CN111378295B - Xanthene dye, coloring composition containing the same, colorant for color filter, and color filter - Google Patents

Xanthene dye, coloring composition containing the same, colorant for color filter, and color filter Download PDF

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CN111378295B
CN111378295B CN201911218223.4A CN201911218223A CN111378295B CN 111378295 B CN111378295 B CN 111378295B CN 201911218223 A CN201911218223 A CN 201911218223A CN 111378295 B CN111378295 B CN 111378295B
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carbon atoms
substituent
group
linear
general formula
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CN111378295A (en
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神田大三
山县直哉
金学奎
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Hodogaya Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Abstract

The present invention provides a xanthene dye which is a xanthene dye having a solution ultraviolet-visible absorption spectrum and having a maximum absorption wavelength on the long wavelength side of 560nm or more and which has excellent color characteristics (color gamut, brightness, contrast ratio, etc.) and heat resistance, a coloring composition containing the compound, and a color filter containing the coloring composition. A xanthene-based dye represented by the following general formula (1).[ formula, R 1 ～R 4 Each independently represents-H, alkyl, aromatic hydrocarbon group, R 1 And R is R 2 Or R is 3 And R is R 4 The rings may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to each other. R is R 5 And R is 6 Each independently represents-H, a halogen atom, -NO 2 Alkyl. X represents-O- -S-or-Se-. Q represents a heterocyclic group. An represents An anion, a represents An integer of 1 to 3, and b represents An integer of 0 to 3. Wherein the general formula (1) is neutral in charge as a whole.]。

Description

Xanthene dye, coloring composition containing the same, colorant for color filter, and color filter
Technical Field
The present invention relates to a xanthene dye, a coloring composition containing the dye, a colorant for a color filter containing the coloring composition, and a color filter using the colorant.
Background
Color filters are used in liquid crystal, electroluminescent (EL) display devices, and in CCD and CMOS image pickup devices. The color filter is manufactured by laminating a coloring layer such as a pigment thin film or a pigment-resin composite film on a light-transmitting substrate such as glass or transparent resin by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like.
The xanthene-based coloring matter is a compound used as a coloring agent for color filters because of its vividness (patent documents 1 and 2, etc.). For example, a combination of a xanthene-based dye such as c.i. acid red 289 represented by the following formula (B-1) and c.i. acid red 52 represented by the following formula (B-2) and an azopyridone-based dye gives an excellent red color tone (patent document 1). Wherein c.i. means color index.
[ chemical formula 1 ]
[ chemical formula 2 ]
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2002-265834
Patent document 2: japanese patent application laid-open No. 2012-207224
Patent document 3: japanese patent No. 6118213
Patent document 4: japanese patent No. 5703630
Non-patent literature
Non-patent document 1: "Chemical Communications", (UK), 2017, volume 53, pages 1064-1067, supporting Information
Disclosure of Invention
Problems to be solved by the invention
In the development of the present display devices, high performance (high definition, wide color gamut, low voltage) is demanded year by year, and the performance (high transmittance, high color purity, and other color characteristics) of color filters to be used is also demanded year by year. As for the coloring matter used for the color filter, for example, xanthene-based coloring matter, a coloring matter having a maximum absorption wavelength of a solution in an ultraviolet-visible absorption spectrum in a range of 520 to 560nm has been used in a red color filter so far (patent documents 1 and 2), but a coloring matter having a maximum absorption wavelength on a longer wavelength side has been demanded. However, it is difficult to synthesize a dye having a wavelength of a great absorption at 560 to 600nm with respect to the molecular structure of a conventional xanthene dye.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a xanthene dye which is a solution of a xanthene dye having a wavelength on the long-wavelength side of 560nm or more in the maximum absorption wavelength of the ultraviolet visible absorption spectrum, and which is excellent in color characteristics (color gamut, brightness, contrast ratio, etc.), and heat resistance, a coloring composition containing the compound, and a color filter containing the coloring composition.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems and achieve the above object, and as a result, have completed a xanthene-based dye of the present invention having a maximum absorption wavelength in a wavelength range of from 350 to 700nm in the ultraviolet-visible absorption spectrum of a solution (solvent: propylene Glycol Monomethyl Ether (PGME), etc.) of 560nm or more and a long wavelength side as compared with conventional xanthene-based dyes. That is, the present invention has the following matters as gist.
1. A xanthene-based dye represented by the following general formula (1).
[ chemical 3 ]
[ formula, R 1 ～R 4 Each independently represents-H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R 1 and R is R 2 Or R is 3 And R is R 4 The rings may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to each other.
R 5 R is R 6 Each independently represents-H, a halogen atom, -NO 2 And a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent.
X represents-O- -S-or-Se-.
Q represents a heterocyclic group having 2 to 30 carbon atoms which may have a substituent.
An represents An anion, a represents An integer of 1 to 3, and b represents An integer of 0 to 3.
Wherein the general formula (1) is neutral in charge as a whole. ]
2. The xanthene dye is characterized in that in the general formula (1), Q is a heterocyclic group represented by the following general formula (Q1).
[ chemical formula 4 ]
[ formula, R 7 represents-H, halogen atom, -OH, -CN, -OCH 3 、-NO 2 、-SO 3 - 、-SO 3 H、-SO 3 M、-CO 2 - 、-CO 2 H、-CO 2 M is a linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 28 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent, or an amino group having 0 to 28 carbon atoms which may have a substituent.
Z 1 represents-O-, -S-, -N= -NR 8 -or-CR 8 ＝，
Z 2 represents-O-, -S-, -N= -NR 9 -or-CR 9 ＝，
Z 3 represents-O-, -S-, -N= -NR 10 -or-CR 10 ＝，
R 8 ～R 10 Each independently represents-H, a linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 28 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent,
R 7 ～R 10 the adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
M represents an organic cation or an inorganic cation, and in the case where a plurality of cations are present, they may be the same or different. ]
3. The xanthene dye is characterized in that in the general formula (1), Q is a heterocyclic group represented by the following general formula (Q11).
[ chemical 5 ]
[ formula, R 11 ～R 15 Each independently represents-H, a halogen atom, -OH, -CN, -OCH 3 、-NO 2 、-SO 3 - 、-SO 3 H、-SO 3 M、-CO 2 - 、-CO 2 H、-CO 2 M is a linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent, or an amino group having 0 to 21 carbon atoms which may have a substituent,
R 16 r is R 17 Each independently represents-H, a linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent,
R 11 ～R 15 、R 16 and R is R 17 The adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.
M represents an organic cation or an inorganic cation, and in the case where a plurality of cations are present, they may be the same or different. ]
4. The xanthene dye is characterized in that in the general formula (1), Q is a heterocyclic group represented by the following general formula (Q12).
[ 6 ] A method for producing a polypeptide
[ formula, R 18 ～R 21 Each independently represents-H, a halogen atom, -OH, -CN, -OCH 3 、-NO 2 、-SO 3 - 、-SO 3 H、-SO 3 M、-CO 2 - 、-CO 2 H、-CO 2 M is a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent, and may beAn aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent, may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom between adjacent groups to form a ring.
R 22 represents-H, halogen atom, -OH, -CN, -OCH 3 、-NO 2 、-SO 3 - 、-SO 3 H、-SO 3 M、-CO 2 - 、-CO 2 H、-CO 2 M is a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent.
R 23 represents-H, a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent.
M represents an organic cation or an inorganic cation, and in the case where a plurality of cations are present, they may be the same or different. ]
5. Xanthene pigments, wherein M is an alkali metal ion in the general formula (Q1), (Q11) or (Q12).
6. Xanthene pigments, wherein X is-O-.
7. Xanthene-based coloring matter, wherein, in the general formula (1), an is Cl - 、Br - 、I - 、(CF 3 SO 2 ) 2 N - 、(CF 3 SO 2 ) 3 C - 、(CN) 2 N - 、(CN) 3 C - 、NC-S - 、(C 2 F 5 ) 3 F 3 P - 、(C 6 H 4 SO 3 - )O(C 6 H 3 (C 12 H 25 )(SO 3 - ))、C 6 H 4 (C 12 H 25 )(SO 3 - )、PF 6 - 、BF 4 - Or (PW) 12 O 40 ) 3- And b is an integer of 1 to 3.
8. The xanthene dye uses Propylene Glycol Monomethyl Ether (PGME) solution with concentration of 0.005-0.02 mmol/L, and has a wavelength range of 560-600 nm in ultraviolet-visible absorption spectrum (wavelength range of 350-700 nm) measured at 23-27 ℃.
9. A coloring composition comprising the above xanthene-based coloring matter.
10. A colorant for color filters, which contains the above-mentioned coloring composition.
11. A color filter using the above-mentioned colorant for color filter.
ADVANTAGEOUS EFFECTS OF INVENTION
The xanthene dye of the present invention is useful as a colorant for a color filter having excellent color characteristics (color gamut, brightness, contrast ratio, etc.) and heat resistance, because the maximum absorption wavelength in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) of a solution (solvent: propylene Glycol Monomethyl Ether (PGME), etc.) is in the range of 560nm or more, and is located on the long wavelength side as compared with conventional xanthene dyes.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented by various modifications within the scope of the gist thereof. First, a xanthene-based dye represented by the above general formula (1) will be described.
In the general formula (1), R is 1 ～R 6 The "linear or branched alkyl group having 1 to 20 carbon atoms" in the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" is specifically exemplified by linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl, and 2-ethylhexyl.
In the general formula (1), R is 1 ～R 4 The "aromatic hydrocarbon group" in the "aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent" represented by the above formula includes an aryl group and a condensed polycyclic aryl groupThe aromatic group is an "aromatic hydrocarbon group having 6 to 20 carbon atoms", and specifically includes phenyl, biphenyl, terphenyl, naphthyl, anthryl (anthracenyl group), phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and benzo [9,10 ]]Aromatic hydrocarbon groups such as phenanthryl.
In the general formula (1), R is 5 R is R 6 The "halogen atom" is exemplified by fluorine atom, chlorine atom, bromine atom, iodine atom and the like, and is preferably chlorine atom or bromine atom.
In the general formula (1), R is 1 ～R 6 The "straight-chain or branched alkyl group having 1 to 20 carbon atoms and having a substituent" represented by R 1 ～R 4 The "substituent" in the "substituted C6-20 aromatic hydrocarbon group" or "substituted methylene group" represented by "is specifically exemplified by a heavy hydrogen atom, -OH, -CN and-CF 3 、-NO 2 ；-SO 3 - 、-SO 3 H、-SO 3 M represents a sulfonic acid group, or-CO 2 - 、-CO 2 H、-CO 2 A carboxylic acid group represented by M (wherein M represents an organic cation or an inorganic cation); halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; a linear or branched alkyl group having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; a linear or branched alkenyl group having 2 to 20 carbon atoms; straight-chain or branched alkoxy groups having 1 to 20 carbon atoms; a cycloalkoxy group having 3 to 20 carbon atoms, a 1-adamantyloxy group, or a 2-adamantyloxy group; acyl with 1-20 carbon atoms; an aromatic hydrocarbon group having 6 to 20 carbon atoms or a condensed polycyclic aromatic group; a heterocyclic group having 2 to 20 carbon atoms; aryloxy group having 6 to 20 carbon atoms; unsubstituted amino; mono-or di-substituted amino groups having 1 to 20 carbon atoms, and the like. These "substituents" may be 1 or more, and may be the same or different from each other when they are contained in plural. In addition, these "substituents" may further have the substituents exemplified above. In the case where the "substituent" includes a carbon atom, the carbon atom is incorporated into the above-mentioned "carbon atom number 1 to 20" and "carbon atom number 6 to 20". In addition These substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.
In the general formula (1), when "inorganic cation" or "organic cation" represented by "M" exists, specific examples of "organic cation" include R 24 R 25 R 26 R 27 N + Represented ammonium ion, R 24 ～R 27 Each independently represents-H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and may be bonded to each other to form a ring. Wherein R is 24 ～R 27 Details of the "substituent", "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" in the above formula (1) are applicable to R in the above formula 1 ～R 4 The same description applies. Examples of the "inorganic cation" include alkali metal ions such as lithium ions and sodium ions, and alkaline earth metal ions such as magnesium ions, calcium ions and barium ions. As M, alkali metal ions are preferred.
In the general formula (1), R is 1 ～R 6 Among the above-mentioned various "groups" having "substituents" represented by the above-mentioned "groups" are exemplified by "substituent", "straight-chain or branched alkyl group having 1 to 20 carbon atoms", "cycloalkyl group having 3 to 20 carbon atoms", "straight-chain or branched alkenyl group having 2 to 20 carbon atoms", "straight-chain or branched alkoxy group having 1 to 20 carbon atoms", "cycloalkoxy group having 3 to 20 carbon atoms", "acyl group having 1 to 20 carbon atoms", "aromatic hydrocarbon group having 6 to 20 carbon atoms or condensed polycyclic aromatic group", "heterocyclic group having 2 to 20 carbon atoms", "aryloxy group having 6 to 20 carbon atoms" or "mono-or di-substituted amino group having 1 to 20 carbon atoms", and specific examples thereof include straight-chain methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl and the like Or branched alkyl; cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl; alkenyl groups such as vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, and isobutenyl, or straight-chain or branched alkenyl groups obtained by combining a plurality of these alkenyl groups; straight-chain or branched alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, isopropoxy, isobutyloxy, sec-butyloxy, tert-butyloxy, and isooctyloxy; a C3-20 cycloalkoxy group such as cyclopropyloxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cyclononyloxy, and cyclodecyloxy; acyl groups such as formyl, acetyl, propionyl, acryloyl and benzoyl; phenyl, biphenyl, terphenyl, naphthyl, anthracenyl (anthracenyl group), tetracenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzo [9,10 ]]Aromatic hydrocarbon groups such as phenanthryl groups or condensed polycyclic aromatic groups; thienyl, furyl (furyl), pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, naphthyridinyl, acridinyl, phenanthrolinyl, naphthyridinyl, carbolinyl and the like; aryloxy groups such as phenoxy, tolyloxy, biphenyloxy, naphthyloxy, anthracenyloxy, phenanthryloxy and the like; and mono-or di-substituted amino groups such as methylamino, dimethylamino, diethylamino, ethylmethylamino, dipropylamino, dibutylamino, di (2-ethylhexyl) group, di (2-ethylhexyl) amino, di-t-butylamino, and diphenylamino groups having linear or branched alkyl groups, and aromatic hydrocarbon groups.
In the general formula (1), R 1 And R is R 2 Or R is 3 And R is R 4 The ring may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to each other, and in the case of forming a ring, it is preferable thatSelected from 5-membered ring or 6-membered ring, more preferably 6-membered ring.
In the general formula (1), the amino acid sequence of the compound, X represents an oxygen atom (-O-), a sulfur atom (-S-) or a selenium atom (-Se-), preferably-O-or-S-, more preferably-O-.
In the general formula (1), examples of the "heterocyclic group having 2 to 30 carbon atoms" in the "heterocyclic group having 2 to 30 carbon atoms which may have a substituent" represented by the "Q" include thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazole, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, naphthyridinyl, acridinyl, phenanthroline, naphthyridinyl, carboline and the like. The "substituent" in the "heterocyclic group having 2 to 30 carbon atoms as a substituent" includes the substituent represented by R in the general formula (1) 1 ～R 6 Among the above-mentioned various "groups" having "substituents" indicated, the same groups as those listed as "substituents" are listed. When the "substituent" includes a carbon atom, the carbon atom is calculated as "the number of carbon atoms is 2 to 30" in "Q" in the above general formula (1).
In the general formula (1), "a" represents the number of parts of the compound (xanthene-based dye) represented by the following general formula (1-C) in the general formula (1). "An" represents An anion, and "b" represents the number of An. In the case where the molecule of the following formula (1-C) in the general formula (1) is a cation having a total charge of 1 or more in the whole molecule, that is, b is An integer of 1 to 3, a complex can be formed with An arbitrary anion represented by "An" as a counter ion. Among the compounds represented by the general formula (1), a and b are selected so as to be neutral in charge as a whole. a represents an integer of 1 to 3, preferably 1 or 2.b represents an integer of 0 to 3, preferably an integer of 1 to 3.
[ chemical 7 ]
[ formula, R 1 ～R 6 And X has the same definition as that in the above general formula (1).]
In the general formula (1), "An" is not particularly limited, and examples thereof include inorganic anions such as halide ions, and organic anions. Specifically, cl - 、Br - 、I - ；(CF 3 SO 2 ) 2 N - 、(CF 3 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 2 N - 、(C 4 F 9 SO 2 ) 2 N - 、(CN) 2 N - 、(CN) 3 C - 、NC-S - 、(C 2 F 5 ) 3 F 3 P - 、(C 6 H 4 SO 3 - )O(C 6 H 3 (C 12 H 25 )(SO 3 - ))、C 6 H 4 (C 12 H 25 )(SO 3 - )、PF 6 - 、BF 4 - 、(PW 12 O 40 ) 3- Or anions represented by the structural formulae (J-1) to (J-16) below.
[ chemical formula 8 ]
[ chemical formula 9 ]
[ chemical formula 10 ]
[ chemical formula 11 ]
[ chemical formula 12 ]
[ chemical formula 13 ]
[ chemical formula 14 ]
[ 15 ] A method of producing a polypeptide
[ 16 ] the preparation method
[ chemical formula 17 ]
In the general formula (1), R is as follows 1 ～R 4 preferably-H, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent.
In the general formula (1), R is as follows 5 R is R 6 preferably-H, or a chlorine or bromine atom.
In the general formula (1), Q represents a heterocyclic group having 2 to 30 carbon atoms and having a substituent, and is preferably a heterocyclic group represented by the above general formula (Q1). That is, the general formula (1) is preferably the following general formula (1-Q1).
[ chemical formula 18 ]
[ formula, R 1 ～R 6 X, an, a and b have the same meanings as defined in the above formula (1), R 7 Z is as follows 1 ～Z 3 Has the same definition as that in the above general formula (Q1).]
In the general formula (Q1), R is 7 The "halogen atom" is exemplified by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and preferably a fluorine atom or a chlorine atom.
In the general formula (Q1), R is 7 、Z 1 Of "-NR 8 -or-CR 8 R in= 8 、Z 2 Of "-NR 9 -or-CR 9 R in= 9 And Z 3 Of "-NR 10 -or-CR 10 R in= 10 The "linear or branched alkyl group having 1 to 28 carbon atoms" of the "linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent", "linear or branched alkenyl group having 2 to 28 carbon atoms", "aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent" of the "aromatic hydrocarbon group having 6 to 28 carbon atoms", or "amino group having 0 to 28 carbon atoms" of the "amino group having 0 to 28 carbon atoms which may have a substituent" shown in the above description, specifically, examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl, and 2-ethylhexyl; alkenyl groups such as vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, etc., or these alkenyl groupsA plurality of linear or branched alkenyl groups bonded together; phenyl, biphenyl, terphenyl, naphthyl, anthracenyl (anthracenyl group), tetracenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzo [9,10 ] ]Aromatic hydrocarbon groups (including aryl groups and condensed polycyclic aromatic groups) such as phenanthryl groups; methylamino, ethylamino, dimethylamino, diethylamino, ethylmethylamino, dipropylamino, dibutylamino, di (2-ethylhexyl) group, di-tert-butylamino, diphenylamino, ethylphenylamino, etc.
In the general formula (Q1), R is 7 ～R 10 Examples of the "substituent" in the "linear or branched alkyl group having 1 to 28 carbon atoms with a substituent", "linear or branched alkenyl group having 2 to 28 carbon atoms with a substituent", "aromatic hydrocarbon group having 6 to 28 carbon atoms with a substituent" or "amino group having 0 to 28 carbon atoms with a substituent" represented by the general formula (1) include R 1 ～R 6 The "straight-chain or branched alkyl group having 1 to 20 carbon atoms and having a substituent" represented by R 1 ～R 4 The "substituent" in the "substituted aromatic hydrocarbon group having 6 to 20 carbon atoms" is the same as the group listed as the "substituent". These "substituents" may be 1 or more, and may be the same or different from each other when they are contained in plural. In addition, these "substituents" may further have the substituents exemplified above. When the "substituent" includes a carbon atom, the carbon atom is calculated as "the number of carbon atoms is 2 to 30" in "Q" in the above general formula (1). In addition, these substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.
In the general formula (Q1), R is 7 ～R 10 In particular, R is preferred, in which adjacent groups can be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring 8 And R is R 9 、R 9 And R is R 7 、R 7 And R is R 10 Form between adjacent groups of (a)And rings to which adjacent groups may be further bonded to form a ring. In addition, the ring formed is preferably a 5-membered ring or a 6-membered ring.
In the general formula (Q1), as the "organic cation" or "inorganic cation" represented by "M", the same "organic cation" or "inorganic cation" as the "organic cation" or "inorganic cation" when "M" is present in the general formula (1) described above can be mentioned. Namely, R is as follows 24 R 25 R 26 R 27 N + Represented ammonium ion, R 24 ～R 27 Each independently represents a hydrogen 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, and may be bonded to each other to form a ring. Wherein R is 24 ～R 27 The details of the "substituent", "linear or branched alkyl group having 1 to 20 carbon atoms" and "aromatic hydrocarbon group having 6 to 20 carbon atoms" in (a) are applicable to R 1 ～R 4 The same description applies. The "inorganic cation" includes alkali metal ions and alkaline earth metal ions, and lithium ions, sodium ions, and potassium ions are preferable.
Q in the general formula (1) is preferably a heterocyclic group represented by the above general formula (Q1), more preferably a heterocyclic group represented by the above general formula (Q11) or (Q12). That is, the general formula (1) is preferably the following general formula (1-Q11) or the following general formula (1-Q12).
[ chemical formula 19 ]
[ formula, R 1 ～R 6 X, an, a and b have the same meanings as defined in the above formula (1), R 11 ～R 17 Has the same definition as that in the above general formula (Q11).]
[ chemical formula 20 ]
[ formula, R 1 ～R 6 X, an, a and b have the same meanings as defined in the above formula (1), R 18 ～R 22 Has the same definition as that in the above general formula (Q12).]
In the general formula (Q11), R is 11 ～R 15 The "halogen atom" is exemplified by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and preferably a fluorine atom or a chlorine atom.
In the general formula (Q11), R is 11 ～R 17 The "straight-chain or branched alkyl group having 1 to 21 carbon atoms which may have a substituent" represented by R 11 ～R 15 The "straight-chain or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent" represented by R 11 ～R 17 The "C6-21 aromatic hydrocarbon group which may have a substituent" represented by the formula or R 11 ～R 15 Examples of the "group" of the "amino group having 0 to 21 carbon atoms which may have a substituent" include those represented by the general formula (Q1) and represented by R 7 The "linear or branched alkyl group having 1 to 28 carbon atoms which may have a substituent", "linear or branched alkenyl group having 2 to 28 carbon atoms which may have a substituent", "aromatic hydrocarbon group having 6 to 28 carbon atoms which may have a substituent", or "amino group having 0 to 28 carbon atoms which may have a substituent" are the same groups as those exemplified for the various "groups" exemplified for the "groups, and examples thereof are groups having a maximum carbon number of 21.
As the "substituent" which these "groups" may have, there may be mentioned those represented by R in the general formula (Q1) 7 The "substituents" which the various "groups" may have 1 or more substituents, and may be the same or different from each other when the plurality of substituents are contained. In addition, these "substituents" may further have the substituents exemplified above. When the "substituent" includes a carbon atom, the carbon atom is calculated as "the number of carbon atoms is 2 to 30" in "Q" in the above general formula (1). In addition, these substituents The ring may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to each other.
In the general formula (Q11), R is 11 ～R 15 Or R is 16 And R is R 17 In particular, the adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, and the formed ring is preferably a 5-membered ring or a 6-membered ring.
R as a component of the formula (Q11) 11 ～R 15 preferably-H, -CN, halogen atom, -NO 2 "a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" or "a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent". In addition, as R 16 And R is 17 preferably-H is a "linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent" or a "aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent".
In the general formula (Q11), as the "organic cation" or "inorganic cation" represented by "M", the same "organic cation" or "inorganic cation" as the "organic cation" or "inorganic cation" represented by "M" in the general formula (Q1) described above can be mentioned.
As R in the general formula (Q12) 18 ～R 21 The "halogen atom" is exemplified by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and preferably a fluorine atom or a chlorine atom.
In the general formula (Q12), R is 18 ～R 23 The expression "straight-chain or branched alkyl group having 1 to 22 carbon atoms which may have a substituent", "aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent", or "R" is used 18 ～R 22 The "amino group having 0 to 22 carbon atoms which may have a substituent" represented by the general formula (Q1) may be represented by R 7 The expression "straight-chain or branched alkyl group having 1 to 28 carbon atoms as a substituent", "straight-chain or branched alkenyl group having 2 to 28 carbon atoms as a substituent" and "carbon atom as a substituent" as used hereinThe aromatic hydrocarbon group having 6 to 28 carbon atoms or the "amino group having 0 to 28 carbon atoms which may have a substituent" may be the same as the groups listed as the "group", and the maximum number of carbon atoms may be 22.
As the "substituent" which these "groups" may have, there may be mentioned those represented by R in the general formula (Q1) 7 The "substituents" which the various "groups" may have 1 or more substituents, and may be the same or different from each other when the plurality of substituents are contained. In addition, these "substituents" may further have the substituents exemplified above. When the "substituent" includes a carbon atom, the carbon atom is calculated as "the number of carbon atoms is 2 to 30" in "Q" in the above general formula (1). In addition, these substituents may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.
In the general formula (Q12), R is 18 ～R 21 In particular, the adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, and the formed ring is preferably a 5-membered ring or a 6-membered ring.
R as a component of the formula (Q12) 18 ～R 21 preferably-H, a halogen atom, or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent.
In addition, as R 22 preferably-H, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or an amino group having 0 to 10 carbon atoms which may have a substituent.
In addition, as R 23 The linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and the aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent are preferable.
In the general formula (Q12), as the "organic cation" or "inorganic cation" represented by "M", the same "organic cation" or "inorganic cation" as the "organic cation" or "inorganic cation" represented by "M" in the general formula (Q1) described above can be mentioned.
The xanthene-based dye represented by the general formula (1) can be synthesized by the following known methods (for example, patent documents 3 and 4 and non-patent document 1). A reaction mixture is filtered by condensing a dialkylaminoxanthone having a corresponding group in the general formula (1) such as 3, 6-bis (diethylamino) xanthone with a heterocyclic compound having a corresponding group in the general formula (1) such as N-ethyl-N, 4-diphenyl-1, 3-thiazol-2-amine in a toluene solvent using phosphorus oxychloride under an appropriate heating condition, thereby obtaining a product containing the compound represented by the general formula (1).
Specific examples of the preferred compounds as the xanthene-based dye of the present invention represented by the general formula (1) are shown in the following formulas (a-1) to (a-42), but the present invention is not limited to these compounds. The cationic moiety represented by the general formula (1-C) is shown, and the anionic moiety represented by An is omitted. In the following structural formula, a part of hydrogen atoms are omitted. In addition, even in the case where stereoisomers exist, the planar structural formula thereof is described.
[ chemical formula 21 ]
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[ chemical formula 22 ]
[ chemical formula 23 ]
[ chemical 24 ]
[ chemical 25 ]
[ chemical 26 ]
[ chemical formula 27 ]
[ chemical 28 ]
[ chemical 29 ]
[ chemical formula 30 ]
[ chemical 31 ]
[ chemical formula 32 ]
[ chemical formula 33 ]
[ chemical 34 ]
[ 35 ]
[ chemical formula 36 ]
[ FORMS 37 ]
[ chemical 38 ]
[ chemical formula 39 ]
[ 40 ]
[ chemical formula 41 ]
The xanthene-based dye of the present invention may be used in combination (for example, mixed) of 1 or 2 or more kinds of the xanthene-based dyes having different molecular structures. When the above 2 or more kinds are used, the concentration ratio by weight of the least 1 kind of xanthene dye is 0.1 to 50% by weight of the concentration ratio by weight of the whole xanthene dye. The xanthene-based pigment is preferably 1 or 2 kinds.
In the synthesis of the xanthene-based dye of the present invention, a method of purifying the product includes purification by column chromatography; refining by adsorption of silica gel, activated carbon, activated clay, etc.; by known methods such as recrystallization from a solvent and crystallization. Further, as needed, in the identification and analysis of these compounds, nuclear magnetic resonance analysis (NMR), absorbance measurement by a spectrophotometer, ultraviolet-visible absorption spectroscopy (UV-Vis) measurement, calorimetric measurement-differential thermal analysis (TG-DTA), and the like can be performed. These methods can also be used for solubility, color evaluation, heat resistance evaluation, and the like of the obtained compound.
The xanthene-based pigment of the present invention can be mixed with various resin solutions and coated on a glass substrate to produce a coating film. The color of the obtained coating film was measured by a spectrocolorimeter to obtain a color value of the coating film, whereby the color evaluation was possible. For color values, CIEL is generally used * a * b * Color system, and the like. Specifically, the color value L of the film sample is measured * 、a * 、b * Color difference (delta E) of color values before and after heating at an appropriate temperature ＊ ab ) The heat resistance can be judged. In the case of application to a color filter, a color difference at a temperature of around 230 ℃ can be used as an index of heat resistance. Delta E ＊ ab The smaller the value, the smaller the discoloration of the color due to thermal decomposition, preferably 10 or less, more preferably 3 or less.
In the xanthene-based dye, the coloring composition containing the dye, and the colorant for color filters containing the coloring composition of the present invention, in the colorant for color filters and the process for producing color filters, it is necessary to satisfactorily dissolve or disperse the xanthene-based dye in an organic solvent containing a resin or the like, and therefore, it is preferable that the solubility in an organic solvent and the dispersibility be high. The organic solvent is not particularly limited, and specific examples thereof include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether, propylene Glycol Monomethyl Ether (PGME), and ethylene glycol monoethyl ether (ethylcellosolve); 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 (chloroform), and the like. These solvents may be used alone or in combination of 2 or more.
The xanthene dye represented by the general formula (1) has a maximum absorption wavelength at which the maximum absorbance is observed in the visible light region (for example, the wavelength range of 350 to 700 nm) of the ultraviolet-visible absorption spectrum measured in the vicinity of room temperature (for example, 23 to 27 ℃) using a solution prepared by dissolving the xanthene dye in an organic solvent. In the present invention, the maximum absorption wavelength is preferably in the range of 560nm to 610nm, more preferably in the range of 570nm to 600 nm. The pigment concentration is preferably 0.005 to 0.02mmol/L. The solvent is not limited as long as the pigment is dissolved, and is preferably a solvent in which the absorption wavelength of the ultraviolet-visible absorption spectrum does not greatly shift due to the dissolution conditions, and Propylene Glycol Monomethyl Ether (PGME) is preferred.
The colorant for color filters of the present invention comprises: a coloring composition containing at least one xanthene dye represented by general formula (1) and components generally used in the production of color filters. In a general color filter, for example, in the case of a method using a photolithography process, a substrate such as glass or resin is coated with a liquid prepared by mixing a dye such as a dye or pigment, a resin component (including a monomer or an oligomer), and a solvent, and the mixture is photopolymerized using a photomask to produce a colored pattern of a dye-resin composite film that is soluble or insoluble in the solvent, and the colored pattern is washed and then heated to obtain the color filter. In addition, in the electrodeposition method and the printing method, a colored pattern is also produced by using a product obtained by mixing a pigment with a resin and other components. Therefore, specific components in the colorant for a color filter of the present invention include at least one of a xanthene-based dye represented by the general formula (1), other dyes, pigments such as pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Further, these components may be selected from among them, and other components may be added as needed.
When the coloring composition containing the xanthene-based coloring matter of the present invention is used as a coloring matter for color filters, it can be used for color filters of respective colors, and preferably used as a coloring matter for red color filters.
The colorant for color filters containing the xanthene-based colorant of the present invention may be used alone of 1 or 2 or more xanthene-based colorants, and other known colorants such as dyes and pigments may be mixed for adjustment of color tone. When used as a colorant for a red color filter, examples thereof include, but are not particularly limited to, red pigments such as c.i. pigment red 177, 209, 242, 254, 255, 264, 269, and c.i. pigment orange 38, 43, and 71; other red-based lake pigments; yellow pigments such as c.i. pigment yellow 138, 139, 150; red dyes such as c.i. acid red 88 and c.i. basic violet 10. When used as a colorant for a cyan color filter, basic dyes such as c.i. basic blue 3, 7, 9, 54, 65, 75, 77, 99, 129, etc. are not particularly limited; c.i. acid blue 9, 74, etc. acid dyes; disperse blue 3, 7, 377 disperse dyes; spiro-cyclic dye; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, indanthrene, oxazine, dioxazine, azo, xanthene not according to the invention; other cyan dyes or pigments such as cyan lake pigments.
The mixing ratio of the other coloring matters in the coloring matter for color filter containing the xanthene-based coloring matter of the present invention is preferably 5 to 2000% by weight, more preferably 10 to 1000% by weight, relative to the xanthene-based coloring matter (total of these in the case of 2 or more). The mixing ratio of the coloring matter component such as dye in the liquid coloring matter for color filter is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the entire coloring matter.
As the resin component in the colorant for a color filter of the present invention, a known resin component can be used as long as the resin component has desired properties in the production system and use of a color filter resin film formed using the resin component. Examples thereof include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (varnish) resins, other transparent resins, photocurable resins, and thermosetting resins, and monomer or oligomer components thereof can be appropriately combined and used. In addition, copolymers of these resins may be used in combination. The content of the resin in the colorant for color filters is preferably 5 to 95% by weight, more preferably 10 to 50% by weight in the case of a liquid colorant.
In order to improve the performance as a colorant for a color filter, the coloring composition of the present invention may contain, as components other than the compound, a surfactant, a dispersant, an antifoaming agent, a leveling agent, an additive mixed during the production of another colorant for a color filter, and the like. However, the content of these additives in the coloring composition is preferably an appropriate amount, and is preferably a content in a range that does not reduce or excessively increase the solubility in the solvent of the coloring composition of the present invention and that does not affect the effects of other additives of the same type used in the production of color filters. These additives can be added at any timing in the preparation of the coloring composition.
Examples of other additives in the colorant for color filters of the present invention include components necessary for polymerization and curing of the resin, such as photopolymerization initiators and crosslinking agents, and surfactants and dispersants necessary for stabilizing the properties of the components in the colorant for color filters in liquid form. These additives are not particularly limited, and any known additive for manufacturing color filters can be used. The mixing ratio of the total amount of these additives in the solid content of the colorant for color filters is preferably 5 to 60% by weight, more preferably 10 to 40% by weight.
Examples
Hereinafter, embodiments of the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. The compounds obtained in the synthesis examples were identified by 1H-NMR analysis (model: magnet System 300MHz/54mm UltraShield, manufactured by the Searche company).
Synthesis example 1 Synthesis of Compound (D-1)
The following chemical reactions were carried out under a nitrogen flow. A100 mL-capacity 4-necked flask equipped with a condenser, a stirrer and a thermometer was charged with 3.00g (8.28 mmol) of an intermediate represented by the following formula (100) synthesized by a known method (non-patent documents 1 and Supporting Information), 2.51g (8.52 mmol) of an intermediate represented by the following formula (Q-100) synthesized by a known method (patent document 3) and 40mL of toluene, and after dissolution, 3.94g (25.7 mmol) of phosphorus oxychloride was added. The reaction mixture was stirred at 50℃for 19.5 hours and at 80℃for 3.5 hours. The reaction mixture was naturally cooled to 30℃or lower, filtered under reduced pressure, and the solid was dissolved in 150mL of methylene chloride and washed with water. The aqueous layer was re-extracted with 150mL of methylene chloride, and the organic layer was mixed, dried over anhydrous magnesium sulfate, and filtered under reduced pressure. The solvent of the filtrate was distilled off under reduced pressure, and the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol=5/1 (volume ratio)). After purification, the dried black-violet solid was washed with ethyl acetate, and dried under reduced pressure at 80℃to obtain the objective compound (D-1) (4.43 g, yield 79%) as a black-violet solid.
[ chemical 42 ]
[ chemical formula 43 ]
The following signals of 43 hydrogens were detected by NMR measurement of the black-violet solid obtained, and the structure of the compound represented by the following formula (D-1) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.56-7.45(5H)、7.44-7.36(3H)、7.30-7.22(5H)、7.04(2H)、3.77-3.63(8H)、3.56(2H)、2.33(3H)、1.76-1.50(12H)、1.31(3H)。
[ 44 ]
Synthesis example 2 Synthesis of Compound (D-2)
The following chemical reactions were carried out under a nitrogen flow. 2.00g (2.96 mmol) of the above-mentioned compound (D-1) and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI, li) were placed in a 100 mL-capacity 4-necked flask equipped with a condenser, a stirrer and a thermometer + (CF 3 SO 2 ) 2 N - ) 0.93g (3.34 mmol) and 45mL of DMF are stirred at 50℃for 3.5 h. The reaction mixture was naturally cooled to 30℃or lower, poured into 300mL of water, stirred at room temperature (25 ℃) for 30 minutes, and then filtered under reduced pressure. The residue was washed with 150mL of water, filtered under reduced pressure, and the residue was dried under reduced pressure at 80℃to give the objective compound (D-2) (2.29 g, yield 84%) as a dark bluish-violet solid.
The following 43 signals of hydrogen were detected by NMR measurement of the dark blue-violet solid obtained, and the structure of the compound represented by the following formula (D-2) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.55-7.44(6H)、7.43-7.36(2H)、7.29-7.21(5H)、7.04(2H)、3.78-3.66(10H)、2.33(3H)、1.76-1.54(12H)、1.31(3H)。
[ chemical 45 ]
Synthesis example 3 Synthesis of Compound (D-3)
In synthetic example 1, the objective compound (D-3) (4.87 g, yield 82%) was obtained as a black cyan solid by the same method except that 3.00g (8.86 mmol) of the following formula intermediate (101) was used in place of the above-mentioned intermediate (100), 3.06g (9.80 mmol) of the following formula intermediate (Q-101) was used in place of the above-mentioned intermediate (Q-100), 4.22g (27.5 mmol) of phosphorus oxychloride was used, and the mixture was stirred at 60℃for 4 hours, 80℃for 14 hours, and 100℃for 24 hours.
[ chemical 46 ]
[ chemical formula 47 ]
The following signals of 42 hydrogens were detected by NMR measurement of the black-cyan solid obtained, and the structure of the compound represented by the following formula (D-3) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.69-7.61(1H)、7.60-7.46(4H)、7.45-7.27(3H)、7.26-7.15(1H)、7.13-6.98(3H)、6.87-6.77(2H)、4.30-3.79(2H)、3.72-3.52(8H)、2.35(3H)、1.29(3H)、1.16(12H)。
[ chemical formula 48 ]
Synthesis example 4 Synthesis of Compound (D-4)
In the same manner as in Synthesis example 2 except that 1.00g (1.49 mmol) of the above-mentioned compound (D-3) and 0.47g (1.6 mmol) of lithium bis (trifluoromethanesulfonyl) imide were used in place of the compound (D-1), the objective compound (D-4) (1.28, yield 94%) was obtained as a dark purple solid.
The following signals of 42 hydrogens were detected by NMR measurement of the dark purple solid obtained, and the structure of the compound represented by the following formula (D-4) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.69-7.61(1H)、7.60-7.46(4H)、7.45-7.37(2H)、7.36-7.26(1H)、7.25-7.15(1H)、7.13-6.98(3H)、6.87-6.77(2H)、4.30-3.79(2H)、3.72-3.52(8H)、2.35(3H)、1.29(3H)、1.16(12H)。
[ chemical formula 49 ]
Synthesis example 5 Synthesis of Compound (D-5)
In synthetic example 1, the same procedure was repeated except that 4.50g (13.3 mmol) of the above-mentioned intermediate (101) was used in place of the intermediate (100), 4.58g (13.3 mmol) of the below-mentioned intermediate (Q-102) was used in place of the intermediate (Q-100), 6.32g (41.2 mmol) of phosphorus oxychloride was used, and stirring was carried out at 70℃for 24 hours to obtain the objective compound (D-5) (4.87 g, yield 82%) as a dark red-violet solid.
[ 50 ] of the formula
The following 45 signals of hydrogen were detected by NMR measurement of the dark red-violet solid obtained, and the structure of the compound represented by the following formula (D-5) was identified.
1 H-NMR(300MHz、CDCl 3 )：δ(ppm)＝8.15(1H)、7.85-7.59(5H)、7.55-7.30(7H)、6.93-6.71(4H)、4.52-4.28(1H)、4.12-3.89(1H)、3.77-3.45(8H)、2.41(3H)、1.56-1.12(15H)。
[ chemical formula 51 ]
Synthesis example 6 Synthesis of Compound (D-6)
In the same manner as in Synthesis example 2 except that 6.00g (8.55 mmol) of the above-mentioned compound (D-5) and 2.70g (9.40 mmol) of lithium bis (trifluoromethanesulfonyl) imide were used in place of the compound (D-1), the objective compound (D-6) (7.50 g, yield 93%) was obtained as a dark red-purple solid.
The following 45 signals of hydrogen were detected by NMR measurement of the dark red-violet solid obtained, and the structure of the compound represented by the following formula (D-6) was identified.
1 H-NMR(300MHz、CDCl 3 )：δ(ppm)＝8.16(1H)、7.83-7.61(5H)、7.52-7.34(7H)、6.83-6.68(4H)、4.52-4.28(1H)、4.15-3.89(1H)、3.70-3.49(8H)、2.42(3H)、1.56-1.15(15H)。
[ chemical formula 52 ]
Synthesis example 7 Synthesis of Compound (D-7)
In synthetic example 1, the objective compound (D-7) (5.81 g, yield 101%) was obtained as a purple solid by the same method, except that 3.00g (8.86 mmol) of the above-mentioned intermediate (101) was used in place of the intermediate (100), 3.37g (9.78 mmol) of the below-mentioned intermediate (Q-103) was used in place of the intermediate (Q-100), 4.23g (27.6 mmol) of phosphorus oxychloride was used, and stirred at 100℃for 3.5 hours.
[ FORMATION 53 ]
The following 49 signals of hydrogen were detected by NMR measurement of the obtained purple solid, and the structure of the compound represented by the following formula (D-7) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.62-7.55(2H)、7.48-7.42(2H)、7.27-7.19(3H)、7.11-7.04(2H)、6.93-6.87(2H)、3.72-3.49(12H)、1.70(4H)、1.38(4H)、1.19(12H)、0.96(6H)。
[ FORMS 54 ]
Synthesis example 8 Synthesis of Compound (D-8)
In synthetic example 2, the same procedure was repeated except for using 5.50g (8.52 mmol) of the above-mentioned compound (D-7) and 2.69g (9.37 mmol) of lithium bis (trifluoromethanesulfonyl) imide instead of 2.00g (2.96 mmol) of the compound (D-1), to obtain the objective compound (D-8) (7.22 g, yield 95%) as a dark green solid.
The following 49 signals of hydrogen were detected by NMR measurement of the obtained black-green solid, and the structure of the compound represented by the following formula (D-8) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.62-7.54(2H)、7.49-7.41(2H)、7.28-7.20(3H)、7.11-7.03(2H)、6.93-6.87(2H)、3.72-3.49(12H)、1.70(4H)、1.38(4H)、1.19(12H)、0.96(6H)。
[ chemical formula 55 ]
Synthesis example 9 Synthesis of Compound (D-9)
In synthetic example 1, the objective compound (D-9) (5.04 g, yield 77%) was obtained as a black-violet solid by the same method except that 4.00g (8.65 mmol) of the following formula intermediate (102) was used in place of the intermediate (100), 2.61g (9.51 mmol) of the following formula intermediate (Q-104) was used in place of the intermediate (Q-100), 4.11g (26.8 mmol) of phosphorus oxychloride was used, and stirred under heating reflux at 105℃for 144 hours.
[ chemical formula 56 ]
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[ chemical formula 57 ]
The following signals of 51 hydrogens were detected by NMR measurement of the black-violet solid obtained, and the structure of the compound represented by the following formula (D-9) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.73-7.66(1H)、7.58-7.21(13H)、6.38-6.24(1H)、5.93-5.82(1H)、4.08-3.80(2H)、3.56-340(6H)、2.30-1.98(15H)、1.32-1.01(12H)。
[ chemical 58 ]
Synthesis example 10 Synthesis of Compound (D-10)
In the same manner as in Synthesis example 2 except that 4.00g (5.29 mmol) of the above-mentioned compound (D-9) and 1.70g (5.92 mmol) of lithium bis (trifluoromethanesulfonyl) imide were used in place of the compound (D-1), the objective compound (D-10) (4.68 g, yield 79%) was obtained as a purple solid.
The following signals of 51 hydrogens were detected by NMR measurement of the obtained purple solid, and the structure of the compound represented by the following formula (D-10) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝7.73-7.66(1H)、7.58-7.21(13H)、6.38-6.24(1H)、5.93-5.82(1H)、4.08-3.80(2H)、3.56-340(6H)、2.30-1.98(15H)、1.32-1.01(12H)。
[ chemical formula 59 ]
Synthesis example 11 Synthesis of Compound (D-11)
The following chemical reactions were carried out under a nitrogen flow. Into a 100 mL-capacity 4-necked flask equipped with a condenser, a stirrer and a thermometer, 1.63g (67.0 mmol) of magnesium powder, 1 particle of iodine and 50mL of dry Tetrahydrofuran (THF) were placed, and the mixture was stirred at room temperature for 10 minutes. 9.00g (55.2 mmol) of 2-bromothiophene was added over 15 minutes to prepare the Grignard reagent.
The following chemical reactions were carried out under a nitrogen flow. A250 mL-capacity 4-necked flask equipped with a condenser, a stirrer and a thermometer was charged with 4.00g (11.0 mmol) of the intermediate represented by the above formula (100) and 80mL of dry THF, and cooled to 0℃in a methanol/dry ice refrigerant. The Grignard reagent prepared above (total amount) was added dropwise with 5mL of dry THF over 15 minutes, and then the mixture was warmed to room temperature and stirred for 17 hours. After the reaction was stopped by adding 10mL of concentrated hydrochloric acid to the reaction mixture, 150mL of water was added and the mixture was extracted 2 times with 300mL of methylene chloride. The organic layer was washed with water and saturated brine, and then mixed, followed by drying over anhydrous sodium sulfate. The mixture was filtered under reduced pressure, the solvent of the filtrate was distilled off under reduced pressure, and then the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol=5/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 80℃overnight to give the objective compound (D-11) (4.89 g, yield 95%) as a dark green solid.
The following 29 signals of hydrogen were detected by NMR measurement of the dark green solid obtained, and the structure of the compound represented by the following formula (D-11) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝8.20-8.13(1H)、7.62-7.54(3H)、7.49-7.43(1H)、7.42-7.34(2H)、7.17-7.12(2H)、3.83-3.73(8H)、1.77-1.59(12H)。
[ chemical formula 60 ]
Synthesis example 12 Synthesis of Compound (D-12)
In the same manner as in Synthesis example 2 except that 2.00g (4.30 mmol) of the above-mentioned compound (D-11) and 1.33g (4.78 mmol) of lithium bis (trifluoromethanesulfonyl) imide were used in place of the compound (D-1), the objective compound (D-12) (2.78 g, yield 91%) was obtained as a bluish-violet solid.
The following 29 signals of hydrogen were detected by NMR measurement of the obtained bluish violet solid, and the structure of the compound represented by the following formula (D-12) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝8.20-8.13(1H)、7.62-7.54(3H)、7.48-7.43(1H)、7.42-7.34(2H)、7.17-7.12(2H)、3.83-3.73(8H)、1.79-1.58(12H)。
[ chemical formula 61 ]
Synthesis example 13 Synthesis of Compound (D-13)
The following chemical reactions were carried out under a nitrogen flow. A100 mL-capacity 4-necked flask equipped with a condenser, a stirrer and a thermometer was charged with 2.46g (11.5 mmol) of 3-bromobenzo [ b ] thiophene and 30mL of THF, and after cooling to-50℃7.20mL (11.5 mmol) of n-butyllithium (n-BuLi) (1.6M in n-hexane) was added over 5 minutes. After stirring at-50℃for 30 minutes, 3.00g (8.86 mmol) of the above intermediate (101) was dissolved in 15mL of THF and added over 5 minutes. The reaction mixture was stirred at-50℃for 1.5 hours, then warmed to room temperature over 2 hours, and stirred at room temperature for 18 hours. The reaction mixture was cooled to 0℃and 20mL of water was added thereto to stop the reaction, and 20mL of concentrated hydrochloric acid was added thereto to make the reaction mixture acidic, followed by stirring at room temperature for 30 minutes. The reaction mixture was diluted with 100mL of water, extracted 2 times with 150mL of methylene chloride, and then the organic layer was washed with water and saturated brine in this order. The organic layers were mixed, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent of the filtrate was distilled off under reduced pressure. After the residue was adsorbed onto 10g of silica gel, the residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane/methanol=5/1 (volume ratio)), and the solvent was distilled off under reduced pressure. The residue was dried under reduced pressure at 80℃overnight to give the objective compound (D-13) (0.80 g, yield 18%) as a black solid.
The following 31 signals of hydrogen were detected by NMR measurement of the black solid obtained, and the structure of the compound represented by the following formula (D-13) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝8.32-7.88(3H)、7.77-7.52(3H)、7.42-7.32(1H)、7.25-7.12(2H)、7.10-6.96(2H)、3.69(8H)、1.23(12H)。
[ chemical formula 62 ]
Synthesis example 14 Synthesis of Compound (D-14)
In synthetic example 2, the objective compound (D-14) (0.74 g, yield 76%) was obtained as a dark green solid by the same method except that 0.70g (1.4 mmol) of the above-mentioned compound (D-13) was used in place of 2.00g (2.96 mmol) of the compound (D-1) and 0.46g (1.6 mmol) of lithium bis (trifluoromethanesulfonyl) imide was used.
The following 31 signals of hydrogen were detected by NMR measurement of the dark green solid obtained, and the structure of the compound represented by the following formula (D-14) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝8.32-7.88(3H)、7.77-7.52(3H)、7.42-7.32(1H)、7.25-7.12(2H)、7.10-6.95(2H)、3.68(8H)、1.23(12H)。
[ chemical formula 63 ]
Synthesis example 15 Synthesis of Compound (D-15)
In synthetic example 1, the objective compound (D-15) (4.50 g, yield 77%) was obtained as a dark red-purple solid by the same method except that 3.50g (10.3 mmol) of the above intermediate (101) was used in place of the intermediate (100), 2.14g (10.3 mmol) of 1-methyl-2-phenylindole was used in place of the above intermediate (Q-100), and 4.92g (32.1 mmol) of phosphorus oxychloride was used and stirred at 70℃for 24 hours.
The following 38 signals of hydrogen were detected by NMR measurement of the dark red-violet solid obtained, and the structure of the compound represented by the following formula (D-15) was identified.
1 H-NMR(300MHz、CDCl 3 )：δ(ppm)＝7.67-7.30(8H)、7.27-7.18(3H)、6.90-6.54(4H)、3.92(3H)、3.81-3.42(8H)、1.57-1.17(12H)。
[ chemical 64 ]
Synthesis example 16 Synthesis of Compound (D-16)
In the same manner as in Synthesis example 2 except that 4.50g (7.98 mmol) of the above-mentioned compound (D-15) and 2.52g (8.78 mmol) of lithium bis (trifluoromethanesulfonyl) imide were used in place of the compound (D-1), the objective compound (D-16) (5.30 g, yield 82%) was obtained as a red-violet solid.
The following 38 signals of hydrogen were detected by NMR measurement of the obtained red-violet solid, and the structure of the compound represented by the following formula (D-16) was identified.
1 H-NMR(300MHz、CDCl 3 )：δ(ppm)＝7.62-7.56(1H)、7.55-7.47(2H)、7.45-7.38(1H)、7.36-7.30(4H)、7.27-7.18(3H)、6.83-6.78(2H)、6.72-6.63(2H)、3.92(3H)、3.80(8H)、1.30(12H)。
[ chemical 65 ]
Synthesis example 17 Synthesis of Compound (D-17)
In the same manner as in Synthesis example 13, except that 1.14g (10.6 mmol) of benzothiazole was used in place of 3-bromobenzo [ b ] thiophene, the title compound (D-17) (4.01 g, yield 92%) was obtained as a dark purple solid.
The following signals of 30 hydrogens were detected by NMR measurement of the black-violet solid obtained, and the structure of the compound represented by the following formula (D-17) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝8.38(1H)、8.30(1H)、7.79-7.64(2H)、7.64-7.57(2H)、7.24-7.14(2H)、7.08-7.00(2H)、3.70(8H)、1.23(12H)。
[ chemical 66 ]
Synthesis example 18 Synthesis of Compound (D-18)
In the same manner as in Synthesis example 2 except that 3.90g (7.93 mmol) of the above-mentioned compound (D-17) and 2.52g (8.78 mmol) of lithium bis (trifluoromethanesulfonyl) imide were used in place of the compound (D-1), the objective compound (D-16) (5.29 g, yield 90.6%) was obtained as a dark green solid.
The following signals of 30 hydrogens were detected by NMR measurement of the obtained black-green solid, and the structure of the compound represented by the following formula (D-18) was identified.
1 H-NMR(300MHz、DMSO-d 6 )：δ(ppm)＝8.37(1H)、8.30(1H)、7.79-7.57(4H)、7.24-7.14(2H)、7.08-7.00(2H)、3.70(8H)、1.23(12H)。
[ chemical 67 ]
Example 1
The compound (D-2) obtained in Synthesis example 2 was dissolved in Propylene Glycol Monomethyl Ether (PGME), a solution having a concentration of 0.02mmol/L was prepared, and the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) was measured at room temperature (25 ℃) using an ultraviolet-visible spectrophotometer (model: V-650, manufactured by Japanese spectroscopy Co., ltd.) to determine the maximum absorption wavelength in the measured wavelength range. The measurement results are shown in table 1. In addition, 5.0g of a 2 wt% DMF solution of the methacrylic acid-acrylic acid ester copolymer and 20mg of the above-mentioned compound (D-2) were put into a 20 mL-capacity sample bottle, stirred for 30 minutes, and mixed. The resulting colored resin solution was filtered with a needle filter, and the filtrate was applied to a glass substrate (film formation method: 1g of filtrate was dropped onto glass, and film formation was performed at 300rpm for 10 seconds using a spin coater) The film was formed by heating at 100℃for 2 minutes. The color value of the produced film was measured by using a spectrocolorimeter (model: CM-5, manufactured by Kenicamantadine Co., ltd.). Then, the mixture was heated at 230℃for 20 minutes, and the color value was measured similarly. Color difference (ΔE) of color values before and after heating at 230 DEG C ＊ ab ) Table 1 summarizes the results of the evaluation on the following 3 grades as an index of heat resistance.
“○”：ΔE ＊ ab ≤3.0
“△”：3.0＜ΔE ＊ ab ≤10.0
“×”：ΔE ＊ ab ＞10.0
Comparative examples 1 to 3
For comparison, the maximum absorption wavelength in the wavelength range of 350 to 700nm of PGME solution and the color difference (. DELTA.E) of the color values before and after heating (230 to 20 minutes) of the produced film were measured in the same manner as in example 1, except that C.I. acid red 289, C.I. acid red 52 represented by the above-mentioned formulas (B-1) and (B-2), or C.I. basic violet 10 represented by the following formula (B-3) were used as the xanthene-based pigment compound not belonging to the present invention instead of the compound (D-1) of example ＊ ab ) Evaluation was performed. The results are summarized in Table 1.
[ chemical formula 68 ]
[ Table 1 ]
As shown in table 1, the xanthene dye which is the compound of the present invention has a very large absorption wavelength on the long wavelength side in the ultraviolet-visible absorption spectrum (wavelength range of 350 to 700 nm) of the solution, compared with the conventional xanthene dye as in the comparative example. The coloring composition containing the xanthene-based coloring matter of the example has good heat resistance when forming a film, and is practically no problem as a coloring agent for color filters. The heat resistance of the coloring composition of the example at the time of film formation is equal to or higher than that of the comparative example, and is useful as a coloring agent for color filters.
Industrial applicability
The coloring composition containing the xanthene-based coloring matter according to the present invention is excellent in heat resistance, is useful as a coloring agent for color filters, and can produce color filters excellent in color characteristics (color gamut, brightness, contrast ratio, etc.).

Claims (9)

1. A xanthene-based pigment represented by the following general formula (1):
wherein R is 1 ～R 4 Each independently represents-H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R 1 and R is R 2 Or R is 3 And R is R 4 A ring may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to each other,
R 5 r is R 6 Each independently represents-H, a halogen atom, -NO 2 A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
x represents-O- -S-or-Se-,
q is a heterocyclic group represented by the following general formula (Q11),
an represents An anion, a represents An integer of 1 to 3, b represents An integer of 0 to 3,
wherein the general formula (1) is neutral in charge as a whole,
wherein R is 11 ～R 15 Each independently represents-H, a halogen atom, -OH, -CN, -OCH 3 、-NO 2 、-SO 3 - 、-SO 3 H、-SO 3 M、-CO 2 - 、-CO 2 H、-CO 2 M is a linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 21 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent, or an amino group having 0 to 21 carbon atoms which may have a substituent,
R 16 And R is 17 Each independently represents-H, a linear or branched alkyl group having 1 to 21 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 21 carbon atoms which may have a substituent,
R 11 ～R 15 、R 16 and R is R 17 The adjacent groups may be bonded to each other via a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring,
as R as described above 1 ～R 6 、R 11 ～R 17 A substituent in the case of having a substituent and a substituent in the case of having a substituent as described above for the methylene group are heavy hydrogen atoms; -OH; -CN; -CF 3 ；-NO 2 ；
-SO 3 - 、-SO 3 H、-SO 3 A sulfonic acid group represented by M;
-CO 2 - 、-CO 2 H、-CO 2 a carboxylic acid group represented by M;
a halogen atom;
a linear or branched alkyl group having 1 to 20 carbon atoms;
cycloalkyl having 3 to 20 carbon atoms;
a linear or branched alkenyl group having 2 to 20 carbon atoms;
straight-chain or branched alkoxy groups having 1 to 20 carbon atoms;
a cycloalkoxy group having 3 to 20 carbon atoms, a 1-adamantyloxy group, or a 2-adamantyloxy group;
acyl with 1-20 carbon atoms;
an aromatic hydrocarbon group having 6 to 20 carbon atoms or a condensed polycyclic aromatic group;
a heterocyclic group having 2 to 20 carbon atoms;
aryloxy group having 6 to 20 carbon atoms;
unsubstituted amino; or alternatively
The substituent is a mono-or di-substituted amino group having 1 to 20 carbon atoms and having a linear or branched alkyl group or an aromatic hydrocarbon group,
These "substituents" may be 1 or more, and in the case of a plurality, they may be the same or different from each other; in addition, these "substituents" may further have the substituents exemplified above; when the "substituent" includes a carbon atom, the carbon atom is added to the above-mentioned "carbon atom number 1 to 20" and "carbon atom number 6 to 20",
m represents an organic cation or an inorganic cation, and when a plurality of cations are present, the cations may be the same or different.
2. A xanthene-based pigment represented by the following general formula (1):
wherein R is 1 ～R 4 Each independently represents-H, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
R 1 and R is R 2 Or R is 3 And R is R 4 A ring may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to each other,
R 5 r is R 6 Each independently represents-H, a halogen atom, -NO 2 A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
x represents-O- -S-or-Se-,
q is a heterocyclic group represented by the following general formula (Q12),
an represents An anion, a represents An integer of 1 to 3, b represents An integer of 0 to 3,
Wherein the general formula (1) is neutral in charge as a whole,
wherein R is 18 ～R 21 Each independently represents-H, a halogen atom, -OH, -CN, -OCH 3 、-NO 2 、-SO 3 - 、-SO 3 H、-SO 3 M、-CO 2 - 、-CO 2 H、-CO 2 M is a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, or an amino group having 0 to 22 carbon atoms which may have a substituent,
between adjacent groups, a ring may be formed by bonding a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to each other,
R 22 represents an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent,
R 23 represents-H, a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 22 carbon atoms which may have a substituent,
as R as described above 1 ～R 6 、R 18 ～R 23 A substituent in the case of having a substituent and a substituent in the case of having a substituent as described above for the methylene group are heavy hydrogen atoms; -OH; -CN; -CF 3 ；-NO 2 ；
-SO 3 - 、-SO 3 H、-SO 3 A sulfonic acid group represented by M;
-CO 2 - 、-CO 2 H、-CO 2 a carboxylic acid group represented by M;
a halogen atom;
a linear or branched alkyl group having 1 to 20 carbon atoms;
cycloalkyl having 3 to 20 carbon atoms;
a linear or branched alkenyl group having 2 to 20 carbon atoms;
Straight-chain or branched alkoxy groups having 1 to 20 carbon atoms;
a cycloalkoxy group having 3 to 20 carbon atoms, a 1-adamantyloxy group, or a 2-adamantyloxy group;
acyl with 1-20 carbon atoms;
an aromatic hydrocarbon group having 6 to 20 carbon atoms or a condensed polycyclic aromatic group;
a heterocyclic group having 2 to 20 carbon atoms;
aryloxy group having 6 to 20 carbon atoms;
unsubstituted amino; or alternatively
The substituent is a mono-or di-substituted amino group having 1 to 20 carbon atoms and having a linear or branched alkyl group or an aromatic hydrocarbon group,
these "substituents" may be 1 or more, and in the case of a plurality, they may be the same or different from each other; in addition, these "substituents" may further have the substituents exemplified above; when the "substituent" includes a carbon atom, the carbon atom is added to the above-mentioned "carbon atom number 1 to 20" and "carbon atom number 6 to 20",
m represents an organic cation or an inorganic cation, and when a plurality of cations are present, the cations may be the same or different.
3. The xanthene-based pigment according to claim 1 or 2, wherein M in the general formula (Q11) or (Q12) is an alkali metal ion.
4. The xanthene-based pigment according to claim 1 or 2, wherein in the general formula (1), X is-O-.
5. The xanthene-based pigment according to claim 1 or 2, wherein in the general formula (1), an is Cl - 、Br - 、I - 、(CF 3 SO 2 ) 2 N - 、(CF 3 SO 2 ) 3 C - 、(CN) 2 N - 、(CN) 3 C - 、NC-S - 、(C 2 F 5 ) 3 F 3 P - 、(C 6 H 4 SO 3 - )O(C 6 H 3 (C 12 H 25 )(SO 3 - ))、C 6 H 4 (C 12 H 25 )(SO 3 - )、PF 6 - 、BF 4 - Or (PW) 12 O 40 ) 3- And b is an integer of 1 to 3.
6. The xanthene dye according to claim 1 or 2, wherein the maximum absorption wavelength is in the wavelength range of 560 to 600nm in the wavelength range of 350 to 700nm of the ultraviolet visible absorption spectrum measured at 23 to 27 ℃ using a propylene glycol monomethyl ether solution having a concentration of 0.005 to 0.02mmol/L of the xanthene dye.
7. A coloring composition comprising the xanthene-based pigment according to any one of claims 1 to 6.
8. A colorant for color filters, which contains the coloring composition according to claim 7.
9. A color filter using the colorant for color filters according to claim 8.
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