TWI805622B - Coloring composition containing salt-forming compound comprising xanthene-based cationic dye and organic anion, coloring agent for color filter, and color filter - Google Patents

Abstract

所表示之二苯并哌喃系陽離子染料及有機陰離子之成鹽化合物之著色組合物、用於色域擴大之色相之調整優異的彩色濾光片用著色劑、顯色性(色域、亮度、對比率等)優異之彩色濾光片。The present invention provides a kind of compound comprising following general formula (1)

Coloring composition of dibenzopyran cationic dye and salt-forming compound of organic anion, colorant for color filters excellent in hue adjustment for color gamut expansion, color rendering properties (color gamut, brightness) , contrast ratio, etc.) excellent color filter.

Description

Coloring composition containing salt-forming compound containing dibenzopyran cationic dye and organic anion, colorant for color filter, and color filter

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

There are cases where color filters are used in liquid crystal or electroluminescence (EL, Electroluminescence) display devices. A color filter is manufactured by laminating a colored layer on a translucent substrate such as glass by dyeing, pigment dispersion, printing, electrodeposition, or the like. Colorants used in the colored layer are roughly classified into pigments and dyes, and pigments excellent in heat resistance and light resistance are generally widely used (for example, refer to Patent Documents 1 to 3). However, since pigments are generally insoluble in solvents, they exist in the form of fine particles in color filters containing resins and the like. Therefore, it is known that color filters using pigments affect transparency or color purity due to the reflection and scattering of the transmitted light on the surface of pigment particles in the filter, and also have depolarization due to reflection. Therefore, color liquid crystal display devices The contrast ratio is reduced.

In order to solve the problem of such a decrease in contrast ratio, a method of using only a dye as a colorant, a method of using a dye and a pigment in combination, and the like have been proposed. Since dyes are soluble in solvents, color filters using dyes can suppress depolarization and have excellent spectral characteristics compared to the case of using only pigments as colorants. As dyes used for color filters, dibenzopyran dyes and the like are known because they have excellent color rendering properties, heat resistance, and light resistance (for example, refer to Patent Documents 4 to 8). In addition, it is described that a dibenzopyran-based dye such as C.I. Acid Red 289 represented by the following formula (D-1) or C.I. Acid Red 52 represented by the following formula (D-2) and azopyridine When used in combination with a ketone dye, an excellent red hue can be obtained (for example, refer to Patent Document 4). Here, C.I. means color index.

[chemical 1]

[Chem 2]

Also, it is known that by using these dibenzopyran dyes or their derivatives in combination with phthalocyanine dyes, it is possible to produce a blue color filter with high contrast ratio and color purity (for example, refer to Patent Document 6, 7). It is believed that such a color filter that uses dyes and pigments in combination forms an aggregate by mixing the two with different colors, and immediately produces charge transfer between the dye molecules excited by light and the nearby pigment molecules, Therefore, it also has the effect of mutually inhibiting oxidation and decomposition. Compared with the color filter made by using dye alone, it can maintain color rendering and improve light resistance. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-220520 [Patent Document 2] Japanese Patent Publication No. 2007-533802 [Patent Document 3] Japanese Patent Laid-Open No. 2012-12498 [Patent Document 4] Japanese Patent Laid-Open No. 2002-265834 [Patent Document 5] Japanese Patent Laid-Open No. 2012-207224 [Patent Document 6] Japanese Patent Laid-Open No. 2010-254964 [Patent Document 7] Japanese Patent Laid-Open No. 2014-12814 [Patent Document 8] Japanese Patent Laid-Open No. 2014-59538 [Patent Document 9] Japanese Patent Laid-Open No. 2006-064993

[Problem to be solved by the invention]

Common displays display various colors by controlling the mixing ratio of the three primary colors of red (R), green (G), and blue (B). However, the color displayed on the display can only reproduce the color (color gamut) of the area inside the triangle surrounded by the points of the three primary colors on the coordinates of the chromaticity diagram, so with the evolution of the display, faithful color reproduction can be achieved Expectations for wide color gamut displays are rising. As a method of expanding the color gamut, there are methods of increasing the number of primary colors to multiply primary colors, and methods of improving the color purity of primary colors. The former is intended to polygonize the color gamut of the current triangle to expand the area, and the latter is to expand the area to expand the size of the existing triangle. Therefore, in order to expand the color gamut by multi-primary colors, development of a dye for color filters having a hue different from the three primary colors of RGB is expected (for example, Patent Document 9).

The present invention was made in order to solve the above-mentioned problems, and its object is to provide a dibenzopyran-based dye that is excellent in adjustment of hue for expanding the color gamut as a colorant for color filters, and is contained in color filters. Coloring composition having dibenzopyran-based dye in solid (powder, etc.) state necessary for exhibiting good solubility or dispersibility in the sheet manufacturing process, and for color filters containing the coloring composition A colorant, and a color filter using the colorant for a color filter excellent in color rendering properties (color gamut, brightness, contrast ratio, etc.). [Technical means to solve the problem]

The inventors of the present invention have found that a dye whose maximum absorption wavelength is extended by the current dibenzopyran dye is used as a coloring agent suitable for widening the color gamut of color filters, and further found that it contains The coloring composition of the dye has the heat resistance required for the manufacture of color filters. The present invention has been accomplished by finding that a color filter excellent in color reproducibility can be obtained by using such a coloring composition.

That is, the present invention is the result of diligent research to achieve the above object, and the following is the gist.

1. A coloring composition comprising a salt-forming compound comprising a dibenzopyran cationic dye represented by the following general formula (1) and an organic anion:

[Chem 3]

[In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms that may have a substituent, and a C 3 to 20 alkyl group that may have a substituent A cycloalkyl group, a straight-chain or branched alkenyl group with 2 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent, or a substituent For a heterocyclic group with 2 to 20 carbon atoms, R ¹ and R ² , or R ³ and R ⁴ may also be bonded to each other to form a ring; R ⁵ to R ⁸ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, - SO ₃ ^- , a linear or branched alkyl group having 1 to 20 carbon atoms that may have a substituent, a cycloalkyl group having 3 to 20 carbon atoms that may have a substituent, a carbon atom that may have a substituent A linear or branched alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent, a linear or branched chain having 2 to 20 carbon atoms which may have a substituent A branched alkenyl group, an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents, or a heterocyclic group with 2 to 20 carbon atoms that may have substituents, R ⁵ to R ⁸ may also be adjacent The groups are bonded to each other to form a ring; R ⁹ and R ¹⁰ each independently represent a straight-chain or branched chain alkyl group with 1 to 20 carbon atoms that may have a substituent, and a carbon number 3 that may have a substituent A cycloalkyl group of ∼20 carbon atoms, a linear or branched alkenyl group with 2 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent, or a substituted The heterocyclic group with 2 to 20 carbon atoms in the group, R ⁹ and R ¹⁰ may also bond with each other to form a ring; X represents an organic anion, and y represents an integer of 1 or 2].

2. A coloring composition wherein, in the above general formula (1), X is an organic anion having a sulfonic acid group.

[式中，B表示-O-、伸苯基、氧基伸苯基、或伸苯氧基， p表示0或1， A表示苯環或萘環， q表示0或1， R⁰ 表示 可具有取代基之碳原子數1～32之直鏈狀或支鏈狀之烷基、 可具有取代基之碳原子數3～32之環烷基、 可具有取代基之碳原子數1～32之直鏈狀或支鏈狀之烷氧基、 可具有取代基之碳原子數3～32之環烷氧基、 可具有取代基之碳原子數2～32之直鏈狀或支鏈狀之烯基、 可具有取代基之碳原子數6～32之芳香族烴基、 可具有取代基之碳原子數2～32之雜環基、或 氫原子， R²⁰ 表示 可具有取代基之碳原子數1～32之直鏈狀或支鏈狀之烷基、 可具有取代基之碳原子數3～32之環烷基、 可具有取代基之碳原子數1～32之直鏈狀或支鏈狀之烷氧基、 可具有取代基之碳原子數3～32之環烷氧基、 可具有取代基之碳原子數2～32之直鏈狀或支鏈狀之烯基、 可具有取代基之碳原子數6～32之芳香族烴基、或 可具有取代基之碳原子數2～32之雜環基， r表示0～6之整，s表示1～2之整數]。3. A coloring composition, wherein in the above general formula (1), X is an organic anion represented by the following general formula (20): [Chem. 4]

[In the formula, B represents -O-, phenylene, oxyphenylene, or phenoxy, p represents 0 or 1, A represents a benzene ring or a naphthalene ring, q represents 0 or 1, and R ⁰ represents that it can have A straight-chain or branched alkyl group having 1 to 32 carbon atoms as a substituent, a cycloalkyl group having 3 to 32 carbon atoms that may have a substituent, a straight-chain or branched alkyl group having 1 to 32 carbon atoms that may have a substituent Chain or branched alkoxy, cycloalkoxy with 3 to 32 carbon atoms which may have substituents, straight or branched alkenyl with 2 to 32 carbon atoms which may have substituents , an aromatic hydrocarbon group with 6 to 32 carbon atoms that may have a substituent, a heterocyclic group with 2 to 32 carbon atoms that may have a substituent, or a hydrogen atom, R ²⁰ represents a carbon atom that may have a substituent with 1 to 32 32 straight-chain or branched-chain alkyl, optionally substituted cycloalkyl with 3 to 32 carbon atoms, optionally substituted straight-chain or branched-chain alkanes with 1 to 32 carbon atoms Oxygen, a cycloalkoxy group having 3 to 32 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 32 carbon atoms which may have a substituent, a carbon atom which may have a substituent An aromatic hydrocarbon group having 6 to 32 carbon atoms, or a heterocyclic group having 2 to 32 carbon atoms which may have a substituent, r represents an integer of 0 to 6, and s represents an integer of 1 to 2].

4. A coloring composition wherein, in the above general formula (1), X is an organic anion represented by the following general formulas (2) to (7).

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[wherein, R ¹¹ to R ¹⁷ each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkane having 3 to 20 carbon atoms which may have a substituent Group, a straight-chain or branched alkoxy group having 1 to 20 carbon atoms that may have a substituent, a cycloalkoxy group having 3 to 20 carbon atoms that may have a substituent, a carbon atom that may have a substituent A linear or branched alkenyl group having 2 to 20 carbon atoms, 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 ¹⁶ and R ¹⁷ may also be bonded to each other to form a ring; m represents an integer of 1-3, and n represents an integer of 0-7. ]

5. A coloring composition, wherein in the above-mentioned general formula (1), R ¹ to R ⁴ , R ⁹ and R ¹⁰ are linear or branched alkanes having 1 to 10 carbon atoms which may have substituents base.

6. A colorant for color filters comprising the above-mentioned coloring composition.

7. A color filter using the above-mentioned colorant for color filters. [Effect of Invention]

The coloring composition of the present invention containing a salt-forming compound comprising a dibenzopyran-based cationic dye and an organic anion has excellent heat resistance or solubility, and can be used as a colorant for color filters. Moreover, the color filter which expanded the color gamut by multi-primary colorization can be produced using this colorant.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various changes can be implemented within the range of the summary.

In the salt-forming compound comprising the dibenzopyran cationic dye represented by the general formula (1) and an organic anion, the dibenzopyran cationic dye represented by the following general formula (8) and X Represented organic anion. In the general formula (1), y represents the number of dibenzopyran cationic dyes represented by the following general formula (8), and y represents an integer of 1 or 2. When X is a monovalent organic anion, y is 1, and when X is a divalent organic anion, y is 2. When X is a mixture of a monovalent organic anion and a divalent organic anion, y is 1 or 2 in order to make the whole charge neutral. Hereinafter, the dibenzopyran system cationic dye represented by General formula (8) is demonstrated.

[chemical 11]

In the general formula (8), as "a straight-chain or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ "with 1 to 20 carbon atoms straight-chain or branched-chain alkyl", specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. Chain-like alkyl groups; branched-chain alkyl groups such as isopropyl, isobutyl, second-butyl, third-butyl, and isooctyl.

In the general formula (8), 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 ¹⁰ is specifically Examples thereof include cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

In the general formula (8), as "a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ "with 2 to 20 carbon atoms straight-chain or branched-chain alkenyl", for example: vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexene group, isopropenyl group, isobutenyl group, or a linear or branched alkenyl group formed by bonding a plurality of these alkenyl groups.

In the general formula (8), the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" or "heterocyclic ring having 2 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ "Aromatic hydrocarbon group with 6 to 20 carbon atoms" or "heterocyclic group with 2 to 20 carbon atoms" in "group", specifically, phenyl, naphthyl, biphenyl, anthracenyl ( Anthracenyl), phenanthrenyl, pyrenyl, indenyl, fenyl, terphenyl, perylene and other aromatic hydrocarbon groups (or condensed polycyclic aromatic groups); pyridyl, pyrimidyl, triazinyl, pyrrolyl , imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbolinyl, acridinyl, phenanthrinyl, Furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, oxazolyl, benzofuryl, thiazolyl, benzothiazolyl and other heterocyclic groups ( or heteroaryl) etc.

In the general formula (8), as "a linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" represented by R ¹ to R ¹⁰ or "a carbon atom having a substituting group having 2 The "substituent" in the "linear or branched alkenyl group of ∼20" specifically includes: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; -SO ₃ ^- ; cyclopropane Cycloalkyl groups with 3 to 19 carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy straight-chain alkoxy groups with 1 to 19 carbon atoms, such as heptyloxy, octyloxy, nonyloxy, decyloxy, etc.; isopropoxy, isobutoxy, second butoxy, second butoxy Branched-chain alkoxy groups with 3 to 19 carbon atoms such as tributoxy and isooctyloxy; 19 cycloalkoxy groups; phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, pyrenyl, terphenyl, indenyl, fenyl and other aromatic hydrocarbon groups with 6 to 19 carbon atoms or condensed multi Ring aromatic group; pyridyl, pyrimidyl, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridyl, indolyl, benzimidazolyl , carbazolyl, carbolinyl, acridinyl, phenanthranyl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, oxazolyl, benzene Heterocyclic groups having 2 to 19 carbon atoms such as oxazolyl, thiazolyl, and benzothiazolyl. These "substituents" may contain only one kind or plural kinds, and when plural kinds are contained, they may be the same as or different from each other. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formula (8), as "a cycloalkyl group having 3 to 20 carbon atoms having a substituent" or "an aromatic hydrocarbon group having a substituent having 6 to 20 carbon atoms" represented by R ¹ to R ¹⁰ Or the "substituent" in the "heterocyclic group having 2 to 20 carbon atoms having a substituent", specifically, include: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; -SO ₃ ^- ; Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and other straight-chain alkyl groups with 1 to 14 carbon atoms; isopropyl, isobutyl Branched-chain alkyl groups with 3 to 14 carbon atoms, such as butyl, 2-butyl, 3-butyl, and isooctyl; carbon such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl Cycloalkyl with 3 to 14 atoms; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, etc. Straight-chain alkoxy groups with 1 to 14 carbon atoms; branches with 3 to 14 carbon atoms such as isopropoxy, isobutoxy, second butoxy, tertiary butoxy, isooctyloxy, etc. Chain alkoxy; Cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy and other cycloalkoxy groups with 3 to 14 carbon atoms; Vinyl, 1-propenyl, allyl , 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or a plurality of these alkenyl groups bonded together with 2 to 14 carbon atoms straight-chain or branched-chain alkenyl; phenyl, naphthyl, biphenyl, anthracenyl, phenanthrenyl, indenyl, fenyl, and other aromatic hydrocarbon groups with 6 to 14 carbon atoms or condensed polycyclic aromatics Base; pyridyl, pyrimidyl, triazinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridyl, indolyl, benzimidazolyl, carbazole Base, carbolinyl, acridinyl, phenanthrinyl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, oxazolyl, benzofuryl C2-14 heterocyclic groups such as thiazolyl, benzothiazolyl, etc. These "substituents" may contain only one kind or plural kinds, and when plural kinds are contained, they may be the same as or different from each other. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formula (8), examples of the "halogen atom" represented by R ⁵ to R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "halogen atom" is preferably a fluorine atom or a chlorine atom.

In the general formula (8), as "a linear or branched alkoxy group having 1 to 20 carbon atoms that may have a substituent" or "a carbon that may have a substituent" represented by R ⁵ to R ⁸ The "linear or branched alkoxy group with 1 to 20 carbon atoms" or "cycloalkoxy group with 3 to 20 carbon atoms" in "cycloalkoxy group with 3 to 20 atoms", specifically In other words, examples include: straight-chain alkanes such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy. Oxygen; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyl and other branched alkoxy; cyclopropoxy, cyclobutoxy, cyclopentyl Cycloalkoxy groups such as oxy, cyclohexyloxy; etc.

In the general formula (8), as "a straight-chain or branched alkoxy group having 1 to 20 carbon atoms having a substituent" or "a carbon number having a substituent" represented by R ⁵ to R ⁸ The "substituent" in "cycloalkoxy group of 3 to 20" specifically includes: halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; -SO ₃ ^- ; cyclopropyl group, cyclopentyl group , cyclohexyl, cyclooctyl and other cycloalkyl groups with 3 to 17 carbon atoms; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy , nonyloxy, decyloxy and other linear alkoxy groups with 1 to 17 carbon atoms; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy branched alkoxy groups with 1 to 17 carbon atoms; cycloalkoxy groups with 3 to 17 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy; vinyl , 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or multiple bonds of these alkenyl groups A linear or branched alkenyl group with 2 to 17 carbon atoms; an aromatic hydrocarbon group with 6 to 18 carbon atoms such as phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic hydrocarbon group with 6 to 18 carbon atoms The condensed polycyclic aromatic group of 17, etc. These "substituents" may contain only one kind or plural kinds, and when plural kinds are contained, they may be the same as or different from each other. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formula (8), as R ¹ to R ⁴ , preferably a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkyl group having 5 carbon atoms which may have a substituent The cycloalkyl group of ∼12 is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent.

In the general formula (8), the combination of R ¹ and R ² and the combination of R ³ and R ⁴ may be the same or different.

In the general formula (8), R ¹ and R ² , R ³ and R ⁴ , adjacent groups among R ⁵ to R ⁸ , or R ⁹ and R ¹⁰ may also bond with each other to form a ring, and these rings are also The ring may be formed by a single bond, or by bonding of any one of a nitrogen atom, an oxygen atom, or a sulfur atom. Also, as the ring formed in this case, a five-membered ring or a six-membered ring is preferable.

In the general formula (8), R ⁵ to R ⁸ are preferably hydrogen atoms, halogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms which may have substituents, or may have The substituent is a linear or branched alkoxy group having 1 to 20 carbon atoms, more preferably a hydrogen atom.

In the general formula (8), R ⁹ and R ¹⁰ are preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent An aromatic hydrocarbon group having 6 to 20 carbon atoms as a group, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.

The compound represented by the general formula (8) can be, for example, 3,6-dichlorospiro[9H-dibenzopyran-9,3'-[3H][2, 1] Benzooxythiol]1',1'-dioxide (or dichlorosulfofluoran) derivatives were used as starting materials for synthesis. The general formula ( 10) Intermediates represented by (for example, refer to Patent Document 8, etc.). Then, the dibenzopyran cationic dye represented by the general formula (8) can be synthesized by reacting the intermediate represented by the general formula (10) with thionyl chloride in a solvent, and then reacting with an amine.

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In the above general formulas (9) to (10), R ¹ to R ⁸ represent the same definitions as those in the general formula (8).

In the synthesis method of the dibenzopyran-based cationic dye represented by the general formula (8), when the precipitated dibenzopyran-based dye adheres firmly and becomes an obstacle to stirring, in order to eliminate or alleviate it , can also be mixed with organic solvents. As the mixed organic solvent, as long as it has sufficient solubility of the corresponding dibenzopyran dyes, there is no special limitation, and aromatic hydrocarbons such as toluene and xylene can be used alone; acetone, 2-butanone, 2- Ketones such as pentanone and 3-pentanone; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, etc., or used in combination .

The dibenzopyran cationic dye represented by the general formula (8) can be purified by column chromatography as needed by utilizing the product obtained by the above-mentioned synthesis method; by silica gel, activated carbon, active Adsorption purification of white clay, etc.; obtained by dispersion and washing of solvents or known purification such as recrystallization, crystallization, and salting out. The solvents used in these purification methods are not particularly limited, and alcohols such as water, methanol, and ethanol; halomethanes such as methylene chloride and chloroform; toluene, etc. can be used alone or in combination.

Specific examples of preferred compounds of the dibenzopyran cationic dye of the present invention represented by the general formula (8) are shown in the following formulas (A-1) to (A-20), but the present invention is not limited to such compounds. In addition, in the following structural formula, some hydrogen atoms are omitted and described. Moreover, even when a stereoisomer exists, the planar structural formula is also described. Furthermore, the anion part is omitted.

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The dibenzopyran cationic dye represented by the general formula (8) of the present invention can also be used alone, or two or more different molecular structures can be used in combination (for example, mixed). Among the weight concentration ratios in the whole, the weight concentration ratio of the smallest dibenzopyran cationic dye is 0.1-50% by weight. That is, among the two or more dibenzopyran-based cationic dyes, the least amount of one dibenzopyran-based cationic dye accounts for 0.1 to 50% by weight of the total of the two or more dibenzopyran-based cationic dyes . The type of dibenzopyran cationic dye is preferably one or two.

The organic anion represented by "X" is contained in the salt-forming compound containing the dibenzopyran cationic dye represented by General formula (1), and an organic anion. In the general formula (1), the "organic anion" represented by "X" specifically includes organic anions having a sulfonic acid group (-SO ₃ ^- ), a carboxyl group (-COO ^- ), and the like, An organic anion having a sulfonic acid group is preferred.

In the general formula (1), the "organic anion having a sulfonic acid group" represented by "X" specifically includes: an aromatic hydrocarbon group having 6 to 32 carbon atoms which may have a substituent, which may have A straight-chain or branched-chain alkyl group having 1 to 32 carbon atoms as a substituent, a straight-chain or branched-chain alkoxy group having 1 to 32 carbon atoms that may have a substituent, or a substituent may have a substituent An organic anion formed by bonding a carboxyl group with 1 to 32 carbon atoms and a sulfonic acid group.

[式中，B表示-O-、伸苯基、氧基伸苯基、或伸苯氧基， p表示0或1， A表示苯環或萘環， q表示0或1， R⁰ 表示 可具有取代基之碳原子數1～32、較佳為1～20、更佳為1～10之直鏈狀或支鏈狀之烷基、 可具有取代基之碳原子數3～32、較佳為3～20、更佳為5～12之環烷基、 可具有取代基之碳原子數1～32、較佳為1～20之直鏈狀或支鏈狀之烷氧基、 可具有取代基之碳原子數3～32、較佳為3～20之環烷氧基、 可具有取代基之碳原子數2～32、較佳為2～20之直鏈狀或支鏈狀之烯基、 可具有取代基之碳原子數6～32、較佳為6～20之芳香族烴基、 可具有取代基之碳原子數2～32、較佳為2～20之雜環基、或氫原子， R²⁰ 表示 可具有取代基之碳原子數1～32、較佳為1～20、更佳為1～10之直鏈狀或支鏈狀之烷基、 可具有取代基之碳原子數3～32、較佳為3～20、更佳為5～12之環烷基、 可具有取代基之碳原子數1～32、較佳為1～20之直鏈狀或支鏈狀之烷氧基、 可具有取代基之碳原子數3～32、較佳為3～20之環烷氧基、 可具有取代基之碳原子數2～32、較佳為2～20之直鏈狀或支鏈狀之烯基、 可具有取代基之碳原子數6～32、較佳為6～20之芳香族烴基、或 可具有取代基之碳原子數2～32、較佳為2～20之雜環基， 上述取代基例如為鹵素原子、-SO₃ ^- 、碳原子數1～17之直鏈狀或支鏈狀之烷基、碳原子數1～14之直鏈狀之烷基、碳原子數3～14之支鏈狀之烷基、碳原子數3～17、或3～14之環烷基、碳原子數1～19、或1～17之直鏈狀之烷氧基、碳原子數1～17、3～19、或3～14之支鏈狀之烷氧基、碳原子數3～19、3～17、或3～14之環烷氧基、碳原子數2～17、或2～14之直鏈狀或支鏈狀之烯基、碳原子數6～19、6～18、或6～14之芳香族烴基或碳原子數6～19、6～17、或6～14之縮合多環芳香族基、碳原子數2～19、或2～14之雜環基， r表示0～6之整，s表示1～2之整數]。The organic anion in which sulfonic acid groups are bonded is preferably an organic anion represented by the following general formula (20). [chem 35]

[In the formula, B represents -O-, phenylene, oxyphenylene, or phenoxy, p represents 0 or 1, A represents a benzene ring or a naphthalene ring, q represents 0 or 1, and R ⁰ represents that it can have The substituent has 1 to 32 carbon atoms, preferably 1 to 20, more preferably 1 to 10 linear or branched alkyl groups, and may have a substituent with 3 to 32 carbon atoms, preferably 3-20, more preferably 5-12 cycloalkyl, may have a substituent, C1-32, preferably 1-20 linear or branched alkoxy group, may have a substituent A cycloalkoxy group having 3 to 32 carbon atoms, preferably 3 to 20, a linear or branched alkenyl group having 2 to 32 carbon atoms, preferably 2 to 20 carbon atoms which may have a substituent, An aromatic hydrocarbon group optionally having 6 to 32 carbon atoms, preferably 6 to 20 carbon atoms, a heterocyclic group optionally having 2 to 32 carbon atoms, preferably 2 to 20 carbon atoms, or a hydrogen atom, R ²⁰ represents a linear or branched alkyl group with 1 to 32 carbon atoms that may have substituents, preferably 1 to 20, more preferably 1 to 10 carbon atoms, and 3 to 3 carbon atoms that may have substituents. 32. A cycloalkyl group preferably having 3-20, more preferably 5-12, a straight-chain or branched alkoxy group having 1-32 carbon atoms, preferably 1-20 carbon atoms which may have a substituent , a cycloalkoxy group which may have a substituent having 3 to 32 carbon atoms, preferably 3 to 20 carbon atoms, a linear or branched group which may have a substituent having 2 to 32 carbon atoms, preferably 2 to 20 carbon atoms Alkenyl group, an aromatic hydrocarbon group with 6 to 32 carbon atoms, preferably 6 to 20 carbon atoms which may have a substituent, or a heterocyclic ring with 2 to 32 carbon atoms, preferably 2 to 20 carbon atoms which may have a substituent The above-mentioned substituents are, for example, halogen atoms, -SO ₃ ^- , linear or branched alkyl groups with 1 to 17 carbon atoms, linear alkyl groups with 1 to 14 carbon atoms, Branched-chain alkyl group with 3-14 carbon atoms, cycloalkyl group with 3-17 carbon atoms, or cycloalkyl group with 3-14 carbon atoms, straight-chain alkoxy group with 1-19 carbon atoms, or 1-17 carbon atoms, 1-17, 3-19, or 3-14 branched alkoxy groups, 3-19, 3-17, or 3-14 cycloalkoxy groups, 2-17 carbon atoms, or 2-14 linear or branched alkenyl groups, 6-19, 6-18, or 6-14 aromatic hydrocarbon groups, or 6-19, 6-17, or 6-14 carbon atoms A condensed polycyclic aromatic group, a heterocyclic group with 2 to 19 carbon atoms, or a heterocyclic group with 2 to 14 carbon atoms, r represents an integer of 0 to 6, and s represents an integer of 1 to 2].

Among the organic anions formed by bonding sulfonic acid groups, the organic anions having sulfonic acid groups represented by the above-mentioned general formulas (2) to (7) are preferred, and the organic anions represented by the general formula (2) are more preferred. An organic anion with a sulfonic acid group. Also, the "aromatic hydrocarbon group", "linear or branched alkyl group" or "linear or branched alkoxy group" listed as the "substituent" bonded to the above group Specific examples include the same substituents as those described in the above general formula (8).

Hereinafter, the organic anion represented by General formula (20) and General formula (2)-(7) is demonstrated.

In the general formulas (2) to (7), as "a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ¹¹ to R ¹⁷ , "which may have a substitution A cycloalkyl group with 3 to 20 carbon atoms in the group", "a straight-chain or branched alkoxy group with 1 to 20 carbon atoms that may have a substituent", "a C3 to carbon atom group that may have a substituent Cycloalkoxy group with ∼20 carbon atoms", "straight-chain or branched alkenyl group with 2 to 20 carbon atoms which may have substituents", "aromatic hydrocarbon group with 6 to 20 carbon atoms which may have substituents ", or "a straight-chain or branched alkyl group with 1 to 20 carbon atoms" in "heterocyclic group with 2 to 20 carbon atoms that may have substituents", "heterocyclic group with 3 to 20 carbon atoms Cycloalkyl", "straight chain or branched alkoxy group with 1 to 20 carbon atoms", "cycloalkoxy group with 3 to 20 carbon atoms", "straight chain alkoxy group with 2 to 20 carbon atoms Shaped or branched alkenyl", "aromatic hydrocarbon group with 6 to 20 carbon atoms", or "heterocyclic group with 2 to 20 carbon atoms", specifically, methyl, ethyl, Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and other linear alkyl groups; isopropyl, isobutyl, second butyl, third butyl, isooctyl branched chain alkyl such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and other cycloalkyl groups; methoxy, ethoxy, propoxy straight-chain alkoxy groups such as butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy; isopropoxy, isobutoxy, second Branched alkoxy groups such as butoxy, tertiary butoxy, and isooctyloxy; cycloalkoxy groups such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy; vinyl , 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or multiple bonds of these alkenyl groups Straight chain or branched alkenyl, phenyl, naphthyl, biphenyl, anthracenyl and other aromatic hydrocarbon groups or condensed polycyclic aromatic groups; pyridyl, imidazolyl, furyl, benzofuran Heterocyclic groups such as thienyl, benzothienyl, etc. These are also examples of "groups other than substituents" of the various groups that may have substituents represented by R ⁰ and R ²⁰ in the general formula (20).

In the general formulas (2) to (7), as "a linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" or "a substituent" represented by R ¹¹ to R ¹⁷ The "substituent" in the "linear or branched alkenyl group having 2 to 20 carbon atoms" specifically includes: a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; -SO ₃ ^- ; Cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl and other cycloalkyl groups with 3 to 17 carbon atoms; Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy straight-chain alkoxy groups with 1 to 17 carbon atoms, such as heptyloxy, octyloxy, nonyloxy, decyloxy, etc.; isopropoxy, isobutoxy, second butoxy, second Branched-chain alkoxy groups with 1 to 17 carbon atoms such as tributoxy and isooctyloxy; cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy with 3 to 17 cycloalkoxy groups; phenyl, naphthyl, biphenyl, anthracenyl and other aromatic hydrocarbon groups with 6 to 18 carbon atoms or condensed polycyclic aromatic groups with 6 to 17 carbon atoms; pyridyl, imidazolyl , furyl, benzofuryl, thienyl, benzothienyl and other heterocyclic groups having 2 to 19 carbon atoms. These are also examples of "substituents" of various groups that may have substituents represented by R ⁰ and R ²⁰ in the general formula (20). These "substituents" may contain only one kind or plural kinds, and when plural kinds are contained, they may be the same as or different from each other. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formulas (2) to (7), the "cycloalkyl group having 3 to 20 carbon atoms having a substituent" represented by R ¹¹ to R ¹⁷ and "the cycloalkyl group having 1 to 20 carbon atoms having a substituent Straight-chain or branched alkoxy", "cycloalkoxy with 3 to 20 carbon atoms with substituents", "aromatic hydrocarbon with 6 to 20 carbon atoms with substituents" or "with The "substituent" in the "heterocyclic group having 2 to 20 carbon atoms in the substituent" includes, specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; -SO ₃ ^- ; methyl group , ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, hexyl, heptyl, octyl, isooctyl and other straight chains with 1 to 17 carbon atoms or branched alkyl; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl and other cycloalkyl groups with 3 to 17 carbon atoms; methoxy, ethoxy, propoxy, butoxy, Pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy and other linear alkoxy groups with 1 to 17 carbon atoms; isopropoxy, isobutoxy, Branched chain alkoxy groups with 1 to 17 carbon atoms such as dibutoxy, tertiary butoxy, and isooctyloxy; cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy Cycloalkoxy groups with 3 to 17 carbon atoms; Vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, iso Pronyl, isobutenyl, or straight-chain or branched-chain alkenyl formed by multiple bonding of these alkenyl groups; phenyl, naphthyl, biphenyl, anthracenyl and other aromatics with 6 to 18 carbon atoms Hydrocarbon groups or condensed polycyclic aromatic groups with 6 to 17 carbon atoms; pyridyl, imidazolyl, furyl, benzofuryl, thienyl, benzothienyl and other heterocyclic groups with 2 to 19 carbon atoms, etc. . These are also examples of "substituents" of various groups that may have substituents represented by R ⁰ and R ²⁰ in the general formula (20). These "substituents" may contain only one kind or plural kinds, and when plural kinds are contained, they may be the same as or different from each other. Moreover, these "substituents" may further have the substituents exemplified above.

In the general formulas (2) to (7), R ¹¹ to R ¹⁷ are preferably a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkyl group which may have a substituent. The cycloalkyl group having 5 to 12 carbon atoms is more preferably a linear or branched chain alkyl group having 1 to 20 carbon atoms which may have a substituent.

Commercially available items can be used as the organic anion of the present invention represented by general formula (20) or general formulas (2) to (7). Specifically, Sandet BL (manufactured by Sanyo Chemical Industry Co., Ltd.), Sandet ALH (manufactured by Sanyo Chemical Industry Co., Ltd.), NEOPELEX (manufactured by Kao Chemicals), Emal 10 (manufactured by Kao Corporation), and Docusate Sodium are commercially available. (manufactured by Tokyo Chemical Industry Co., Ltd.), or a composition containing such an organic anion as a main component. These can be used as they are to prepare the colored composition of the present invention, and those purified by the same method as that of the above-mentioned dibenzopyran dye can be used to prepare the colored composition of the present invention.

Specific examples of preferred compounds as the organic anions of the present invention represented by general formula (20) or general formulas (2) to (7) are shown in the following formulas (B-1) to (B-8), but this The invention is not limited to these compounds. In addition, in the following structural formula, some hydrogen atoms are omitted and described. In addition, even when stereoisomers exist, the planar structural formulas are also described. Furthermore, the cation part is omitted.

[chem 36]

[chem 37]

[chem 38]

[chem 39]

[chemical 40]

[chem 41]

[chem 42]

[chem 43]

The organic anions represented by general formula (20) or general formulas (2) to (7) of the present invention may be used alone or in combination of two or more different molecular structures.

Hereinafter, the coloring composition containing the salt-forming compound which consists of a dibenzopyran cationic dye and an organic anion represented by the general formula (1) of this invention is demonstrated in detail.

The powder containing the dibenzopyran-based cationic dye of the present invention may contain solvent molecules, water, molecular structure components other than the dibenzopyran-based cationic dye of the present invention, and other components. These powders can be used directly, but those that have been refined are preferred. However, even by any purification method, there may be a certain ratio of impurities, but as long as it is a dye that can be produced in the current technical level, it can be used.

However, the coloring composition of the present invention is set to contain a salt-forming compound of a dibenzopyran cationic dye represented by the general formula (1) and an organic anion as a main component in its solid content. Those containing water or other solvent molecules within a certain concentration range. The presence of moisture in the coloring composition is considered to be one of the factors that cause the crystal structure of the powder of the dibenzopyran dye to change. As a result, the dissolution of the dibenzopyran dye in an organic solvent such as PGME is considered Sex changes. For example, by adjusting the ratio of the weight of water to the weight of the entire coloring composition containing a dibenzopyran dye (moisture content (weight %)), while maintaining heat resistance, it can be obtained in an organic solvent such as PGME. A coloring composition with high solubility. The water content in the coloring composition can be adjusted arbitrarily within the range of 0.1 to 20% by weight.

As a method for measuring the water content of the coloring composition, there are Karl Fischer (KF, Karl Fischer) method using coulometric titration or volumetric titration; thermogravimetry-differential thermal analysis (TG-DTA, Thermogravimetry/Differential Thermal Analyzer) ) device thermal analysis method; heating drying method using a heating and drying moisture meter, etc.; gas chromatography (GC, Gas Chromatography) method, infrared or near-infrared absorption method; nuclear magnetic resonance absorption method; resistance method; dielectric constant method; distillation method; and other methods. In addition, the analysis of the type or amount of impurities other than moisture can also be performed by powder state observation, weight measurement, NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance) analysis, GC (Gas Chromatography, gas chromatography) analysis, etc. to presume.

As other components, in order to improve the performance of the colorant for color filters as the coloring composition of the present invention, surfactants, dispersants, defoamers, leveling agents, and other colorants for color filters can be added Additives and other organic compounds that are mixed during manufacture. However, the content of these additives in the coloring composition is preferably an appropriate amount, preferably to reduce the solubility in the solvent of the coloring composition of the present invention, or increase it to more than necessary, and does not affect the color filter. The content rate within the range of the effect of other additives of the same kind used in the manufacture. These additives can be added at any point in the preparation of the coloring composition.

The state of the powder of the coloring composition of this invention can observe the shape using an optical microscope, a scanning electron microscope (SEM), etc. The shape of the coloring composition of the present invention is generally used in the state of solid powder in the shape of crystals, microcrystals, fine powders, flakes, needle crystals, granules, etc., and is not particularly limited.

By measuring the particle size distribution, surface area, pore size distribution, powder density, etc. of the powder of the coloring composition of the present invention, the overall and average information of the powder shape can be obtained in more detail. For example, the Coulter method of measuring the electrical resistance of an electrolyte solution in which powder is dispersed, the centrifugal precipitation method of obtaining the effective diameter of Stokes by measuring the absorbance of a powder dispersion, and the method of measuring the effective diameter of a powder dispersion can be used. Measured by laser diffraction and scattering methods for diffraction and scattering pattern analysis. The coloring composition of the present invention preferably has a particle diameter ranging from 0.1 μm to several mm, but the shape of the particles changes depending on the manufacturing conditions or the recovery method of the dried powder, so it is not limited to specific particles. However, in order to achieve higher solubility, the particle size is preferably smaller, and the median value of the particle size distribution is preferably in the range of 0.1 to 100 μm.

The decomposition initiation temperature of the powder can be analyzed by performing thermogravimetry-differential thermal analysis (TG-DTA) of the coloring composition of the present invention. The decomposition initiation temperature is preferably above 250°C, more preferably above 300°C, especially preferably above 360°C. When applied to color filters, the higher the decomposition initiation temperature, the better. In addition, as the temperature corresponding to the decomposition initiation temperature, the temperature at the point when the weight of the sample is reduced by a certain ratio (%) after heating can also be used.

The solubility of the powder of the coloring composition of the present invention is represented by solubility, and the solubility refers to the ratio of the maximum amount of the coloring composition that the powdered coloring composition can be dissolved in a specific solvent, for example, in "wt% (solvent) name, temperature)" and other units. Solubility is obtained, for example, by mixing the sample in a specific solvent, stirring the solvent at a certain temperature for a certain period of time, and measuring the concentration of the prepared saturated solution. It can also be obtained by liquid chromatography (LC, Liquid Chromatography) or obtained by concentration measurement such as absorbance measurement.

The coloring composition contained in the colorant for color filters must be well dissolved or dispersed in an organic solvent containing a resin or the like during the manufacturing steps of the colorant for color filters and the color filter, so it is preferable Because of its high solubility in organic solvents. The organic solvent is not particularly limited, but specifically, esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and propylene glycol monomethyl ether (PGME); propylene glycol monomethyl ether acetate ( Ether esters such as PGMEA); ketones such as acetone and cyclohexanone; alcohols such as methanol and ethanol; diacetone alcohol (DAA), etc.; aromatic hydrocarbons such as benzene, toluene and xylene; N,N-dimethyl Amides such as formamide (DMF) and N-methylpyrrolidone (NMP); dimethylsulfoxide (DMSO), etc. These solvents may be used alone or in combination of two or more kinds. Among them, the coloring composition containing the dibenzopyran dye of the present invention is preferably excellent in solubility in PGME or PGMEA, and particularly preferably excellent in solubility in PGMEA.

The spectroscopic properties (transmittance, reflectance) of the powder of the coloring composition of the present invention are important in either the case where the pigment is used alone as a colorant for color filters or mixed with other pigments. Affects the color characteristics of color filters. The measurement method includes the method of measuring the absorption (or transmission) spectrum of a solution or dispersion liquid state, or the absorption (or transmission) spectrum of a film coated on a glass or transparent resin substrate. Also, it is a method of directly irradiating the powder with light and measuring the light reflected or scattered on the surface of the particle or near the surface of the particle.

The coloring agent for color filters of this invention contains the coloring composition containing the dibenzopyran system dye represented by General formula (1), and the component normally used for manufacturing a color filter. For example, in the case of a method using a photolithography step, a general color filter can be coated with a liquid prepared by mixing pigments such as dyes or pigments with resin components (including monomers and oligomers) or solvents. Spread on glass or resin substrates, use a photomask to carry out photopolymerization, make a colored pattern of soluble/insoluble pigment-resin composite film, and heat it after washing. Moreover, in the electrodeposition method or the printing method, it is also possible to produce a coloring pattern using what mixed the pigment, resin, or other components. Therefore, specific components in the colorant for color filters of the present invention include: dibenzopyran dyes represented by general formula (1), pigments such as other dyes or pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. In addition, these components can be selected and selected, and other components can also be added as needed.

When the coloring composition containing the dibenzopyran cationic dye of the present invention and a salt-forming compound of an organic anion is used as a colorant for a color filter, it can also be used as a color filter for various colors. It is best used as a colorant for blue or red color filters.

In the coloring agent for color filters comprising the coloring composition containing the dibenzopyran cationic dye of the present invention and a salt-forming compound of an organic anion, the dibenzopyran cationic dye may be used alone or may be used for color tone adjustment. Known pigments such as other dyes or pigments are mixed. When it is used as a colorant for red color filters, there are no special limitations, examples include: C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 242, C.I. Pigment Red 254 and other red pigments; other red color Lake pigments; red dyes such as C.I. Acid Red 88, C.I. Basic Violet 10, etc. When it is used as a colorant for blue color filters, there is no special limitation, examples include: basic dyes such as C.I. Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129; C.I. Acid dyes such as acid blue 9, 74; disperse dyes such as disperse blue 3, 7, 377; Spron dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, anion Danthrene-based, 㗁𠯤-based, di-㗁𠯤-based, azo-based, dibenzopyran-based, other blue-based lake pigments and other blue-based dyes or pigments.

The mixing ratio of other pigments in the colorant for color filters comprising the coloring composition containing the dibenzopyran-based cationic dye of the present invention and a salt-forming compound of an organic anion is better than that of the dibenzopyran-based dye (In the case of two or more, the sum of these) is 5 to 2000% by weight, more preferably 10 to 1000% by weight. The mixing ratio of pigment components such as dyes in the liquid colorant for color filters is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the entire colorant.

As the resin component in the coloring agent for color filters comprising the coloring composition containing the dibenzopyran cationic dye of the present invention and a salt-forming compound of an organic anion, as long as it has the color filter formed by using them Known ones can be used for the production method of the resin film or the properties required for use. Examples include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolak) resins, and other transparent resins. , photocurable resin, or thermosetting resin can be used in combination with these monomer or oligomer components as appropriate. Moreover, the copolymer of these resins can also be used in combination. In the case of a liquid colorant, the content of the resin in these colorants for color filters is preferably from 5 to 95% by weight, more preferably from 10 to 50% by weight.

Examples of other additives in the coloring agent for color filters containing the coloring composition containing the dibenzopyran cationic dye of the present invention and a salt-forming compound of an organic anion include photopolymerization initiators and crosslinking agents Components necessary for polymerization or hardening of resins, etc., and surfactants or dispersants necessary for stabilizing the properties of components in liquid color filter colorants, etc., may be mentioned. Those known for color filter production can be used without any particular limitation. The mixing ratio of the total amount of these additives in the solid content of the colorant for color filters is preferably from 5 to 60% by weight, more preferably from 10 to 40% by weight. [Example]

Hereinafter, embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited only to the following examples. In addition, the identification of the compound obtained in the Example was performed by ¹ H-NMR analysis (NMR apparatus manufactured by JEOL Ltd., JNM-ECA-600).

[Synthesis Example 1] Add 3,6-dichlorospiro[9H-dibenzopyran-9,3'-[3H][2,1]benzoxythiol]1',1'-dioxide to the reaction vessel Compound (DCSF) 40.0 g (98.7 mmol), diethylamine 28.9 g (395 mmol), n-methylpyrrolidone (NMP) 400 mL, stirred at 120°C for 5 hours. The reaction solution was put into 1200 mL of water, and concentrated hydrochloric acid was added until the pH became 2. Further, 100 g of sodium chloride was added to perform salting out. After the supernatant was discarded, it was dissolved in 500 mL of chloroform, and saturated saline was added for liquid separation. The organic layer was taken out and washed with water, and then the organic layer was extracted again. After drying by adding sodium sulfate, filtration was performed, and the filtrate was concentrated under reduced pressure to obtain a purple viscous oil. A solid was precipitated by adding hexane thereto and heating to reflux, and was collected by filtration. The obtained solid was dried under reduced pressure at 70° C. to obtain 42.5 g of a brown solid (A-1 intermediate product) (90% yield). Next, 10.0 g (20.9 mmol) of (A-1 intermediate), 1.85 g (25.4 mmol) of N,N-dimethylformamide (DMF), 100 mL of chloroform, and Thionyl chloride 8.04 g was heated at reflux temperature for 2 hours. Concentrate the reaction solution into a reaction vessel replaced with nitrogen, dissolve it in 100 mL of chloroform, add 1.24 g (16.9 mmol) of diethylamine and 3.42 g (33.8 mmol) of triethylamine, and store at 50°C The reaction was carried out for 4 hours. The reaction solution was washed with saturated brine, and the organic layer was extracted. Sodium sulfate was added, dried and filtered. The filtrate was concentrated under reduced pressure, and the obtained purple oil was purified by silica gel column chromatography (carrier: silica gel, solvent: chloroform→chloroform:methanol=9:1). The target component was recovered, concentrated, washed with hexane, and the solid was collected by filtration. The obtained solid was dried under reduced pressure to obtain a brown solid (4.8 g, yield 40%) which is a complex compound of (A-1) and chloride anion.

[chem 44]

[Synthesis Example 2] Except changing the diethylamine used in Synthesis Example 1 into 51.0 g (395 mmol) of dibutylamine, the same operation was performed to obtain 54.0 g (A-2 intermediate) (yield 92%). Next, the same reaction with thionyl chloride as in Synthesis Example 1 was carried out using (A-2 intermediate) to obtain 3.5 g of complexes of (A-2) and chloride anions (yield 30%).

[chem 45]

[Synthesis Example 3] The diethylamine used in Synthesis Example 1 was changed to 95.3 g (395 mmol) of di-2-ethylhexylamine, except that, the same operation was carried out to obtain (A-4 intermediate) 50.7 g (product rate of 63%). Next, the same reaction with thionyl chloride as in Synthesis Example 1 was carried out using (A-4 intermediate) to obtain 5.6 g of a complex compound of (A-4) and chloride anion (yield 50%).

[chem 46]

[Synthesis Example 4] Synthesis of Salt-Forming Compounds Comprising (A-1) and (B-1) Add 6.3 g (11.1 mmol) of the complex compound of (A-1) and chloride anion and 120 mL of water into the reaction vessel, and heat and dissolve at about 70°C. A mixture of 3.0 g (5.53 mmol) of sodium salt of (B-1) and 30 mL of water was slowly added dropwise into the solution. After the dropwise addition, the mixture was stirred at 80° C. for 1 hour to complete the reaction. After cooling to 25°C, the supernatant of the reaction liquid was removed, 100 mL of water was added, and dispersion washing was carried out at 80°C. After cooling to 25° C., the supernatant was removed, and ethanol was added to dissolve the contents. The solution was concentrated and dried, dispersed and washed with hexane, the solid was collected by filtration, and dried under reduced pressure to obtain a salt-forming compound comprising (A-1) and (B-1) as a brown solid (4.9 g, yield 56 %).

[chem 47]

[Synthesis Example 5] Synthesis of Salt-Forming Compounds Comprising (A-2) and (B-1) The complex compound of (A-1) and chloride anion used in Synthesis Example 4 was changed to the complex compound of (A-2) and chloride anion, except that, the same operation was carried out to obtain (A-2) Salt-forming compound with (B-1) (5.4 g, yield 54%).

[Synthesis Example 6] Synthesis of Salt-Forming Compounds Comprising (A-4) and (B-1) The complex compound of (A-1) and chlorine anion used in the synthesis example 4 was changed to the complex compound of (A-4) and chlorine anion, except that, the same operation was carried out to obtain (A-4 ) and (B-1) salt compound (6.6 g, yield 53%).

[Synthesis Example 7] Synthesis of Salt-Forming Compounds Comprising (A-4) and (B-3) Change the complex compound of (A-1) and chloride anion used in Synthesis Example 4 to the complex compound of (A-4) and chloride anion, change (B-1) to (B-3), Except for that, the same operation was performed to obtain the salt-forming compound (2.3 g, yield 87%) of (A-4) and (B-3).

[chem 48]

[Synthesis Example 8] Synthesis of Salt-Forming Compounds Comprising (A-21) and (B-1) The complex compound of (A-1) and chloride anion used in Synthetic Example 4 was changed to the complex compound of (A-21) and chloride anion, except that, the same operation was carried out to obtain (A-21 ) and (B-1) salt compound (1.0 g, yield 63%).

[chem 49]

[Example 1] Regarding the salt-forming compound comprising dibenzopyran-based cationic dye (A-1) and organic anion (B-1) obtained in Synthesis Example 4, a spectrophotometer (manufactured by Hitachi, Ltd., U- 3000) for UV-vis absorption spectroscopy. Assays were performed at room temperature using PGME as solvent. From the obtained ultraviolet-visible absorption spectrum, the maximum absorption wavelength in the visible light region was calculated. In addition, using a thermogravimetric measurement-differential thermal analysis device (manufactured by MAC Science Co., Ltd., TG-DTA 2000S type), under nitrogen flow, TG-DTA measurement (sample weight: 5 ± 1.5 mg, heating rate: 20 °C/min), to measure the 5% weight loss temperature. Next, the solubility in PGME solvent (PGME, 25±2°C) at room temperature (25±2°C) was measured. These measurement results are shown in Table 1.

[Table 1]

[Example 2 to Example 5] Regarding the salt-forming compounds obtained in Synthesis Example 5 to Synthesis Example 8, the visible absorption spectrum, 5% weight loss temperature, and solubility (PGME, 25±2° C.) were measured in the same manner as in Example 1. The measurement results are shown together with the results of Example 1 in Table 1.

[Comparative example 1] For comparison, regarding C.I. Acid Red 289 represented by the general formula (D-1), the visible absorption spectrum, 5% weight loss temperature, and solubility (PGME, 25±2° C.) were measured in the same manner as in Example 1. The measurement results are shown together with the results of Example 1 in Table 1.

[Comparative Example 2 to Comparative Example 5] For comparison, (A-1), (A-2), (A-4) synthesized in Synthesis Example 1 to Synthesis Example 3, (A-21) synthesized by the same method, and chlorine For the anion complex, the visible absorption spectrum, 5% weight loss temperature and solubility (PGME, 25±2°C) were measured in the same manner as in Example 1. The measurement results are shown together with the results of Example 1 in Table 1.

As shown above, the coloring composition containing the dibenzopyran-based cationic dye of the present invention and a salt-forming compound of an organic anion has a maximum absorption shifted by a long wavelength compared with existing dyes, so it is used as a multi-primary color Colorants for color filters that expand the color gamut are more useful. Furthermore, it has good solubility in PGME used in the production of color filters, and has the same heat resistance as existing dyes. [Industrial availability]

The coloring composition of the present invention containing a salt-forming compound containing a dibenzopyran cationic dye and an organic anion is useful as a colorant for a color filter, and can be used to produce a color filter with an expanded color gamut through multi-primary colorization. light sheet.

Claims (5)

A coloring composition containing a salt-forming compound comprising a dibenzopyran cationic dye represented by the following general formula (1) and an organic anion,

[In the formula, R ¹ to R ⁴ independently represent a hydrogen atom, a straight-chain or branched alkyl group with 1 to 20 carbon atoms that may have a substituent, and an alkyl group with 3 to 20 carbon atoms that may have a substituent. Cycloalkyl groups, straight-chain or branched alkenyl groups with 2 to 20 carbon atoms that may have substituents, aromatic hydrocarbon groups with 6 to 20 carbon atoms that may have substituents, or For a heterocyclic group with 2 to 20 carbon atoms, R ¹ and R ² , or R ³ and R ⁴ can also be bonded to each other to form a ring; R ⁵ to R ⁸ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, - SO ₃ -, a straight-chain or branched alkyl group with 1 to 20 carbon atoms that may have a substituent, a cycloalkyl group with 3 to 20 carbon atoms that may have a substituent, and a carbon atom that may have a substituent A straight-chain or branched alkoxy group with a number of 1 to 20, a cycloalkoxy group with a carbon number of 3 to 20 that may have a substituent, a straight-chain or branched group with a carbon number of 2 to 20 that may have a substituent A branched alkenyl group, an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents, or a heterocyclic group with 2 to 20 carbon atoms that may have substituents, R ⁵ to R ⁸ may also be adjacent The groups are bonded to each other to form a ring; R ⁹ and R ¹⁰ independently represent a straight-chain or branched chain alkyl group with 1 to 20 carbon atoms that may have a substituent, and a carbon number 3 that may have a substituent A cycloalkyl group with ~20 carbon atoms, a straight-chain or branched alkenyl group with 2 to 20 carbon atoms that may have a substituent, an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent, or a substituent A heterocyclic group with 2 to 20 carbon atoms in the base; R ⁹ and R ¹⁰ can also be bonded to each other to form a ring; y represents an integer of 1 or 2; X is the following general formula (B-1), (B- Organic anions represented by 3), (4) or (7):

In the formula, R ¹³ , R ¹⁶ and R ¹⁷ independently represent a linear or branched alkyl group with 1 to 20 carbon atoms that may have a substituent, a C 3 to 20 alkyl group that may have a substituent Cycloalkyl, a straight-chain or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 3 to 20 carbon atoms which may have a substituent, A linear or branched alkenyl group with 2 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms that may have a substituent, or a heterocyclic group with 2 to 20 carbon atoms that may have a substituent , R ¹⁶ and R ¹⁷ may also be bonded to each other to form a ring]. The coloring composition according to claim 1, wherein in the above general formula (1), X is an organic anion represented by the following general formula (B-1) or (B-3):

The coloring composition according to claim 1 or 2, wherein in the above general formula (1), R ¹ ~ R ⁴ , R ⁹ and R ¹⁰ are linear or branched chains with 1 to 10 carbon atoms that may have substituents. chain of alkyl groups. A colorant for color filters, which contains the coloring composition according to any one of claims 1 to 3. A color filter using the colorant for color filters according to Claim 4.