furthermore, the present invention relates to a salt-forming compound having a solubility in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. ± 2 ° C. of 2% by weight or more in the solubility of powder dissolved in a solvent.

Moreover, this invention is a coloring composition containing the said salt-forming compound.

The present invention is a colorant for a color filter containing the coloring composition.

The present invention is a color filter using the color filter colorant.

The salt-forming compound comprising the coumarin-based cationic dye of the present invention and an organic anion has high solubility in an organic solvent such as PGME and has a decomposition initiation temperature measured by thermogravimetry-differential thermal analysis (TG-DTA). Is excellent in heat resistance and is suitable as a colorant used in a color filter.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The salt-forming compound composed of a coumarin-based cationic dye represented by the general formula (1) and an organic anion includes a coumarin-based cationic dye represented by the following general formula (2). First, the coumarin type | system | group cationic dye represented by General formula (2) is demonstrated.

（２）

(2)

In general formula (2), R ^{1 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent,
An optionally substituted acyl group having 1 to 20 carbon atoms,
An amino group having 0 to 20 carbon atoms which may have a substituent;
Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
R ² and R ³ , R ^{4 to} R ⁷ may be bonded to each other at adjacent groups to form a ring,
Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ ;
R ⁸ and R ⁹ are each a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cyclohexane having 3 to 20 carbon atoms which may have a substituent. An alkyl group,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or
Represents a heterocyclic group having 2 to 20 carbon atoms which may have a substituent;
R ⁸ and R ⁹ may be bonded to each other to form a ring,
Z represents —NH—, —N (CH ₃ ) —, —N ⁺ (CH ₃ ) ₂ —, an oxygen atom, or a sulfur atom.

In the general formula (2), “the number of carbon atoms is 1” in “a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ^{1 to} R ^7. Specific examples of the “-20 linear or branched alkyl group” include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. And a branched alkyl group such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isooctyl group.

In the general formula (2), the “cycloalkyl group having 3 to 20 carbon atoms” in the “cycloalkyl group having 3 to 20 carbon atoms which may have a substituent” represented by R ^{1 to} R ⁷ Specific examples of "" include cycloalkyl groups such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

In the general formula (2), “the number of carbon atoms is 2” in the “linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent” represented by R ^{1 to} R ^7. -20 linear or branched alkenyl groups include vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl and isopropenyl. , An isobutenyl group, or a linear or branched alkenyl group in which a plurality of these alkenyl groups are bonded to each other.

In the general formula (2), the “acyl group having 1 to 20 carbon atoms” in the “acyl group having 1 to 20 carbon atoms which may have a substituent” represented by R ^{1 to} R ⁷ Formyl group, acetyl group, propionyl group, isopropionoyl group, butyroyl group, isobutyroyl group, pentanoyl group, hexanoyl group, acrylyl group, cyclohexanoyl group, cycloheptanoyl group, benzoyl group, methylbenzoyl group, phenylacetyl Groups, naphthanoyl groups, and the like.

In the general formula (2), the “amino group having 0 to 20 carbon atoms” in the “optionally substituted amino group having 0 to 20 carbon atoms” represented by R ^{1 to} R ⁷ As amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, methylethylamino group, propylamino group, dipropylamino group, methylpropylamino group, ethylpropylamino group, butylamino group, dibutyl Examples thereof include an amino group, a pentanylamino group, a propenylamino group, a butenylamino group, a cyclohexylamino group, a dicyclohexylamino group, a phenylamino group, a diphenylamino group, and a naphthylamino group.

In the general formula (2), represented by R ^{1 to} R ^7, which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a substituent. Specific examples of the “aromatic hydrocarbon group having 6 to 20 carbon atoms” and the “heterocyclic group having 2 to 20 carbon atoms” in the “heterocyclic group having 2 to 20 carbon atoms” include a phenyl group and naphthyl. Group, biphenyl group, anthryl group (anthracenyl group), phenanthryl group, pyrenyl group, indenyl group, fluorenyl group, triphenylyl group, perylenyl group and other aromatic hydrocarbon groups (or condensed polycyclic aromatic groups);
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group , Furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group and other heterocyclic groups (or heteroaromatic hydrocarbon groups) ), Etc.

In the general formula (2), represented by R ^{1 to} R ⁷ , “a linear or branched alkyl group having 1 to 20 carbon atoms having a substituent” or “2 to 2 carbon atoms having a substituent” As the “substituent” in “20 linear or branched alkenyl groups”, specifically,
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; —SO ₃ ^— ;
A cycloalkyl group having 3 to 19 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group;
A linear alkoxy group having 1 to 19 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group;
A branched alkoxy group having 3 to 19 carbon atoms such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group and isooctyloxy group;
A cycloalkoxy group having 3 to 19 carbon atoms, such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group;
An aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 19 carbon atoms such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylenyl group, indenyl group, fluorenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group A heterocyclic group having 2 to 19 carbon atoms such as furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, Etc. Only one of these “substituents” may be included, or a plurality of “substituents” may be included. When a plurality of “substituents” are included, they may be the same or different. Further, these “substituents” may further have the substituents exemplified above.

In the general formula (2), represented by R ^{1 to} R ⁷ , “a substituted cycloalkyl group having 3 to 20 carbon atoms”, “a substituted aromatic hydrocarbon group having 6 to 20 carbon atoms” Specific examples of the “substituent” in the “group” or “heterocyclic group having 2 to 20 carbon atoms having a substituent” include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; —SO ₃ ⁻ ;
A linear alkyl group having 1 to 14 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group;
A branched alkyl group having 3 to 14 carbon atoms such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group;
A cycloalkyl group having 3 to 14 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group;
A linear alkoxy group having 1 to 14 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group;
Branched alkoxy groups having 3 to 14 carbon atoms such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group and isooctyloxy group;
A cycloalkoxy group having 3 to 14 carbon atoms such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group;
Number of carbon atoms in which a 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 plurality of these alkenyl groups are bonded. 2 to 14 linear or branched alkenyl groups;
An aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group A heterocyclic group having 2 to 14 carbon atoms such as furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, Etc. Only one of these “substituents” may be included, or a plurality of “substituents” may be included. When a plurality of “substituents” are included, they may be the same or different. Further, these “substituents” may further have the substituents exemplified above.

In the general formula (2), examples of the “halogen atom” represented by R ^{1 to} R ⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the “halogen atom”, a fluorine atom or a chlorine atom is preferable.

In the general formula (2), “an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms” represented by R ^{1 to} R ⁷ or “having a substituent” As the “cycloalkoxy group having 3 to 20 carbon atoms”, the “linear or branched alkoxy group having 1 to 20 carbon atoms” or “cycloalkoxy group having 3 to 20 carbon atoms” , Specifically,
Linear alkoxy groups such as 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 -Branched alkoxy groups such as butoxy, t-butoxy and isooctyloxy;
And cycloalkoxy groups such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, and the like.

In the general formula (2), “a linear or branched alkoxy group having 1 to 20 carbon atoms having a substituent” represented by R ^{1 to} R ⁷ or “a carbon atom having 3 to 20 carbon atoms having a substituent”. As the “substituent” in the “cycloalkoxy group of
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; —SO ₃ ^— ;
A cycloalkyl group having 3 to 17 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group;
A straight-chain alkoxy group having 1 to 17 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group; A branched alkoxy group having 1 to 17 carbon atoms such as propoxy group, isobutoxy group, s-butoxy group, t-butoxy group, isooctyloxy group;
A cycloalkoxy group having 3 to 17 carbon atoms such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group;
Number of carbon atoms in which a 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 plurality of these alkenyl groups are bonded. 2 to 17 linear or branched alkenyl groups;
Examples thereof include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as phenyl group, naphthyl group, biphenyl group and anthracenyl group, and condensed polycyclic aromatic groups having 6 to 17 carbon atoms. Only one of these “substituents” may be included, and a plurality of “substituents” may be included. Further, these “substituents” may further have the substituents exemplified above.

In the general formula (2), R ² and R ³ , and adjacent groups in R ^{4 to} R ⁷ may be bonded to each other to form a ring, and these rings are a single bond or a nitrogen atom. In addition, a ring may be formed by a bond through either an oxygen atom or a sulfur atom. Moreover, as a ring formed in that case, a 5-membered ring or a 6-membered ring is preferable.

In General Formula (2), “Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ , and R ⁸ and R ⁹ may have a substituent. Specific examples of the “linear or branched alkyl group having 1 to 20 carbon atoms” in the “1-20 linear or branched alkyl group” include a methyl group, an ethyl group, a propyl group, and a butyl group. Linear alkyl groups such as pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; branched structures such as isopropyl group, isobutyl group, s-butyl group, t-butyl group and isooctyl group An alkyl group can be mentioned.

In General Formula (2), “Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ , and R ⁸ and R ⁹ may have a substituent. As the “cycloalkyl group having 3 to 20 carbon atoms” in “3 to 20 cycloalkyl group”, specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group And cycloalkyl groups such as

In General Formula (2), “Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ , and R ⁸ and R ⁹ may have a substituent. "Aromatic hydrocarbon group having 6 to 20 carbon atoms" and "carbon" in 6 to 20 aromatic hydrocarbon group or heterocyclic group having 2 to 20 carbon atoms which may have a substituent Specific examples of the heterocyclic group having 2 to 20 atoms include phenyl group, naphthyl group, biphenyl group, anthryl group (anthracenyl group), phenanthryl group, pyrenyl group, indenyl group, fluorenyl group, triphenylyl group, perylenyl group, etc. Aromatic hydrocarbon group (or condensed polycyclic aromatic group);
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group , Furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group and other heterocyclic groups (or heteroaromatic hydrocarbon groups) ), Etc.

In General Formula (2), “Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ , and R ⁸ and R ⁹ may have a substituent. As the “substituent” in the “1-20 linear or branched alkyl group” or the “C3-C20 cycloalkoxy group having a substituent”, specifically,
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; —SO ₃ ^— ;
A cycloalkyl group having 3 to 19 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group;
A linear alkoxy group having 1 to 19 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group;
A branched alkoxy group having 3 to 19 carbon atoms such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group and isooctyloxy group;
A cycloalkoxy group having 3 to 19 carbon atoms, such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group;
An aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 19 carbon atoms such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, pyrenyl group, triphenylenyl group, indenyl group, fluorenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group A heterocyclic group having 2 to 19 carbon atoms such as furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, Etc. Only one of these “substituents” may be included, or a plurality of “substituents” may be included. When a plurality of “substituents” are included, they may be the same or different. Further, these “substituents” may further have the substituents exemplified above.

In General Formula (2), “Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ , and R ⁸ and R ⁹ may have a substituent. Specific examples of the “substituent” in the “aromatic hydrocarbon group of 6 to 20 or the heterocyclic group having 2 to 20 carbon atoms which may have a substituent” include a fluorine atom, a chlorine atom, and bromine. Halogen atoms such as atoms and iodine atoms; —SO ₃ ^— ;
A linear alkyl group having 1 to 14 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group;
A branched alkyl group having 3 to 14 carbon atoms such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group;
A cycloalkyl group having 3 to 14 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group;
A linear alkoxy group having 1 to 14 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group;
Branched alkoxy groups having 3 to 14 carbon atoms such as isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group and isooctyloxy group;
A cycloalkoxy group having 3 to 14 carbon atoms such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group;
Number of carbon atoms in which a 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 plurality of these alkenyl groups are bonded. 2 to 14 linear or branched alkenyl groups;
An aromatic hydrocarbon group or condensed polycyclic aromatic group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group;
Pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzoimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group A heterocyclic group having 2 to 14 carbon atoms such as furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, Etc. Only one of these “substituents” may be included, or a plurality of “substituents” may be included. When a plurality of “substituents” are included, they may be the same or different. Further, these “substituents” may further have the substituents exemplified above.

In the general formula (2), R ⁸ and R ⁹ may be bonded to each other to form a ring, and these rings are bonded via a single bond or any atom of a nitrogen atom, an oxygen atom or a sulfur atom. A ring may be formed by the bond. Moreover, as a ring formed in that case, a 5-membered ring or a 6-membered ring is preferable.

The compound represented by the general formula (2) can be synthesized, for example, by a reaction between an aminosalicylaldehyde derivative and a benzimidazole derivative as shown in the following general reaction formula (1). (See, for example, Patent Document 9). Then, the coumarin type | system | group cationic dye shown to General formula (3)-(5) is compoundable by making the obtained coumarin dye react with dimethyl sulfate.
(Reaction Formula 1)

（３）

(3)

（４）

(4)

（５）

(5)

In the general formulas (3) to (5), R ^{1 to} R ⁹ have the same definitions as those in the general formula (2).

If necessary, the coumarin-based cationic dye represented by the general formula (2) can be purified by column chromatography; the product obtained by the above synthesis method; adsorption purification by silica gel, activated carbon, activated clay, etc .; It can be obtained by performing known purification such as dispersion washing, recrystallization, crystallization, and salting out. The solvent used in these purification methods is not particularly limited, and water, alcohols such as methanol and ethanol; halomethanes such as dichloromethane and chloroform; toluene and the like can be used alone or in combination.

Specific examples of preferable compounds as the coumarin-based cationic dye of the present invention are shown in the following formulas (A-1) to (A-20), but the present invention is not limited to these compounds. In the following structural formula, some hydrogen atoms are omitted. Further, even when stereoisomers exist, the planar structural formula is described. Furthermore, the anion portion is omitted.

（例示化合物Ａ−１）

(Exemplary Compound A-1)

（例示化合物Ａ−２）

(Exemplary Compound A-2)

（例示化合物Ａ−３）

(Exemplary Compound A-3)

（例示化合物Ａ−４）

(Exemplary Compound A-4)

（例示化合物Ａ−５）

(Exemplary Compound A-5)

（例示化合物Ａ−６）

(Exemplary Compound A-6)

（例示化合物Ａ−７）

(Exemplary Compound A-7)

（例示化合物Ａ−８）

(Exemplary Compound A-8)

（例示化合物Ａ−９）

(Exemplary Compound A-9)

（例示化合物Ａ−１０）

(Exemplary Compound A-10)

（例示化合物Ａ−１１）

(Exemplary Compound A-11)

（例示化合物Ａ−１２）

(Exemplary Compound A-12)

（例示化合物Ａ−１３）

(Exemplary Compound A-13)

（例示化合物Ａ−１４）

(Exemplary Compound A-14)

（例示化合物Ａ−１５）

(Exemplary Compound A-15)

（例示化合物Ａ−１６）

(Exemplary Compound A-16)

（例示化合物Ａ−１７）

(Exemplary Compound A-17)

（例示化合物Ａ−１８）

(Exemplary Compound A-18)

（例示化合物Ａ−１９）

(Exemplary Compound A-19)

（例示化合物Ａ−２０）

(Exemplary Compound A-20)

The coumarin cationic dye may be used alone (or a mixture of two or more different molecular structures) (for example, mixed), and one of the smallest molecular structures in the weight concentration ratio of the entire coumarin cationic dye. The weight concentration ratio of the coumarin dye is 0.1 to 50% by weight. The type of coumarin cationic dye is preferably one or two.

The salt-forming compound represented by the general formula (1) composed of the coumarin-based cationic dye represented by the general formula (2) and the organic anion includes an organic anion represented by “X ⁻ ”. In the general formula (1), the “organic anion” represented by “X ⁻ ” specifically includes an organic anion having a group such as a sulfonic acid group (—SO ₃ ⁻ ), a carboxyl group (—COO ⁻ ), etc. An organic anion having a sulfonic acid group is preferable.

In the general formula (1), the “organic anion having a sulfonic acid group” represented by “X ⁻ ” is specifically an aromatic carbon atom having 1 to 32 carbon atoms which may have a substituent. A hydrogen group, a linear or branched alkyl group having 1 to 32 carbon atoms which may have a substituent, and a linear or branched group having 1 to 32 carbon atoms which may have a substituent. And an organic anion in which a sulfonic acid group is bonded to a group such as an alkoxy group having a shape or a carboxy group having 1 to 32 carbon atoms which may have a substituent. Further, specific examples of the “aromatic hydrocarbon group”, “linear or branched alkyl group” or “linear or branched alkoxy group” mentioned as the “substituent” bonded to the above group Examples thereof include the same substituents as those described in the general formula (2).

Specific examples of preferable compounds as the organic anion of the present invention are shown in the following formulas (B-1) to (B-10), but the present invention is not limited to these compounds. In the following structural formula, some hydrogen atoms are omitted. Further, even when stereoisomers exist, the planar structural formula is described. Furthermore, the cation part is omitted.

（例示化合物Ｂ−１）

(Exemplary Compound B-1)

（例示化合物Ｂ−２）

(Exemplary Compound B-2)

（例示化合物Ｂ−３）

(Exemplary Compound B-3)

（例示化合物Ｂ−４）

(Exemplary Compound B-4)

（例示化合物Ｂ−５）

(Exemplary Compound B-5)

（例示化合物Ｂ−６）

(Exemplary Compound B-6)

（例示化合物Ｂ−７）

(Exemplary Compound B-7)

（例示化合物Ｂ−８）

(Exemplary Compound B-8)

（例示化合物Ｂ−９）

(Exemplary Compound B-9)

（例示化合物Ｂ−１０）

(Exemplary Compound B-10)

The organic anions used in the present invention may be used alone or in combination of two or more having different molecular structures.

Hereinafter, the coloring composition containing a salt-forming compound composed of a coumarin-based cationic dye and an organic anion represented by the general formula (1) of the present invention will be described in detail.

The powder containing the coumarin-based cationic dye of the present invention may contain solvent molecules, moisture, components having a molecular structure other than the coumarin-based cationic dye of the present invention, and other components. Any of these powders may be used as they are, but those subjected to purification treatment are preferred. However, a certain proportion of impurities may be present by any purification method, but any dye that can be produced in the current state of the art can be used.

However, the coloring composition of the present invention contains, as a main component, a salt-forming compound of a coumarin-based cationic dye represented by the general formula (1) and an organic anion in a component in the solid content, and has a certain concentration range. It may contain moisture and other solvent molecules. The presence of moisture or the like in the coloring composition is considered to be one of the factors that change the crystal structure of the coumarin dye powder, and as a result, the solubility of the coumarin dye in organic solvents such as PGME is low. It is thought to change. For example, the solubility in organic solvents such as PGME can be maintained while maintaining the heat resistance by adjusting the ratio of the weight of water to the total weight of the colored composition containing a coumarin dye (water content (% by weight)). A highly colored composition can be obtained. The water content in the coloring composition can be arbitrarily adjusted in the range of 0.1 to 20% by weight.

As a method for measuring the water content of the colored composition, a Karl Fischer (KF) method using a coulometric titration method or a volumetric titration method; a thermal analysis method using a thermogravimetry-differential thermal analysis (TG-DTA) apparatus; heating Heat drying using a dry moisture meter, etc .; gas chromatography (GC) method, infrared or near infrared absorption method; nuclear magnetic resonance absorption method; electrical resistance method; dielectric constant method; distillation method; . The analysis of the type and amount of impurities other than moisture can be similarly estimated by powder state observation, weight measurement, NMR analysis, GC analysis, and the like.

As other components, in order to enhance the performance of the coloring composition of the present invention as a colorant for color filters, a surfactant, a dispersing agent, an antifoaming agent, a leveling agent, and other color filter colorants are mixed. Additives such as organic compounds can be added. However, the content of these additives in the coloring composition is preferably an appropriate amount, and the solubility of the coloring composition of the present invention in the solvent is reduced or improved more than necessary. The content is preferably in 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.

The state of the powder of the colored composition of the present invention can be observed using an optical microscope, a scanning electron microscope (SEM) or the like. The shape of the colored composition of the present invention is usually used in the form of a solid powder having a shape such as a crystal, a fine crystal, a fine powder, a flake, a needle crystal, and a granule, but is not particularly limited. .

By measuring the particle size distribution, surface area, pore size distribution, powder density, etc. of the powder of the colored composition of the present invention, overall and average information on the shape of the powder can be obtained in more detail. For example, the Coulter method by measuring the electrical resistance of the electrolyte in which the powder is dispersed, the centrifugal sedimentation method for obtaining the effective Stokes diameter by measuring the absorbance of the powder dispersion, the laser diffraction / scattering method by analyzing the diffraction scattering pattern of the powder dispersion, etc. Can be measured. The colored composition of the present invention preferably has a particle size in the range of 0.1 μm to several mm, but the shape of the particles changes depending on the production conditions and the method of collecting the powder after drying. Although not limited, those having a smaller particle size are preferred for high solubility, and those having a median particle size distribution in the range of 0.1 to 100 μm are preferred.

By performing thermogravimetry-differential thermal analysis (TG-DTA) of the colored composition of the present invention, the decomposition start temperature of the powder can be analyzed. The decomposition start temperature is preferably 250 ° C. or higher, more preferably 300 ° C. or higher, and particularly preferably 360 ° C. or higher. When applied to a color filter, the higher the decomposition start temperature, the better. Further, as the temperature corresponding to the decomposition start temperature, the temperature at the time when the weight is reduced by a certain percentage (%) after heating the sample may be used. In the present invention, the temperature corresponding to the decomposition start temperature is determined using the temperature at the time when the weight is reduced by 5% after heating the sample.

The solubility of the powder of the colored composition in the present invention is represented by solubility, and the solubility represents the ratio of the maximum amount of the colored composition in which the powdered colored composition can be dissolved in a specific solvent. Yes, for example, expressed in units of “wt% (solvent name, temperature)”. Solubility is obtained, for example, by mixing a sample with a specific solvent, stirring the solvent for a certain period of time at a certain temperature, and measuring the concentration of the prepared saturated solution. It can also be obtained by concentration measurement.

The color composition contained in the color filter colorant must be well dissolved or dispersed in an organic solvent containing a resin or the like in the color filter colorant and color filter manufacturing process, so the solubility in the organic solvent Is preferably high. Although it does not specifically limit as an organic solvent, Specifically, Esters, such as ethyl acetate and acetic acid-n-butyl; Ethers, such as diethyl ether and propylene glycol monomethyl ether (PGME); Propylene glycol monomethyl ether acetate (PGMEA) Ether esters such as acetone and cyclohexanone; Alcohols such as methanol and ethanol; Diacetone alcohol (DAA) and the like; Aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide Amides such as (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO) and the like. These solvents may be used alone or in combination of two or more. Among these, the coloring composition containing the coumarin dye according to the present invention is preferably excellent in solubility in PGMEA and PGMEA, and particularly preferably excellent in solubility in PGMEA.

The solubility of the colored composition powder in the present invention is measured by adding the powder gradually until it remains in a certain amount of solvent, and the solubility in propylene glycol monomethyl ether (PGME) at 25 ° C. ± 2 ° C. It was obtained by measuring.

The spectral characteristics (transmittance, reflectance) of the powder of the colored composition of the present invention are important both when using a pigment alone as a colorant for a color filter or when mixing with other pigments. Which directly affects the color characteristics of the color filter. As a measuring method, there is a method of measuring an absorption (or transmission) spectrum in a solution or dispersion state, or an absorption (or transmission) spectrum of a thin film coated on glass or a transparent resin substrate. There is also a method of directly irradiating the powder with light and measuring the light reflected or scattered near the particle surface or the particle surface.

The colorant for a color filter of the present invention is generally used for the production of a color filter and a color composition containing a salt-forming compound composed of a coumarin cationic dye and an organic anion represented by the general formula (1). Ingredients used in For example, in the case of a method using a photolithography process, a general color filter is a liquid prepared by mixing a pigment such as a dye or a pigment with a resin component (including monomer or oligomer) or a solvent, such as glass or resin. It is coated on the substrate, photopolymerized using a photomask, a coloring pattern of a dye-resin composite film soluble / insoluble in a solvent is prepared, washed, and then heated. Also in the electrodeposition method and the printing method, a colored pattern is prepared using a mixture of a pigment and a resin or other components. Therefore, as a specific component in the colorant for a color filter of the present invention, a coloring composition containing a salt-forming compound composed of a coumarin cation dye and an organic anion represented by the general formula (1), Other additives such as dyes such as other dyes and pigments, resin components, organic solvents, and photopolymerization initiators. Moreover, you may choose from these components and may add another component as needed.

When the coloring composition containing the salt-forming compound of the coumarin-based cationic dye and organic anion of the present invention is used as a color filter colorant, it may be used for a color filter for each color, but it may be used for a blue or red color filter colorant. It is preferable to use as.

The colorant for a color filter including a coloring composition containing a salt-forming compound of a coumarin-based cationic dye and an organic anion of the present invention may use a coumarin-based cationic dye alone, for adjusting the color tone, You may mix well-known pigment | dyes, such as another dye or a pigment. Although it does not specifically limit when using for the coloring agent for red color filters, C.I. I. Pigment red 177, C.I. I. Pigment red 209, C.I. I. Pigment red 242, C.I. I. Red pigments such as CI Pigment Red 254; other red lake pigments; I. Acid Red 88, C.I. I. Examples thereof include red dyes such as Basic Violet 10. When used as a colorant for a blue color filter, although not particularly limited, C.I. I. Basic dyes such as basic blue 3, 7, 9, 54, 65, 75, 77, 99, 129; I. Acid dyes such as Acid Blue 9 and 74; Disperse dyes such as Disperse Blue 3, 7, and 377; Spiro dyes; Cyanine, Indigo, Phthalocyanine, Anthraquinone, Methine, Triarylmethane, Indanthrene And blue dyes or pigments such as oxazine, dioxazine, azo, and coumarin not belonging to the present invention; other blue lake pigments.

The mixing ratio of other pigments in the colorant for a color filter including a coloring composition containing a salt-forming compound of a coumarin-based cationic dye and an organic anion of the present invention is 5 to 2000% by weight with respect to the coumarin-based dye. Is preferable, and it is more preferable to set it as 10 to 1000 weight%. The mixing ratio of pigment components such as dyes in the liquid color filter colorant is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the whole colorant.

As a resin component in a colorant for a color filter including a coloring composition containing a salt-forming compound of a coumarin-based cationic dye and an organic anion of the present invention, a method for producing a color filter resin film formed using these, Any known material can be used as long as it has properties necessary for use. For example, acrylic resin, olefin resin, styrene resin, polyimide resin, urethane resin, polyester resin, epoxy resin, vinyl ether resin, phenol (novolak) resin, other transparent resin, photo-curing resin or thermosetting resin These monomers or oligomer components can be used in appropriate combination. Also, a copolymer of these resins can be used in combination. In the case of a liquid colorant, the content of the resin in the color filter colorant is preferably 5 to 95% by weight, and more preferably 10 to 50% by weight.

Other additives in the color filter colorant containing a coloring composition containing a salt-forming compound of a coumarin-based cationic dye and an organic anion of the present invention include polymerization and curing of resins such as photopolymerization initiators and crosslinking agents. And necessary surfactants and dispersants for stabilizing the properties of the components in the liquid color filter colorant. Any of these can be used for producing color filters, and are not particularly limited. The mixing ratio of the total amount of these additives in the entire solid content of the colorant for the color filter is preferably 5 to 60% by weight, and more preferably 10 to 40% by weight.

Embodiments of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In addition, the compound obtained in the synthesis example was identified by ¹ H-NMR analysis (Nuclear Magnetic Resonator, JNM-ECA-600 manufactured by JEOL Ltd.).

[Synthesis of Coumarin Dye]
[Synthesis Example 1] Synthesis of Coumarin Compound (C-1) 4- (Diethylamino) salicylaldehyde (10.0 g, 54 mmol), (5,6-dimethyl-benzimidazol-2-yl) -acetonitrile (100 ml Kolben) 10.4 g, 54 mmol), ammonium acetate (8.3 g, 108 mmol) and ethanol (140 ml) were added and heated, and the mixture was stirred at 73 to 76 ° C. (reflux temperature) for 3 hours. The reaction solution was cooled to room temperature, and the precipitated solid was filtered. The solid on the filter paper was washed with 70 ml of ethanol and then dried under reduced pressure at 40 ° C. to obtain 15 g (yield 76%) of a coumarin compound (C-1). Yellow solid, LC purity 97.2%.

¹ H-NMR (600 MHz, CDCL ₃ ): δ (ppm) = 12.41 (1H), 8.54 (1H), 7.52 (1H), 7.37 (1H), 7.30 (1H) 6.51 (1H), 6.36 (1H), 3.42 (4H), 1.24 (6H), 1.22 (6H).

（Ｃ−１）

(C-1)

[Synthesis Example 2] Synthesis of Coumarin Compound (C-2) (5,6-Dimethyl-benzimidazol-2-yl) -acetonitrile of Synthesis Example 1 was converted to (5-chlorobenzimidazol-2-yl) -acetonitrile. A coumarin compound (C-2) was obtained in an amount of 11.8 g (yield 87%). Dark yellow solid, LC purity 98.4%.

¹ H-NMR (600 MHz, CDCL ₃ ): δ (ppm) = 8.55 (1H), 7.72-7.64 (1H), 7.38-7.30 (3H), 7.20 (1H ), 6.52 (1H), 6.36 (1H), 3.43 (4H), 1.23 (6H).

（Ｃ−２）

(C-2)

Synthesis Example 3 Synthesis of Coumarin Compound (C-3) 4- (Butylphenylamino) salicylaldehyde (3.00 g, 11.1 mmol), ethyl (benzimidazol-2-yl) -acetate (2) in 100 ml Kolben .73 g, 13.4 mmol), piperidine (0.09 g, 1.1 mmol) and toluene (24 ml) were added and heated, and the mixture was stirred at 90 to 100 ° C. for 5 hours. Water, ethyl acetate and n-hexane were added and filtered. The solid on the filter paper was dried under reduced pressure to obtain 4.5 g (yield 100%) of a coumarin compound (C-3). Orange solid, LC purity 94.8%.

¹ H-NMR (600 MHz, CDCL ₃ ): δ (ppm) = 11.25 (1H), 8.95 (1H), 7.79 (1H), 7.48-7.54 (3H), 7. 42 (1H), 7.37 (1H), 7.25-7.32 (4H), 6.62-6.66 (2H), 3.80 (2H), 1.75 (2H), 1. 42 (2H), 0.98 (3H).

（Ｃ−３）

(C-3)

[Synthesis Example 4] Synthesis of Coumarin Compound (C-4) 4- (dibutylamino) salicylaldehyde (5.00 g, 20.1 mmol), ethyl (benzimidazol-2-yl) -acetate (4. 91 g, 24.1 mmol), piperidine (0.17 g, 2.0 mmol) and toluene (40 ml) were added and heated, followed by stirring at 90-100 ° C. for 5 hours. The reaction solution was concentrated to half volume under reduced pressure, crystallized by adding 20 ml of n-hexane, and filtered. The solid on the filter paper was dried under reduced pressure to obtain 7.2 g (yield 92%) of the coumarin compound (C-4). Orange solid, LC purity 96.0%.

¹ H-NMR (600 MHz, CDCL ₃ ): δ (ppm) = 11.25 (1H), 8.93 (1H), 7.76 (1H), 7.50 (1H), 7.45 (1H) 6.65 (1H), 6.53 (1H), 3.38 (4H), 1.59 (4H), 1.38 (4H), 0.98 (6H).

（Ｃ−４）

(C-4)

[Synthesis Example 5] Methylation of Coumarin Compound (C-1) (Synthesis of Exemplified Compound A-14)
To 300 ml Kolben, the coumarin compound (C-1) synthesized in Synthesis Example 1 (8.00 g, 22.1 mmol), magnesium oxide (2.68 g, 66.4 mmol) and sulfolane (40 ml) were added, and the mixture was heated and stirred at 80 ° C. , Dimethyl sulfate (8.38 g, 66.4 mmol) was added, and the mixture was stirred at 100 ° C. for 10 hours. During this time, dimethyl sulfate (16.8 g, 133 mmol) was added. After standing to cool, it was poured into 200 ml of water and filtered. The filtrate was concentrated under reduced pressure, acetone was added and the precipitated solid was removed by filtration. The filtrate was concentrated under reduced pressure, and the column was purified (chloroform / ethyl acetate = 9/1 → 7/3 → chloroform / methanol = 9/1) to obtain 5.7 g (yield 61%) of exemplary compound A-14. It was.

Synthesis Example 6 Methylation of Coumarin Compound (C-2) (Synthesis of Exemplary Compound A-15)
Except that the coumarin compound (C-1) synthesized in Synthetic Example 1 of Synthesis Example 5 was changed to the coumarin compound (C-2) synthesized in Synthetic Example 2, the same procedure was followed, and Exemplified Compound A-15 was converted to 5 0.7 g (61% yield) was obtained.

Synthesis Example 7 Methylation of Coumarin Compound (C-3) (Synthesis of Exemplary Compound A-10)
To 100 ml Kolben, the coumarin compound (C-3) synthesized in Synthesis Example 3 (4.50 g, 11.0 mmol), magnesium oxide (1.33 g, 33.0 mmol) and sulfolane (23 ml) were added, and the mixture was heated and stirred at 80 ° C. Dimethyl sulfate (4.16 g, 33.0 mmol) was added in three portions, and the mixture was stirred at 100 ° C. for 5 hours. Ethyl acetate and water were added, and the organic layer was extracted and concentrated under reduced pressure. The precipitated solid was collected by filtration to obtain 3.4 g (yield 66%) of Exemplary Compound A-10. LC purity 96.4%.

[Synthesis Example 8] Methylation of Coumarin Compound (C-4) (Synthesis of Exemplary Compound A-11)
The same procedure was followed except that the coumarin compound (C-3) synthesized in Synthesis Example 7 was changed to the coumarin compound (C-4) synthesized in Synthesis Example 4, and purified by column chromatography. 5.5 g (yield 69%) of Exemplified Compound A-11 was obtained. LC purity 98.6%.

[Synthesis Example 9] Salt formation of exemplary compound A-1 (salt formation reaction with exemplary compound B-6)
To 1000 ml Kolben, 5.0 g of basic yellow (Exemplary Compound A-1) 40 and 400 ml of water were added, and the mixture was heated and stirred at 80 ° C. Thereto, 7.57 g of Sandet BL (Exemplary Compound B-6) dissolved in 50 ml of water was added dropwise over 30 minutes. After completion of dropping, stirring was continued at 80 ° C. for 1 hour, and then cooled to room temperature. The solvent was distilled off from the reaction solution under reduced pressure to obtain a solid. The resulting solid was washed with water. The solid was dispersed in chloroform and filtered to obtain 6.0 g of a yellow solid as a salt-form of Example Compound A-1 (yield 78%).

[Synthesis Example 10] Salt formation of exemplary compound A-1 (salt formation reaction with exemplary compound B-1)
Except that the surfactant having a sulfonic acid group in Synthesis Example 9 was changed from Exemplified Compound B-6 to Exemplified Compound B-1 (sodium dodecylbenzenesulfonate), salt formation of Exemplified Compound A-1 As a product, 8.0 g (yield 92%) of a yellow solid was obtained. LC purity 99.0%.

[Synthesis Example 11] Salt formation of exemplary compound A-14 (salt formation reaction with exemplary compound B-6)
Example Compound A-14 (3.50 g, 8.3 mmol), water (50 ml), Sandet BL (Exemplary Compound B-6) (6.20 g, 12.5 mmol) synthesized in Synthesis Example 5 was added to 300 ml Kolben and added 80 Heated to ° C and stirred for 1 hour. After cooling, the mixture was extracted with chloroform and concentrated under reduced pressure. Crystallization was performed with n-hexane to obtain 3.1 g (yield 41%) of the salt form of Exemplified Compound A-14.

[Synthesis Example 12] Salt formation of exemplary compound A-15 (salt formation reaction with exemplary compound B-6)
Except that Exemplified Compound A-14 synthesized in Synthetic Example 5 of Synthetic Example 11 was changed to Exemplified Compound A-15 synthesized in Synthetic Example 6, it was changed in the same manner. Obtained .55 g (yield 5%).

[Synthesis Example 13] Salt formation of exemplary compound A-10 (salt formation reaction with exemplary compound B-6)
Example Compound A-10 synthesized in Synthesis Example 7 (2.00 g, 4.4 mmol), water (26 ml), methanol (5 ml), 1 mol / L hydrochloric acid (13 ml) was added to 100 ml Kolben and heated to 80 ° C. Sandet BL (Exemplary Compound B-6) (3.3 g, 6.6 mmol) was added, and the mixture was stirred at 80 ° C. for 1 hour. The mixture was allowed to cool to room temperature, extracted with chloroform, and concentrated under reduced pressure to obtain 1.9 g (yield 61%) of a salt form of Exemplified Compound A-10.

[Synthesis Example 14] Salt formation of exemplary compound A-11 (salt formation reaction with exemplary compound B-6)
Except that Exemplified Compound A-10 synthesized in Synthetic Example 7 of Synthetic Example 13 was changed to Exemplified Compound A-11 synthesized in Synthetic Example 8, the same procedure was followed to obtain a salt-form of Exemplified Compound A-11. 0.5 g (yield 75%) was obtained.

[Example 1]
[Dye Evaluation]
The decomposition start temperature and solubility in PGME of the dye, which is a coumarin salt-forming compound obtained in Synthesis Example 9, were measured, and the measurement results are summarized in Table 1.

[Examples 2 to 6]
The pigments that are coumarin salt forming compounds obtained in Synthesis Examples 10 to 14 were also measured in the same manner as in Example 1 and are summarized in Table 1.

[Comparative Example 1]
For comparison, commercially available C.I. I. The decomposition start temperature of Basic Yellow 40 and the solubility in PGME were measured, and the measurement results are summarized in Table 1.

[Comparative Examples 2 to 5]
For comparison, the decomposition start temperature and the solubility in PGME of the coumarin compounds synthesized in Synthesis Examples 1 to 4 were measured, and the measurement results are shown in Table 1.

As shown in Table 1, the dye which is a coumarin salt forming compound of the examples of the present invention is highly soluble in PGME while maintaining a decomposition start temperature higher than that of the comparative compound (commercially available CI Basic Yellow 40). It is clear that it is suitable as a color filter dye.

The colorant, which is a coumarin salt forming compound according to the present invention, is excellent in heat resistance and solubility in an organic solvent (such as PGME), a colored composition containing the salt forming compound, and a color filter using the composition It is useful as a coloring matter.

Claims (10)

A salt-forming compound represented by the following general formula (1), comprising a coumarin-based cationic dye and an organic anion.

(1)
[Wherein R ^{1 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent,
A C3-C20 cycloalkoxy group optionally having a substituent, a C2-C20 linear or branched alkenyl group optionally having a substituent,
An optionally substituted acyl group having 1 to 20 carbon atoms,
An amino group having 0 to 20 carbon atoms which may have a substituent;
Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent,
R ² and R ³ , R ^{4 to} R ⁷ may be bonded to each other at adjacent groups to form a ring.
X represents an organic anion,
Y represents —NR ⁸ R ⁹ or —N ⁺ (CH ₃ ) R ⁸ R ⁹ ;
R ⁸ and R ⁹ are each a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cyclohexane having 3 to 20 carbon atoms which may have a substituent. An alkyl group,
An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or
Represents a heterocyclic group having 2 to 20 carbon atoms which may have a substituent;
R ⁸ and R ⁹ may be bonded to each other to form a ring,
Z represents —NH—, —N (CH ₃ ) —, —N ⁺ (CH ₃ ) ₂ —, an oxygen atom, or a sulfur atom, and a and b represent integers of 1 to 6. ] The salt-forming compound according to claim 1, wherein, in the general formula (1), X is an organic anion having a sulfonic acid group. The salt-forming compound according to claim 1 or 2, wherein in the general formula (1), Y is -N ⁺ (CH ₃ ) R ⁸ R ⁹ . The salt-forming compound according to claim 1 or 2, wherein, in the general formula (1), Z is -N ⁺ (CH ₃ ) _2- . In the general formula (1), Y ^is, -N ₊ (CH ³⁾ a R 8 ^{R 9,} Z _{^{is, -N + (CH 3) 2}} - which is, according to claim 1 or claim 2 Salt-forming compound. The salt-forming compound according to any one of claims 1 to 5, wherein a decomposition initiation temperature measured by performing thermogravimetry-differential thermal analysis (TG-DTA) is in a range of 250 to 400 ° C. . The structure according to any one of claims 1 to 6, wherein the solubility of the powder dissolved in the solvent is 2% by weight or more in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C ± 2 ° C. Salt compound. The coloring composition containing the salt-forming compound as described in any one of Claims 1-7. The colorant for color filters containing the coloring composition of Claim 8. A color filter using the color filter colorant according to claim 9.