JP7240187B2 - Xanthene compound, coloring composition containing said compound, colorant for color filter and color filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a xanthene compound, a coloring composition containing the compound, a colorant for color filters containing the coloring composition, and a color filter using the coloring agent.

Color filters used in liquid crystal displays and electroluminescence (EL) display devices are made by laminating a colored layer on a translucent substrate such as glass or transparent resin using a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. Manufactured by Colorants used in the colored layer are broadly classified into pigments and dyes, and pigments, which are said to be excellent in heat resistance and light resistance, are generally used (for example, Patent Documents 1 to 3). However, it is known that a color filter using a pigment has a depolarization effect due to reflection and scattering of transmitted light on the surface of pigment particles in the filter, which reduces the contrast ratio of the color display device.

In order to solve the problem of such a decrease in contrast ratio, a method of using a dye consisting of a xanthene compound as a coloring agent, a method of using only the dye, or a method of using the dye and the pigment in combination has been proposed (for example, Patent Documents 4 to 4). 8). Since dyes are soluble in solvents, color filters using dyes have less depolarization and superior spectral characteristics compared to the case where only pigments are used as colorants. However, although many improvements have been made as colorants for color filters, satisfactory performance in terms of color gamut expansion and high tinting strength has not been obtained, and the creation of new xanthene compounds has been desired. there is

Conventionally, as a xanthene compound dye, C.I. I. Acid Red 52 and C.I. I. Basic Violet 10 is known, and many coloring compositions and coloring agents for color filters using these dyes have been proposed. However, there are almost no reports of colorants for color filters using xanthene compounds into which, for example, sulfonyloxy groups are introduced instead of these substituents. By bonding various substituents to this sulfonyl group, various dyes can be synthesized, and the range of applications and performance can be further expanded. Here, C.I. I. means color index.

Japanese Patent Application Laid-Open No. 2001-220520 Japanese Patent Publication No. 2007-533802 Japanese Unexamined Patent Application Publication No. 2012-12498 JP-A-2002-265834 JP 2012-207224 A JP 2010-254964 A JP 2014-12814 A JP 2014-59538 A

An object of the present invention is to provide a novel xanthene compound having properties (color properties, solubility, heat resistance, etc.) suitable for various uses, and a coloring composition containing the compound. Another object of the present invention is to provide a colorant for a color filter containing the coloring composition and having good color characteristics (color gamut, brightness, contrast ratio, etc.) and a color filter using the colorant.

The present invention was obtained as a result of intensive studies to solve the above problems, and the gist thereof is as follows.

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

[In the formula, R ¹ to R ⁴ are each independently a hydrogen atom,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
Adjacent groups may be bonded to each other to form a ring.
R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, or
It represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms.
^R7 is
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
an optionally substituted linear or branched alkoxy group having 1 to 20 carbon atoms,
an optionally substituted cycloalkyl group or cycloalkoxy group having 3 to 20 carbon atoms,
an optionally substituted linear or branched alkenyl group having 2 to 20 carbon atoms,
an optionally substituted acyl group having 1 to 20 carbon atoms,
an optionally substituted amino group having 0 to 20 carbon atoms,
an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or
It represents an optionally substituted heterocyclic group having 2 to 20 carbon atoms.
X represents an inorganic or organic anion,
a represents an integer of 1-4, and b represents an integer of 0-4.
However, general formula (1) shall be neutral in charge as a whole. ]

2. A xanthene compound in which R ¹ to R ⁴ in the general formula (1) are linear or branched alkyl groups having 1 to 8 carbon atoms which may have a substituent.

3. A xanthene compound in which R ¹ and R ³ in the general formula (1) are a phenyl group which may have a substituent.

4. A xanthene compound according to the general formula (1), wherein R ⁵ and R ⁶ are a hydrogen atom, a halogen atom or a methyl group.

5. In the general formula (1), R ⁷ is an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, or an optionally substituted carbon A xanthene compound which is an amino group having 1 to 8 atoms.

6. A xanthene compound in which X in the general formula (1) is a halide ion or an organic anion having a sulfonic acid group or a carboxylic acid group.

7. A coloring composition containing the xanthene compound.

8. A coloring agent for a color filter containing the coloring composition.

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

The xanthene compound according to the present invention has excellent heat resistance and solubility, and the coloring composition containing the compound has excellent color development (color gamut, brightness, contrast ratio, etc.) Coloring for color filters useful as an agent.

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be implemented in various forms within the scope of the present invention.

The xanthene compound represented by the general formula (1) is composed of a compound represented by the following general formula (2) and an organic or inorganic anion represented by "X" to form a complex. be able to. In general formula (1), "a" represents the number of compounds represented by general formula (2), and "b" represents the number of Xs. However, in general formula (1), a or b is selected so as to be neutral in charge as a whole. a represents an integer of 1 to 4, preferably 1 or 2; b represents an integer of 0-4, preferably an integer of 0-3. In the case of b=0, the following general formula (2) alone can be electrically neutral by having an appropriate substituent.

[In the formula, R ¹ to R ⁷ are the same as defined in general formula (1). ]

In the general formula ^{( 1 )} , the "carbon atom Linear or branched alkyl group of number 1 to 20" specifically,
linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group;
Examples include branched alkyl groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, 2-methylpentyl group and isooctyl group.

In the general formula (1), R ¹ to R ⁴ or R ⁷ represents “an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms” "Aromatic hydrocarbon group" specifically includes a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, an indenyl group, a fluorenyl group, a triphenylyl group, a perylenyl group, a phenyloxy group, a tolyloxy group, a biphenyl aromatic hydrocarbon groups (including condensed polycyclic aromatic groups, aryl groups, and aryloxy groups) such as lyloxy, naphthyloxy, anthracenyloxy, and phenanthrenyloxy groups; .

In the general formula (1), "a linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" or "6 to 20 carbon atoms having a substituent" represented by R ¹ to R ⁴ The "substituent" in the "aromatic hydrocarbon group of
Specifically, halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;
hydroxyl group; nitro group; cyano group; amino group (unsubstituted amino group);
—COO ⁻ , a carboxylic acid group represented by —COOH or —COOM,
A sulfonic acid group represented by —SO ₃ ⁻ , —SO ₃ H or —SO ₃ M (where M is an alkali metal atom such as a lithium atom, a sodium atom, a potassium atom, a beryllium atom, a magnesium atom, a calcium atom, Represents an alkaline earth metal atom such as a barium atom.);
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 having 1 to 20 carbon atoms such as heptyl group, octyl group, isooctyl group, nonyl group and decyl group;
a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group;
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 , a linear or branched alkoxy group having 1 to 20 carbon atoms such as an isooctyloxy group;
cycloalkoxy groups having 3 to 20 carbon atoms such as cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group;
Formyl group, acetyl group, propionyl group, isopropionyl group, butyroyl group, isobutyroyl group, acryl group, cyclohexanoyl group, cyclohexanoyl group, benzoyl group, methylbenzoyl group, phenylacetyl group, etc., having 1 to 20 carbon atoms the acyl group of
methylamino group, dimethylamino group, ethylamino group, diethylamino group, methylethylamino group, propylamino group, isopropylamino group, dipropylamino group, diisopropylamino group, methylpropylamino group, butylamino group, 2-ethylhexylamino an amino group having 1 to 20 carbon atoms such as a group;
phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, pyrenyl group, tetracenyl group, triphenylenyl group, indenyl group, fluorenyl group, phenyloxy group, tolyloxy group, biphenylyloxy group, naphthyloxy group, anthracenyloxy group aromatic hydrocarbon groups having 6 to 20 carbon atoms such as groups, phenanthrenyloxy groups (including condensed polycyclic aromatic groups, aryl groups or aryloxy groups);
pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group , a heterocyclic group having 2 to 20 carbon atoms such as a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group and a benzothiazolyl group, etc. can be given. Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above. When the "substituent" for R ¹ to R ⁴ above contains a carbon atom, the carbon atom is included in the maximum "20" of the "number of carbon atoms" in each of R ¹ to R ⁴ . be. Further, these substituents may be bonded to each other through a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

^{[ _} A linear or branched alkyl group having 1 to 6 carbon atoms" specifically
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; isopropyl group, isobutyl group, s-butyl group, t-butyl group and 2-methylpentyl group Examples include branched alkyl groups.

In the general formula (1), the "substituent" in the "substituted linear or branched alkyl group having 1 to 6 carbon atoms" represented by R ⁵ and R ⁶ is
"A linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" or "6 to 20 carbon atoms having a substituent" represented by R ¹ to R ⁴ in the above general formula (1) The same as those mentioned as the "substituent" in the "aromatic hydrocarbon group of" can be mentioned. Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above. When the "substituent" for R ⁵ and R ⁶ contains a carbon atom, the carbon atom is included in the maximum "number of carbon atoms" of "6" in each of R ⁵ and R ⁶ . be. Further, these substituents may be bonded to each other through 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), the “linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent” represented by R ⁷ A chain or branched alkoxy group" is specifically
Linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy; isopropoxy, isobutoxy, s -butoxy group, t-butoxy group, branched alkoxy group such as isooctyloxy group;

In the general formula (1), the "cycloalkyl group having 3 to 20 carbon atoms" in the "optionally substituted cycloalkyl group or cycloalkoxy group having 3 to 20 carbon atoms" represented by R ⁷ Or cycloalkoxy group" specifically,
cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group;
Cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group, and the like.

In the general formula (1), the “linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent” represented by R ⁷ A chain or branched alkenyl group" includes vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 1-hexenyl group, isopropenyl group, isobutenyl group, Or a linear or branched alkenyl group in which a plurality of these alkenyl groups are bonded, and the like.

In the general formula (1), the "acyl group having 1 to 20 carbon atoms" in the "acyl group having 1 to 20 carbon atoms which may have a substituent" represented by R ⁷ is a formyl group, acetyl group, propionyl group, isopropionyl group, butyroyl group, isobutyroyl group, pentanoyl group, hexanoyl group, acrylyl group, cyclohexanoyl group, cycloheptanoyl group, benzoyl group, methylbenzoyl group, phenylacetyl group, naphthanoyl group, etc.

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 ⁷ is an amino group , methylamino group, dimethylamino group, ethylamino group, diethylamino group, methylethylamino group, propylamino group, dipropylamino group, methylpropylamino group, ethylpropylamino group, butylamino group, dibutylamino group, pentanyl amino group, propenylamino group, butenylamino group, cyclohexylamino group, dicyclohexylamino group, phenylamino group, diphenylamino group, naphthylamino group, and the like.

In the general formula (1), the “heterocyclic group having 2 to 20 carbon atoms” in the “heterocyclic group having 2 to 20 carbon atoms which may have a substituent” represented by R ⁷ is specifically in general,
pyridyl group, pyrimidinyl group, triazinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, quinolyl group, isoquinolyl group, naphthyridinyl group, indolyl group, benzimidazolyl group, carbazonyl group, carbolinyl group, acridinyl group, phenanthrolinyl group , furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, dibenzothienyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, and other heterocyclic groups (heteroaromatic hydrocarbon groups) etc.

In the general formula (1), "a linear or branched alkyl group having 1 to 20 carbon atoms and having a substituent" represented by R ⁷ ,
"substituted alkoxy group having 1 to 20 carbon atoms",
"a substituted cycloalkyl group or cycloalkoxy group having 3 to 20 carbon atoms",
"a linear or branched alkenyl group having 2 to 20 carbon atoms having a substituent",
"acyl group having 1 to 20 carbon atoms having a substituent",
"Amino group having 0 to 20 carbon atoms having a substituent",
The "substituent" in the "substituted aromatic hydrocarbon group having 6 to 20 carbon atoms" or "heterocyclic group having 2 to 20 carbon atoms having a substituent" is
"A linear or branched alkyl group having 1 to 20 carbon atoms having a substituent" or "Aromatic hydrocarbon group having 6 to 20 carbon atoms having a substituent" represented by R ¹ to R ⁴ Examples are the same as those mentioned as the "substituent" in the above. Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above. In addition, when the "substituent" in the above ^R7 contains a carbon atom, the carbon atom is included in the maximum value of "20" for the "number of carbon atoms" in ^R7 . Further, these substituents may be bonded to each other through a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

In general formula (1), R ¹ to R ⁴ are linear or branched alkyl groups having 1 to 10 carbon atoms which may have a substituent, or R ¹ and R ³ is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent which may have a substituent, and the number of carbon atoms which may have a substituent More preferably, it is a linear or branched alkyl group of 1 to 8, or R ¹ and R ³ are optionally substituted phenyl groups.

In general formula (1), combinations of R ¹ to R ⁴ may be the same or different. Adjacent groups in R ¹ and R ² and R ³ and R ⁴ may be bonded to each other to form a ring, and the ring may be a single bond or a nitrogen atom, an oxygen atom or a sulfur atom. A bond may be formed through any atom to form a ring. The ring formed in that case is preferably a 5- or 6-membered ring.

In general formula (1), R ⁵ and R ⁶ are preferably a hydrogen atom, a halogen atom or a methyl group, and the halogen atom is preferably a chlorine atom or a bromine atom.

In general formula (1), R ⁷ is an optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom An amino group having a number of 1 to 10 is preferable, and a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or the number of carbon atoms which may have a substituent 1 to 8 amino groups are more preferred.

A xanthene compound represented by the general formula (1) can be synthesized, for example, by a method shown in the following reaction formula (3). First, salicylaldehyde and a sulfonyl chloride having a suitable substituent ^R7 , such as methylsulfonyl chloride, are reacted in a suitable solvent such as a mixed solvent of triethylamine (TEA) and methylene chloride at a suitable temperature to obtain the following reaction formula ( In 3), a sulfonate such as methanesulfonate represented by the general formula (intermediate 1) is synthesized. Next, the following formula (Intermediate 1) and an aminophenol having appropriate substituents R ¹ , R ² and R ⁵ such as m-(dialkylamino)phenol are combined with p-toluenesulfonic acid (TsOH) or acetic acid. A condensation reaction is carried out at a suitable temperature in the presence of a suitable acid such as (CH ₃ COOH) and a catalyst to synthesize the following formula (intermediate 2) represented by the following reaction formula (3). Furthermore, the following formula (intermediate 2) is oxidized with an oxidizing agent such as chloranil in a suitable solvent such as a methanol/chloroform mixed solvent at an appropriate temperature to obtain a sulfonyloxy group represented by the general formula (1). As a xanthene compound having, for example, a complex product (formula (A-0) below) of the compound (2) and chloride ion in the following reaction formula (3) can be obtained. In addition, R ¹ , R ² , R ⁵ and R ⁷ in the following reaction formula (3) have the same definitions as in general formula (1), and in this reaction, R ¹ in general formula (1) and An example in which R ³ , R ² and R ⁴ , and R ⁵ and R ⁶ are the same is shown.

In the synthesis of the xanthene compound represented by the general formula (1), an organic solvent inert to the reaction can be used in order to improve reaction efficiency and ensure safety. The organic solvent is not particularly limited as long as it is inert to the reaction substrate, and aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane and n-heptane; acetone and 2-butanone. , 2-pentanone, ketones such as 3-pentanone; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran (THF), dioxane and diethyl ether; methanol, ethanol, propanol, isopropanol, butanol, pentanol, Alcohols such as hexanol; halogenated hydrocarbons such as dichloromethane and chloroform; N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and the like can be used alone or in combination.

The xanthene compound represented by the general formula (1) is obtained by purification by column chromatography of the product obtained in the above synthesis process; adsorption purification by silica gel, activated carbon, activated clay, etc.; It can be obtained by performing known purification such as recrystallization, crystallization, and salting out. Solvents used in these purification methods are not particularly limited, and alcohols such as water, methanol and ethanol; halogenated hydrocarbons such as dichloromethane and chloroform; aromatic hydrocarbons such as toluene and xylene; - Aliphatic hydrocarbons such as heptane can be used alone or in combination.

Specific examples of the xanthene compound of the present invention are shown in the following formulas (A-1) to (A-20) using preferred specific example compounds as the compound represented by the general formula (2). Not limited. In the specific examples below, examples in which the compound contains a chloride ion “Cl ⁻ ” as an anion are shown, but the anion is not limited to “Cl ⁻ ”, and a complex with other organic anions or inorganic anions can be formed. In the following structural formulas, some hydrogen atoms are omitted. In addition, even when stereoisomers exist, their planar structural formulas are described.

In the general formula (1), the "inorganic anion" or "organic anion" represented by "X" specifically includes halide ions such as fluoride ion, chloride ion, bromide ion, and iodide ion; chlorite ion, chlorite ion, oxoacid ion such as chlorate ion; hydroxy ion; cyanide ion;
(CN) ₂ N ⁻ , (CN) ₃ C ⁻ , NC—S ⁻ , PF ₆ ⁻ , BF ₄ ⁻ ,
(C ₂ F ₅ ) ₃ F ₃ P ⁻ , (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 ⁻ , (PW ₁₂ O ₄₀ ) ³⁻ ,
organic anions having a group such as a sulfonic acid group (—SO ₃ ⁻ ) or a carboxyl group (—COO ⁻ ).

Among the "organic anions" represented by the general formula (1), bind to the "sulfonic acid group" or "carboxylic acid group" in the "organic anion having a sulfonic acid group" or the "organic anion having a carboxylic acid group" When the “group” is represented by “R ⁸ ”, R ⁸ in “R ⁸ —SO ₃ ⁻ ” or “R ⁸ —COO ⁻ ” specifically includes
an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms,
an optionally substituted linear or branched alkoxy group having 1 to 18 carbon atoms,
an aromatic hydrocarbon group having 1 to 24 carbon atoms which may have a substituent,
Heterocyclic groups having 2 to 18 carbon atoms which may have a substituent are mentioned, and these "groups" are specifically represented by R ⁷ in the general formula (1),
"A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent",
"Optionally substituted C1-C20 linear or branched alkoxy group", "Optionally substituted C6-C20 aromatic hydrocarbon group ",
Examples thereof are the same as those exemplified as the “optionally substituted heterocyclic group having 2 to 20 carbon atoms”. Further, as the "substituent" in these "groups", specifically,
—SO ₃ ⁻ , —SO ₃ H, —COOH, —COO ^— , —O—, —S—, or the same as the “substituent” in the “group” represented by R ⁷ in the general formula (1) can be given.
Only one of these "substituents" may be included, or a plurality of them may be included, and when a plurality of "substituents" are included, they may be the same or different. Moreover, these "substituents" may further have the substituents exemplified above. When the "substituent" contains carbon atoms, the carbon atoms are included in the above "1 to 18 carbon atoms", "6 to 24 carbon atoms" and "2 to 18 carbon atoms". . Further, these substituents may be bonded to each other through a single bond, a double bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the compounds contained in the above organic anions represented by "X" in the general formula (1) are shown in the following formulas (B-1) to (B-16). is not limited to In the following structural formulas, some hydrogen atoms are omitted. In addition, even when stereoisomers exist, their planar structural formulas are described.

In general formula (1), when "X" is an organic anion, an organic anion having a sulfonic acid group is preferred. Moreover, when "X" is an inorganic anion, a halide ion is preferable, and a chloride ion is more preferable.

In the coloring composition of the present invention, the xanthene compound represented by general formula (2) in general formula (1) may be used singly or in combination of two or more having different molecular structures (for example, mixed). When two or more of these dyes are used, the weight concentration ratio of the least one kind of xanthene dye to the total xanthene compounds is 0.1 to 50% by weight. One or two kinds of xanthene dyes are preferable. Further, in the coloring composition of the present invention, the organic anion or inorganic anion represented by "X" in the general formula (1) may be used singly or in combination of two or more different kinds. Seeds are preferred.

In order to enhance the performance as a colorant for color filters, the coloring composition of the present invention contains surfactants, dispersants, defoaming agents, leveling agents, various solvents, and other color filters as other components of the compound. Additives that are mixed during the production of the colorant for use can be added. These components of the coloring composition of the present invention can take a solid (or powder) form, a liquid form, or an intermediate form thereof by adding additives, and are preferably solid. However, it is preferable that the content of these additives in the coloring composition is an appropriate amount, and the solubility in the solvent of the coloring composition of the present invention is reduced, or is improved more than necessary, and the color filter is produced. It is preferable that the content is within a range that does not affect the effects of other additives. These additives can be added at any time during preparation of the coloring composition.

The shape of the powdery state of the xanthene compound of the present invention and the colored composition containing the compound can be observed using an optical microscope, a scanning electron microscope (SEM), or the like. The coloring composition of the present invention is usually used in a solid state such as crystals, microcrystals, fine powders, flakes, needle crystals, and granules, but is not particularly limited.

Detailed information on the shape of the powder can be obtained by known powder measurement techniques such as the particle size distribution, surface area, pore size distribution, and powder density of the powder of the coloring composition of the present invention. The coloring composition of the present invention preferably has a particle size in the range of 0.1 μm to several mm. It is preferable that the particle diameter is smaller, and that the median value of the particle diameter distribution is in the range of 0.1 to 100 μm.

Thermogravimetric measurement of the xanthene compound of the present invention and the colored composition containing the compound - by performing differential thermal analysis (TG-DTA), the decomposition initiation temperature which is an index of heat resistance of the compound and the colored composition is evaluated. can do. As the temperature corresponding to the decomposition initiation temperature, the temperature at which the weight of the sample is reduced by a certain percentage (%) after heating may be used for evaluation. The decomposition initiation temperature is preferably 250° C. or higher, more preferably 300° C. or higher, and particularly preferably 360° C. or higher. When applied to colorants for color filters, the decomposition initiation temperature is preferably as high as possible.

The solubility of the xanthene compound of the present invention and the coloring composition containing the compound is represented by the solubility. Solubility represents the maximum amount of the powdered coloring composition that can be dissolved in a specific solvent. expressed. Solubility can be obtained, for example, by mixing a sample in a specific solvent, stirring the solvent at a constant temperature for a certain period of time, and measuring the concentration of the prepared saturated solution. It can also be obtained by concentration measurement, such as by measurement.

The coloring composition contained in the colorant for color filters must be well dissolved or dispersed in an organic solvent containing a resin or the like in the process of producing the colorant for color filters and the color filter. Therefore, the xanthene compound of the present invention and the colored composition containing the compound preferably have high solubility in organic solvents. The organic solvent is not particularly limited, but specifically esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and propylene glycol monomethyl ether (PGME); propylene glycol monomethyl ether acetate (PGMEA ) and other ether esters; acetone, ketones such as cyclohexanone; methanol, ethanol and other alcohols; diacetone alcohol (DAA); benzene, toluene, xylene and other aromatic hydrocarbons; N,N-dimethylformamide ( DMF), amides such as N-methylpyrrolidone (NMP); dimethylsulfoxide (DMSO); chloroform, and the like. These solvents may be used alone or in combination of two or more. Among these, the colored composition containing the xanthene compound according to the present invention preferably has excellent solubility in PGME and PGMEA, and particularly preferably has excellent solubility in PGMEA.

Specifically, the solubility of the xanthene compound of the present invention and the coloring composition containing the compound is, for example, at room temperature of 23 to 27 ° C., a certain weight of solvent (for example, the above organic solvent such as PGME or PGMEA). It can be obtained by a method of gradually adding powder until it remains undissolved and measuring its dissolved concentration. The solubility in the organic solvent at room temperature is preferably at least 1% by weight or more.

The xanthene compound of the present invention is measured at around room temperature (eg, 23 to 27° C.) using a solution prepared by dissolving it in an organic solvent as described above, and the visible region of the ultraviolet-visible absorption spectrum (eg, 350 to 750 nm). (wavelength range), a maximum absorption wavelength indicating maximum absorbance is observed. The maximum absorption wavelength of the xanthene compound of the present invention is preferably observed in the range of, for example, 550 to 610 nm, but is not limited to this range depending on the desired color tone. The concentration of the sample to be measured is preferably 0.005-0.02 mmol/L. The solvent is not limited as long as it dissolves the xanthene compound, but it is preferable that the absorption wavelength of the UV-visible absorption spectrum does not shift significantly depending on the dissolution conditions such as concentration and pH, and propylene glycol monomethyl ether (PGME) is preferable.

The spectral characteristics (transmittance, reflectance) of the xanthene compound of the present invention and the coloring composition containing the compound are determined when these dyes are used alone as colorants for color filters, or when mixed with other dyes. is important in both cases and directly affects the color properties of the color filter. As for the measurement method, for example, similar to the measurement of the ultraviolet-visible absorption (or transmission) spectrum of the solution or dispersion state as described above, the thin film applied to the glass or transparent resin substrate is measured by a spectrophotometer such as a spectrophotometer. There is a method of measuring the ultraviolet-visible absorption (or transmission) spectrum using , and measuring the maximum absorption wavelength. There is also a method of directly irradiating the powder with light and measuring the light reflected/scattered on the particle surface or near the particle surface. In addition, by making a color filter from the actually applied thin film (coating film) and measuring the color difference as the spectral characteristics before and after heating and drying, we can determine the heat resistance as a colorant for color filters from the degree of color change due to thermal decomposition. can be evaluated.

The colorant for color filters of the present invention comprises a coloring composition containing a xanthene compound represented by general formula (1), and components commonly used in the production of color filters. For example, in the case of the photolithography process, general color filters are prepared by mixing dyes and pigments with resin components (including monomers and oligomers) and solvents. and photopolymerization using a photomask to prepare a colored pattern of a solvent-soluble/insoluble dye-resin composite film, followed by washing and heating. Also in the electrodeposition method and the printing method, a colored pattern is produced by using a mixture of a pigment and a resin or other components. Therefore, specific components in the colorant for color filters of the present invention include a xanthene compound represented by the general formula (1), other dyes such as dyes and pigments, a resin component, an organic solvent, and a photopolymerization initiator. Other additives such as In addition, these components may be selected, and other components may be added as necessary.

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

The colorant for color filters containing the coloring composition containing the xanthene compound of the present invention may use the xanthene compound alone, or may be mixed with a known dye such as another dye or pigment to adjust the color tone. You may When used as a coloring agent 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 or other red-based lake pigments; C.I. I. Acid Red 88, C.I. I. a red dye such as Basic Violet 10; C.I. I. Yellow pigments such as Pigment Yellow 83, 138, 139, and 150 are included. 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 and 74; Disperse dyes such as Disperse Blue 3, 7 and 377; Spiron dyes; Cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, and indanthrene , oxazine-based, dioxazine-based, azo-based, xanthene-based dyes not belonging to the present invention; and other blue lake pigments.

The mixing ratio of other pigments in the colorant for color filters containing the coloring composition containing the xanthene compound of the present invention is 5 to 2000% by weight with respect to the xanthene compound (the total thereof when two or more are used). is preferred, and 10 to 1000% by weight is more preferred. The mixing ratio of pigment components such as dyes in the liquid colorant for color filters is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, based on the total colorant.

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

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. Surfactants, dispersants, and the like necessary for stabilizing the properties are mentioned. Any of these can use known ones for manufacturing color filters, and are not particularly limited. The mixing ratio of the total amount of these additives in the total solid content of the colorant for color filters is preferably 5 to 60% by weight, more preferably 10 to 40% by weight.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples. The compounds obtained in Synthesis Examples were identified by ¹ H-NMR analysis (nuclear magnetic resonance spectrometer manufactured by Bruker, model number: Magnet System 300 MHz/54 mm UltraShield), and the measurement results are shown in the Synthesis Examples below. .

[Synthesis Example 1] Synthesis of compound (A-1) 8.00 g (65.5 mmol) of salicylaldehyde, 7.95 g (78.6 mmol) of triethylamine (TEA), and 80.0 mL of methylene chloride are placed in a 100 mL container under a nitrogen stream. was added, stirred, cooled to 5° C., and 12.0 g (105 mmol) of methylsulfonyl chloride was added dropwise to the solution over 45 minutes. After dropping, the mixture was heated to room temperature (25°C) and stirred for 3 hours. The reaction solution was filtered, the solid was separated by filtration, and the filtrate was washed with saturated saline. The organic layer was extracted, washed with water, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a compound represented by the following formula (Intermediate 3) as a yellow oil (14.6 g, Yield 111.6%) (reaction formula (4) below).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 10.25 (1H), 7.94-7.91 (1H), 7.86-7.80 (1H), 7.61 -7.55 (1H), 3.59 (3H).

5.00 g (25.0 mmol) of the above formula (Intermediate 3), 11.1 g (50.0 mmol) of N,N-dibutyl-3-aminophenol, and p-toluenesulfonic acid (TsOH) were placed in a 100 mL container under a nitrogen stream. 0.71 g (3.75 mmol) of monohydrate and 50.0 mL of acetic acid were added and stirred at 70° C. for 4.5 hours. The reaction solution was cooled to room temperature (25° C.) and 100 mL of methylene chloride was added. The reaction solution was neutralized with a saturated aqueous sodium hydrogencarbonate solution, and the organic layer was extracted, dried over magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, heptane was added to crystallize, and the solid was collected by filtration. The solid was dried under reduced pressure at 60° C. to obtain a compound represented by the following formula (intermediate 4) as a pale red solid (10.6 g, yield 68.0%) (reaction formula (5) below).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.40-7.14 (4H), 6.58-6.55 (2H), 6.19-6.14 (4H), 6 .59 (1H), 5.18 (2H), 3.24-3.19 (8H), 3.10 (3H), 1.61-1.51 (4H), 1.40-1.28 ( 4H), 0.98-0.93 (12H).

3.00 g (4.80 mmol) of the above formula (Intermediate 4), 1.77 g (7.20 mmol) of chloranil, 30.0 mL of methanol, and 30.0 mL of chloroform are placed in a 100 mL container and stirred at room temperature (25° C.) for 17 hours. bottom. The crude product obtained by concentrating the reaction solution under reduced pressure was purified by column chromatography (carrier: 150 g of silica gel, solvent: methylene chloride→methylene chloride/methanol=9/1 (volume ratio)). After purification, it was concentrated and dried, dispersed and washed with heptane, and the solid was collected by filtration. The solid was dried under reduced pressure at 60° C. to obtain a complex with chloride ion represented by the following formula (A-1) as a brown solid (0.21 g, yield 7.2%).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 7.85-7.55 (4H), 7.14 (4H), 6.98 (2H), 3.60 (8H), 3.24 (3H), 1.61 (4H), 1.40 (4H), 0.96-0.92 (12H).

[Synthesis Example 2] Synthesis of compound (A-2) 8.00 g (65.5 mmol) of salicylaldehyde and N,N,N',N'-tetramethylethylenediamine were added to a 100 mL Kolben container under a nitrogen stream under a nitrogen stream. 56.0 mL was added and heated at 80° C. with stirring, and 9.41 g (65.5 mmol) of dimethylsulfamoyl chloride was added dropwise to the solution over 15 minutes. After dropping, the mixture was heated at 90° C. and stirred for 1.5 hours. The reaction solution was filtered, the solid was separated by filtration, and the filtrate was washed with a 2 mol/L hydrochloric acid aqueous solution. The organic layer was washed with water, dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a compound represented by the following formula (intermediate 5) as a brown oil (14.1 g, yield 93 .7%).

¹ H-NMR (300 MHz, DMSO-d ₆ ): δ (ppm) = 10.28 (1H), 7.92-7.89 (1H), 7.85-7,79 (1H), 7.57 -7.52 (2H), 3.01 (6H).

5.00 g (25.0 mmol) of the above formula (Intermediate 5), 9.65 g (50.0 mmol) of N,N-dibutyl-3-aminophenol, and p-toluenesulfonic acid monohydrate were placed in a 100 mL container under a nitrogen stream. 0.71 g (43.6 mmol) of the substance and 50.0 mL of acetic acid were added, and the mixture was stirred at 70° C. for 6 hours. The reaction solution was cooled to room temperature (25° C.) and 100 mL of methylene chloride was added. Neutralize with saturated aqueous sodium bicarbonate, extract the organic layer, wash the organic layer with water, dry over magnesium sulfate, and filter. The filtrate was concentrated under reduced pressure, heptane was added to crystallize, and the solid was collected by filtration. The obtained crude product was purified by column chromatography (carrier: 250 g of silica gel, solvent: methylene chloride→methylene chloride/ethyl acetate=9/1). After purification, it was concentrated and dried, dispersed and washed with heptane, and the solid was collected by filtration. The solid was dried under reduced pressure at 60° C. to obtain a compound represented by the following formula (intermediate 6) as a pale purple solid (8.63 g, yield 60.5%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.45-7.21 (3H), 7.11-7.08 (1H), 6.53-6.50 (2H), 6 .21-6.20 (2H), 6.17-6.13 (2H), 5.88 (1H), 5.29 (2H), 3.24-3.19 (8H), 2.98 ( 6H), 1.62-1.51 (8H), 1.40-1.28 (8H), 0.98-0.93 (12H).

8.60 g (13.2 mmol) of the above formula (intermediate 6) and 43 mL of 90% sulfuric acid were placed in a 100 mL container and stirred at 60° C. for 19 hours. The reaction solution was poured into 200 mL of ice water, and the precipitated solid was collected by filtration. The solid was dispersed and washed with 90 mL of methylene chloride, and the solid was collected by filtration. The obtained solid, 68 mL of methanol, and 8.53 g of iron chloride (III) were placed in a 100 mL container and stirred at 60° C. for 14 hours. The reaction solution was filtered, the filtrate was concentrated under reduced pressure, and the obtained crude product was purified by column chromatography (carrier: silica gel 250 g, solvent: methylene chloride→methylene chloride/acetone=1/1). After purification, it was concentrated to dryness, washed with water, and the solid was collected by filtration. The solid was dried under reduced pressure at 80° C. to obtain a complex with chloride ion represented by the following formula (A-2) as a brown solid (1.35 g, yield 15.3%).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.73 (1H), 7.82 (2H), 7.15 (2H), 6.85 (2H), 3.6 (8H) , 3.4 (6H), 1.6 (8H), 1.3 (8H), 0.9 (12H).

[Example 1]
As a xanthene compound, the compound (A-1) obtained in Synthesis Example 1 was dissolved in a PGME solvent to prepare a solution with a concentration of 0.02 mmol/L, and an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, model number : V-650), the ultraviolet-visible absorption spectrum (wavelength range from 300 to 750 nm) was measured at room temperature (25°C), and the maximum absorption wavelength and molar extinction coefficient in the measurement wavelength range were measured. Next, using a thermogravimetry-differential thermal analyzer (manufactured by Mac Science Co., Ltd., model number: TG-DTA 2000S), TG-DTA measurement (sample weight: about 5 mg (3.5- 6.5 mg range), temperature increase rate: 20° C./min), and the 5% weight loss temperature was measured. Also, using the same solution as above, the solubility in PGMEA and PGME solvents at room temperature (25° C.) was measured. Table 1 shows the results.

[Example 2]
As a xanthene compound, compound (A-2) obtained in Synthesis Example 2 was subjected to ultraviolet-visible absorption spectrum measurement, 5% weight loss temperature and solubility in the same manner as in Example 1. The results are summarized in Table 1.

[Comparative Example 1]
For comparison, the compound (A-1) of Example 1 was replaced with the following compound (C-1), which is a dye not belonging to the present invention, and the same measurements as in Examples were performed. The results are summarized in Table 1.

As shown in Table 1, the xanthene compound of the present invention can dissolve well in solvents used in colorants for color filters. A xanthene compound having a sulfonyloxy group according to the present invention has a spectrum similar to that of a dye compound having a sulfonamide group as a comparative example. In addition, the xanthene compound of the present invention has a higher 5% weight loss temperature and excellent heat resistance than the comparative example compounds.

The xanthene compound according to the present invention and the colored composition containing the compound are useful as colorants for color filters having excellent heat resistance and solubility, and have excellent color characteristics (color gamut, brightness, contrast ratio, etc.). Suitable for making color filters.

Claims (8)

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

[In the formula, R ¹ to R ⁴ are each independently a hydrogen atom,
an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms,
or represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,
Adjacent groups may be bonded to each other to form a ring.
R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, or
It represents an optionally substituted linear or branched alkyl group having 1 to 6 carbon atoms.
R ⁷ is an optionally substituted linear or branched C 1-8 alkyl group or an optionally substituted C 1-8 amino group represents
X represents an inorganic or organic anion,
a represents an integer of 1-4, and b represents an integer of 0-4.
However, general formula (1) shall be neutral in charge as a whole. ] The xanthene according to claim 1, wherein in the general formula (1), R ¹ to R ⁴ are linear or branched alkyl groups having 1 to 8 carbon atoms which may have a substituent. Compound. The xanthene compound according to claim 1, wherein in the general formula (1), R ¹ and R ³ are phenyl groups optionally having substituents. 4. The xanthene compound according to any one of claims 1 to 3, wherein in the general formula (1), R ⁵ and R ⁶ are a hydrogen atom, a halogen atom or a methyl group. The xanthene compound according to any one of claims 1 to 4 , wherein in the general formula (1), X is a halide ion or an organic anion having a sulfonic acid group or a carboxylic acid group. A coloring composition containing the xanthene compound according to any one of claims 1 to 5 . A colorant for color filters, comprising the coloring composition according to claim 6 . A color filter using the colorant for color filters according to claim 7 .