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

Abstract

To provide a xanthene dye excellent in solubility and coloring power for a coating film. To provide a coloring composition containing the dye, a colorant for a color filter, and a color filter. 【Solution means】 A xanthene dye represented by the following general formula (1). TIFF2026104991000040.tif33165 [In the formula, R 1 ~R 4 each independently represents H, an alkyl group, or an aromatic hydrocarbon group, and at least one of R 1 , R 2 contains an alkylene group, and a group having an amino group or an ammonium group at the terminal of R 1 or R 2 . R 5 , R 6 each independently represents H, a halogen atom, an alkyl group, or an aromatic hydrocarbon group. R 7 represents -SO3 - , -CO2 - , a sulfonyl group, a sulfonamide group, a carbonyl group, an amide group, etc., and R 7 may contain a cation. n represents an integer from 0 to 5. An represents an anion, x represents an integer from 1 to 3, and y represents an integer from 0 to 6. ]

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

[0003] [ka] [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-265834 [Patent Document 2] Japanese Patent Publication No. 2012-207224 [Patent Document 3] U.S. Patent Application Publication No. 2002 / 0115018 [Patent Document 4] U.S. Patent Application Publication No. 2010 / 0233710 [Patent Document 5] International Publication No. 2014 / 029888 [Patent Document 6] Japanese Patent Publication No. 2017-083852 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In the development of current display devices, high performance (high brightness, wide color gamut, low voltage) is always required, and the demands on the performance of color filters (high transmittance, high color purity, and other color characteristics) are also increasing. For example, pigments currently used as colorants for color filters exist in a particulate state, which causes a decrease in transmittance and a decrease in contrast due to light scattering and interference. To solve these problems, the use of dyes that are highly soluble and function in a molecular state is being considered (e.g., Patent Document 2).

[0006] Televisions and other display devices require long-term stability, so color filters need to be robust, including heat resistance and light resistance. Generally, dyes are less robust than pigments, so increasing the amount of dye used to improve the color vibrancy of a color filter tends to affect its robustness. Therefore, even when the amount of dye used is kept to a minimum, there is a need for dyes that exhibit high absorbance (low transmittance) in the desired absorption wavelength range, i.e., dyes with high coloring power, in order to achieve high brightness display devices while maintaining robustness. Furthermore, in order to use such dyes as colorants for color filters, they must also be highly soluble in order to form a better coating film.

[0007] However, conventional xanthene dyes have not satisfied both the solubility as a coloring agent for color filters and the high coloring power for coating films. The present invention was made to solve the above problems and aims to provide a xanthene dye that is excellent in both solubility and coloring power for coating films. It also aims to provide a coloring composition containing the dye, a coloring agent for color filters, and a color filter. [Means for solving the problem]

[0008] As a result of intensive studies to solve the above problems and achieve the above object, the present inventors have found a xanthene dye excellent in solubility and coloring power in a coating film. That is, the present invention has the following gist.

[0009] 1. A xanthene dye represented by the following general formula (1).

[0010] [Chemical formula]

[0011] [In formula (1), R 1 ~R 4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 1 and R 2 at least one of which contains an alkylene group having 1 to 20 carbon atoms which may have a substituent, and at the end of R 1 or R 2 represents a group having an unsubstituted or substituted amino group having 0 to 20 carbon atoms or an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms at the end. R 5 and R 6 are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, R 3 and R 5 or R 4 and R 6 may each be bonded to form a ring. R 7These are halogen atoms, -OH, and -SO3 - , -CO2 - , -NH2, or, R represents a sulfonyl group, sulfonamide group, carbonyl group, amide group, amino group, saturated hydrocarbon group, unsaturated hydrocarbon group, alkoxy group, aromatic hydrocarbon group, or aryloxy group having 1 to 20 carbon atoms, which may have substituents. 7 It may contain cations. n represents an integer from 0 to 5, and when n is 2 or greater, there are multiple R values. 7 They may be the same or different. An represents an anion, x represents an integer from 1 to 3, and y represents an integer from 0 to 6. When b is 2 or greater, multiple Ans may be the same or different.

[0012] 2. In the above general formula (1), R 1 and R 2 At least one of them A xanthene pigment, which is a group represented by the following general formula (2) or (3).

[0013] [ka]

[0014] [In formula (2), L represents an alkylene group having 1 to 20 carbon atoms, which may have substituents. 8 and R 9 Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 20 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. The dashed line represents the connection point with N in the general formula (1) above.

[0015] [ka]

[0016] [In formula (3), L represents an alkylene group having 1 to 20 carbon atoms, which may have substituents. 8 ~R 10 Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 20 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. The dashed line represents the connection point with N in the general formula (1) above.

[0017] 3. In the above general formula (1), R 1 and R 2 Xanthene pigments in which each of the groups is represented by the general formula (2) or (3) described above.

[0018] 4. In the above general formula (1), R 1 ~R 4 Xanthene pigments in which each of the groups is represented by the general formula (2) or (3) described above.

[0019] 5. In the above general formula (1), R 3 and R 4 but, A linear or branched alkyl group having 2 to 20 carbon atoms and having substituents, The substituents are halogen atoms, -NO2, -CN, -OH, -O-, Xanthene dyes that are unsubstituted or substituted alkoxy groups, unsubstituted or substituted amino groups, unsubstituted or substituted amide groups, unsubstituted or substituted ammonium groups, unsubstituted or substituted phenyl groups, or unsubstituted or substituted phenoxy groups.

[0020] 6. In the above general formula (1), R 3 and R 4 but, A phenyl group having 6 to 20 carbon atoms and having substituents, Xanthene dyes whose substituents are halogen atoms, -NO2, -CN, -OH, -O-, linear or branched alkyl groups having 1 to 4 carbon atoms, unsubstituted or substituted alkoxy groups, unsubstituted or substituted amino groups, or unsubstituted or substituted phenoxy groups.

[0021] 7. In the general formula (1) above, An is a halide ion, (CF3SO2)2N - xanthene pigments that are sulfonylimid anions or sulfonate anions.

[0022] 8. 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 ultraviolet-visible absorption spectrum in the wavelength range of 350-750 nm, Xanthene dyes whose maximum absorption wavelength is in the range of 535-560 nm.

[0023] 9. A coloring composition containing the xanthene pigment.

[0024] 10. A coloring agent for color filters containing the coloring composition.

[0025] 11. A color filter using the coloring agent for color filters. [Effects of the Invention]

[0026] The xanthene dye of the present invention exhibits excellent solubility in organic solvents such as PGME and coloring ability (or color development in coating films), making colored compositions containing this dye useful as colorants for color filters. [Modes for carrying out the invention]

[0027] 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.

[0028] The xanthene pigment of the present invention is represented by the following general formula (1).

[0029] [ka]

[0030] In general formula (1), R 1 ~R 6 In the expression "linear or branched alkyl group having 1 to 40 carbon atoms which may have substituents" or "linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents," examples of linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; and branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group, and 2-ethylhexyl group.

[0031] In general formula (1), R 1 ~R 6 In the "aromatic hydrocarbon group having 6 to 20 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 20 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.

[0032] In general formula (1), R 1 ~R 6In the expressions "a linear or branched alkyl group having 1 to 40 carbon atoms which may have substituents," "a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents," or "an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents," the "substituents" are, specifically, Deuterium atom, -OH, -CN, -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 20 carbon atoms; Cycloalkyl groups with 3 to 20 carbon atoms; A linear or branched alkenyl group having 2 to 20 carbon atoms; A linear or branched alkynyl group having 2 to 20 carbon atoms; A linear or branched alkoxy group having 1 to 20 carbon atoms; Cycloalkoxy groups with 3 to 20 carbon atoms; Acyl groups with 1 to 20 carbon atoms; Aromatic hydrocarbon groups or fused polycyclic aromatic groups having 6 to 20 carbon atoms; Heterocyclic groups with 2 to 20 carbon atoms; Aryloxy groups with 6 to 20 carbon atoms; Amino groups with 0 to 20 carbon atoms; Amide groups with 1 to 20 carbon atoms, Examples include ammonium groups having 0 to 20 carbon atoms. These "substituents" may be present one at a time or multiple at a time, and if multiple substituents are present, they may be identical or different from each other. Furthermore, these "substituents" may or may not have the substituents exemplified above. Therefore, these "substituents" may be expressed as, for example, "linear or branched unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms," "unsubstituted or substituted cycloalkyl groups having 3 to 20 carbon atoms," "linear or branched unsubstituted or substituted alkenyl groups having 2 to 20 carbon atoms," "linear or branched alkynyl groups having 2 to 20 carbon atoms," "unsubstituted or substituted cycloalkoxy groups having 3 to 20 carbon atoms," "unsubstituted or substituted aryloxy groups having 6 to 20 carbon atoms," "unsubstituted or substituted amino groups having 0 to 20 carbon atoms," "unsubstituted or substituted amide groups having 1 to 20 carbon atoms," "unsubstituted or substituted ammonium groups having 0 to 20 carbon atoms," "unsubstituted or substituted phenyl groups having 6 to 20 carbon atoms," "unsubstituted or substituted phenoxy groups having 6 to 20 carbon atoms," or "phenyl groups having 6 to 20 carbon atoms substituted with linear or branched alkyl groups having 1 to 20 carbon atoms substituted with halogen atoms." Furthermore, if a "substituent" includes a carbon atom, that carbon atom is counted in the above categories of "1 to 20 carbon atoms," "1 to 40 carbon atoms," and "6 to 20 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.

[0033] In general formula (1), if a "cation" is included, "cation" means either an "inorganic cation" or an "organic cation". If an "inorganic cation" or an "organic cation" represented by "M" exists in general formula (1), then the "organic cation" specifically refers to R 11 R 12 R 13 R 14 N + Examples of ammonium ions represented by R 11 ~R 14Each of these independently represents -H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents (however not all of them are -H), and they may be bonded to each other to form a ring. Note that in formula (1), R 11 ~R 14 Details of the "substituent," "linear or branched alkyl group having 1 to 20 carbon atoms," or "aromatic hydrocarbon group having 6 to 20 carbon atoms" represented by the above general formula (1) are as follows: 1 ~R 6 The same applies. Furthermore, "inorganic cations" include hydrogen ions; alkali metal ions such as lithium ions and sodium ions; and alkaline earth metal ions such as magnesium ions, calcium ions, and barium ions. M can be an alkali metal ion or R. 11 R 12 R 13 R 14 N + It is preferable that R 11 ~R 14 Preferably, the group is a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

[0034] Note that in general formula (1), R 1 ~R 6 In the above various "groups" having a "substituent" represented by, the "substituent" listed is "Linear or branched alkyl groups with 1 to 20 carbon atoms," "Cycloalkyl groups with 3 to 20 carbon atoms" "Linear or branched alkenyl groups with 2 to 20 carbon atoms," "Linear or branched alkynyl groups with 2 to 20 carbon atoms," "Linear or branched alkoxy groups with 1 to 20 carbon atoms," "Cycloalkoxy groups with 3 to 20 carbon atoms" "Acyl groups with 1 to 20 carbon atoms" "Aromatic hydrocarbon groups or condensed polycyclic aromatic groups with 6 to 20 carbon atoms," "Heterocyclic groups with 2 to 20 carbon atoms" "Aryloxy groups with 6 to 20 carbon atoms" "Unsubstituted or substituted amino groups with 0 to 20 carbon atoms," Examples of "unsubstituted or substituted ammonium groups with 0 to 20 carbon atoms" include the following groups: Linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, 2-ethylhexyl group, heptyl group, octyl group, isooctyl group, nonyl group, and decyl group; Cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups, or adamantyl 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, propargyl, and butynyl groups, or linear or branched alkynyl groups formed by the bonding of multiple such groups; mixed alkenyl and alkynyl groups such as penta-3-en-1-inyl and hexa-2-en-4-inyl 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 20 carbon atoms, such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclononyloxy, and cyclodecyloxy groups, or 1-adamantyloxy and 2-adamantyloxy groups; Acyl groups such as formyl, acetyl, propionyl, acryl, and benzoyl groups; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetracerenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perilenyl group, fluoranthenyl group, triphenylenyl group; Heterocyclic groups such as thienyl group, furyl group (furanyl group), pyrrolyl group, thiazolyl group, oxazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, benzothienyl group, benzofuranyl group, indolyl group, isoindolyl group, benzothiazolyl group, 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 carbonyl group; Aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group, and phenantrenyloxy group; "-NR" groups such as amino group (-NH2), methylamino group, ethylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di(2-ethylhexyl) group, di-t-butylamino group, and diphenylamino group. 8 R 9 Unsubstituted or substituted amino groups (monosubstituted amino groups, disubstituted amino groups) with 0 to 20 carbon atoms, represented by ". 8 and R 9 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents, and the "alkyl group" or "aromatic hydrocarbon group" in the formula is the same as the R 1 ~R 6 This is synonymous with the same notation "alkyl group" or "aromatic hydrocarbon group" found within [the relevant section]. Ammonium group (-NH4 + ), trimethylammonium group (―N +(CH3), triethylammonium group (―N + (CH2CH3)3), diethyl(methyl)ammonium group, diisopropyl(methyl)ammonium group, -N + (CH3)(C3H7)2, diphenylmethylammonium group, phenyldiethylammonium group, etc. "-N" + R 8 R 9 R 10 An unsubstituted or substituted ammonium group having 0 to 20 carbon atoms, represented by " (however, R 8 ~R 10 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents, and "-NR 8 R 9 R in "unsubstituted or substituted amino groups with 0 to 20 carbon atoms" 8 or R 9 (This is synonymous with...)

[0035] The xanthene dye according to the present invention has R in general formula (1). 1 and R 2 At least one of them contains an alkylene group having 1 to 20 carbon atoms, which may have substituents, and R 1 or R 2 It has the characteristic of having an unsubstituted or substituted amino group with 0 to 20 carbon atoms, or an unsubstituted or substituted ammonium group with 0 to 20 carbon atoms, at its terminal end. An alkylene group with 1 to 20 carbon atoms, which may have substituents, is R 1 and R 2It is included in the "linear or branched alkyl group having 1 to 40 carbon atoms which may have a substituent" represented by the formula, and is bonded to N in the general formula (1) at the end. At the other end (terminal) of the alkylene group, an "unsubstituted or substituted amino group having 0 to 20 carbon atoms" or an "unsubstituted or substituted ammonium group having 0 to 20 carbon atoms" is bonded. When the alkylene group has a "substituent", the alkylene group and the "unsubstituted or substituted amino group" or the "unsubstituted or substituted ammonium group" may be bonded via various "substituents" of the alkylene group, or may be bonded without passing through. That is, in the xanthene dye according to the present invention, in the general formula (1), R 1 and R 2 at least one (preferably both) of them has the feature that it is an "alkylene group having 1 to 20 carbon atoms which may have a substituent and has an unsubstituted or substituted amino group having 0 to 20 carbon atoms or an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms bonded at the end", or the feature that it is a "group having an unsubstituted or substituted amino group having 0 to 20 carbon atoms or an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms bonded at the end of an alkylene group having 1 to 20 carbon atoms which may have a substituent".

[0036] In the general formula (1), R 1 and R 2 Examples of the "alkylene group having 1 to 20 carbon atoms" in the "alkylene group having 1 to 20 carbon atoms which may have a substituent" contained in at least one of them include a methylene group, an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an i-butylene group, an s-butylene group, a t-butylene group, a hexylene group, an octylene group, and a decylene group. Further, examples of the "substituent" in the "alkylene group having 1 to 20 carbon atoms which may have a substituent" are the same as those of the "substituent" in the "linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" represented by the above R 1 and R 2 .

[0037] In general formula (1), R 1 and R 2 Of these, at least one contains "an alkylene group having 1 to 20 carbon atoms which may have a substituent, and at the end of R 1 or R 2 There is a group having an unsubstituted or substituted amino group having 0 to 20 carbon atoms or an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms". The "unsubstituted or substituted amino group having 0 to 20 carbon atoms or the group having an unsubstituted or substituted ammonium group having 0 to 20 carbon atoms" includes those similar to the "substituent" in the above-mentioned R 1 and R 2 The "unsubstituted or substituted amino group having 0 to 20 carbon atoms" and "unsubstituted or substituted ammonium group having 0 to 20 carbon atoms" represented by

[0038] In general formula (1), R 5 ~R 7 Specific examples of the "halogen atom" represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0039] In general formula (1), R 5 and R 6 Are preferably a hydrogen atom, a chlorine atom, a bromine atom or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent.

[0040] In general formula (1), the "sulfonyl group, sulfonamide group, carbonyl group, amide group, amino group, saturated hydrocarbon group, unsaturated hydrocarbon group, alkoxy group, aromatic hydrocarbon group or aryloxy group having 20 or less carbon atoms which may have a substituent" represented by R 7 refers to "A sulfonyl group having 0 to 20 carbon atoms which may have a substituent" "A sulfonamide group having 0 to 20 carbon atoms which may have a substituent", "A carbonyl group having 1 to 20 carbon atoms which may have a substituent", "An amide group having 1 to 20 carbon atoms which may have a substituent", "An amino group having 0 to 20 carbon atoms, which may have substituents," "A saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents." "An unsaturated hydrocarbon group having 2 to 20 carbon atoms, which may have substituents," "An alkoxy group having 1 to 20 carbon atoms, which may have substituents," "Aromatic hydrocarbon groups having 6 to 20 carbon atoms, which may have substituents," or, This means "an aryloxy group having 6 to 20 carbon atoms, which may have substituents."

[0041] In general formula (1), R 7 The "sulfonyl group having 0 to 20 carbon atoms which may have substituents" represented by "-SO2-R 100 (or, "-S(=O)2-R 100 The substituent R is represented as ") 100 This refers to a sulfonyl group having "-SO2-R 100 " may be a group that does not contain carbon atoms.

[0042] In general formula (1), R 7 The "sulfonamide group having 0 to 20 carbon atoms which may have substituents" represented by "-SO2-NR" is a "sulfonamide group having 0 to 20 carbon atoms which may have substituents" 101 R 102 (or, "-S(=O)2-NR 101 R 102 The substituent R is represented as ") 101 and R 102 This refers to a sulfonamide group having "-SO2-NR". 101 R 102 " may be a group that does not contain carbon atoms.

[0043] In general formula (1), R 7 The "carbonyl group having 1 to 20 carbon atoms that may have substituents" is represented as "―(C=O)―R 103 substituent R represented by " 103 This refers to a group having substituent R. 103This group may contain carbon atoms or may not contain carbon atoms.

[0044] In general formula (1), R 7 The "amide group having 1 to 20 carbon atoms, which may have substituents" represented by "―(C=O)―NR" is a "-(C=O)―NR 101 R 102 substituent R represented by " 101 and R 102 This refers to an amide group having a specific characteristic.

[0045] In general formula (1), R 7 The "amino group having 0 to 20 carbon atoms which may have substituents" represented by "-NR" is 101 R 102 substituent R represented by " 101 and R 102 It means an amino group having an amino group.

[0046] In general formula (1), R 7 The expression "saturated hydrocarbon group having 1 to 20 carbon atoms which may have substituents" means "linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms which may have substituents." 7 In this context, "a linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents" is defined as R 5 and R 6 Examples include those similar to the "linear or branched alkyl group having 1 to 20 carbon atoms, which may have substituents" represented by R. 7 Examples of "cyclic alkyl groups having 1 to 20 carbon atoms that may have substituents" include cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups; and adamantyl groups.

[0047] In general formula (1), R 7Examples of "unsaturated hydrocarbon groups having 2 to 20 carbon atoms that may have substituents" include alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, etc., or linear or branched alkenyl groups formed by the bonding of multiple such groups; alkynyl groups such as ethynyl group, propargyl group, butynyl group, etc., or linear or branched alkynyl groups formed by the bonding of multiple such groups; cycloalkenyl groups or cycloalkynyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, 1,4-cyclohexadienyl group, 1,5-cyclooctadienyl group, cyclooctinyl group, etc.

[0048] In general formula (1), R 7 Examples of "alkoxy groups having 1 to 20 carbon atoms that may have substituents" include 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; and cycloalkoxy groups having 3 to 20 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclononyloxy, and cyclodecyloxy groups.

[0049] In general formula (1), R 7 As an example of an "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents", R 1 ~R 6 Examples include those similar to the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents" represented by . Also, in general formula (1), R 7 The "aryloxy group having 6 to 20 carbon atoms which may have substituents" represented by R 7 When defined as the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents", the "-O-R 7This refers to the aryloxy group represented by ".

[0050] In general formula (1), R 7 In the phrase "sulfonyl groups, sulfonamide groups, carbonyl groups, amide groups, amino groups, saturated hydrocarbon groups, unsaturated hydrocarbon groups, alkoxy groups, aromatic hydrocarbon groups, or aryloxy groups having 20 or fewer carbon atoms which may have substituents", the term "substituent" and "substituent R" are used. 100 ~R 103 " is R 1 ~R 6 Examples of substituents similar to those in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents" represented by [the formula] include [the same substituents]. In general formula (1), R 7 The group represented by may contain a "cation," and "cation" means the same as the "inorganic cation" or "organic cation" mentioned above.

[0051] In general formula (1), n ​​is R 7 This represents a number, and can be an integer from 0 to 5. n is preferably 1 or 2.

[0052] In general formula (1), "x" represents the number of xanthene pigment parts in the formula. "An" represents an anion, and "y" represents the number of An. In general formula (1), if the xanthene pigment part is a cation with a total charge of 1 or more in the entire molecule, that is, if y is an integer from 1 to 3, 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), x and y are selected so that the compound as a whole is electrically neutral. x represents an integer from 1 to 3, with 1 or 2 being preferred. y represents an integer from 0 to 6, with 1 to 4 being preferred.

[0053] In general formula (1), "An" is not particularly limited and can be an inorganic anion such as a halide ion, or an organic anion. Specifically, Cl - , Br - , I- ;(CF3SO2)2N - , (CF3SO2)3C - , (C2F5SO2)2N - (C4F9SO2)2N - , (C6F5SO2)2N - , (CN)2N - (CN)3C - NC-S-, (C2F5)3F3P - , (C6H4SO3 - )O(C6H3(C 12 H 25 )(SO3 - )), C6H4(C 12 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.

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] 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.

[0059] In general formula (1), R 1 and R 2 At least one of them is preferably a group represented by the following general formula (2) or general formula (3). 1 and R 2 These may be the same or different groups. Specifically, in general formula (1), R 1 and R 2 At least one of them is an alkylene group having 1 to 20 carbon atoms which may have substituents, represented by the linking group "-L-", and R 1 or R 2 It is a group having an unsubstituted or substituted amino group with 0 to 20 carbon atoms, or an unsubstituted or substituted ammonium group with 0 to 20 carbon atoms, bonded to its terminal end. 1 and R 2 It is more preferable that each of these groups is represented by the following general formula (2) or general formula (3), and R 1 and R 2 It is even more preferable that they are the same group. Also, in general formula (1), R 1 ~R 4 However, any of these may be groups represented by the following general formula (2) or general formula (3).

[0060] [ka]

[0061] [In formula (2), L represents an alkylene group having 1 to 20 carbon atoms, which may have substituents. 9 and R 10 Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 20 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. The dashed line represents the connection point with N in the general formula (1) above.

[0062] [ka]

[0063] [In formula (3), L represents an alkylene group having 1 to 20 carbon atoms, which may have substituents. 8 ~R 10 Each of them independently consists of a hydrogen atom, Linear or branched alkyl groups having 1 to 20 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. The dashed line represents the connection point with N in the general formula (1) above.

[0064] In general formulas (2) and (3), the "alkylene group having 1 to 20 carbon atoms that may have substituents" represented by L is the same as the "R" in general formula (1). 1 and R 2 This is equivalent to "an alkylene group having 1 to 20 carbon atoms which may have substituents" which is included in "at least one of the"

[0065] In general formulas (2) and (3), R 8 ~R 10 The "linear or branched alkyl group having 1 to 20 carbon atoms which may have substituents" or the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have substituents" represented by the above general formula (1) are, respectively, R 1 ~R 4 The "substituents" that may be present are synonymous with "linear or branched alkyl groups having 1 to 20 carbon atoms" or "aromatic hydrocarbon groups having 6 to 20 carbon atoms."

[0066] In general formulas (2) and (3), L is preferably an alkylene group having 1 to 10 carbon atoms, which may have substituents, and is preferably an ethylene group, n-propylene group, or n-butylene group, which may have substituents. From the viewpoint of achieving both solubility and fastness of the xanthene dye represented by general formula (1), it is preferable that L in general formulas (2) and (3) has substituents.

[0067] In general formulas (2) and (3), R 8 ~R 10 For example, hydrogen atoms, Linear or branched alkyl groups having 1 to 10 carbon atoms without substituents, or phenyl groups are preferred, linear alkyl groups having 1 to 4 carbon atoms without substituents are more preferred, and methyl groups, ethyl groups, and n-propyl groups are even more preferred.

[0068] In general formula (1), R 3 and R 4 From the viewpoint of achieving desired spectral characteristics, it is preferable that the group has an electron-withdrawing group, or is an electron-withdrawing group. In general formula (1), R 3 and R 4 Specifically, the following are preferred: "a linear or branched alkyl group having 2 to 20 carbon atoms with substituents" or "a phenyl group having 6 to 20 carbon atoms with substituents." R 3 and R 4 As for, A linear or branched alkyl group having 2 to 20 carbon atoms and having substituents, The substituents on the alkyl group are a halogen atom, -NO2, -CN, -OH, -O-, A linear or branched alkyl group having 2 to 20 carbon atoms is preferred, which is an unsubstituted or substituted alkoxy group, an unsubstituted or substituted amino group, an unsubstituted or substituted amide group, an unsubstituted or substituted ammonium group, an unsubstituted or substituted phenyl group, or an unsubstituted or substituted phenoxy group.3 and R 4 Preferably, the substituent is a linear or branched alkyl group having 2 to 20 carbon atoms, having at least one substituent selected from the group consisting of halogen atoms, -NO2, -CN, -OH, -O-, =O, unsubstituted or substituted alkoxy groups, unsubstituted or substituted amino groups, unsubstituted or substituted amide groups, unsubstituted or substituted ammonium groups, unsubstituted or substituted phenyl groups, and unsubstituted or substituted phenoxy groups. 3 and R 4 More preferably, alkyl groups having 1 to 20 carbon atoms and having -NO2, -CN, or a substituted amino group as a substituent are preferred. Similarly, R 3 and R 4 As for, A phenyl group having 6 to 20 carbon atoms and having substituents, The substituent is a halogen atom, -NO2, -CN, -OH, -O-, A phenyl group having 6 to 20 carbon atoms is preferred, which is a linear or branched alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted amino group, or an unsubstituted or substituted phenoxy group. 3 and R 4 Preferably, the substituent is a phenyl group having 6 to 20 carbon atoms having at least one substituent selected from the group consisting of a halogen atom, -NO2, -CN, -OH, -O-, =O, a linear or branched alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted amino group, and an unsubstituted or substituted phenoxy group. A methyl group or an ethyl group is more preferred as the linear or branched alkyl group having 1 to 4 carbon atoms.

[0069] In general formula (1), R 3 and R 4 From the viewpoint of increasing solubility, it is preferable that the alkyl group be a linear or branched alkyl group having 1 to 20 carbon atoms, which may have substituents, and an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, or hexyl group is preferred. 3and R 4 The appropriate material can be selected based on the balance between the spectral characteristics and solubility.

[0070] In general formula (1), R 1 and R 2 If only one of them is the general formula (2) or (3), then the remaining R 1 or R 2 As such, the desired properties, such as the spectral characteristics and solubility mentioned above, can be appropriately selected.

[0071] Xanthene dyes represented by general formula (1) can be synthesized as follows by applying known methods (e.g., Patent Documents 2 and 3) and using reagents having various corresponding groups of general formula (1) or other suitable reagents: A xanthene derivative having the corresponding substituent, such as 3,6-dichloro-9-(2-sulfonatophenyl)xanthilium, and a secondary amine having the corresponding substituent, such as 3-[3-(diethylamino)propylamino]propionitrile, are condensed in a solution such as N-methylpyrrolidone under appropriate heating conditions 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 given below. remember As shown in formulas (G-1) to (G-33), the present invention is not limited to these compounds. Note that in the general formula (1) above, the xanthene pigment portion is shown, and the anionic portion represented by An is omitted. In the following structural formulas, some hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included, and planar structural formulas are shown.

[0073] [ka]

[0074] [ka]

[0075]

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[0076]

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[0077]

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[0085] 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.

[0086] 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.

[0087] 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.

[0088] The solubility of the xanthene dye of the present invention in organic solvents can be measured, for example, as follows: The xanthene dye and the organic solvent are mixed in an appropriate ratio, subjected to sonication, and then the solubility can be evaluated by 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.

[0089] 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.

[0090] The xanthene dye of the present invention 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) using a solution prepared by dissolving the dye in an organic solvent. In the present invention, the maximum absorption wavelength in the PGME solution is preferably 530 nm or higher, more preferably 532 nm or higher, even more preferably 534 nm or higher, preferably 560 nm or lower, more preferably 556 nm or lower, and even more preferably 553 nm or lower. For example, it is preferably in the range of 535 to 560 nm, and more preferably in the range of 545 to 555 nm. The dye concentration is preferably 0.005 to 0.02 mmol / L.

[0091] A coating film can be prepared by mixing the xanthene dye of the present invention with various resin solutions and applying them to a glass substrate. The resulting coating film can be color-evaluated by measuring its color using a spectrophotometer to obtain its ultraviolet-visible absorption spectrum and color value. Specifically, the coloring power (or color development) of the dye in the coating film can be determined by measuring the ultraviolet-visible absorption (or transmission) spectrum of the film sample. In the present invention, "high coloring power of the coating film" means that the absorbance is high at the maximum absorption wavelength of the ultraviolet-visible absorption spectrum in the 360-740 nm range of the coating film sample. In other words, it means that the minimum transmittance of the ultraviolet-visible transmission spectrum obtained in the same wavelength range is small. Specifically, when measured by the same method as in the examples, 35% or less is preferred, 20% or less is more preferred, and 10% or less is even more preferred.

[0092] Furthermore, the color value of the aforementioned coating 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.

[0093] 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.

[0094] When using the coloring composition containing the xanthene pigment 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.

[0095] 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.

[0096] 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.

[0097] As the resin component in the colorant for color filters of the present invention, any known resin (for example, "binder resin (B1)" described in Patent Document 4) 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.

[0098] 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.

[0099] 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.

[0100] 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 compounds obtained in the synthesis examples were identified by 1H-NMR analysis (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. [Examples]

[0101] [Synthesis Example 1] Synthesis of Compound (J-1) The following reaction was carried out under a nitrogen atmosphere. 40.0 g (98.7 mmol) of 3,6-dichloro-9-(2-sulfonatophenyl)xanthilium (see intermediate (100) below), 81.5 g (445 mmol) of 3-[3-(diethylamino)propylamino]propionitrile, and 200 mL of N-methylpyrrolidone were added to a 300 mL four-necked flask equipped with a condenser, stirrer, and thermometer, and the mixture was stirred at 90°C for 3 hours. The reaction mixture was allowed to cool to room temperature, 400 mL of 1 M sodium hydroxide aqueous solution was added, and after stirring for a while, the mixture was extracted twice with 400 mL of dichloromethane. The organic layer was sequentially washed with 400 mL of 1 M sodium hydroxide aqueous solution, 400 mL of water, and 400 mL of saturated saline solution, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was removed by distillation under reduced pressure. The residue was purified by column chromatography (support: silica gel, solvent: dichloromethane / methanol = 3 / 1 to 1 / 1 (volume ratio)), and after removing the solvent under reduced pressure, the residue was dissolved in 150 mL of saturated sodium bicarbonate solution and extracted three times with 300 mL of dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was removed under reduced pressure. The residue was dissolved in 10 mL of dichloromethane and added to 200 mL of n-heptane to precipitate a solid, which was then filtered under reduced pressure. The residue was dried overnight under reduced pressure at 60°C to obtain compound (J-1) (13.9 g, yield 20%) as a dark red solid.

[0102] [ka]

[0103] NMR measurements were performed on the obtained dark red solid, and signals from the following 50 hydrogen atoms were detected, identifying the structure of the compound represented by the following formula (J-1).

[0104] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.01(1H), 7.65(1H), 7.56(1H), 7.26-6.77(7H), 4.12-3.9 2(4H), 3.79-3.57(4H), 3.01-2.88(4H), 2.60-2.37(12H), 1.86-1.67(4H), 1.12-0.88(12H).

[0105] [ka]

[0106] [Synthesis Example 2] Synthesis of Compound (J-2) In Synthesis Example 1, using 12.8 g (31.5 mmol) of the intermediate (100) and 60 mL of N-methylpyrrolidone, and in the same manner as above, except that 32.6 g (157 mmol) of 3-((3-(dimethylamino)-2,2-dimethylpropyl)aminopropionitrile was used instead of 3-[3-(diethylamino)propylamino]propionitrile, the target compound (J-2) (1.0 g, yield 5%) was obtained as a dark red solid.

[0107] NMR measurements were performed on the obtained dark red solid, and signals from the following 50 hydrogen atoms were detected, identifying the structure of the compound represented by the following formula (J-2).

[0108] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.09(1H), 7.67(1H), 7.56(1H), 7.40-6.82(7H), 4 .18-3.90(4H), 3.88-3.48(4H), 3.01-2.78(4H), 2.70-2.00(16H), 1.20-0.68(12H).

[0109] [ka]

[0110] [Synthesis Example 3] Synthesis of Compound (J-3) In Synthesis Example 1, 5.0 g (12.3 mmol) of the intermediate (100) and 45 mL of N-methylpyrrolidone were used, and the target compound (J-3) (4.1 g, yield 47%) was obtained as a blackish-purple solid by the same method as in the previous example, except that 9.9 g (53.1 mmol) of 1-(diethylamino)-3-(isobutylamino)propane was used instead of 3-[3-(diethylamino)propylamino]propionitrile.

[0111] NMR measurements were performed on the obtained dark red solid, and the following 60 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (J-3).

[0112] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.00(1H), 7.64(1H), 7.55(1H), 7.21(1H), 7.12-6.92(6H), 3.7 3-3.55(4H), 3.55-3.34(4H), 2.56-2.38(12H), 2.16-2.00(2H), 1.80-1.66(4H), 1.12-0.06(24H).

[0113] [ka]

[0114] [Synthesis Example 4] Synthesis of Compound (J-4) The following reaction was carried out under a nitrogen atmosphere. 4.0 g (5.7 mmol) of compound (J-1), 8.3 g (57 mmol) of iodoethane, and 80 mL of acetonitrile were added to a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer. The mixture was heated under reflux and stirred for 17.5 hours. The reaction mixture was allowed to cool to room temperature, filtered under reduced pressure, and the residue was washed with 5 mL of acetonitrile. The residue was dried under reduced pressure at 80°C overnight to obtain the following intermediate (101) (4.9 g, yield 84%) as a dark red solid.

[0115] [ka]

[0116] Next, the following chemical reaction was carried out under a nitrogen atmosphere. 4.5 g (4.4 mmol) of intermediate (101), 3.2 g (11 mmol) of lithium bis(trifluoromethanesulfonyl)imide, and 50 mL of methanol were added to a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer, and the mixture was stirred at room temperature for 14 hours. After removing the solvent from the reaction mixture under reduced pressure, the residue was washed twice with 50 mL of water. The residue was dried under reduced pressure at 80°C overnight to obtain the target compound (J-4) (5.9 g, yield 100%) as a red solid.

[0117] NMR measurements were performed on the obtained dark red solid, and the following 60 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (J-4).

[0118] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.00(1H), 7.66(1H), 7.57(1H), 7.30-7.02(7H), 4.12-3.9 2(4H), 3.82-3.60(4H), 3.37-3.16(16H), 2.98-2.88(4H), 2.03-1.86(4H), 1.32-1.08(18H).

[0119] [ka]

[0120] [Synthesis Example 5] Synthesis of Compound (J-5) In Synthesis Example 4, compound (J-3) 4.0 g (5.7 mmol) was used instead of compound (J-1), and iodoethane 8.9 g (57 mmol) and acetonitrile 40 mL were used. The following intermediate (102) (5.3 g, yield 92%) was obtained as a blackish-purple solid by the same method.

[0121] [ka]

[0122] Next, in Synthesis Example 4, the target compound (J-5) (6.0 g, 92%) was obtained as a dark red solid by the same method as in Example 4, except that 5.0 g (4.9 mmol) of intermediate (102) was used instead of intermediate (101), and 3.4 g (12 mmol) of lithium bis(trifluoromethanesulfonyl)imide and 30 mL of methanol were used.

[0123] NMR measurements were performed on the obtained dark red solid, and the following 60 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (J-5).

[0124] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.00(1H), 7.66(1H), 7.57(1H), 7.30-7.02(7H), 4.12-3.9 2(4H), 3.82-3.60(4H), 3.37-3.16(16H), 2.98-2.88(4H), 2.03-1.86(4H), 1.32-1.08(18H).

[0125] [ka]

[0126] [Synthesis Example 6] Synthesis of Compound (J-6) The following reaction was carried out under a nitrogen atmosphere. 1.0 g (12 mmol) of intermediate (100), 4.7 g (49 mmol) of 3,3'-iminobis(N,N,N-trimethyl-1-propylammonium iodide) prepared by a known method (Patent Document 4, paragraph

[0187] ), 2.0 g (98 mmol) of triethylamine, and 50 mL of N-methylpyrrolidone were added to a 300 mL four-necked flask equipped with a condenser, stirrer, and thermometer. The mixture was then stirred at 90°C for 16 hours. The reaction mixture was allowed to cool to room temperature, 150 mL of 2-propanol was added, and the mixture was stirred for 30 minutes before being filtered under reduced pressure. The residue was added to 150 mL of methanol, stirred for 30 minutes, and then filtered under reduced pressure. The residue was dried overnight under reduced pressure at 60°C to obtain intermediate (103) (1.8 g, yield 82%) as a dark red solid.

[0127] [ka]

[0128] Next, the following chemical reaction was carried out under a nitrogen atmosphere. 4.0 g (3.7 mmol) of the intermediate (103), 5.4 g (19 mmol) of lithium bis(trifluoromethanesulfonyl)imide, and 50 mL of DMF were added to a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer, and the mixture was stirred at 50°C for 3 hours. The reaction mixture was allowed to cool to room temperature, added to 300 mL of tap water, stirred at room temperature for 1 hour, and then decanted. The residue was dried under reduced pressure overnight at 80°C to obtain the target compound (J-6) (5.0 g, yield 72%) as a red solid.

[0129] NMR measurements were performed on the obtained red solid, and the following 70 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (J-6).

[0130] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=8.01(1H), 7.67(1H), 7.58(1H), 7.24-7. 05(7H), 3.76-3.54(8H), 3.43-3.28(8H), 3.18-2.98(36H), 2.15-2.00(8H).

[0131] [Chemical formula]

[0132] [Synthesis Example 7] Synthesis of Compound (J-7) The following reaction was carried out under a nitrogen stream. 3.0 g (5.2 mmol) of the following intermediate (104), 6.5 g (21 mmol) of N-(3-bromopropyl)triethylammonium bromide prepared by a known method (Patent Document 5, page 54), 3.2 g (22 mmol) of sodium iodide, 2.9 g (21 mmol) of potassium carbonate, and 40 mL of NMP were added to a 100 mL four-necked flask equipped with a condenser, a stirrer, and a thermometer. After stirring at 80 °C for 5 hours, the mixture was allowed to cool to room temperature. The reaction solution was diluted with 200 mL of ethanol, filtered under reduced pressure, and then the solvent of the filtrate was distilled off under reduced pressure. 300 mL of ethyl acetate was added to the residue, and after stirring at room temperature for 30 minutes, it was filtered under reduced pressure. The residue was washed with 150 mL of 2-propanol, dissolved in methanol, and added dropwise to 300 mL of ethyl acetate. The mixture was stirred at room temperature for 30 minutes, filtered under reduced pressure, and the residue was dried under reduced pressure at 80 °C overnight to obtain the following intermediate (105) (5.6 g, 97%) as a purple solid.

[0133] <于 [Chemical formula]

[0134] [Chemical formula]

[0135] Next, the following chemical reaction was carried out under a nitrogen atmosphere. 5.5 g (4.9 mmol) of the intermediate (105), 4.0 g (14 mmol) of lithium bis(trifluoromethanesulfonyl)imide, and 30 mL of methanol were added to a 100 mL four-necked flask equipped with a condenser, stirrer, and thermometer, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was added dropwise to 200 mL of tap water, stirred for 1 hour, and then 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 (J-7) (6.9 g, yield 98%) as a red solid.

[0136] NMR measurements were performed on the obtained red solid, and the following 70 hydrogen signals were detected, identifying the structure of the compound represented by the following formula (J-7).

[0137] 1 H-NMR (300MHz, DMSO-d6): δ(ppm)=7.97(1H), 7.73-7.19(12H), 7.03(1H), 6.17- 5.91(2H), 3.94-3.68(4H), 3.36-3.16(16H), 2.18-1.90(12H), 1.28-1.08(22H).

[0138] [ka]

[0139] [Example 1] (Evaluation of maximum absorption wavelength) The compound (J-1) obtained in Synthesis Example 1 was dissolved in propylene glycol monomethyl ether (PGME) to prepare a 0.02 mmol / L solution. The ultraviolet-visible absorption spectrum (wavelength range of 350-750 nm) was measured at room temperature (25°C) using a UV-Vis spectrophotometer (JASCO Corporation, model: V-650), and the maximum absorption wavelength in the measured wavelength range was determined. The measurement results are shown in Table 1.

[0140] (Evaluation of solubility) Mixtures were prepared by weighing 20 mg of compound (J-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.

[0141] (Preparation of binder resin solution) A binder resin solution (solid content concentration: 33% by mass) prepared by a known method (Patent Document 6, paragraph

[0229] <Synthesis of Binder Resin> Synthesis Example 23) was diluted with a propylene glycol monomethyl ether acetate (PGMEA) / dimethylformamide (DMF) mixed solvent (20 / 80 by mass ratio) to obtain a binder resin solution (solid content concentration: 25% by mass).

[0142] (Evaluation of coloring ability on the paint film) 5.0 g of the binder resin solution and 20 mg of the compound (J-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 the 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 the film. The ultraviolet-visible transmission spectrum of the prepared film was measured using a spectrophotometer (Konica Minolta, Inc., model number: CM-5). The minimum value of the transmittance (T(%)) was used as an indicator of the coloring power to the coating film, and the results of the evaluation in the following four stages are shown in Table 1. "A": T ≤ 10% "B": 10% <T≦20% "C": 20% <T≦35% "D":T>35%

[0143] [Examples 2-7] In Example 1, except that the compound shown in Table 1 was used instead of compound (J-1), the spectral characteristics of the PGME solution, the solubility in PGME, and the coloring power in the coating film were measured and evaluated in the same manner as in Example 1. The results are summarized in Table 1.

[0144] [Comparative Examples 1 to Comparative Example 3] For comparison, except that the following xanthene dye compound not belonging to the present invention was used instead of the compound (J-1) of the example, the spectral characteristics of the PGME solution and the solubility in PGME were measured and evaluated in the same manner as in Example 1. The results are summarized in Table 1. Comparative Example Compound (H-1): C.I. Acid Red 289 Comparative Example Compound (H-2): C.I. Acid Red 52 Comparative Example Compound (H-3): C.I. Basic Violet 10

[0145]

Table 1

[0146] As shown in Table 1, the xanthene dye, which is a compound of the example of the present invention, is excellent in that it has high solubility and also has coloring power for the coating film as compared with the conventional xanthene dyes of the comparative examples.

[0147] The coloring composition containing the xanthene dye according to the present invention is excellent in solubility and coloring power (color development property) for the coating film, and can be used as a dye material for various applications such as a coloring agent for a color filter. Further, by using the coloring composition as a coloring agent for a color filter, it is possible to produce a color filter excellent in color characteristics (color gamut, luminance, contrast ratio, etc.).

Claims

1. Xanthene pigments represented by the following general formula (1). 【Chemistry 1】 [In formula (1), R １ and R ２ This is a group represented by the following general formula (3), R ３ and R ４ Each of them operates independently. Linear or branched alkyl groups having 1 to 40 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 20 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 20 carbon atoms, which may have substituents. Alternatively, it represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. R ３ and R ５ or R ４ and R ６ may each combine to form a ring. R ３ ~R ６ and R ８ ~R １０ The substituents in this compound are -CN, linear or branched alkyl groups having 1 to 20 carbon atoms, amino groups having 0 to 20 carbon atoms, amide groups having 1 to 20 carbon atoms, or ammonium groups having 0 to 20 carbon atoms. R ７ is, -SO ３ － , -CO ２ － , represents a sulfonyl group, sulfonamide group, carbonyl group, or amide group having 20 or fewer carbon atoms, which may have substituents, R ７ It may contain cations. n represents an integer from 0 to 5, and when n is 2 or greater, there are multiple R's. ７ They may be the same or different. An represents an anion, x represents an integer from 1 to 3, and y represents an integer from 0 to 6. When y is 2 or greater, multiple Ans may be the same or different. 【Chemistry 2】 [In formula (3), L represents an alkylene group having 1 to 20 carbon atoms, which may have substituents. R ８ ~R １０ Each of these independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, which may have substituents, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. The dashed line represents the connection point with N in the general formula (1) above.

2. In the above general formula (1), R ３ and R ４ The xanthene dye according to claim 1, wherein all of the groups are represented by the general formula (3).

3. In the above general formula (1), R ３ and R ４ The xanthene dye according to claim 1 or claim 2, wherein the xanthene dye is a linear or branched alkyl group having 2 to 20 carbon atoms and having substituents.

4. In the above general formula (1), R ３ and R ４ The xanthene dye according to claim 1, wherein the substituted group is a phenyl group having 6 to 20 carbon atoms.

5. In the above general formula (1), An is a halide ion, (CF ３ SO ２ ) ２ N － , sulfonylimide anion, or sulfonate anion, The xanthene pigment according to any one of claims 1 to 4.

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 ultraviolet-visible absorption spectrum in the wavelength range of 350 to 750 nm, The maximum absorption wavelength is in the range of 535 to 560 nm. The xanthene pigment according to any one of claims 1 to 5.

7. A coloring composition containing a xanthene pigment according to any one of claims 1 to 6.

8. A coloring agent for color filters containing the coloring composition described in claim 7.

9. A color filter using the coloring agent for color filters described in claim 8.

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