JP2020200444A - Xanthene-based pigment, coloring composition containing that pigment, color filter colorant, and color filter - Google Patents

Abstract

To provide a xanthene-based pigment excellent in heat resistance, a coloring composition containing the pigment, a color filter colorant containing the coloring composition, and a color filter.SOLUTION: The xanthene-based pigment is represented by the general formula (1) in the figure. [R1 to R9 each represent an alkyl group or the like; n represents an integer from 1 to 4; if there are multiple R9, they may form a ring together; X represents -O-, -S-, or -Se-; An represents an anion; a represents an integer from 1 to 3; and b represents an integer from 0 to 3.]SELECTED DRAWING: None

Description

The present invention relates to a xanthene dye, a coloring composition containing the dye, a coloring agent for a color filter containing the coloring composition, and a color filter using the coloring agent.

Color filters are used in liquid crystal and electroluminescence (EL) display devices and CCD and CMOS image sensors. A color filter is made by laminating a colored layer such as a dye thin film or a dye-resin composite film on a translucent substrate such as glass or a transparent resin by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. Manufactured by.
Xanthene dyes are compounds used as colorants for color filters because of their sharpness (Patent Documents 1 to 4 and the like). For example, C.I. I. Acid Red 289 and C.I. expressed by the following formula (B-2). I. By using a xanthene dye such as Acid Red 52 in combination with an azopyridone dye, an excellent red color tone can be obtained (Patent Document 1). Here, C.I. I. Means the color index.

JP-A-2002-265834 Japanese Unexamined Patent Publication No. 2012-207224 JP-A-2010-254964 Japanese Unexamined Patent Publication No. 2014-12814

"Chemical Communications" (UK), 2015, Vol. 51, p. 4414-4416, Supporting Information

In the development of current display devices, higher performance (high definition, wide color gamut, low voltage) is always required, and the performance of the color filter used (color characteristics such as high transmittance and high color purity) is met. The demand is also high. Since the color filter needs to be heated in the manufacturing process, heat resistance is required, but the heat resistance of the dye used for the color filter, for example, the xanthene dye, has not been sufficient.

The present invention has been made to solve the above problems, and provides a xanthene dye having excellent heat resistance, a coloring composition containing the dye, a colorant for a color filter containing the coloring composition, and a color filter. The purpose is to provide.

As a result of diligent studies to solve the above problems, the present inventors have found that the xanthene-based dye of the present invention has excellent heat resistance as compared with the conventional dye, and completed the present invention. That is, the gist of the present invention is as follows.

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

[In the formula, R ^{1 to} R ⁴ are independently of −H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it represents a monocyclic, polycyclic or fused ring aromatic hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, which may have a substituent.
R ¹ and R ² , or R ³ and R ⁴ are single-bonded, double-bonded, substituted or unsubstituted methylene groups, bonded to each other with or without oxygen or sulfur atoms to form a ring. You may.
R ⁵ and ^{R 6} are each independently, -H, a halogen atom, -NO _2, linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent.
R ⁷ and R ⁸ are independent of -H, respectively.
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it represents a monocyclic, polycyclic or fused ring aromatic hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, which may have a substituent.
R ⁷ and R ⁸ may be bonded to each other with or without a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom to form a ring.
R ⁹ is a halogen _{^{atom, -OH, -CN, -OCH 3,}} -OCONR 10 R 11, -NO 2, -SO 3 -, -SO 3 H, -SO 3 M, -SO 3 R 10, -SO ₂ NR ¹⁰ R ¹¹ , -CO ₂ H, -CO ₂ M, -CO ₂ R ¹⁰ , -CONR ¹⁰ R ¹¹ , -CH = CHR ¹⁰ ,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
A monocyclic, polycyclic or condensed ring aromatic hydrocarbon group or substituent which may contain a heteroatom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms which may have a substituent. Represents an amino group having 0 to 20 carbon atoms which may have.
n represents an integer of 1 to 4, and when n is 2 or more, a plurality of R ^9s may be the same or different, and may be a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or sulfur. The rings may be formed by bonding with each other with or without atoms.
R ¹⁰ and R ¹¹ are independently of −H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it represents a monocyclic, polycyclic or fused ring aromatic hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, which may have a substituent.
R ¹⁰ and R ¹¹ may be bonded to each other with or without a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom to form a ring.
X represents —O—, —S— or —Se—.
M represents an organic cation or an inorganic cation, and when a plurality of cations are present, they may be the same or different.
An represents an anion, a represents an integer of 1 to 3, and b represents an integer of 0 to 3.
However, it is assumed that the general formula (1) is charge-neutral as a whole. ]

2. 2. In the general formula (1)
R ^{1 to} R ⁴ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ may have a substituent A linear or branched alkyl group having 1 to 10 carbon atoms or a substituent. It is an aromatic hydrocarbon group having 6 to 12 carbon atoms of a monocyclic, polycyclic or condensed ring which may contain a heteroatom which may contain a heteroatom.
R ⁵ and R ⁶ are —H, —Cl, —Br or linear alkyl groups with 1 to 10 carbon atoms.
R ⁹ is _{^{-F, -Cl, -Br, -CN,}} -OCONR 10 R 11, -NO 2, -SO 3 -, be a ^-CONR 10 ^{R 11,} phenyl or _{-N (C 2} H _{5) 2} ,
A xanthene dye in which n is 1 or 2 and X is —O— or —S—.

3. 3. 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⁾ is ^3, and xanthene dyes b is an integer of 1 to 3.

4. A coloring composition containing the xanthene dye.

5. A colorant for a color filter containing the coloring composition.

6. A color filter using the colorant for a color filter.

The xanthene-based dye of the present invention and the coloring composition containing the dye have excellent heat resistance and are useful as a colorant for a color filter.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof. First, the xanthene dye represented by the general formula (1) will be described.

In the general formula (1), the "linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ^{1 to} R ¹¹ has "1 carbon atom number". Specific examples of the "~ 20 linear or branched alkyl group" include
Linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group;
Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group and 2-ethylhexyl group.

In the general formula (1), it is represented by R ^{1 to} R ⁴ and R ^{7 to} R ¹¹ , "having 2 to 20 carbon atoms which may have a substituent, preferably 6 to 20 carbon atoms. In the "aromatic hydrocarbon group of monocyclic, polycyclic or condensed ring which may contain a hetero atom", "a monocyclic or polycyclic group which may contain a hetero atom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms". The "aromatic hydrocarbon group of the ring or fused ring" includes an aryl group and a fused polycyclic aromatic group, and may simply contain a heteroatom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms. Specific examples of the "aromatic hydrocarbon group of ring, polycyclic or condensed ring" include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), phenanthryl group, fluorenyl group, indenyl group and pyrenyl. Examples include aromatic hydrocarbon groups such as groups, perylenyl groups, fluoranthenyl groups and triphenylenyl groups.

In the general formula (1), represented by R ^9, "the optionally carbon atoms which may from 1 to 20 substituted linear or branched alkyl group,""having 1 to 20 carbon atoms in the Specifically, as a "linear or branched alkyl group",
Linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group;
Examples thereof include branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, isooctyl group and 2-ethylhexyl group.
In the general formula (1), represented by R ^9, "good C2-20 have a substituent, preferably an optionally contain a heteroatom having 6 to 20 carbon atoms monocyclic, Monocyclic, polycyclic or condensed ring aromatic hydrocarbons that may contain heteroatoms having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms in the "polycyclic or condensed ring aromatic hydrocarbon group". As a "base", specifically
Aromatic hydrocarbons such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetrasenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, peryleneyl group, fluoranthenyl group, triphenylenyl group Examples include groups (including aryl groups and fused polycyclic aromatic groups).
In the general formula (1), the "amino group having 0 to 20 carbon atoms" in the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by R ⁹ is specifically defined. ,
Amino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di (2-ethylhexyl) group, di-t-butylamino group, diphenylamino Examples include a group, an ethylphenylamino group, and the like.

In the general formula (1), examples of the "halogen atom" represented by R ⁵ , R ⁶ and R ⁹ include fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I). F, Cl or Br is preferable, and Cl or Br is more preferable.

In the general formula (1), "a linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" represented by R ^{1 to} R ¹¹ or R ^{1 to} R ⁴ and R ^{7 to} R ¹¹ "Aromatic hydrocarbon group of monocyclic, polycyclic or condensed ring having a substituent having 2 to 20 carbon atoms, preferably containing a heteroatom having 6 to 20 carbon atoms", R ⁹ Specifically, the "substituent" in the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by
Deuterium atom, -OH, -CN, -CF ₃ , -NO ₂ ;
_{-SO 3} ^-, -SO ₃ H, sulfonate group represented by -SO ₃ M or _-CO ^2, _-, a carboxylic acid group represented by -CO ₂ H, -CO 2 M;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom;
A linear or branched alkyl group having 1 to 20 carbon atoms;
Cycloalkyl group with 3 to 20 carbon atoms;
A linear or branched alkenyl group having 2 to 20 carbon atoms;
A linear or branched alkoxy group having 1 to 20 carbon atoms;
Cycloalkoxy group or 1-adamantyloxy group, 2-adamantyloxy group having 3 to 20 carbon atoms;
Acyl group with 1 to 20 carbon atoms;
Aromatic hydrocarbon groups or condensed polycyclic aromatic groups with 6 to 20 carbon atoms;
Heterocyclic group with 2 to 20 carbon atoms;
Aryloxy group with 6 to 20 carbon atoms;
Unsubstituted amino groups; mono- or di-substituted amino groups having 1 to 20 carbon atoms, and the like can be mentioned. Only one of these "substituents" may be contained, a plurality of these "substituents" may be contained, and when a plurality of these "substituents" are contained, they may be the same or different from each other. In addition, these "substituents" may further have the above-exemplified substituents. When the "substituent" contains a carbon atom, the carbon atom is the above-mentioned "carbon atom number 1 to 20", "carbon atom number 2 to 20", "carbon atom number 6 to 20", and "carbon atom number". It is included in "several 0 to 20". Further, 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 an "organic cation" or an "inorganic cation" represented by "M" is present, the "organic cation" is specifically R ¹² R ¹³ R ¹⁴ R ¹⁵ N ⁺ . ammonium ion represented can be mentioned, R ¹² to R ¹⁵ are each independently, -H, a linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent or, Represents a monocyclic, polycyclic or condensed ring aromatic hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms, preferably 6 to 20 carbon atoms, which may have a substituent. Rings may be formed by bonding with or without a bonded, double-bonded, substituted or unsubstituted methylene group, oxygen atom or sulfur atom. In the formula, "substituents" in R ^{12 to} R ¹⁵ , "linear or branched alkyl groups having 1 to 20 carbon atoms" and "2 to 20 carbon atoms, preferably 6 carbon atoms". The details of the monocyclic, polycyclic or fused ring aromatic hydrocarbon group which may contain ~ 20 heteroatoms are the same as those of R ^{1 to} R ¹¹ in the general formula (1). Further, examples of the "inorganic cation" include alkali metal ions such as lithium ion and sodium ion, and alkaline earth metal ions such as magnesium ion, calcium ion and barium ion. As M, alkali metal ions are preferable.

In addition, in the above-mentioned various "groups" having "substituents" represented by R ^{1 to} R ¹¹ in the general formula (1), they are listed as "substituents".
"Linear or branched alkyl group having 1 to 20 carbon atoms",
"Cycloalkyl group with 3 to 20 carbon atoms",
"Linear or branched alkenyl group having 2 to 20 carbon atoms",
"Linear 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 groups with 6 to 20 carbon atoms or condensed polycyclic aromatic groups",
"Heterocyclic groups with 2 to 20 carbon atoms",
Specifically, the "aryloxy group having 6 to 20 carbon atoms" or the "mono- or di-substituted amino group having 1 to 20 carbon atoms" is specifically defined.
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, Linear or branched alkyl groups such as heptyl group, octyl group, isooctyl group, nonyl group, decyl group;
Cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group;
An alkenyl group such as a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group, an isobutenyl group, or a linear chain in which a plurality of these are bonded. Shaped or branched alkenyl groups;
Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, isopropoxy group, isobutoxy group, s-butoxy group, t-butoxy group , Linear or branched alkoxy groups such as isooctyloxy groups;
Cycloalkoxy groups having 3 to 20 carbon atoms such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cyclononyloxy group, cyclodecyloxy group;
Acyl groups such as formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group;
Aromatic hydrocarbons such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group (anthryl group), tetrasenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, peryleneyl group, fluoranthenyl group, triphenylenyl group Group or fused polycyclic aromatic group;
Thienyl group, frill group (furanyl group), pyrrolyl group, thiazolyl group, oxazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, benzothienyl group, benzofuranyl group, indolyl group, isoindryl group, benzothiazolyl group, benzoxazolyl group, Benomidazolyl group, benzotriazolyl group, prynyl group, carbazolyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidirinyl group, triazinyl group, quinolyl group, isoquinolyl group, naphthyldinyl group, acridinyl group, phenanthrolinyl group , Heterocyclic groups such as naphthyldinyl group, carbolinyl group;
Aryloxy groups such as phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group, phenanthrenyloxy group;
Linear or linear such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, dibutylamino group, di (2-ethylhexyl) group, di-t-butylamino group, diphenylamino group Examples thereof include a branched alkyl group and a mono- or di-substituted amino group having an aromatic hydrocarbon group.

In the general formula (1), R ¹ and R ² , R ³ and R ⁴ , R ⁷ and R ⁸ , and R ¹⁰ and R ¹¹ are single-bonded, double-bonded, substituted or unsubstituted methylene groups, oxygen atoms or Rings may be formed by bonding with each other with or without a sulfur atom, and these rings are preferably a 5-membered ring or a 6-membered ring, and more preferably a 6-membered ring.

In the general formula (1), X represents an oxygen atom (—O—), a sulfur atom (—S—) or a selenium atom (—Se—), preferably —O— or —S—, where —O— More preferred.

In the general formula (1), "a" represents the number of portions of the compound (xanthene 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 general formula (1), when the molecule of the following formula (1-C) is a cation having a total charge of 1 valence or more in the whole molecule, that is, when b is an integer of 1 to 3, the counterion is ". It can be used by forming a complex with any anion represented by "An". However, in the compound represented by the general formula (1), a and b are selected so as to be charge-neutral as a whole. a represents an integer of 1 to 3, and 1 or 2 is preferable. b represents an integer of 0 to 3, and an integer of 1 to 3 is preferable.

[In the formula, R ^{1 to} R ⁹ , n and X are the same as the definitions in the 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. In particular,
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-,
_{CH 3 (CH 2) 11 OSO} 3 - alkyl sulfate ion such as,
_{CH 3 (CH 2) 15 SO} 3 - alkane sulfonate ion such as,
_{CF 3 (CF 2) 7 SO} 3 - perfluoroalkane sulfonate ion such as,
Alternatively, anions represented by the structural formulas (J-1) to (J-13) below can be mentioned.

In the general formula (1), R ^{1 to} R ⁴ include −H,
It may contain a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a heteroatom having 6 to 12 carbon atoms which may have a substituent. Aromatic hydrocarbon groups of rings, polycycles or fused rings are preferred.

In the general formula (1), R ⁵ and R ⁶ are preferably —H, —Cl, —Br or a linear alkyl group having 1 to 10 carbon atoms.

In the general formula (1), R ⁷ and R ⁸ have —H, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. A monocyclic, polycyclic or fused ring aromatic hydrocarbon group which may contain a heteroatom having 6 to 12 carbon atoms is preferable.

In the general formula ^(1), R 9 ^{is, -F, -Cl, -Br, -CN} , -OCONR 10 R 11, -NO 2, -SO 3 -, -CONR 10 R 11, phenyl group or -N ( C ₂ H ₅ ) ₂ is preferable. Further, n represents the number of R ⁹ and represents an integer of 1 to 4, but n is preferably 1 or 2.

The xanthene dye represented by the general formula (1) can be synthesized, for example, as follows. A phthalic anhydride derivative having a corresponding substituent, such as 4-carboxyphthalic anhydride, and an aminophenol derivative having a corresponding substituent, such as N, N-dibutyl-3-aminophenol, are mixed with toluene and A condensation reaction is carried out in a solution such as methanesulfonic acid under appropriate heating conditions to obtain an intermediate represented by the following general formula (X-1) (for example, Non-Patent Document 1). Next, the following general formula (X-1) and amine derivatives having corresponding substituents such as N, N-dipropylamine were added to 1- [bis (dimethylamino) methylene] -1H-1,2, By using a condensing agent such as 3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate (HATU), an intermediate represented by the following general formula (X-2) can be obtained. Further, the following general formula (X-2) and a compound having an anion corresponding to An described in the present specification (for example, bis (trifluoromethanesulfonyl) imide lithium (Li ⁺ (CF ₃ SO ₂ ) ₂ N ⁻ , or LiNTf) A product containing the compound represented by the general formula (1) can be obtained by stirring and exchanging the counter in a solution such as ₂ )) and methanol. In the following general formulas (X-1) and (X-2), R ^{1 to} R ⁹ have the same definition as the definition of the general formula (1).

Specific examples of compounds preferable 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-22), but are not limited to these compounds. The cation portion represented by the general formula (1-C) is shown, and the anion portion represented by An is omitted. In the following structural formula, some hydrogen atoms are omitted, and even if a stereoisomer is present, the planar structural formula is described.

The xanthene dye of the present invention may be used alone or in combination of two or more having different molecular structures (for example, mixed). When the two or more kinds are used, the weight concentration ratio of one kind of xanthene dye having the smallest weight concentration ratio in the whole xanthene dye is 0.1 to 50% by weight. The type of xanthene dye is preferably one or two.

Examples of the method for purifying the product during the synthesis of the compound of the present invention include purification by column chromatography; adsorption purification with silica gel, activated carbon, activated clay, etc.; known methods such as recrystallization and crystallization with a solvent. Be done. If necessary, for identification and analysis of these compounds, nuclear magnetic resonance analysis (NMR), absorbance measurement by a spectrophotometer, ultraviolet-visible absorption spectrum (UV-Vis) measurement, thermogravimetric analysis-differential thermal analysis ( TG-DTA) and the like can be performed. In addition, these methods can also be used for the solubility, color evaluation and heat resistance evaluation of the obtained compound.

A coating film can be prepared by mixing the compound of the present invention with various resin solutions and applying the compound on a glass substrate. The color of the obtained coating film can be evaluated by measuring the color using a spectrophotometer and obtaining the color value of the coating film. As the color value, CIE L ^* a ^* b ^* color system or the like is generally used. Specifically, the color values L ^* , a ^* , and b ^* of the film sample are measured, and the heat resistance can be determined from the color difference (ΔE ^* _ab ) of the color values before and after heating at an appropriate temperature. When applied to a color filter, the color difference at a temperature of around 230 ° C. can be used as an index of heat resistance. The smaller the value of the color difference ΔE ^* _ab , the less the color discoloration due to thermal decomposition, and the color difference is preferably 10 or less, more preferably 3 or less.

The xanthene dye of the present invention, a coloring composition containing the dye, and a colorant for a color filter containing the coloring composition are an organic solvent containing a resin or the like in the manufacturing process of the colorant for a color filter and the color filter. It is preferable that the solubility and dispersibility in an organic solvent are high because it is necessary to dissolve or disperse the mixture well. The organic solvent is not particularly limited, but specifically, esters such as ethyl acetate and -n-butyl acetate; diethyl ether, propylene glycol monomethyl ether (PGME), ethylene glycol monoethyl ether (ethyl cellosolve) and the like. Ethers; 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) and the like; benzene, toluene, xylene Aromatic hydrocarbons such as: N, N-dimethylformamide (DMF), amides such as N-methylpyrrolidone (NMP); dimethylsulfoxide (DMSO); chloroform (trichloromethane), and the like. These solvents may be used alone or in combination of two or more.

The xanthene dye represented by the general formula (1) is a visible light region (for example, an ultraviolet-visible absorption spectrum) of an ultraviolet-visible absorption spectrum measured at around room temperature (for example, 23 to 27 ° C.) using a solution prepared by dissolving it in an organic solvent. The maximum absorption wavelength is observed, which shows the maximum absorbance in the wavelength range of 350 to 700 nm. In the present invention, the maximum absorption wavelength is preferably in the range of 530 nm to 610 nm, and more preferably in the range of 530 nm to 580 nm. The dye concentration is preferably 0.005 to 0.02 mmol / L. The solvent is not limited as long as it dissolves the dye, but it is preferable that the absorption wavelength of the ultraviolet-visible absorption spectrum does not shift significantly depending on the dissolution conditions, and propylene glycol monomethyl ether (PGME) is preferable.

The colorant for a color filter of the present invention contains a coloring composition containing at least one xanthene-based dye represented by the general formula (1), and a component generally used for producing a color filter. For a general color filter, for example, in the case of a method using a photolithography process, a liquid prepared by mixing a dye such as a dye or a pigment with a resin component (including a monomer or an oligomer) or a solvent is prepared by mixing a liquid such as glass or resin. It is obtained by applying it on the substrate of No. 1 and photopolymerizing it using a photomask to prepare a coloring pattern of a dye-resin composite film soluble / insoluble in a solvent, washing it, and then heating it. Also in the electrodeposition method and the printing method, a coloring pattern is produced by using a dye mixed with a resin or other components. Therefore, specific components in the colorant for color filters of the present invention include at least one xanthene-based dye represented by the general formula (1), other dyes and pigments such as pigments, resin components, organic solvents, and the like. And other additives such as photopolymerization initiators. Moreover, you may select from these components, and you may add other components as needed.

When the coloring composition containing the xanthene dye of the present invention is used as a colorant for a color filter, it may be used for each color filter, but it is preferably used as a colorant for a red color filter.

The colorant for a color filter containing a xanthene dye of the present invention may use one or more xanthene dyes alone, and other dyes or pigments are known for adjusting the color tone. Dyes may be mixed. When used as a colorant for a red color filter, it is not particularly limited, but C.I. I. Pigment Red 177, 209, 242, 254, 255, 264, 269, C.I. I. Pigment Orange 38, 43, 71 and other red pigments; other red lake pigments; C.I. I. Pigment Yellow 138, 139, 150 and other yellow pigments; I. Acid Red 88, C.I. I. Examples include red dyes such as Basic Violet 10. When used as a colorant for a blue color filter, it is not particularly limited, but C.I. I. Basic dyes such as Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129; C.I. I. Acid dyes such as Acid Blue 9, 74; Dispersion dyes such as Disperse Blue 3, 7, 377; Spiron dyes; Cyanine, Indigo, Phthalocyanine, Anthraquinone, Metin, Triarylmethane, Indanthrone , Oxazine-based, dioxazine-based, azo-based, xanthene-based dyes not belonging to the present invention; other blue-based lake pigments, and other blue-based dyes or pigments.

The mixing ratio of other dyes in the colorant for color filters containing the xanthene dye of the present invention is 5 to 2000 parts by weight based on 100 parts by weight of the xanthene dye (the total of two or more kinds). It is preferably present, and more preferably 10 to 1000 parts by weight. The mixing ratio of the dye component such as the dye in the liquid colorant for the color filter is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the entire colorant.

As the resin component in the colorant for a color filter of the present invention, a known one may be used as long as it has the properties required for the production method and use of the color filter resin film formed by using them. it can. For example, acrylic resin, olefin resin, styrene resin, polyimide resin, urethane resin, polyester resin, epoxy resin, vinyl ether resin, phenol (Novolak) resin, polycarbonate resin, cellulose resin and other transparent resins, photocurable resin, thermocurable Examples thereof include resins, thermoplastic resins, and composites of these resins, and these monomers or oligomer components can be appropriately combined and used. Further, copolymers of these resins can be used in combination. In the case of a liquid colorant, the content of the resin in these colorants for color filters is preferably 5 to 95% by weight, more preferably 10 to 50% by weight.

In order to enhance the performance as a colorant for color filters, the coloring composition of the present invention contains, as other components of the compound, surfactants, dispersants, defoamers, leveling agents, and other colorants for color filters. Organic compounds such as additives to be mixed at the time of production can be added. However, the content of these additives in the coloring composition is preferably an appropriate amount, and the solubility of the coloring composition of the present invention in a solvent may be lowered or improved more than necessary, or a color filter may be used. The content is preferably in a range that does not affect the effects of other additives of the same type used during production. These additives can be added at any time 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 resins such as photopolymerization initiators and cross-linking agents, and components in liquid color filters for color filters. Examples include surfactants and dispersants necessary for stabilizing the properties of. Any of these can be known for producing a color filter, and is not particularly limited. The mixing ratio of the total amount of these additives in the total solid content of the colorant for the color filter is preferably 5 to 60% by weight, more preferably 10 to 40% by weight.

Hereinafter, embodiments of the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The following synthesis example shows the results of compound identification performed by ¹ H-NMR analysis (Nuclear magnetic resonance apparatus manufactured by Bruker, 300 MHz).

[Synthesis Example 1] Synthesis of compound (D-1) The following reaction was carried out under a nitrogen stream. 28.8 g (150.0 mmol) of trimellitic acid anhydride, 80.4 g (360.0 mmol) of N, N-dibutyl-3-aminophenol in a 1 L 4-necked flask equipped with a condenser, agitator, and thermometer. , 375 mL of methanesulfonic acid and 150 mL of toluene were added, and the mixture was stirred at 110 ° C. for 64 hours. After allowing the reaction mixture to cool to room temperature (23 to 27 ° C.), it was poured into 4.2 L of ice water and stirred at room temperature for 30 minutes. The mixture was filtered under reduced pressure, and the filtered solid was dissolved in 500 mL of methanol and added dropwise to 5 L of a 1N aqueous hydrochloric acid solution. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain the following intermediate (100) (64.5 g, yield 62%).

Subsequently, the following reaction was carried out under a nitrogen stream. 5.7 g (9.0 mmol) of the intermediate (100), 2.6 g (36.0 mmol) of diethylamine, 8.9 g (23.4 mmol) of HATU in a 300 mL four-necked flask equipped with a cooling tube, agitator, and a thermometer. ), 1.9 g (18.9 mmol) of triethylamine and 90 mL of DMF were added, and the mixture was stirred at 90 ° C. for 4 hours. The reaction mixture was allowed to cool to room temperature (23-27 ° C.) and then poured into 600 ml of a 1N aqueous hydrochloric acid solution. The precipitated solid was filtered under reduced pressure, filtered off, added to 100 mL of water, stirred at room temperature for 30 minutes, and then the mixture was filtered under reduced pressure. The following intermediate (101) was obtained as a solid by filtration.

Subsequently, the following reaction was carried out under a nitrogen stream. 7.7 g (9.0 mmol) of intermediate (101), 5.2 g (18.0 mmol) of lithium bistrifluoromethanesulfonylimide, and 67 mL of methanol are placed in a 300 mL four-necked flask equipped with a cooling tube, agitator, and thermometer. After the addition, the mixture was stirred at 60 ° C. for 30 minutes. Then, after adding 100 mL of water, the mixture was stirred at 70 ° C. for 30 minutes. The reaction mixture was allowed to cool to room temperature (23 to 27 ° C.) and then allowed to stand to remove the supernatant. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain compound (D-1) (6.5 g, yield 73%) as a dark red solid.

The obtained dark red solid was subjected to NMR measurement, and the following 65 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (D-1).

^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.70-7.50 (2H), 7.50-7.30 (3H), 6.95 (2H), 6.76 (2H) ), 3.70-3.40 (12H), 3.30-3.10 (4H), 1.70 (8H), 1.44 (8H), 1.40-1.10 (9H), 1 0.01 (12H), 0.66 (3H).

[Synthesis Example 2] Synthesis of compound (D-2) The following reaction was carried out under a nitrogen stream. 9.1 g (50.0 mmol) of 3-chlorophthalic anhydride and 22.3 g (360.0 mmol) of N, N-dibutyl-3-aminophenol in a 300 mL four-necked flask equipped with a condenser, agitator, and thermometer. ), 80 mL of methanesulfonic acid and 50 mL of toluene were added, and the mixture was stirred at 110 ° C. for 54 hours. After allowing the reaction mixture to cool to room temperature (23 to 27 ° C.), it was poured into 1 L of ice water and stirred at room temperature for 30 minutes. The mixture was filtered under reduced pressure, and the filtered solid was dissolved in 100 mL of methanol and added dropwise to 1 L of a 1N aqueous hydrochloric acid solution. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain the following intermediate (102) (22.4 g, yield 65%).

Subsequently, the following reaction was carried out under a nitrogen stream. 6.2 g (9.0 mmol) of the intermediate (102), 2.6 g (36.0 mmol) of diethylamine, 4.4 g (11.7 mmol) of HATU in a 300 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer. ), 1.0 g (9.9 mmol) of triethylamine and 67 mL of DMF were added, and the mixture was stirred at 90 ° C. for 4 hours. The reaction mixture was allowed to cool to room temperature (23-27 ° C.) and then poured into 500 mL of a 1N aqueous hydrochloric acid solution. The precipitated solid was filtered under reduced pressure, filtered off, added to 100 mL of water, stirred at room temperature for 30 minutes, and then the mixture was filtered under reduced pressure. The following intermediate (103) was obtained as a solid by filtration.

Subsequently, the following reaction was carried out under a nitrogen stream. In a 300 mL four-necked flask equipped with a condenser, agitator, and a thermometer, 6.7 g (9.0 mmol) of intermediate (103), 5.2 g (18.0 mmol) of lithium bistrifluoromethanesulfonylimide, and 67 mL of methanol were placed. After the addition, the mixture was stirred at 60 ° C. for 30 minutes. Then, after adding 100 mL of water, the mixture was stirred at 70 ° C. for 30 minutes. The reaction mixture was allowed to cool to room temperature (23 to 27 ° C.) and then allowed to stand to remove the supernatant. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain compound (D-2) (7.2 g, yield 86%) as a dark red solid.

The obtained dark red solid was subjected to NMR measurement, and the following 55 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (D-2).

^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.68 (1H), 7.60 (1H), 7.30-7.20 (3H), 7.00-6.70 (4H) ), 3.70-2.70 (12H), 1.80-1.30 (16H), 1.00 (15H), 0.67 (3H).

［合成実施例３］ 化合物（Ｄ−３）の合成

[Synthesis Example 3] Synthesis of compound (D-3)

The following reaction was carried out under a nitrogen stream. 5.7 g (9.0 mmol) of the intermediate (100), 3.6 g (36.0 mmol) of dipropylamine, and 8.9 g (23) of HATU in a 300 mL four-necked flask equipped with a cooling tube, agitator, and a thermometer. .4 mmol), 1.9 g (18.9 mmol) of triethylamine, and 90 mL of DMF were added, and the mixture was stirred at 90 ° C. for 16 hours. The reaction mixture was allowed to cool to room temperature (23-27 ° C.) and then poured into 600 ml of a 1N aqueous hydrochloric acid solution. The precipitated solid was filtered under reduced pressure, filtered off, added to 100 mL of water, stirred at room temperature for 30 minutes, and then the mixture was filtered under reduced pressure. The following intermediate (105) was obtained as a solid by filtration.

Subsequently, the following reaction was carried out under a nitrogen stream. 8.2 g (9.0 mmol) of intermediate (105), 13.6 g (3.1 mmol) of phosphotungstic acid / n-hydrate, methanol in a 1 L 4-necked flask equipped with a cooling tube, agitator, and thermometer. After adding 108 mL, the mixture was stirred at 60 ° C. for 30 minutes. Then, after adding 400 mL of water, the solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain compound (D-3) (14.0 g, yield 98%) as a dark red solid. ..

The obtained dark red solid was subjected to NMR measurement, and the following 73 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (D-3).

^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.70-7.58 (2H), 7.50 (1H), 7.25-7.05 (4H), 6.97 (2H) ), 3.70-3.50 (8H), 3.30-2.70 (7H), 1.70-1.30 (22H), 1.00-0.65 (24H), 0.41 ( 3H).

[Synthesis Example 4] Synthesis of compound (D-4) The following reaction was carried out under a nitrogen stream. 14.4 g (75.0 mmol) of trimellitic anhydride and 34.8 g (180.0 mmol) of N, N-dipropyl-3-aminophenol in a 300 mL four-necked flask equipped with a condenser, agitator, and thermometer. , 187 mL of methanesulfonic acid and 75 mL of toluene were added, and the mixture was stirred at 110 ° C. for 120 hours. The reaction mixture was allowed to cool to room temperature (23 to 27 ° C.), poured into 2.1 L of a 10% aqueous sodium chloride solution, and stirred at room temperature for 30 minutes. The mixture was filtered under reduced pressure, the filtered solid was dissolved in 500 mL of dichloromethane, and 1 L of ethyl acetate was added. The mixture was heated to 70 ° C. and concentrated to 500 mL. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain the following intermediate (106) (24.7 g, yield 52%).

The following reaction was carried out under a nitrogen stream. 6.4 g (10.0 mmol) of the intermediate (106), 6.5 g (80.0 mmol) of dimethylamine hydrochloride, and 9.9 g of HATU in a 500 mL four-necked flask equipped with a cooling tube, agitator, and a thermometer. 26.0 mmol), 4.2 g (41.0 mmol) of triethylamine, and 200 mL of DMF were added, and the mixture was stirred at room temperature (23 to 27 ° C.) for 2 hours. The reaction mixture was allowed to cool to room temperature and then poured into 400 ml of a 1N aqueous hydrochloric acid solution. The precipitated solid was filtered under reduced pressure, the filtered solid was dissolved in 100 mL of methanol, and 300 mL of water was added. After stirring at room temperature for 30 minutes, the mixture was filtered under reduced pressure. The following intermediate (107) was obtained as a solid by filtration.

Subsequently, the following reaction was carried out under a nitrogen stream. 7.4 g (10.0 mmol) of intermediate (107), 5.7 g (26.0 mmol) of lithium bistrifluoromethanesulfonylimide, and 75 mL of methanol are placed in a 300 mL four-necked flask equipped with a cooling tube, agitator, and thermometer. After the addition, the mixture was stirred at 60 ° C. for 30 minutes. Then, after adding 400 mL of water, the mixture was stirred at 60 ° C. for 30 minutes. The mixture was allowed to cool to room temperature (23-27 ° C.) and then allowed to stand to remove the supernatant. After adding 200 mL of water to the mixture, the mixture was stirred at room temperature for 30 minutes. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain compound (D-4) (7.7 g, yield 88%) as a dark red solid.

The obtained dark red solid was subjected to NMR measurement, and the following 49 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (D-4).

^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.72 (1H), 7.60 (1H), 7.39 (1H), 7.35-7.25 (2H), 7. 00-6.90 (2H), 6.75 (2H), 3.70-3.40 (8H), 3.17 (3H), 3.11 (3H), 2.97 (3H), 2. 79 (3H), 1.80-1.70 (8H), 1.10-1.00 (12H).

[Synthesis Example 5] Synthesis of compound (D-5) The following reaction was carried out under a nitrogen stream. 1.9 g (10.0 mmol) of trimellitic anhydride and 5.3 g (24.0 mmol) of N, N-diisobutyl-3-aminophenol in a 300 mL four-necked flask equipped with a condenser, agitator, and thermometer. , 3.8 g of para-toluenesulfonic acid and 20 mL of toluene were added, and the mixture was stirred at 80 ° C. for 16 hours. The reaction mixture was allowed to cool to room temperature (23-27 ° C.), poured into 150 mL of a 10% aqueous sodium chloride solution, and stirred at 70 ° C. for 30 minutes. After allowing the mixture to cool to room temperature, the pH was adjusted to 4 with a 1 M aqueous hydrochloric acid solution, and the solid obtained by vacuum filtration was dried under reduced pressure at 80 ° C. overnight to obtain the following intermediate (108) (6.4 g, yield). A rate of 83%) was obtained.

The following reaction was carried out under a nitrogen stream. 5.7 g (9.0 mmol) of the intermediate (108), 5.8 g (36.0 mmol) of 1,1'-carbonyldiimidazole, in a 500 mL four-necked flask equipped with a condenser, agitator and a thermometer. After adding 135 mL of dichloromethane, the mixture was stirred at room temperature for 4 hours. After adding 7.3 g (90.0 mmol) of dimethylamine hydrochloride and 9.1 g (90.0 mmol) of triethylamine to the reaction mixture, the mixture was stirred at room temperature (23 to 27 ° C.) for 2 hours. The reaction mixture was washed 3 times with 100 mL of 1N aqueous hydrochloric acid solution, 2.4 g (27.0 mmol) of sodium disianamide and 100 ml of water were added, and the mixture was stirred at room temperature for 1 hour. The organic layer was extracted, 400 ml of heptane was added, and the mixture was stirred for 30 minutes, and then the supernatant was removed. 50 ml of dichloromethane was added to the remaining solid to dissolve it, and the solid obtained by filtration under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain compound (D-5) (4.2 g, yield 65%) as a dark red solid. ..

The obtained dark red solid was subjected to NMR measurement, and the following 57 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (D-5).

^{1 1} H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.73 (1H), 7.64 (1H), 7.42 (1H), 7.36-7.27 (2H), 7. 03-6.95 (2H), 6.80-6.75 (2H), 3.55-3.30 (8H), 3.20-3.00 (9H), 2.80 (3H), 2 .17 (4H), 1.00 (24H).

[Synthesis Example 6] Synthesis of compound (D-6) The following reaction was carried out under a nitrogen stream. 2.50 g (13.0 mmol) of trimellitic acid anhydride, N-isobutyl-N- (2,2,2-trifluoroethyl)-in a 100 mL four-necked flask equipped with a cooling tube, agitator, and thermometer. After adding 7.12 g (28.8 mmol) of 3-aminophenol, 9.92 g (52.2 mmol) of p-toluenesulfonic acid monohydrate, and 50 mL of toluene, the mixture was stirred at 110 ° C. for 87 hours. The reaction mixture was allowed to cool to room temperature (23 to 27 ° C.), allowed to stand, and then the supernatant was removed. The residue was dried under reduced pressure, dissolved in 30 mL of methanol, and added dropwise to 120 mL of a 1N aqueous hydrochloric acid solution. The solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to obtain the following intermediate (109) (6.92 g, yield 77%).

Subsequently, the following reaction was carried out under a nitrogen stream. 5.50 g (8.00 mmol) of the intermediate (109) and 50 mL of tetrahydrofuran are placed in a 100 mL four-necked flask equipped with a cooling tube, a stirrer, and a thermometer, and then oxalyl chloride at 15 to 30 ° C. under water cooling. 6.15 g (48.4 mmol) was added dropwise. The reaction mixture was stirred at room temperature (23 to 27 ° C.) for 1 hour, the solvent was evaporated under reduced pressure, and the mixture was dissolved in 50 mL of chloroform. To the reaction solution, 12.83 g (96.32 mmol) of bis (2-methoxyethyl) amine and 16.20 g (160.1 mmol) of triethylamine were added to the reaction solution under water cooling at 15 to 30 ° C., and then at room temperature (23 to 27 ° C.). Was stirred for 2.5 hours. Water (100 mL) was added to the reaction mixture, and the mixture was extracted with 200 mL of chloroform. The organic layer was washed successively with 100 mL of water, 100 ml of 2N aqueous hydrochloric acid solution and 100 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered under reduced pressure, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (carrier: silica gel, solvent: dichloromethane / methanol = 40/1 to 10/1), dried under reduced pressure overnight at room temperature, and the following intermediate (110) (6.82 g, 97%). Got

Subsequently, the following reaction was carried out under a nitrogen stream. 5.50 g (6.24 mmol) of intermediate (110), 2.20 g (7.66 mmol) of lithium bistrifluoromethanesulfonylimide, and 50 mL of methanol in a 100 mL four-necked flask equipped with a condenser, agitator, and thermometer. After the addition, the mixture was stirred at room temperature (23 to 27 ° C.) for 3 hours. The solvent of the reaction mixture was evaporated under reduced pressure, 200 mL of water was added, and the mixture was stirred at room temperature (23 to 27 ° C.) for 30 minutes. The reaction mixture was allowed to stand, the supernatant was removed, and the residue was dried under reduced pressure at 80 ° C. overnight to give compound (D-6) (6.76 g, 73% yield) as a dark red solid.

The obtained dark red solid was subjected to NMR measurement, and the following 59 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (D-6).

^{1 1} H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.79-7.55 (3H), 7.53-7.30 (6H), 4.98-4.65 (4H) 3.79-3.38 (16H), 3.31-3.08 (11H), 2.83 (3H), 2.68 (2H), 2.16 (2H), 0.93 (12H) ..

[Synthetic Comparative Example 1] Synthesis of Comparative Example Compound (E-1) The following reaction was carried out under a nitrogen stream. 8.9 g (20.0 mmol) of rodamine B, 4.0 g (40.0 mmol) of dipropylamine, 9.9 g (26.0 mmol) of HATU, triethylamine in a 300 mL four-necked flask equipped with a cooling tube, agitator, and a thermometer. After adding 4.0 g (40.0 mmol) and 60 mL of dichloromethane, the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure and 100 mL of acetonitrile was added. Impurities were removed by filtration under reduced pressure. The filtrate was concentrated under reduced pressure, 150 mL of ethyl acetate was added, and the mixture was stirred at room temperature for 30 minutes. After adding 100 mL of heptane to the mixture, the mixture was filtered under reduced pressure. The following intermediate (104) was obtained as a solid by filtration.

Subsequently, the following reaction was carried out under a nitrogen stream. 0.8 g (1.2 mmol) of intermediate (104), 1.0 g (3.6 mmol) of lithium bistrifluoromethanesulfonylimide, and 15 mL of methanol are placed in a 100 mL four-necked flask equipped with a cooling tube, agitator, and thermometer. After the addition, the mixture was stirred at 60 ° C. for 30 minutes. Then, after adding 15 mL of water, the mixture was stirred at 70 ° C. for 30 minutes. After allowing the reaction mixture to cool to room temperature (23 to 27 ° C.), the solid obtained by filtering the mixture under reduced pressure was dried under reduced pressure at 80 ° C. overnight to compound (E-1) (0.8 g, yield 83%). Was obtained as a dark red solid.

The obtained dark red solid was subjected to NMR measurement, and the following 44 hydrogen signals were detected and identified as the structure of the compound represented by the following formula (E-1).

^{1 1} H-NMR (300 MHz, dimethyl sulfoxide (DMSO) -d ₆ ): δ (ppm) = 7.75 (2H), 7.59-7.52 (2H), 7.19-7.13 (4H) , 6.96 (2H), 3.66 (8H), 3.03 (2H), 2.91 (2H), 1.47 (2H), 1.21 (12H), 0.86 (2H), 0.74 (3H), 0.44 (3H).

[Example 1]
5.0 g of a 2 wt% N, N-dimethylformamide (DMF) solution of a copolymer of methacrylic acid and acrylic acid ester and 20 mg of the compound (D-1) obtained in Synthesis Example 1 in a 20 mL sample bottle. It was added, stirred for 30 minutes and mixed. The obtained colored resin solution is filtered with a syringe filter, and the filtrate is applied onto a glass substrate (film forming method: 1 g of the filtrate is dropped on the glass, and a film is formed at 300 rpm for 10 seconds using a spin coater). A film was formed by heating at 100 ° C. for 2 minutes. The color value of the produced film was measured by transmitted light using a spectrophotometer (manufactured by Konica Minolta Co., Ltd., model number: CM-5). Then, it heated at 230 degreeC for 20 minutes, and the color value was measured in the same manner. The color difference (ΔE ^* _ab ) of the color values before and after heating at 230 ° C. is used as an index of heat resistance, and the results of evaluation in the following three stages are shown in Table 1.
"○": ΔE ^* _ab ≤ 3.0
"Δ": 3.0 <ΔE ^* _ab ≤ 10.0
"X": ΔE ^* _ab > 10.0

[Examples 2 to 6]
Compound (D-2), Compound (D-3), Compound (D-4), Compound (D-5), and Compound (D-5) obtained in Synthesis Examples 2 to 6 instead of compound (D-1). The color difference (ΔE ^* _ab ) of the color values before and after heating (230 ° C.-20 minutes) of the film prepared in the same manner as in Example 1 was measured and evaluated except that each of D-6) was used. The results are shown in Table 1.

[Comparative Example 1]
A conventional dye compound not belonging to the present invention was prepared in the same manner as in Example 1 except that the compound (E-1) obtained in Synthesis Example 3 was used instead of the compound (D-1). The color difference (ΔE ^* _ab ) of the color values before and after heating the film (230 ° C.-20 minutes) was measured and evaluated. The results are shown in Table 1.

As shown in Table 1, the xanthene-based dye of the example compound of the present invention exhibits high heat resistance during film formation, and the coloring composition containing the dye of the present invention has no practical problem as a colorant for a color filter. .. Further, the xanthene-based dye of the example of the present invention has higher heat resistance than that of the comparative example at the time of film formation, and the coloring composition containing the dye of the present invention is useful as a colorant for a color filter.

By using the coloring composition containing the xanthene-based dye according to the present invention as a colorant for a color filter, it is possible to produce a color filter having excellent heat resistance.

Claims (6)

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

[In the formula, R ^{1 to} R ⁴ are independently of −H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it represents a monocyclic, polycyclic or condensed ring aromatic hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms which may have a substituent.
R ¹ and R ² , or R ³ and R ⁴ are single-bonded, double-bonded, substituted or unsubstituted methylene groups, bonded to each other with or without oxygen or sulfur atoms to form a ring. You may.
R ⁵ and ^{R 6} are each independently, -H, a halogen atom, -NO _2, linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent.
R ⁷ and R ⁸ are independent of -H, respectively.
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it represents a monocyclic, polycyclic or condensed ring aromatic hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms which may have a substituent.
R ⁷ and R ⁸ may be bonded to each other with or without a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom to form a ring.
R ⁹ is a halogen _{^{atom, -OH, -CN, -OCH 3,}} -OCONR 10 R 11, -NO 2, -SO 3 -, -SO 3 H, -SO 3 M, -SO 3 R 10, -SO ₂ NR ¹⁰ R ¹¹ , -CO ₂ H, -CO ₂ M, -CO ₂ R ¹⁰ , -CONR ¹⁰ R ¹¹ , -CH = CHR ¹⁰ ,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
It may have a substituent. It may contain a heteroatom having 2 to 20 carbon atoms. It may contain a monocyclic, polycyclic or condensed ring aromatic hydrocarbon group, or it may have a substituent. Represents 0 to 20 amino groups.
n represents an integer of 1 to 4, and when n is 2 or more, a plurality of R ^9s may be the same or different, and may be a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or sulfur. The rings may be formed by bonding with each other with or without atoms.
R ¹⁰ and R ¹¹ are independently of −H,
A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent,
Alternatively, it represents an aromatic hydrocarbon group having 2 to 20 carbon atoms which may have a substituent.
R ¹⁰ and R ¹¹ may be bonded to each other with or without a single bond, double bond, substituted or unsubstituted methylene group, oxygen atom or sulfur atom to form a ring.
X represents —O—, —S— or —Se—.
M represents an organic cation or an inorganic cation, and when a plurality of cations are present, they may be the same or different.
An represents an anion, a represents an integer of 1 to 3, and b represents an integer of 0 to 3.
However, it is assumed that the general formula (1) is charge-neutral as a whole. ] In the general formula (1)
R ^{1 to} R ⁴ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are —H, linear or branched alkyl groups with 1 to 10 carbon atoms which may have substituents, or substitutions. It is an aromatic hydrocarbon group having 6 to 12 carbon atoms of a monocyclic, polycyclic or condensed ring which may contain a heteroatom which may have a group.
R ⁵ and R ⁶ are —H, —Cl, —Br or linear alkyl groups with 1 to 10 carbon atoms.
R ⁹ is _{^{-F, -Cl, -Br, -CN,}} -OCONR 10 R 11, -NO 2, -SO 3 -, be a ^-CONR 10 ^{R 11,} phenyl or _{-N (C 2} H _{5) 2} ,
n is 1 or 2 and X is —O— or —S—,
The xanthene dye according to claim 1. In the general formula (1)
An is 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 - or _{(PW 12 O} ⁴⁰⁾ is ^3, and, b is an integer of 1 to 3, claim 1 Alternatively, the xanthene dye according to claim 2. A coloring composition containing the xanthene-based dye according to any one of claims 1 to 3. A colorant for a color filter containing the coloring composition according to claim 4. A color filter using the colorant for a color filter according to claim 5.