xanthene pigment, coloring composition containing the pigment, coloring agent for color filters, and color filters

Abstract

Provided is a xanthene dye excellent in solubility, clarity, and heat resistance. 【Solution means】A xanthene dye represented by general formula (1). TIFF2026065145000049.tif15169 [In formula (1), Xn 1 , Xn 2 each independently represents a group represented by formula (2), Ar represents an aromatic hydrocarbon group or a heterocyclic group, An represents an anion, a represents an integer of 1 to 3, and b represents an integer of 0 to 6. When b is 2 or more, the plurality of An may be the same or different. R 1 ~R 4 each independently represents H, an alkyl group, or an aromatic hydrocarbon group. R 5 , R 6 each independently represents H, a halogen atom, an alkyl group, or an aromatic hydrocarbon group, and R 1 ~R 6 may be bonded to each other to form a ring with adjacent groups. The wavy line represents the bonding part with Ar.] TIFF2026065145000050.tif30169

Description

[Technical Field]

[0001] The present invention relates to xanthene pigments, coloring compositions containing the pigments, colorants for color filters containing the pigments or coloring compositions, and color filters using the colorants. [Background technology]

[0002] Pigments are broadly classified into natural pigments and synthetic pigments, and synthetic pigments are further divided into inorganic pigments and organic pigments. Organic pigments are further subdivided into dyes (or synthetic dyes), organic pigments, and lakes (lake pigments, or lake dyes). Since the discovery of mauve in 1856, dyes have been studied extensively and are classified into direct dyes, acid dyes, basic dyes, etc., according to their dyeing properties. They are also classified by their chemical structure, such as azo dyes, anthraquinone dyes, triphenylmethane dyes, and xanthene dyes. These dyes generally have beautiful colors and are used in the formulation and coloring of resins, paints, pigments, printing inks, cosmetics, etc. (Non-patent documents 1, 2, etc.).

[0003] Color filters are used in liquid crystal and electroluminescent (EL) display devices and image sensors for CCDs and CMOS sensors. They are manufactured by laminating colored layers, such as thin dye films or dye-resin composite films, onto translucent substrates such as glass or transparent resin using dyeing, pigment dispersion, printing, or electrodeposition methods. Xanthene dyes, represented by formulas (B-1) to (B-3) below, are compounds used as colorants for color filters due to their vividness (Patent Documents 1 to 3, etc.). For example, by using xanthene dyes such as CI Acid Red 289 (formula (B-1)) or CI Acid Red 52 (formula (B-2)) (CI is an abbreviation for color index) in combination with azopyridone dyes, excellent red tones can be obtained (Patent Document 1).

[0004] [ka] [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2002-265834 [Patent Document 2] Japanese Patent Publication No. 2012-207224 [Patent Document 3] Japanese Patent Publication No. 2018-076403 [Patent Document 4] Japanese Patent Publication No. 2013-57052 [Non-patent literature]

[0006] [Non-Patent Document 1] Hiroshi Horiguchi, “Advanced Theory of Synthetic Dyes,” Sankyo Publishing Co., Ltd., July 15, 1969 (Showa 44), p.1-3 [Non-Patent Document 2] The Society of Synthetic Organic Chemistry, ed., "New Edition: Handbook of Dyes," Maruzen Co., Ltd., July 20, 1970 (Showa 45), pp. 8-13. [Non-Patent Document 2] "Chemical Communications," (UK), 2017, Vol. 53, pp. 1064-1067, Supporting Information [Overview of the project] [Problems that the invention aims to solve]

[0007] In the development of current display devices, there is a constant demand for high performance (high brightness, wide color gamut, low voltage), and the demands on the performance of color filters (high transmittance, high color purity, and other color characteristics) are also increasing. For example, in order to realize a display device with high color purity and high brightness, it is necessary to transmit the necessary light and absorb the unwanted light, so the dyes used as colorants for color filters must have a steep slope in the ultraviolet-visible transmission spectrum, that is, high clarity.

[0008] Furthermore, pigments currently used as colorants for color filters exist in particulate form, leading to reduced transmittance, light scattering, and decreased contrast due to interference. To address these issues, the use of dyes that are highly soluble and function in molecular form is being considered (e.g., Patent Document 2). On the other hand, dyes used as colorants for color filters require fastness, particularly high heat resistance to withstand the heating processes involved in the manufacturing of color filters.

[0009] In this context, the dyes used as colorants for color filters are required to possess a combination of clarity, solubility, and heat resistance. However, conventional xanthene dyes, while possessing high clarity, did not satisfy both the solubility and heat resistance requirements for use as colorants in color filters.

[0010] Furthermore, Patent Document 4 describes a dye that has excellent dyeing properties and heat resistance, represented by the following formula (B-4), which has two pigment skeletons in the molecule via a nitrogen atom directly bonded to an aromatic group. However, our own research has shown that when an aromatic group having an amino group is bonded to the xanthene 9-position in a xanthene dye, unwanted absorption occurs in the ultraviolet-visible absorption spectrum, impairing the high vividness that is a characteristic of xanthene dyes.

[0011] [ka]

[0012] The present invention was made to solve the aforementioned problems and aims to provide a xanthene dye that is excellent in solubility and heat resistance and also possesses high clarity. Furthermore, it aims to provide a coloring composition containing the dye, a coloring agent for color filters, and a color filter. [Means for solving the problem]

[0013] As a result of diligent research to achieve the above objective, the inventors have discovered a xanthene dye that exhibits excellent solubility in organic solvents (such as propylene glycol monomethyl ether (PGME)) and heat resistance, as well as high clarity. In other words, the gist of the present invention is as follows.

[0014] 1. A xanthene pigment represented by the following general formula (1).

[0015] [ka]

[0016] [In formula (1), Xn 1 and Xn 2 Each of these independently represents a group represented by the following general formula (2): Ar is an aromatic hydrocarbon group having 6 to 60 carbon atoms, which may have substituents, or This represents a heterocyclic group having 1 to 60 carbon atoms, which may have substituents. An represents an anion, a represents an integer from 1 to 3, and b represents an integer from 0 to 6. When b is 2 or greater, multiple Ans may be the same or different.

[0017] [ka]

[0018] [In formula (2), R 1 ~R 4 Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. R 5 and R 6 These are, independently, a hydrogen atom, a halogen atom, Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, R 1 ~R 6 may be bonded to each other among adjacent groups to form a ring. The wavy line represents the bonding part with Ar.]

[0019] 2. The xanthene dye according to 1, wherein in the general formula (1), Ar is a group represented by the following general formula (3).

[0020]

Chemical formula

[0021] [In formula (3), Ar 1 and Ar 2 are each independently, an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 1 to 30 carbon atoms which may have a substituent. L is a linking group, and is a group containing at least one selected from the group consisting of ―O―, ―S―, ―S(=O)2―, ―(C=O)―, a linear or branched alkanediyl group having 1 to 30 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, The wavy line represents the bonding part with the group represented by the general formula (2).]

[0022] 3. The xanthene dye according to 2, wherein in the general formula (3), Ar 1 and Ar 2 are phenyl groups having 6 to 30 carbon atoms which may have a substituent.

[0023] 4. The xanthene dye according to 2, wherein in the general formula (3), Ar 1 and Ar 2 are indolyl groups having 8 to 30 carbon atoms which may have a substituent.

[0024] 5. In the general formula (1) above, An is a halide ion, (CF3SO2)2N - A xanthene dye according to any one of 1 to 4, which is at least one selected from the group consisting of sulfonylimide anions and sulfonate anions.

[0025] 6. The concentration of the xanthene dye is 0.005 to 0.02 mmol / L Using a propylene glycol monomethyl ether (PGME) solution, Measure at 23-27°C. In the wavelength range of 350-750 nm In an ultraviolet-visible transmission spectrum where the transmittance at the maximum absorption wavelength is 5%, For the range where the transmittance at wavelengths longer than the maximum absorption wavelength is between 90% and 97%, The regression coefficient S of the regression line calculated using the least squares method. a The value is 0.7 or higher. A xanthene pigment as described in any of 1 to 5.

[0026] A coloring composition containing a xanthene pigment as described in any of sections 7.1 to 7.6.

[0027] A coloring agent for color filters containing the coloring composition described in 8.7.

[0028] A color filter using the colorants for color filters described in 9.8. [Effects of the Invention]

[0029] The xanthene dye of the present invention exhibits excellent solubility in organic solvents such as PGME, as well as superior clarity and heat resistance. Coloring compositions containing this dye are useful as colorants for color filters. [Brief explanation of the drawing]

[0030] [Figure 1] This figure illustrates a specific example of the ultraviolet-visible transmission spectrum of the xanthene dye of the present invention. [Modes for carrying out the invention]

[0031] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below and can be implemented in various ways within the scope of its gist.

[0032] The xanthene pigment of the present invention is represented by the following general formula (1).

[0033] [ka]

[0034] In general formula (1), the "aromatic hydrocarbon group" in the "aromatic hydrocarbon group having 6 to 60 carbon atoms that may have substituents" represented by Ar includes aryl groups and condensed polycyclic aromatic groups. Specifically, examples of "aromatic hydrocarbon groups having 6 to 60 carbon atoms" include aromatic hydrocarbon groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, and triphenylenyl group.

[0035] In general formula (1), the "heterocyclic group" in the "aromatic heterocyclic group having 1 to 60 carbon atoms that may have substituents" represented by Ar includes fused polycyclic aromatic heterocyclic groups, and specifically, the "heterocyclic group having 1 to 60 carbon atoms" is: Pyridyl group, pyrimidinyl group, quinolyl group, isoquinolyl group, pyrazinyl group, triazinyl group, naphthilidinyl group, acridinyl group, phenanthrolinyl group, carbolinyl group, prinyl group, indolidinyl group, naphthilidinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, synnolinyl group, pteridinyl group, phenanthridinyl group, perimidinyl group, antilydinyl group, Pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, dihydropyrrolopyrrolyl group, indolyl group, isoindolyl group, indollidinyl group, indazolyl group, benzimidazolyl group, benzotriazolyl group, azaindolyl group, azaindazolyl group, pyrazolopyrimidinyl group, prinyl group, adenyl group, guanidinyl group, acridinyl group, phenadinyl group, Furanyl group, thiophenyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothiophenyl group, dibenzofuranyl group, dibenzothienyl group, Oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, phlopyrrolyl group, thienopyrrolyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzothiadiazolyl group, phenoxathiinyl group, Examples include heterocyclic groups such as the benzo[1,2-b:4,5-b']dithiophenyl group and the bipyridinyl group.

[0036] In general formula (1), the "substituents" in the "aromatic hydrocarbon group having 6 to 60 carbon atoms that may have substituents" or the "heterocyclic group having 1 to 60 carbon atoms that may have substituents" represented by Ar are, specifically, Deuterium atom, -OH, -CN, -CH2F, -CHF2, -CF3, -NO2; ―SO3 - , a sulfonic acid group represented by -SO3H, -SO3M, or ―CO2 - Carboxylic acid groups represented as -CO2H or -CO2M (where M represents an organic or inorganic cation); Halogen atoms such as fluorine, chlorine, bromine, and iodine; A linear or branched alkyl group having 1 to 30 carbon atoms; Cycloalkyl groups with 3 to 30 carbon atoms; A linear or branched alkenyl group having 2 to 30 carbon atoms; A linear or branched alkoxy group having 1 to 30 carbon atoms; Cycloalkoxy groups or 1-adamantyloxy groups, 2-adamantyloxy groups, having 3 to 30 carbon atoms; Acyl groups with 1 to 30 carbon atoms; Aromatic hydrocarbon groups or fused polycyclic aromatic groups having 6 to 30 carbon atoms; Heterocyclic groups with 2 to 30 carbon atoms; Alternatively, examples include aryloxy groups with 6 to 30 carbon atoms. These "substituents" may consist of only one or more, and if multiple substituents are present, they may be identical or different from one another. Furthermore, these "substituents" may also have the substituents exemplified above. If a "substituent" contains a carbon atom, that carbon atom is included in the above-mentioned "6 to 60 carbon atoms" and "1 to 60 carbon atoms." In addition, these substituents may be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring.

[0037] In general formula (1), if there is an "inorganic cation" or "organic cation" represented by "M", then the "organic cation" is specifically R 21 R 22 R 23 R 24 N + Examples of ammonium ions represented by R 21 ~R 24 Each of these independently represents -H, a linear or branched alkyl group having 1 to 30 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, and they may be bonded to each other to form a ring. 21 ~R 24 In the above general formula (2), the "linear or branched alkyl group having 1 to 30 carbon atoms which may have substituents" and the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents" specifically refer to the R 1 ~R 6The same applies as the "linear or branched alkyl groups having 1 to 30 carbon atoms that may have substituents" and "aromatic hydrocarbon groups having 6 to 30 carbon atoms that may have substituents" represented by . Furthermore, examples of "inorganic cations" include alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions such as magnesium ions, calcium ions, and barium ions. Alkali metal ions are preferred for M.

[0038] Furthermore, in the various "groups" listed above that have a "substituent" represented by Ar in general formula (1), the "substituent" is as follows: "Linear or branched alkyl groups with 1 to 30 carbon atoms," "Cycloalkyl groups with 3 to 30 carbon atoms" "Linear or branched alkenyl groups with 2 to 30 carbon atoms," "Linear or branched alkoxy groups with 1 to 30 carbon atoms," "Cycloalkoxy groups with 3 to 30 carbon atoms" "Acyl groups with 1 to 30 carbon atoms" "Aromatic hydrocarbon groups or condensed polycyclic aromatic groups with 6 to 30 carbon atoms," "Heterocyclic groups with 1 to 30 carbon atoms," or, Specifically, "aryloxy groups with 6 to 30 carbon atoms" include: Linear or branched alkyl groups such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl, n-butyl (n-Bu), isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, and decyl groups; Cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups; Alkenyl groups such as vinyl groups, 1-propenyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups, 1-pentenyl groups, 1-hexenyl groups, isopropenyl groups, and isobutenyl groups, or linear or branched alkenyl groups formed by the bonding of multiple such groups; Alkynyl groups such as ethynyl groups, propargyl groups, and butynyl groups, or linear or branched alkynyl groups formed by the bonding of multiple such groups; Linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, isopropoxy, isobutoxy, s-butoxy, t-butoxy, and isooctyloxy groups; Cycloalkoxy groups with 3 to 30 carbon atoms, such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclononyloxy, and cyclodecyloxy groups; Acyl groups such as formyl, acetyl, propionyl, acryl, and benzoyl groups; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl, biphenylyl, terphenylyl, naphthyl, anthryl, tetracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perilenyl, fluoranthenyl, and triphenylenyl groups; Heterocyclic groups such as thienyl group, furyl group, pyrrolyl group, thiazolyl group, oxazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, benzothienyl group, benzofuranyl group, indolyl group, isoindolyl group, benzothiazolyl group, benzooxazolyl group, benzimidazolyl group, benzotriazolyl group, prinyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidylinyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthilidinyl group, acridinyl group, phenanthrolinyl group, naphthilidinyl group, and carbolinyl group; Examples include phenyloxy groups, tolyloxy groups, biphenylyloxy groups, naphthyloxy groups, anthracenyloxy groups, phenantrenyloxy groups, and other aryloxy groups.

[0039] In general formula (1), "a" is Xn 1 ―Ar―Xn 2 This represents the number of parts of the compound (xanthene pigment) represented by . "An" represents anion, and "b" represents the number of An. In general formula (1), Xn 1 ―Ar―Xn 2 If the part is a cation whose total charge across the entire molecule is 1 or greater, that is, if b is an integer from 1 to 3, then it can form a salt or complex with any anion represented by 1 or 2 or more "An" as a counterion. However, in the compound represented by general formula (1), a and b are selected so that the compound as a whole is electrically neutral. a represents an integer from 1 to 3, with 1 or 2 being preferred. b represents an integer from 0 to 6, with 1 to 4 being preferred.

[0040] In general formula (1), "An" is not particularly limited and can include, for example, inorganic anions such as halide ions, or organic anions such as sulfonylimid anions and sulfonate anions. Specifically, Cl - , Br - , I - Halide ions such as (CF3SO2)2N - (or Tf2N) - ), (CF3SO2)3C - (or Tf3C) - ), (C2F5SO2)2N - (C4F9SO2)2N - , (C6F5SO2)2N - , (CN)2N - (CN)3C - NC-S - (C2F5)3F3P - , (C6H4SO3 - )O(C6H3(C 12 H 25 )(SO3 - )), C6H4(C12 H 25 )(SO3 - ), PF6 - BF4 - , (PW 12 O 40 )3 - , Alternatively, anions represented by the structural formulas (Z-1) to (Z-16) below are examples.

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] In general formula (1), An may be a single anion or a combination of two or more different anions, preferably a single anion or any combination of two or three anions selected from the examples given above, such as a halide ion or (CF3SO2)2N - It is more preferable that the anion be a single or any combination of two or three selected from either a sulfonylimid anion or a sulfonate anion.

[0048] In general formula (1), Xn 1 and Xn 2 Each of these independently represents a group containing a xanthene skeleton represented by the following general formula (2), and they may be the same or different, Xn 1 and Xn 2 It is preferable that they are the same.

[0049] [ka]

[0050] In general formula (2), R 1 ~R 6 In the expression "linear or branched alkyl group having 1 to 30 carbon atoms which may have substituents," the "linear or branched alkyl group having 1 to 30 carbon atoms" specifically refers to: Linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; Examples of branched alkyl groups include isopropyl, isobutyl, s-butyl, t-butyl, isooctyl, and 2-ethylhexyl groups.

[0051] In general formula (2), R 1 ~R 6 In the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents" represented by , the "aromatic hydrocarbon group" includes aryl groups and condensed polycyclic aromatic groups. Specifically, examples of "aromatic hydrocarbon groups having 6 to 30 carbon atoms" include aromatic hydrocarbon groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, and triphenylenyl group.

[0052] In general formula (2), R 5 and R 6Examples of "halogen atoms" represented by include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms or bromine atoms being preferred.

[0053] In general formula (2), R 1 ~R 6 In the "substituted linear or branched alkyl group having 1 to 30 carbon atoms" or "substituted aromatic hydrocarbon group having 6 to 60 carbon atoms" represented by general formula (1), the "substituents" are specifically the same as those in the "substituted aromatic hydrocarbon group having 6 to 30 carbon atoms" or "substituted heterocyclic group having 1 to 60 carbon atoms" represented by Ar in general formula (1), as well as unsubstituted amino groups; monosubstituted or disubstituted amino groups having 1 to 30 carbon atoms. Specifically, "monosubstituted or disubstituted amino groups having 1 to 30 carbon atoms" include linear or branched alkyl groups such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group, and diphenylamino group, or monosubstituted or disubstituted amino groups having an aromatic hydrocarbon group. These "substituents" may consist of only one or more, and if multiple substituents are present, they may be identical or different from one another. Furthermore, these "substituents" may also have the substituents exemplified above. If a "substituent" contains a carbon atom, that carbon atom is included in the above-mentioned "6 to 60 carbon atoms" and "1 to 60 carbon atoms." In addition, these substituents may be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring.

[0054] In general formula (2), R 1 and R 2 , R 3 and R 4 , R 1 Or R 2 and R 5 , or R 3 Or R 4 and R 6These elements may be bonded to each other via single bonds, double bonds, substituted or unsubstituted methylene groups, oxygen atoms, or sulfur atoms to form a ring. If a ring is formed, it is preferably a five-membered or six-membered ring, and more preferably a six-membered ring.

[0055] In general formula (1), Ar is independently either an "aromatic hydrocarbon group having 6 to 60 carbon atoms that may have substituents" or a "heterocyclic group having 1 to 60 carbon atoms that may have substituents." These may be groups in which the same or different "aromatic hydrocarbon groups having 6 to 60 carbon atoms that may have substituents" or "heterocyclic groups having 1 to 60 carbon atoms that may have substituents" are linked to each other by single bonds or linking groups L. Specifically, in general formula (1), Ar is represented by the following general formula (3), Ar 1 and Ar 2 It is preferable that the group is bonded via a linking group "-L-".

[0056] [ka]

[0057] In general formula (3), Ar 1 and Ar 2 In the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents" represented by , the "aromatic hydrocarbon group" includes aryl groups and condensed polycyclic aromatic groups. Specifically, examples of "aromatic hydrocarbon groups having 6 to 30 carbon atoms" include aromatic hydrocarbon groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, and triphenylenyl group.

[0058] In general formula (3), Ar 1 and Ar 2In the "heterocyclic group having 1 to 30 carbon atoms which may have substituents" represented by , the "heterocyclic group" includes fused polycyclic aromatic heterocyclic groups, and specifically, the "heterocyclic group having 1 to 30 carbon atoms" includes pyridyl group, pyrimidinyl group, quinolyl group, isoquinolyl group, pyrazinyl group, triazinyl group, naphthilidinyl group, acridinyl group, phenanthrolinyl group, carbolinyl group, prinyl group, indolidinyl group, naphthilidinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, synnolinyl group, pteridinyl group, phenantridinyl group, perimidinyl group, antilidinyl group, Pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, dihydropyrrolopyrrolyl group, indolyl group, isoindolyl group, indollidinyl group, indazolyl group, benzimidazolyl group, benzotriazolyl group, azaindolyl group, azaindazolyl group, pyrazolopyrimidinyl group, prinyl group, adenyl group, guanidinyl group, acridinyl group, phenadinyl group, Furanyl group, thiophenyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothiophenyl group, dibenzofuranyl group, dibenzothienyl group, Oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, phlopyrrolyl group, thienopyrrolyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzothiadiazolyl group, phenoxathiinyl group, Examples include heterocyclic groups such as the benzo[1,2-b:4,5-b']dithiophenyl group and the bipyridinyl group.

[0059] In general formula (3), the "linking group" represented by L is, —O—, —S—, sulfonyl group (—S(=O)2—), carbonyl group (—(C=O)—), This term represents a group containing one or more of the following: "a linear or branched alkanediyl group having 1 to 30 carbon atoms, which may have substituents" or "an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents." In the "linear or branched alkanediyl group having 1 to 30 carbon atoms which may have a substituent" which may be contained in L, the "linear or branched alkanediyl group having 1 to 30 carbon atoms" specifically includes linear alkanediyl groups such as a methylene group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, and a decane-1,10-diyl group; branched alkanediyl groups such as a propane-2,2-diyl group, a propane-1,2-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, a butane-2,2-diyl group, an octane-1,2-diyl group, and a 2-ethylhexane-1,6-diyl group can be mentioned.

[0060] In General Formula (3), in the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" which may be contained in L, the "aromatic hydrocarbon group having 6 to 30 carbon atoms" is the same as the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" represented by R 1 ~R 6 in General Formula (2). The same ones are applicable.

[0061] In General Formula (3), in the "linear or branched alkanediyl group having 1 to 30 carbon atoms which may have a substituent" or "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent" which may be contained in L, the "substituent" specifically includes the same ones as the "substituent" in the "linear or branched alkyl group having 1 to 30 carbon atoms which has a substituent" or "aromatic hydrocarbon group having 6 to 30 carbon atoms which has a substituent" represented by R 1 ~R 6 in General Formula (2). The same ones are applicable.

[0062] In the general formula (3), the linking group represented by L may be a combination of two or more of the above-mentioned “—O—”, “—S—”, sulfonyl group (—S(=O)2—), carbonyl group (—(C=O)—), “linear or branched alkanediyl group having 1 to 30 carbon atoms which may have a substituent” or “aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent”. For example, it may be a carboxy group (—(C=O)—O—) or a sulfonic acid group (—S(=O)2—O—). Further, —(C=O)— or —S(=O)2— may be bonded to an amino group which may have a substituent to form an amide group (—CO—NR 100 —) which may have a substituent R 100 —, or a sulfonamide group (—SO2—NR 101 —) which may have a substituent R 101 —. More specifically, L may be formed using R 7 , R 8 , R 100 and R 101 as follows: —R 7 —, —R 7 —R 8 —R 7 —, —O—, —O—R 7 —O—, —O—R 7 —R 8 —R 7 —O—, —S—R 7 —S—, —S—R 7 —R 8 —R 7 —S—, —CO—R 7 —CO—, —CO—R 7 —R 8 —R 7 —CO—, —CO—O—R 7 —O—CO—, —CO—O—R 7 —R 8 —R 7 —O—CO—, —CONR 100 —R 6 —N 100 CO—, —CONR 100 —R 7 —R8 ―R 7 ―N 100 CO-, ―SO2―R 7 ―SO2―, ―SO2―R 7 ―R 8 ―R 7 ―SO2― ―SO2―O―R 7 ―O―SO2―, ―SO2―O―R 7 ―R 8 ―R 7 ―O―SO2―, ―SO2NR 101 ―R 7 ―N 101 O2S—or ―SO2NR 101 ―R 7 ―R 8 ―R 7 ―N 101 It is preferable that it be O2S-. However, R 7 and R 8 R represents a linear or branched alkanediyl group having 1 to 30 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. 100 and R 101 R represents a linear or branched alkyl group having 1 to 30 carbon atoms, which may have substituents, a linear or branched alkanediyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. 7 , R 8 , R 100 and R 101 These may be the same or different, but R 7 and R 8 If R is included, 7 and R 8 It is preferable that they are different.

[0063] In general formula (1), Ar 1 and Ar 2 teeth, A phenyl group having 6 to 30 carbon atoms, which may have substituents, or It is preferable that the indolyl group has 8 to 30 carbon atoms, which may have substituents. Specifically, in the general formula (1) above, it is preferable that Ar is a group represented by the following general formula (4) or (5).

[0064] [ka]

[0065] In general formula (4), L has the same definition as in general formula (3). R 9 and R 10 Each of them operates independently. halogen atom, -OH, -CN, -OR 11 , —NO2; ―SO3 - , a sulfonic acid group represented by -SO3H, -SO3M, or ―CO2 - Carboxylic acid groups represented by -CO2H and -CO2M (wherein "-SO3M" and "-CO2M" represent the same groups as "-SO3M" and "-CO2M" listed as "substituents" for Ar in general formula (1) above). ―SO3R 11 ,―SO2NR 11 R 12 ,―CO2R 11 ,—CONR 11 R 12 ; Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. Adjacent groups may bond to each other to form a ring. R 11 and R 12 Each of them operates independently. Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. m and n each independently represent integers from 0 to 4. When m or n is 2 or greater, there are multiple R 9 or R 10 They may be the same or different. The dashed line represents the bond with the group represented by the general formula (2) above.

[0066] In general formula (4), R 9 ~R 12 The "linear or branched alkyl group having 1 to 30 carbon atoms which may have substituents" and the "aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents" represented by the formula R in general formula (2) are, specifically, 1 ~R 6 The same applies as the "linear or branched alkyl groups having 1 to 30 carbon atoms that may have substituents" and "aromatic hydrocarbon groups having 6 to 30 carbon atoms that may have substituents" represented by .

[0067] [ka]

[0068] In general formula (5), L has the same definition as in general formula (3), R 9 , R 10 , m and n have the same definitions as those in the general formula (4) above. R 13 and R 14 Each of them operates independently. Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. The dashed line represents the bond with the group represented by the general formula (2) above.

[0069] In general formula (5), R 13 and R 14The "linear or branched alkyl group having 1 to 30 carbon atoms that may have substituents" or the "aromatic hydrocarbon group having 6 to 30 carbon atoms that may have substituents" represented by R in general formula (2) are, specifically, 1 ~R 6 The same applies as the "linear or branched alkyl groups having 1 to 30 carbon atoms that may have substituents" and "aromatic hydrocarbon groups having 6 to 30 carbon atoms that may have substituents" represented by .

[0070] In the above, the linear or branched alkyl group having 1 to 30 carbon atoms, which may have substituents, is preferably a linear alkyl group having 1 to 30 carbon atoms, which may have substituents, and a branched alkyl group having 3 to 30 carbon atoms, which may have substituents. The optionally substituted linear or branched alkanediyl groups having 1 to 30 carbon atoms are preferably linear alkanediyl groups having 1 to 30 carbon atoms and branched alkanediyl groups having 2 to 30 carbon atoms. The linear or branched alkoxy groups having 1 to 30 carbon atoms are preferably linear alkoxy groups having 1 to 30 carbon atoms and branched alkoxy groups having 3 to 30 carbon atoms. "R 1 ~R 6 The phrase "the groups may bond with each other to form a ring" preferably means R 1 and R 2 , R 2 and R 5 , R 5 and R 1 , R 3 and R 4 , R 4 and R 6 , R 6 and R 3 This means that they may be joined to each other to form a ring.

[0071] Xanthene dyes represented by general formula (1) can be synthesized as follows by applying known methods (e.g., Patent Documents 2 and 3, Non-Patent Document 2, etc.) and using reagents having various corresponding groups of general formula (1) or other suitable reagents: A dialkylaminoxanthone derivative such as 3,6-bis(diethylamino)xanthone and an aromatic hydrocarbon compound such as bis(4-bromophenyl) ether are condensed in a suitable solvent such as tetrahydrofuran (THF) using n-butyllithium under appropriate cooling conditions, and the reaction mixture is filtered to obtain a product containing the compound represented by general formula (1).

[0072] Specific examples of preferred compounds as xanthene dyes of the present invention, represented by general formula (1), are shown in the following formulas (A-1) to (A-20), but the present invention is not limited to these compounds. In general formula (1), Xn 1 ―Ar―Xn 2 The part represented by is shown, and the anion part represented by An is omitted. In the structural formula below, some hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included, and the planar structural formula is shown.

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] The xanthene dyes of the present invention may be used individually or in combination (e.g., mixed) of two or more types with different molecular structures. When using two or more types, the mass concentration ratio of the least abundant xanthene dye in the total mass concentration ratio of the xanthene dyes is 0.1 to 50% by mass. It is preferable that there be one or two types of xanthene dyes.

[0084] During the synthesis of the xanthene pigments of the present invention, known methods for purifying the product include purification by column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and recrystallization or crystallization using solvents. Furthermore, if necessary, nuclear magnetic resonance analysis (NMR), absorbance measurement or ultraviolet-visible absorption spectroscopy (UV-Vis) measurement using a spectrophotometer, and thermogravimetric analysis-differential thermal analysis (TG-DTA) can be used for identification and analysis of these compounds. These methods can also be used to evaluate the solubility, heat resistance, and color of the obtained compounds.

[0085] The xanthene dye, the coloring composition containing the dye, and the coloring agent for color filters containing the dye or the coloring composition of the present invention need to be well dissolved or dispersed in an organic solvent containing resin or the like during the manufacturing process of the coloring agent and the color filter. Therefore, it is preferable that they have high solubility and dispersibility in organic solvents. The organic solvent is not particularly limited, but specifically includes esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether, propylene glycol monomethyl ether (PGME), and ethylene glycol monoethyl ether (ethyl cellosolve); ether esters such as propylene glycol monomethyl ether acetate (PGMEA); ketones such as acetone and cyclohexanone; alcohols such as methanol, ethanol, and 2-propanol; diacetone alcohol (DAA), etc.; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); chloroform (trichloromethane), etc., with PGME, PGMEA, cyclohexanone, or DAA being preferred, and PGME or cyclohexanone being particularly preferred from the viewpoint of balancing the solubility of the resin and the solubility of the xanthene dye. These solvents may be used individually or in mixtures of two or more types.

[0086] The solubility of the xanthene dye of the present invention can be evaluated by mixing the xanthene dye with an organic solvent in an appropriate ratio, sonicating the mixture, and then visually checking for the presence or absence of insoluble matter at room temperature (25°C). The organic solvent used for measuring solubility is not particularly limited, and any of the above-mentioned organic solvents can be used, but PGME, PGMEA, cyclohexanone, or DAA are preferred, and PGME or PGMEA are more preferred.

[0087] The xanthene dye of the present invention exhibits excellent solubility in organic solvents, particularly in PGME. The solubility in PGME is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. When considering application to high-contrast color filters, higher solubility is preferable.

[0088] The xanthene dye of the present invention, when prepared by dissolving it in an organic solvent, exhibits a maximum absorption wavelength in the visible light region (e.g., wavelength range of 350 to 750 nm) of the ultraviolet-visible absorption spectrum measured at around room temperature (e.g., 23 to 27°C). In the present invention, this maximum absorption wavelength is preferably in the range of 530 nm to 610 nm, and more preferably in the range of 530 nm to 580 nm. The dye concentration is preferably 0.005 to 0.02 mmol / L. The solvent is not limited as long as it dissolves the dye, but it is preferable that the absorption wavelength of the ultraviolet-visible absorption spectrum does not shift significantly depending on the dissolution conditions, and PGME is preferred.

[0089] In the xanthene dye of the present invention, the ultraviolet-visible absorption spectrum measured using the solution can be converted from the Lambert-Beer law relationship between transmittance and absorbance to an ultraviolet-visible transmission spectrum with an arbitrary transmittance at the maximum absorption wavelength. Specifically, since the absorbance relationship can be arbitrarily changed, calculated, or observed depending on the solution concentration and medium length (or cell length), an ultraviolet-visible transmission spectrum with an arbitrary transmittance at the maximum absorption wavelength can be obtained. Furthermore, the least squares method can be used to determine the regression coefficient (S) of the regression line in an arbitrary wavelength range for the measured transmittance data obtained in a certain wavelength range of the ultraviolet-visible transmission spectrum. a By calculating this, an approximate value of the slope of the ultraviolet-visible transmission spectrum in that range can be obtained. In this invention, the "vividness" of a xanthene dye is evaluated by the steepness of the slope of the rising portion at the peak with the greatest absorption in the ultraviolet-visible absorption spectrum. Dyes with such steeply rising peaks selectively absorb unwanted light and transmit only the necessary light at longer wavelengths than the absorption peak to the maximum extent. A color filter using such a dye can realize a display device with high brightness and color purity. In this invention, "high clarity" means that the value of the regression coefficient is high. Using a PGME solution with a dye concentration of 0.005 to 0.02 mmol / L, From the ultraviolet-visible absorption spectrum in the wavelength range of 350 nm to 750 nm, measured at around room temperature (e.g., 23-27°C), In the ultraviolet-visible transmission spectrum where the transmittance (T) at the maximum absorption wavelength is 5%, For the range of transmittance between 90% and 97% at wavelengths longer than the maximum absorption wavelength, The regression coefficient S of the regression line calculated using the least squares method. a However, it is preferable that it be 0.7 or higher, and more preferably 0.9 or higher. Thus, the regression coefficient S is obtained from the ultraviolet-visible transmission spectrum of the xanthene dye solution of the present invention. a As a concrete example of how to determine this, Figure 1 shows a diagram illustrating a specific method for analyzing the ultraviolet-visible transmission spectrum. In Figure 1, the area of ​​the ultraviolet-visible transmission spectrum for which we want to determine the slope is shown within the dashed circle and in the enlarged view. The equation in Figure 1 is the regression coefficient S a The formula for finding λ l , T l and k are the wavelength λ (nm) value and transmittance T, respectively. l (increase, and λ l or T l This represents the total number of measurement data points within the relevant wavelength range. ave or T ave is λ l or T l This represents the average value for each category.

[0090] The xanthene dye of the present invention can be mixed with various resin solutions and applied to a glass substrate to produce a coating film. The resulting coating film can be color-evaluated by measuring its color using a spectrophotometer and obtaining its color value. The color value is CIE L * a * b * Color systems are commonly used. Specifically, the color value L of a film sample is used. * a * , b * Measure the color difference (ΔE) of the color values ​​before and after heating at an appropriate temperature. * ab ) allows us to determine heat resistance. When applied to color filters, the color difference at temperatures around 230°C can be used as an indicator of heat resistance. ΔE * ab The smaller the value, the less discoloration due to thermal decomposition; a value of 10 or less is preferable, and 3 or less is more preferable.

[0091] The coloring agent for color filters of the present invention comprises a coloring composition containing at least one xanthene dye represented by general formula (1), and components commonly used in the manufacture of color filters. A typical color filter is obtained, for example, by using a photolithography process, in which a liquid prepared by mixing dyes or pigments with resin components (including monomers and oligomers) and a solvent is applied to a substrate such as glass or resin, photopolymerized using a photomask to create a colored pattern of a dye-resin composite film that is soluble / insoluble in the solvent, and then heated after washing. In electrodeposition and printing methods, a colored pattern is also created using a mixture of dyes with resin and other components. Therefore, specific components of the coloring agent for color filters of the present invention include at least one xanthene dye represented by general formula (1), other dyes or pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Furthermore, these components may be selected or omitted, and other components may be added as needed.

[0092] When using the coloring composition containing the xanthene dye of the present invention as a coloring agent for color filters, it may be used for color filters of each color, but it is preferable to use it as a coloring agent for red color filters.

[0093] The colorants for color filters containing xanthene dyes of the present invention may use one or more xanthene dyes alone, or other known dyes such as other dyes or pigments may be mixed in to adjust the color tone. When used as a colorant for red color filters, examples include, but are not particularly limited, red pigments such as CI Pigment Red 177, 209, 242, 254, 255, 264, 269, CI Pigment Orange 38, 43, 71; other red lake pigments; yellow pigments such as CI Pigment Yellow 138, 139, 150; and red dyes such as CI Acid Red 88, CI Basic Violet 10. When used as a coloring agent for blue color filters, examples of blue dyes or pigments include, but are not particularly limited, basic dyes such as CI Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, and 129; acid dyes such as CI Acid Blue 9 and 74; disperse dyes such as Disperse Blue 3, 7, and 377; spiron dyes; cyanine-based, indigo-based, phthalocyanine-based, anthraquinone-based, methine-based, triarylmethane-based, indanthrene-based, oxazine-based, dioxazine-based, azo-based, xanthene-based (not belonging to the present invention); and other blue lake pigments.

[0094] In the colorant for color filters containing the xanthene dye of the present invention, the mixing ratio of other dyes is preferably 5 to 2000% by mass, and more preferably 10 to 1000% by mass, relative to the xanthene dye (or the total of two or more dyes). In the liquid colorant for color filters, the mixing ratio of pigment components such as dyes is preferably 0.5 to 70% by mass, and more preferably 1 to 50% by mass, relative to the total colorant.

[0095] As for the resin component in the colorant for color filters of the present invention, any known resin can be used as long as it has the properties necessary for the manufacturing method and use of the color filter resin film formed using it. Examples include acrylic resin, olefin resin, styrene resin, polyimide resin, urethane resin, polyester resin, epoxy resin, vinyl ether resin, phenol (novolac) resin, other transparent resins, photocurable resins, or thermosetting resins, and these can be used in appropriate combinations with monomer or oligomer components. Copolymers of these resins can also be used in combination. The resin content in these colorant for color filters is preferably 5 to 95% by mass, and more preferably 10 to 50% by mass, in the case of liquid colorants.

[0096] To enhance the performance of the coloring composition of the present invention as a coloring agent for color filters, other components of the compound may include organic compounds such as surfactants, dispersants, defoamers, leveling agents, and other additives mixed during the manufacture of coloring agents for color filters. However, the content of these additives in the coloring composition is preferably appropriate, and is preferably within a range that does not decrease or excessively increase the solubility of the coloring composition in the solvent, nor does it affect the effect of other similar additives used during the manufacture of color filters. These additives can be added at any time during the preparation of the coloring composition.

[0097] Other additives in the colorant for color filters of the present invention include components necessary for the polymerization and curing of resins, such as photopolymerization initiators and crosslinking agents, as well as surfactants and dispersants necessary for stabilizing the properties of the components in the liquid colorant for color filters. Known additives for color filter manufacturing can be used for any of these, and are not particularly limited. The mixing ratio of the total amount of these additives in the total solid content of the colorant for color filters is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass. [Examples]

[0098] The embodiments of the present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. The identification of the compounds obtained in the synthesis examples is as follows: 1 The analysis was performed using 1H-NMR (Bruker nuclear magnetic resonance spectrometer, model: Magnet System 300MHz / 54mm UltraShield), and the measurement results and identified structures are shown in the synthesis examples below.

[0099] [Synthesis Example 1] Synthesis of Compound (D-1) The following chemical reaction was carried out under a nitrogen atmosphere. 6.00 g (18.3 mmol) of bis(4-bromophenyl) ether and 100 mL of dry THF were added to a 300 mL four-necked flask equipped with a condenser, stirrer, and thermometer. After cooling to -50°C in dry ice / methanol refrigerant, 24.0 mL of n-butyllithium (n-BuLi) (1.6 M n-hexane solution) was added, and the mixture was stirred at -40°C for 15 minutes. 13.62 g (40.24 mmol) of the intermediate (100) powder and 10.0 mL of dry THF were added to the reaction mixture, and the mixture was stirred for 3 hours while slowly raising the temperature to 10°C without adding dry ice as refrigerant. The reaction mixture was cooled to -40°C, 20 mL of tap water was added to stop the reaction, and then 20 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was diluted with 1000 mL of water and then extracted twice with 500 mL of dichloromethane. The organic layer was washed with 300 mL of water and 300 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was removed under reduced pressure. The residue was purified by column chromatography (support: silica gel, solvent: dichloromethane / methanol = 40 / 1 to 10 / 1 (volume ratio)), and then dried under reduced pressure at 60°C overnight to obtain the following intermediate (101) (8.23 g, yield 36%) as a black solid.

[0100] [ka]

[0101] [ka]

[0102] Next, the following chemical reaction was carried out under a nitrogen atmosphere. 5.50 g (4.42 mmol) of intermediate (101) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI,Li) were placed in a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer. + (CF3SO2)2N - , or Li + (Tf2N - 3.15 g (11.0 mmol) of ) and 45 mL of DMF were added, and the mixture was stirred at 50°C for 3 hours, then allowed to cool to room temperature. 50 mL of water was added to the reaction mixture, and the mixture was stirred at 40°C for 10 minutes, then the mixture was added to 150 mL of water and stirred at room temperature for 30 minutes. The mixture was filtered under reduced pressure, and the residue was added to 100 mL of water and stirred at room temperature for 30 minutes, then filtered under reduced pressure. The residue was dried under reduced pressure overnight at 60°C to obtain compound (D-1) (6.64 g, yield 86.6%) as a red solid.

[0103] NMR measurements were performed on the obtained red solid, and signals from the following 84 hydrogen atoms were detected, identifying the structure of the compound represented by the following formula (D-1).

[0104] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=7.75-7.22(28H), 6.28-6.12(2H), 6.05-5. 88(2H), 3.92-3.62(8H), 2.25-1.98(24H), 1.83-1.57(8H), 1.10-0.86(12H).

[0105] [ka]

[0106] [Synthesis Example 2] Synthesis of Compound (D-2) The following chemical reaction was carried out under a nitrogen atmosphere. In a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer, 2.00 g (13.5 mmol) of 4,4'-oxydiphthalic anhydride, 6.70 g (27.1 mmol) of the intermediate (102), 12.29 g (64.6 mmol) of p-toluenesulfonic acid monohydrate, and 60 mL of xylene were added, and the mixture was stirred at 110 °C for 72 hours under reflux. After the reaction mixture was allowed to cool to room temperature, it was decanted and the supernatant was removed. The residue was washed with 50 mL of toluene and decanted again. After removing the solvent from the residue under reduced pressure, it was dissolved in 50 mL of methanol and added dropwise to 1000 mL of 1 M sodium hydroxide aqueous solution. The mixture was stirred at room temperature for 20 minutes and filtered under reduced pressure. The residue was similarly washed with methanol / 1 M sodium hydroxide aqueous solution, filtered under reduced pressure, and then purified by column chromatography. The solvent was removed by distillation under reduced pressure, and the residue was dried under reduced pressure at 80°C overnight to obtain the following intermediate (103) (4.90 g, yield 62%) as a pale red solid.

[0107] [ka]

[0108] [ka]

[0109] Subsequently, the following chemical reaction was carried out under a nitrogen stream. 4.30 g (3.50 mmol) of intermediate (103) and 45 mL of THF were added to a 100 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer. After that, 2.67 g (21.0 mmol) of oxalyl chloride was added under ice-cooling, and the mixture was stirred at room temperature for 1 hour. Then, the solvent was distilled off under reduced pressure. The residue was dissolved in 45 mL of chloroform and added to a 100 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer. Then, 5.60 g (42.0 mmol) of bis(2-methoxyethyl)amine and 7.21 g (71.2 mmol) of triethylamine were added, and the mixture was stirred at room temperature for 2 hours. 100 mL of water was added to the reaction solution to stop the reaction, and the mixture was extracted with 200 mL of dichloromethane. The organic layer was washed with 100 mL of saturated sodium bicarbonate solution, 100 mL of 1 M dilute hydrochloric acid, and 100 mL of saturated brine, then dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent was distilled off under reduced pressure. 30 mL of ethyl acetate was added to the residue, and the solid was scraped with a spatula and then decanted. The residue was dissolved in MeOH, the solvent was distilled off under reduced pressure, then 50 mL of ethyl acetate was added, and the solid was similarly scraped and decanted. The residue was dried under reduced pressure at room temperature for 3 days to obtain the following intermediate (104) (4.80 g, yield 89%) as a dark purple solid.

[0110]

Chem.

[0111] Subsequently, the following chemical reaction was carried out under a nitrogen stream. 4.50 g (2.93 mmol) of intermediate (104), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, Li + (CF3SO2)2N - , or Li + (Tf2N -)2.09 g (7.28 mmol) was added to 45 mL of methanol, and the mixture was stirred at room temperature (25 °C) for 3 hours. Then, the solvent was distilled off under reduced pressure. 100 mL of water was added to the residue, and the solid was scraped off and then stirred at room temperature for 30 minutes. The mixture was filtered under reduced pressure, and the residue was washed again with 100 mL of deionized water and then filtered under reduced pressure. The residue was dried under reduced pressure at 60 °C overnight to obtain compound (D-2) (5.69 g, yield 87%) as a red solid.

[0112] NMR measurement of the obtained red solid was carried out, and the signals of 90 hydrogens below were detected and identified as the structure of the compound represented by the following formula (D-2).

[0113] 1 1H-NMR (300 MHz, DMSO-d6): δ (ppm) = 7.82 - 7.68 (6H), 7.63 - 7.56 (2H), 7.49 - 7.33 (10H), 4.97 - 4.65 (8H), 3.77 - 3.50 (8H), 3.48 - 3.13 (18H), 2.83 (6H), 2.73 - 2.62 (4H), 2.23 - 2.06 (4H), 1.04 - 0.86 (24H).

[0114]

Chemical formula

[0115] [Synthesis Example 3] Synthesis of Compound (D-3) In Synthesis Example 2, the target compound (D-3) (3.84 g, yield 36%) was obtained as a red solid in the same manner except that 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was used instead of 4,4'-oxydiphthalic anhydride.

[0116] NMR measurement of the obtained red solid was carried out, and the signals of 104 hydrogens below were detected and identified as the structure of the compound represented by the following formula (D-3).

[0117] 1H-NMR (300MHz, DMSO-d6): δ(ppm)=7.76-7.54(2H), 7.50-7.24(20H), 7.23-7.08(4H), 4.99-4.65(8H), 3.79-3.50(8H), 3.49-3.14(14H), 3.09-3.00(4H), 2.91-2.78(6H), 2.75-2.56(4H), 2.26-2.07(4H), 1.80-1.61(6H), 1.02-0.88(24H).

[0118] [ka]

[0119] [Synthesis Example 4] Synthesis of Compound (D-4) The target compound (D-4) (3.17 g, yield 40%) was obtained as a red solid by the same method as in Synthesis Example 2, except that 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was used instead of 4,4'-oxydiphthalic anhydride.

[0120] NMR measurements were performed on the obtained red solid, and the following 90 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (D-4).

[0121] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.04-7.71(6H), 7.50-7.27(12H), 5.00-4.69(8H), 3.78-3. 50(8H), 3.49-3.12(18H), 2.92-2.75(6H), 2.75-2.60(4H), 2.26-2.07(4H), 1.17-0.72(24H).

[0122] [ka]

[0123] [Synthesis Example 5] Synthesis of Compound (D-5) The following chemical reaction was carried out under a nitrogen stream. 5.18 g (9.99 mmol) of the intermediate (100), 2.00 g (4.54 mmol) of the following intermediate (105), 4.42 g (28.8 mmol) of phosphorus oxychloride, and 45 mL of toluene were added to a 100 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer. The mixture was stirred at 89 - 94 °C for 7 hours under heating and reflux. After allowing the reaction solution to cool to room temperature, 10 mL of tap water was added to stop the reaction, and the mixture was stirred at room temperature for 1 hour. The mixture was filtered under reduced pressure, and the residue was dissolved and recovered in a mixed solvent of 200 mL of dichloromethane / 100 mL of methanol. Then, the solvent was distilled off under reduced pressure. The moisture in the residue was sequentially removed by azeotropic distillation with 50 mL of ethanol and 100 mL of toluene, and then dried under reduced pressure at room temperature overnight. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 50 / 1 - 10 / 1 (volume ratio)). After distilling off the solvent under reduced pressure, the residue was dried under reduced pressure at room temperature for 15 minutes. 50 mL of ethyl acetate was added, and the solid was scraped off and filtered under reduced pressure. The residue was dried under reduced pressure at 80 °C overnight to obtain the intermediate (106) (4.91 g, yield 71.4%) as a black solid.

[0124]

Chemical formula

[0125]

Chemical formula

[0126] Subsequently, the following chemical reaction was carried out under a nitrogen stream. 4.50 g (2.97 mmol) of the intermediate (106), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, Li + (CF3SO2)2N - , or Li + (Tf2N -2.05 g (7.45 mmol) of ) and 45 mL of DMF were added, and the mixture was stirred at 50°C for 3 hours, then allowed to cool to room temperature. The reaction mixture was poured into 200 mL of water, ultrasonically washed for 20 minutes, allowed to cool to room temperature, and filtered under reduced pressure. The residue was added to 200 mL of water, ultrasonically washed for 20 minutes, allowed to cool to room temperature, and filtered under reduced pressure. The residue was dried overnight under reduced pressure at 80°C to obtain the target compound (D-5) (5.02 g, yield 84%) as a red solid.

[0127] NMR measurements were performed on the obtained red solid, and signals from the following 102 hydrogen atoms were detected, identifying the structure of the compound represented by the following formula (D-5).

[0128] 1 H-NMR (300MHz, DMSO-d6): δ (ppm) = 7.78-6.44 (38H), 6.06-5.39 (4H), 4.43-3.72 (12H), 2.31-1.10 (36H), 1.10-0.73 (12H).

[0129] [ka]

[0130] [Synthesis Example 6] Synthesis of Comparative Compound (B-5) In Synthesis Example 5, the target compound (B-5) (2.75 g, yield 64%) was obtained as a dark purple solid by the same method as in Example 5, except that intermediate (100) was replaced with 3.00 g (8.86 mmol) of intermediate (107) and intermediate (105) was replaced with 1.70 g (9.93 mmol) of N-ethyl-1-naphthylamine.

[0131] [ka]

[0132] NMR measurements were performed on the obtained dark purple solid, and the following 38 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (B-5).

[0133] 1H-NMR (300MHz, DMSO-d6): δ(ppm)=8.43-8.32(1H), 7.53-7.44(1H), 7.43-7.31(3H), 7.18-7.09(2H), 7 .08-6.94(4H), 6.86-6.77(1H)6.77-6.68(1H), 3.82-3.48(8H), 3.47-3.30(2H), 1.37(3H), 1.20(12H).

[0134] [ka]

[0135] [Synthesis Example 7] Synthesis of Comparative Compound (B-6) The following chemical reaction was carried out under a nitrogen atmosphere. 3.75 g (11.6 mmol) of 4-bromotriphenylamine and 30 mL of dry THF were added to a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer. After cooling to -40°C in dry ice / methanol refrigerant, 7.20 mL of n-butyllithium (n-BuLi) (1.6 M n-hexane solution) was added, and the mixture was stirred at -40°C for 15 minutes. 3.00 g (8.86 mmol) of the intermediate (107) powder and 10 mL of dry THF were added to the reaction mixture, and the mixture was stirred for 3 hours while slowly raising the temperature to 10°C without adding dry ice as refrigerant. The reaction mixture was cooled to -40°C, 20 mL of water was added to stop the reaction, and then 10 mL of concentrated hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. The mixture was adjusted to pH 7 with 1 M sodium hydroxide aqueous solution and extracted with 300 mL of dichloromethane. The organic layer was washed with 150 mL of saturated brine, dried over anhydrous magnesium sulfate, and then filtered under reduced pressure. The solvent of the filtrate was removed by distillation under reduced pressure. 200 mL of toluene was added to the residue, the solid was scraped off with a spatula, and the mixture was stirred at room temperature for 30 minutes, followed by filtration under reduced pressure. The residue was dried under reduced pressure at 80°C overnight to obtain the following intermediate (108) (4.70 g, yield 88%) as a dark purple solid.

[0136] [ka]

[0137] Next, the following chemical reaction was carried out under a nitrogen atmosphere. 1.50 g (2.49 mmol) of intermediate (109) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI,Li) were placed in a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer. + (CF3SO2)2N - , or Li + (Tf2N - 0.80 g (2.8 mmol) of ) and 45 mL of DMF were added, and the mixture was stirred at 50°C for 3 hours, then allowed to cool to room temperature. The reaction mixture was poured into 200 mL of water, ultrasonically washed for 20 minutes, allowed to cool to room temperature, and filtered under reduced pressure. The residue was added to 200 mL of water, stirred at room temperature for 30 minutes, and then filtered under reduced pressure. The residue was dried under reduced pressure overnight at 80°C to obtain the target compound (B-6) (1.87 g, yield 89%) as a purple solid.

[0138] NMR measurements were performed on the obtained purple solid, and the following 40 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (B-6).

[0139] 1 H-NMR (300MHz, DMSO-d6): δ (ppm) = 7.54-7.38 (8H), 7.32-7.09 (10H), 7.02-6.93 (2H), 3.82-3.48 (8H), 1.22 (12H).

[0140] [ka]

[0141] [Example 1] (Evaluation of solubility) Mixtures were prepared by weighing 20 mg of compound (D-1) obtained in Synthesis Example 1 and propylene glycol monomethyl ether (PGME) into 10 mL glass sample bottles so that the dye concentrations were 0.5% by mass, 1% by mass, 3% by mass, and 5% by mass. After sonication for 20 minutes, the mixtures were left at room temperature (25°C) for 24 hours. The dye solutions of each concentration were visually observed, and the highest dye concentration (by mass) in which no insoluble matter was observed was defined as the solubility. The measurement results are shown in Table 1.

[0142] (Assessment of clarity) The compound (D-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a 0.02 mmol / L solution, and the ultraviolet-visible absorption spectrum (wavelength range of 350-700 nm) was measured at room temperature (25°C) using an ultraviolet-visible spectrophotometer (JASCO Corporation, model number: V-650). The following measurement values ​​(Abs) were obtained from the ultraviolet-visible light absorption spectrum. λ and Abs max By using this in the relational expression shown in the following equation (S-1), the transmittance (T) at the maximum absorption wavelength (nm) can be obtained. min When (%) is set to a constant value, the transmittance of each wavelength (T λ )(%) can be calculated. min This represents a value greater than 0 and less than or equal to 100, and can be any number. Abs λ Absorbance at wavelength λ (nm) Abs max Absorbance at the maximum absorption wavelength (nm)

[0143]

number

[0144] For the transmittance in the ultraviolet-visible transmission spectrum at wavelengths longer than the maximum absorption wavelength, the transmittance T at the maximum absorption wavelength (nm) is calculated using the above formula (S-1). min When = 5 (%), the wavelength λ in the range of transmittance between 90% and 97% l (nm) and the transmittance T at the wavelength λ (nm) l The percentage (%) was calculated. Next, the average value λ of those wavelengths was calculated. ave (nm), and the average value of transmittance T ave (%) was calculated. These values ​​and the data (λ l ,T l Using the least squares method, substitute the total number k of ) into the following equation (S-2) to obtain the regression coefficient S of the regression line. a The result was calculated.

[0145]

number

[0146] The obtained S a Based on the values, the clarity was evaluated as follows. "◎": 0.9≦S a "○": 0.7≦S a <0.9 "△": 0.5≦S a <0.7 "×": S a <0.5

[0147] (Evaluation of heat resistance) 5.0 g of a 2% by mass DMF solution of methacrylic acid-acrylic acid ester copolymer and 20 mg of the compound (D-1) were placed in a 20 mL sample bottle and stirred at room temperature (25°C) for 30 minutes to mix. The resulting colored resin solution was filtered through a syringe filter, and the filtrate was applied to a glass substrate (film formation method: 1 g of filtrate was dropped onto the glass, and a spin coater was used to form a film at 300 rpm for 10 seconds). The film was then heated at 100°C for 2 minutes to form a film. The color value of the fabricated film was measured using a spectrophotometer (Konica Minolta, Inc., model number: CM-5) based on transmitted light. Subsequently, the film was heated at 230°C for 20 minutes, and the color value was measured again in the same manner. The color difference (ΔE) of the color values ​​before and after heating at 230°C was measured. * ab The following three-stage evaluation using ) as an indicator of heat resistance is shown in Table 1. "○": ΔE * ab ≤3.0 "△": 3.0 < ΔE * ab ≤10.0 "×": ΔE * ab >10.0

[0148] [Examples 2-5] In Example 1, the only difference was that the compound shown in Table 1 was used instead of compound (D-1). The solubility in PGME, the clarity of the PGME solution, and the color difference (ΔE) of the prepared film before and after heating (230°C-20 min) were the same as in Example 1. * ab The following were measured and evaluated. The results are summarized in Table 1.

[0149] [Comparative Example 1 to Comparative Example 4] For comparison, instead of the compound (D-1) in the example, the following xanthene dye compound not belonging to the present invention may be used: Comparative example compound (B-2): CI Acid Red 52 Comparative example compound (B-3): CI Basic Violet 10 Comparative example compound (B-5): Synthesis example 6 Comparative example compound (B-6): Synthesis example 7 Aside from using these xanthene dyes, the process was the same as in Example 1, and the solubility in PGME, the clarity of the PGME solution, and the color difference (ΔE) of the prepared film before and after heating (230°C-20 mins) were evaluated. * ab The following were measured and evaluated. The results are summarized in Table 1.

[0150] [Table 1]

[0151] As shown in Table 1, the xanthene dyes in the examples of the present invention are superior to the conventional xanthene dyes in the comparative examples in that they have higher solubility and clarity. Furthermore, the coloring compositions containing the xanthene dyes in the examples exhibit good heat resistance during film formation and are practically suitable as colorants for color filters. Moreover, the heat resistance of the coloring compositions in the examples during film formation is equivalent to or better than that of the comparative examples, making them useful as colorants for color filters. [Industrial applicability]

[0152] The coloring composition containing xanthene dye according to the present invention exhibits excellent solubility, vividness, and heat resistance, and can be used as a dye material for various applications, such as a coloring agent for color filters. Furthermore, by using this coloring composition as a coloring agent for color filters, it is possible to produce color filters with excellent color characteristics (color gamut, brightness, contrast ratio, etc.).

Claims

1. Xanthene pigments represented by the following general formula (1). 【Chemistry 1】 [In formula (1), Xn １ and Xn ２ Each of these independently represents a group represented by the following general formula (2): Ar is an aromatic hydrocarbon group having 6 to 60 carbon atoms, which may have substituents. This represents a heterocyclic group having 1 to 60 carbon atoms, which may have substituents, or a group represented by the following general formula (3): An represents an anion, a represents an integer from 1 to 3, and b represents an integer from 0 to 6. When b is 2 or greater, multiple Ans may be the same or different. 【Chemistry 2】 [In formula (2), R １ ~R ４ Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. R ５ and R ６ These are, independently, a hydrogen atom, a halogen atom, Linear or branched alkyl groups having 1 to 30 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. R １ ~R ６ These groups may be bonded to each other to form a ring. The wavy line indicates the connection point with Ar. 【Transformation 3】 [In equation (3), Ar 1 and Ar 2 are each independently, A substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or Pyridyl group, pyrimidinyl group, quinolyl group, isoquinolyl group, pyrazinyl group, triazinyl group, naphthilidinyl group, acridinyl group, phenanthrolinyl group, carbolinyl group, prinyl group, indolidinyl group, naphthilidinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, sinnolinyl group, pteridinyl group, phenanthridinyl group, perimidinyl group, antilydinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, dihydropyrrolopyrrolyl group, isoindolyl group, indolidinyl group, indazolyl group, benzimidazolyl group, benzotriazolyl group, azaindolyl group, azindazolyl group, pyr This represents a lazolopyrimidinyl group, aprinyl group, adenyl group, guanidinyl group, acridinyl group, phenadinyl group, furanyl group, thiophenyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothiophenyl group, dibenzofuranyl group, dibenzothienyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, phlopyrrolyl group, thienopyrrolyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzothiadiazolyl group, phenoxathiinyl group, benzo[1,2-b:4,5-b']dithiophenyl group, or bipyridinyl group. L is a linking group, -O-, -S-, -S(=O)²-, -(C=O)-, This represents a group comprising at least one selected from the group consisting of a linear or branched alkanediyl group having 1 to 30 carbon atoms, which may have substituents, and an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents. The wavy line represents the bond with the base represented by the general formula (2) above.

2. The xanthene dye according to claim 1, wherein in the general formula (3), Ar1 and Ar2 are phenyl groups having 6 to 30 carbon atoms, which may have substituents.

3. The xanthene dye according to claim 1 or claim 2, wherein in the general formula (1), An is at least one selected from the group consisting of a halide ion, (CF3SO2)2N-, a sulfonylimid anion, and a sulfonate anion.

4. The xanthene dye concentration is 0.005 to 0.02 mmol / L Using a propylene glycol monomethyl ether (PGME) solution, Measure at 23-27°C. In the wavelength range of 350 to 750 nm In an ultraviolet-visible transmission spectrum where the transmittance at the maximum absorption wavelength is 5%, For the range where the transmittance at wavelengths longer than the maximum absorption wavelength is between 90% and 97%, The regression coefficient S a of the regression line calculated using the least squares method is 0.7 or greater. The xanthene pigment according to any one of claims 1 to 3.

5. A coloring composition containing the xanthene pigment according to any one of Claims 1 to 4.

6. A coloring agent for color filters containing the coloring composition described in Claim 5.

7. A color filter using the coloring agent for color filters described in Claim 6.

Images