Xanthene compounds, resin compositions, and color filters

Abstract

To provide a salt-forming compound, which is a salt of a xanthene-based compound, exhibiting higher coloring strength and higher color development stability after heat and light history compared with traditional ones, and also to provide a resin composition and a color filter.SOLUTION: There is provided a xanthene-based compound which is a salt composed of an anion forming a xanthene-based chromophore having an anionic functional group represented by general formula (1), and a cation composed of an aromatic nitrogen-containing heterocyclic compound having a linear or branched, saturated or unsaturated hydrocarbon group (optionally containing an ether bond and / or an ester bond within the hydrocarbon group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to xanthene compounds, resin compositions, and color filters, and more particularly to xanthene compounds which are salt-forming compounds of anion having an anionic functional group that forms a xanthene chromophore and a cation consisting of an aromatic nitrogen ring compound, a resin composition containing this xanthene compound, and a color filter containing a cured product of this resin composition. [Background technology]

[0002] CIAcid red289 (hereinafter sometimes abbreviated as Acid red289), a sodium salt of a xanthene compound, has been widely used for over 35 years in applications ranging from textile dyeing to information electronics materials, and in recent years, its performance as a raw material for color filter dyes has been particularly recognized.

[0003] A color filter is a filter in which a pattern composed of three color resists—red (R), green (G), and blue (B)—is formed on a light-transmitting substrate such as glass. When a light source passes through this color filter, it imparts color information to the light.

[0004] Acid red 289 is a suitable dye for producing red (R) color resists, but it has been criticized for its weak coloring power. As a result, improvements to Acid red 289 and compositions containing improved compounds have been proposed.

[0005] Patent Document 1 describes an improved version of Acid red 289, which uses a xanthene compound as used in Acid red 289 and the following general formula (a) [ka] (In general formula (a), R1 to R4 each independently represent an alkyl group or benzyl group having 1 to 20 carbon atoms, and at least two of R1, R2, R3, and R4 have 5 to 20 carbon atoms. -represents an inorganic or organic anion.) discloses a salt-forming compound consisting of a quaternary ammonium salt compound represented thereby.

[0006] Patent Document 2, also as an improved product of Acid red 289, discloses a xanthene compound used in Acid red 289 and the following general formula (b)

Chemical Formula

[0007] Patent Document 3, also as an improved product of Acid red 289, discloses a xanthene compound used in Acid red 289 and the following general formula (c)

Chemical Formula

Chemical Formula

[0008] [Patent Document 1] Patent No. 4492760 [Patent Document 2] Patent No. 6246120 [Patent Document 3] Patent No. 6572990 [Overview of the project] [Problems that the invention aims to solve]

[0009] However, according to the salt-forming compound described in Patent Document 1, when this salt-forming compound and a coloring agent containing a blue pigment are used, a blue coloring composition for color filters can be obtained that provides a stable color filter with excellent color characteristics and heat resistance, but there is no mention of improving the coloring power of Acid Red 289 itself. When the inventors checked the coloring power of a cured film containing the salt-forming compound included in the invention disclosed in Patent Document 1, they were unable to confirm that the salt-forming compound itself had sufficient coloring power.

[0010] According to the salt-forming compound described in Patent Document 2, the resulting color filter exhibits excellent heat resistance and good solubility of the coloring agent for the color filter containing the salt-forming compound in organic solvents. However, there is no description comparing the coloring power of the salt-forming compound itself with that of conventional Acid Red 289.

[0011] Patent Document 3 discloses that the salt-forming compound described herein results in a cured film obtained from a composition containing the salt-forming compound having higher coloring power and higher heat resistance compared to the cured film containing the salt-forming compound described in Patent Document 1. However, when the inventors examined the coloring power and color development stability after the thermal history of the cured film containing the salt-forming compound described in Patent Document 3, they found that no significant improvement was observed even when compared to Acid Red 289.

[0012] Therefore, there was a need for a salt-forming compound that possessed higher coloring power and greater color stability after thermal treatment compared to improved versions of conventional Acid Red 289.

[0013] Furthermore, when using compounds that exhibit a red color in applications where they are exposed to light, such as color filters, color stability after exposure to light is also required.

[0014] The present invention has been made in view of the above-mentioned problems, and its purpose is to provide a salt-forming compound which is a salt of a xanthene compound and has higher coloring power and higher color development stability after thermal and light history than conventional salts, a resin composition containing the salt-forming compound, and a color filter containing a cured product of the resin composition. [Means for solving the problem]

[0015] The aforementioned object of the present invention is, General formula (1) [ka] (In general formula (1), R1 and R2 are independently a hydrogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO3 - , -OR 13 , or R 13 It may also be replaced with R 13 This is a saturated hydrocarbon group having 1 to 6 carbon atoms (however, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms), R3~R 12These are, independently of each other, hydrogen atoms or -SO3 - Alternatively, it is a saturated hydrocarbon group having 1 to 6 carbon atoms. R1~R 12 -SO3 - An anion that forms a xanthene chromophore having an anionic functional group, represented by (where the number of n is determined by the total number of substituents, and n is an integer of 1 or more), It was found that this can be achieved by a cation consisting of a linear or branched aromatic nitrogen ring compound having saturated or unsaturated hydrocarbon groups (which optionally include ether and / or ester bonds within the hydrocarbon groups) and a xanthene compound, which is a salt-forming compound of the same.

[0016] Furthermore, the cation consisting of the aromatic nitrogen ring compound is of general formula (2) [ka] (In general formula (2), R 14 This is a hydrogen atom, or a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (which optionally includes ether and / or ester bonds within the hydrocarbon group). R 15 ~R 19 These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The aforementioned R 14 ~R 19 At least one of them is the aforementioned hydrocarbon group, A quaternary ammonium cation of a pyridine derivative represented by the general formula (3), where m is 1 or 2. [ka] (In general formula (3), R 20 , R 22 These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing ether and / or ester bonds within the hydrocarbon group), R 21 , R 23 , R 24 These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R 20 ~R 24 At least one of them is the aforementioned hydrocarbon group, A quaternary ammonium cation of an imidazole derivative represented as m is 1 or 2. It is preferable that n in the general formula (1) is equal to m in the general formula (2) or (3).

[0017] Furthermore, the aforementioned object of the present invention can also be achieved by a curable resin composition comprising the xanthene compound of the present invention and a binder resin, and a color filter having a cured product of this curable resin composition. [Effects of the Invention]

[0018] The xanthene compounds of the present invention exhibit higher coloring power compared to conventional Acid Red 289 and its improved salt-forming compounds. The cured products of curable resin compositions containing the xanthene compounds of the present invention and the color filters containing these cured products have higher color development stability after thermal and light history than conventional products. [Modes for carrying out the invention]

[0019] <Xanthene compounds> The xanthene compound of the present invention is a salt-forming compound comprising an anion that forms a xanthene chromophore having an anionic functional group, and a cation consisting of a linear or branched aromatic nitrogen ring compound having saturated or unsaturated hydrocarbon groups (which optionally include ether and / or ester bonds within the hydrocarbon groups). Because the cation of the xanthene compound consists of an aromatic nitrogen ring compound, the color development stability after thermal and light history can be enhanced. Furthermore, because the aromatic nitrogen ring compound has the aforementioned hydrocarbon groups, its compatibility with binder resins and solvents is improved. As a result, the coloring power of the xanthene compound can be enhanced.

[0020] [Anions that form xanthene chromophores with anionic functional groups] Anions that form xanthene chromophores having anionic functional groups are defined by general formula (1) [ka] (In general formula (1), R1 and R2 are independently a hydrogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO3 - , -OR 13 , or R 13 It may also be replaced with R 13 This is a saturated hydrocarbon group having 1 to 6 carbon atoms (however, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms), R3~R 12 These are, independently of each other, hydrogen atoms or -SO3 - Alternatively, it is a saturated hydrocarbon group having 1 to 6 carbon atoms. R1~R 12 -SO3 - This is an anion whose value n is determined by the total number of substituents, and n is an integer greater than or equal to 1.

[0021] The present invention relates to anions that form xanthene chromophores having an anionic functional group, wherein the anionic functional group is -SO3 - It refers to the base.

[0022] R1 and R2 are preferably, independently of each other, aromatic hydrocarbon groups having 6 to 10 carbon atoms, and more preferably, aromatic hydrocarbon groups having 6 carbon atoms. Specifically, a phenyl group can be given as an aromatic hydrocarbon group having 6 carbon atoms, and a naphthyl group can be given as an aromatic hydrocarbon group having 10 carbon atoms.

[0023] R 13The saturated hydrocarbon group may have any of the following structures: linear, branched, or cyclic, as long as it has 1 to 6 carbon atoms. The number of carbon atoms is preferably 1 to 3, and more preferably 1.

[0024] R 13 Specific examples of saturated hydrocarbon groups include linear or branched aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups; and alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups.

[0025] R3~R 12 The saturated hydrocarbon groups having 1 to 6 carbon atoms may independently take on any of the following structures: linear, branched, or cyclic, and may have 1 to 3 carbon atoms, or even just 1 carbon atom. Specifically, examples include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups; and alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups.

[0026] R3~R 12 These are, independently of each other, preferably hydrogen atoms or -SO3 - It is a substituent. In general formula (1), n ​​is an integer greater than or equal to 1, preferably an integer between 1 and 4, and particularly preferably n is 1 or 2. [Cations consisting of aromatic nitrogen ring compounds] In the present invention, the cation comprising the above-mentioned aromatic nitrogen ring compound is, for example, a cation comprising a 5- or 6-membered aromatic nitrogen ring compound that contains one or two nitrogen atoms in its aromatic ring structure.

[0027] Examples of cations consisting of such aromatic nitrogen compounds include quaternary ammonium cations of pyridine derivatives, quaternary ammonium cations of pyrazine derivatives, quaternary ammonium cations of pyrimidine derivatives, quaternary ammonium cations of pyrrole derivatives, quaternary ammonium cations of imidazole derivatives, and quaternary ammonium cations of pyrazole derivatives.

[0028] Among these, cations consisting of aromatic nitrogen ring compounds having a straight-chain or branched, saturated or unsaturated hydrocarbon group (optionally including ether and / or ester bonds within the hydrocarbon group) are defined by general formula (2) [ka] (In general formula (2), R 14 This is a hydrogen atom, or a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (which optionally includes ether and / or ester bonds within the hydrocarbon group). R 15 ~R 19 These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The aforementioned R 14 ~R 19 At least one of them is the hydrocarbon group, A quaternary ammonium cation of a pyridine derivative represented as (where m is 1 or 2), It is preferable that n in general formula (1) is equal to m in general formula (2). In addition, in the general formula (2) above, R 14 If the hydrocarbon group is a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and contains an ester bond (-C(=O)-O-), then the one carbon atom constituting the ester bond is not included in the carbon number.

[0029] R 14It is preferably a linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing ether and / or ester bonds within the hydrocarbon group), and more preferably a linear or branched saturated hydrocarbon group having 8 to 18 carbon atoms (optionally containing ester bonds within the hydrocarbon group).

[0030] R 14 Specific examples of linear or branched saturated hydrocarbon groups having 8 to 18 carbon atoms include, for example, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, and their branched saturated hydrocarbon groups (2-ethylhexyl group, 2-methyloctyl group, 8,8-dimethylnonyl group, 3-methylundecyl group, 2-ethylundecyl group, 1-methyl-11-methyldodecyl group, 2-methyltetradecyl group, 3-ethyltetradecyl group, etc.).

[0031] R 14 Examples of cases where a saturated or unsaturated hydrocarbon group with 1 to 20 carbon atoms contains an ether bond within a straight or branched chain include R 14 The following structural formula (5) [ka] This is a case represented by, and an example of a case in which the hydrocarbon group contains an ester bond is, R 14 The following structural formula (6) [ka] This is a case that can be represented by [this formula].

[0032] R 15 ~R 19 These are preferably, independently of each other, hydrogen atoms or linear or branched saturated hydrocarbon groups having 1 to 3 carbon atoms, and more preferably, independently of each other, hydrogen atoms or methyl groups.

[0033] Furthermore, a cation consisting of a linear or branched aromatic nitrogen ring compound having saturated or unsaturated hydrocarbon groups (which optionally include ether and / or ester bonds within the hydrocarbon groups) is defined by general formula (3) [ka] (In general formula (3), R 20 , R 22 These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing ether and / or ester bonds within the hydrocarbon group), R 21 , R 23 , R 24 These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The aforementioned R 20 ~R 24 At least one of them is the hydrocarbon group, A quaternary ammonium cation of an imidazole derivative represented as m is 1 or 2. It is preferable that n in general formula (1) is equal to m in general formula (3). In addition, in the general formula (3) above, R 20 , R 22 If the hydrocarbon group is a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group contains an ester bond (-C(=O)-O-), then the one carbon atom constituting the ester bond is not included in the carbon number.

[0034] R 20 , R 22 Preferably, each of these is a straight-chain or branched saturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing ether and / or ester bonds within the hydrocarbon group).

[0035] R 20 , R 22Specific examples of linear or branched saturated hydrocarbon groups having 1 to 18 carbon atoms include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and their branched saturated hydrocarbon groups (isopropyl, isobutyl, tert-butyl, isopentyl, 2-methylpentyl, 3-ethylheptyl, 2-ethylhexyl, 2-methyloctyl, 8,8-dimethylnonyl, 3-methylundecyl, 2-ethylundecyl, 1-methyl-11-methyldodecyl, 2-methyltetradecyl, 3-ethyltetradecyl, etc.).

[0036] R 20 , R 22 The case in which a saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms is contained within a linear or branched saturated or unsaturated hydrocarbon group is as represented by the above structural formula (5), and the case in which an ester bond is contained within the hydrocarbon group is, for example, R 20 , R 22 This is the case where the structure is represented by the above structural formula (6).

[0037] In particular, R 20 , R 22 It is even more preferable that one of the hydrocarbon groups is a straight-chain or branched saturated hydrocarbon group having 1 to 4 carbon atoms, and the other hydrocarbon group is a straight-chain or branched saturated hydrocarbon group having 6 to 12 carbon atoms (provided that the hydrocarbon group optionally contains an ester bond).

[0038] R 21 , R 23 , R 24 These are preferably, independently of each other, a hydrogen atom or a saturated hydrocarbon group having 1 to 3 carbon atoms, more preferably, independently of each other, a hydrogen atom or a methyl group, and particularly preferably, a hydrogen atom.

[0039] The xanthene compounds of the present invention can be obtained, for example, by a salt exchange reaction between Acid red 289 or a derivative thereof and a quaternary ammonium salt of an aromatic nitrogen ring compound having a linear or branched saturated or unsaturated hydrocarbon group (which optionally includes ether and / or ester bonds within the hydrocarbon group).

[0040] Here, a derivative of Acid red 289 refers to the following structural part of Acid red 289. [ka] This refers to a compound in which a hydrogen atom or methyl group of the benzene ring is substituted with a saturated hydrocarbon group having 1 to 6 carbon atoms (however, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms) or with an alkoxy group having 1 to 6 carbon atoms (however, the alkyl portion of the alkoxy group is a saturated hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms).

[0041] Quaternary ammonium salts of aromatic nitrogen ring compounds can be obtained by the reaction of an aromatic nitrogen ring compound with a compound having a hydrocarbon group, for example, by the alkylation reaction of the aromatic nitrogen ring compound. Furthermore, quaternary ammonium salts of aromatic nitrogen ring compounds containing an ether bond can be obtained, for example, by the dehydration condensation of a quaternary ammonium salt of a pyridine derivative having a hydroxyl group with an alcohol. Quaternary ammonium salts of aromatic nitrogen ring compounds containing an ester bond can be obtained, for example, by the dehydration condensation of a quaternary ammonium salt of a pyridine derivative having a carboxyl group with an alcohol.

[0042] Furthermore, if the anion of Acid red 289 or its derivative is, for example, a mixture of an n=1 anion and an n=2 anion in the general formula (1) of the present invention, the xanthene compound of the present invention obtained by the salt exchange reaction will also be a mixture of an n=m=1 salt-forming compound and an n=m=2 salt-forming compound, but such a mixture will also be included in the xanthene compound of the present invention.

[0043] The xanthene compounds of the present invention include, specifically, compounds having the following structures. Among these, at least one of compounds 1 to 4 is preferred as the xanthene compound of the present invention.

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] <Resin composition> The resin composition of the present invention comprises the xanthene compound of the present invention and a binder resin. The resin composition of the present invention may be in liquid form or in the form of a dry film obtained by drying the liquid resin composition. The xanthene compound has already been described and will not be described here.

[0054] [Binder resin] The binder resin is a binder that forms the main component of cured products such as cured films. While the binder resin is not particularly limited, it is preferably a resin having acidic functional groups such as carboxyl groups and phenolic hydroxyl groups. In particular, a polymer having carboxyl groups is preferred; for example, a copolymer of an ethylene-based unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer can be cited.

[0055] [Crosslinking agent] The resin composition of the present invention may contain a crosslinking agent to adjust the physical properties of the resulting cured product, such as elasticity and hardness.

[0056] A crosslinking agent is a compound having two or more polymerizable functional groups. Examples of polymerizable functional groups include ethylenically unsaturated groups, oxyranyl groups, oxetanyl groups, and N-alkoxymethylamino groups.

[0057] [Photopolymerization initiator] The resin composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator imparts radiation sensitivity to the resin composition of the present invention. That is, it is a compound that generates an active species capable of initiating polymerization of the binder resin and crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far-infrared rays, and X-rays. Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

[0058] [solvent] The resin composition of the present invention may be prepared as a liquid composition by adding a solvent. Examples of solvents include (poly)alkylene glycol monoalkyl ethers, keto alcohols, (poly)alkylene glycol monoalkyl ether acetates, ketones, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate.

[0059] [Other ingredients] The resin composition of the present invention may optionally contain dyes, pigments, thermal polymerization initiators, fillers, polymer compounds, surfactants, antioxidants, UV absorbers, anti-aggregation agents, and the like, other than the xanthene compounds of the present invention.

[0060] The resin composition of the present invention can be obtained, for example, by filtering a solution containing the xanthene compound of the present invention, other dyes and pigments other than the xanthene compound, through a filter to remove minute foreign matter, and / or by filtering a resin composition obtained by mixing and kneading all the components through another filter. Methods for preparing such resin compositions are disclosed, for example, in Japanese Patent Publication No. 2008-58642 and Japanese Patent Publication No. 2010-132874.

[0061] <Color Filter> The color filter of the present invention has a cured product of the resin composition of the present invention. Specifically, the color filter of the present invention comprises a colored layer including a cured film of the resin composition of the present invention.

[0062] An example of a method for manufacturing a color filter is described below. First, a light-shielding layer (black matrix) is formed on the substrate surface, if necessary, to demarcate the areas where pixels will be formed. Next, a solution of the resin composition of the present invention (red coloring composition) is applied to the substrate surface on which the light-shielding layer has been formed, and the solvent is evaporated by pre-baking to form a coating film. The obtained coating film is exposed to light through a photomask and developed using an alkaline developer to dissolve and remove the unexposed areas of the coating film. Subsequently, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined sequence can be obtained.

[0063] Subsequently, using a green or blue radiation-sensitive resin composition, coating, prebaking, exposure, development, and postbaking of the resin composition are performed in the same manner as described above, and a green resin array and a blue pixel array are sequentially formed on the same substrate, whereby the color filter of the present invention, in which pixel arrays of the three primary colors of red, green, and blue are arranged on a substrate, can be obtained.

[0064] The order of forming the pixel arrays of each color is not limited to the order described above, and the color filter of the present invention only needs to be such that the red pixel array is a colored layer containing a cured product of the resin composition of the present invention. [Examples]

[0065] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to only these examples.

[0066] (1. Synthesis of Xanthene Compounds) [Synthesis Example 1] <Synthesis of AR289-1> To a 300 mL flask, 24.0 g (35.5 mmol) of C.I. Acid red 289 and 240 g of ion-exchanged water were added, and dissolved at room temperature. To this solution, a solution obtained by dissolving 5.2 g of 1-dodecylpyridinium chloride in 60 g of ion-exchanged water was added. After stirring at room temperature for 1 hour, the precipitated crystals were filtered, washed with water, and dried to obtain 23 g of a salt-forming product obtained by salt exchange reaction between C.I. Acid red 289 and 1-dodecylpyridinium chloride. 1 It was confirmed by ¹H NMR spectrum measurement that the obtained compound was a compound represented by the following formula.

[0067] 1 ¹H NMR (400 MHz, DMSO-d₆): δ = 9.85 (Ar-NH), 8.11-9.04 (pyridine), 5.91-7.95 (Ar), 4.54 (pyridine-CH₂), 2.07-2.31 (Ar-CH₃), 1.85 (pyridine-CH₂- CH2-), 1.18 (pyridine-CH2-CH2- (CH 2 ) 9-), 0.80 (pyridine-(CH2) 11 - CH 3) The synthesis of the above AR289-1 is represented by the following formula.

[0068]

Chemical Formula

[0069] [Synthesis Example 2] <Synthesis of AR289-2> 24.0 g (35.5 mmol) of C.I. Acid Red 289 and 240 g of ion-exchanged water were added to a 300 mL flask, and dissolved at room temperature. To this solution was added a solution of 16.0 g of diethyl 1-(pentylmalonate)-3-methylimidazolium bromide dissolved in 60 g of ion-exchanged water. After stirring at room temperature for 1 hour, the precipitated crystals were filtered, washed with water and dried to obtain 23 g of a salt-forming product obtained by salt exchange reaction between C.I. Acid Red 289 and diethyl 1-(pentylmalonate)-3-methylimidazolium bromide. 1 It was confirmed by ¹H NMR spectrum measurement that the obtained compound is a compound represented by the following formula.

[0070] 1 ¹H NMR (400 MHz, DMSO-d₆): δ = 9.85 (Ar-NH), 7.71-9.07 (imidazolium), 5.91-7.95 (Ar), 4.08 (O-CH₂-), 4.01 (imidazolium-CH₂), 3.81 (imidazolium-CH₃), 3.39 (imidazolium-(CH₂)₅- CH -), 2.07-2.31 (Ar-CH₃), 1.21-1.71 (imidazolium-CH₂- (CH 2 ) 4-, 1.12 (O-CH₂- CH 3) The synthesis of the above AR289-2 is represented by the following formula.

[0071]

Chem.

[0072] [Synthesis Example 3] <Synthesis of AR289-3> Into a 300 mL flask, 24.0 g (35.5 mmol) of C.I. Acid Red 289 and 240 g of ion-exchanged water were added, and dissolved at room temperature. To this solution, a solution prepared by dissolving 14.5 g of 1-hexadecyl-4-methylpyridinium chloride in 60 g of ion-exchanged water was added. After stirring at room temperature for 1 hour, the precipitated crystals were collected by filtration, washed with water and dried, to obtain 23 g of a salt-forming compound produced by a salt exchange reaction between C.I. Acid Red 289 and 1-hexadecyl-4-methylpyridinium chloride. 1 It was confirmed by 1H NMR spectrum measurement that the obtained compound is a compound represented by the following formula.

[0073] 1 1H NMR (400 MHz, DMSO-d6): δ=9.85 (Ar―NH), 7.94-8.89 (pyridine), 5.91-7.95 (Ar), 4.64 (pyridine―CH2), 2.55 (pyridine―CH3), 2.07-2.31 (Ar―CH3), 1.83 (pyridine―CH2- CH 2-), 1.18 (pyridine―CH2-CH2- (CH 2 ) 13 -), 0.80 (pyridine―(CH2) 15 - CH 3) The synthesis of AR289-3 described above is represented by the following formula.

[0074]

Chem.

[0075] These AR289-1, AR289-2, and AR289-3 are respectively used as the salt-forming compounds according to Examples 1 to 3.

[0076] The salt-forming compounds used in the comparative examples are AR289 (Comparative Example 1), AR289-c2 (Comparative Example 2), and AR289-c3 (Comparative Example 3).

[0077] AR289 is CIAcid red289 and is represented by the following formula.

[0078] [ka]

[0079] AR289-c2 is a salt-forming compound obtained by the salt exchange reaction between CIAcid red289 and benzyltrimethylammonium chloride, and is represented by the following formula.

[0080] [ka]

[0081] AR289-c3 is a salt-forming compound obtained by the salt exchange reaction between CIAcid red289 and tetrabutylphosphonium chloride, and is represented by the following formula.

[0082] [ka]

[0083] (2. Implementation of evaluation tests) Using the salt-forming compounds described above, we measured the absorbance in the visible light region, measured the solubility, and evaluated the color stability of the coating film after thermal and light history, as follows. The results are shown in Table 1.

[0084] [Measurement of absorbance in the visible light region] A resin composition was prepared by mixing 0.01 g of each salt-forming compound, 0.99 g of resin (Daicel Chemicals, Cyclomer P (ACA) Z320), and 0.5 g of Propylene glycol methyl ether (PGME) solvent. The solution of the obtained resin composition was coated onto a glass plate to a thickness of 2 μm and pre-baked on a hot plate at 100°C for 3 minutes. The absorption spectrum of the prepared film was measured using a spectrophotometer (JASCO Corporation, instrument name: V-570). Table 1 shows the absorption spectrum in the range of 350 to 700 nm.

[0085] [Measuring Solubility] Each salt-forming compound was added to a 200 mL sample vial in propylene glycol methyl ether (PGME) solvent, stirred with a stirring bar at 20°C for 15 minutes, then left to stand at 25°C for 10 minutes, and the degree of dissolution was observed visually to determine if it had dissolved.

[0086] The criteria for judgment were as follows: after performing the above procedure, each salt-forming compound dissolved in the PGME solvent at a rate of more than 3% by mass relative to the total mass of the PGME solvent and the salt-forming compound, or dissolved at a rate of less than 3% by mass.

[0087] [Evaluation of color stability of coatings after thermal treatment] A resin composition was prepared by mixing 0.01 g of each salt-forming compound, 0.99 g of resin (Daicel Chemicals Cyclomer P (ACA) Z320), and propylene glycol methyl ether (PGME) solvent. The solution of the obtained resin composition was applied to a glass plate to a thickness of 2 μm and pre-baked on a hot plate at 100°C for 3 minutes. After cooling, the chromaticity 1 (L*(1), a*(1), b*(1)) of the obtained coating film was measured using a spectrophotometer (Konica Minolta, Inc. "CM-5"). Subsequently, as a heat resistance test, the film was heated in an oven at 230°C for 2 hours and the chromaticity 2 (L*(2), a*(2), b*(2)) was measured. Using the measured color difference values, the color difference ΔEab* was calculated using the following formula.

[0088] ΔE*ab = √((L*(2) - L*(1)) 2 +(a*(2)-a*(1)) 2 +(b*(2)-b*(1)) 2 )

[0089] [Evaluation of color stability of coatings after phototherapy] A test glass plate was prepared using the same procedure as for evaluating the color stability of the coating film after the above thermal history, and the chromaticity 1 (L*(1), a*(1), b*(1)) was measured using a spectrophotometer (Konica Minolta, Inc. "CM-5"). The glass plate was then placed in a lightfastness tester (TOYOSEIKI Corporation "SUNTESTCPS+") and subjected to a 60W / m² test. 2 The glass plates were left at 60°C for 24 and 48 hours. After removing the glass plates, the chromaticity 2 (L*(2), a*(2), b*(2)) was measured, and the color difference ΔE*ab was calculated in the same manner as the evaluation of the color stability of the coating after the thermal history described above, and the color stability of the coating after the light history was evaluated.

[0090] [Table 1]

[0091] As can be seen from the comparison between Examples 1-3 and Comparative Examples 1-3 in Table 1, the xanthene compounds of the present invention exhibit higher coloring power compared to conventional Acid Red 289 and its improved versions (see absorption spectrum (350-700 nm)), and the comparison of a*(1) values ​​shows that the xanthene compounds of the present invention have a greater reddish tint. Furthermore, the color development stability after thermal history of the coating film was as good as or slightly better than that of conventional products, and the color development stability after light history of the coating film was higher than that of conventional products.

[0092] Furthermore, it was found that the xanthene compounds of the present invention exhibit higher solubility in solvents compared to conventional Acid Red 289 and its improved versions. [Industrial applicability]

[0093] The xanthene compounds of the present invention can be used as colorants and reagents for various industrial products, and are particularly suitable as colorants for resin compositions used to form color filters.

Claims

1. General formula (1) 【Chemistry 1】 (In general formula (1), R １ , R ２ These are, independently of each other, a hydrogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO ３ － , -OR １３ , or R １３ It may also be replaced with The aforementioned R １３ This is a saturated hydrocarbon group having 1 to 6 carbon atoms (however, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with halogen atoms), R ３ to R １２ are each independently a hydrogen atom, -SO ３ － or a saturated hydrocarbon group having 1 to 6 carbon atoms, The aforementioned R １ ~R １２ -SO ３ － An anion that forms a xanthene chromophore having an anionic functional group, represented by (where the number of n is determined by the total number of substituents, and n is an integer of 1 or more), A cation comprising a linear or branched aromatic nitrogen ring compound having saturated or unsaturated hydrocarbon groups (optionally including ether and / or ester bonds within the hydrocarbon groups), and a xanthene compound which is a salt-forming compound thereof, A colorant for resin compositions used to form color filters.

2. The cation consisting of the aforementioned aromatic nitrogen ring compound is general formula (2) 【Chemistry 2】 (In general formula (2), R １４ This is a hydrogen atom, or a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (which optionally includes ether and / or ester bonds within the hydrocarbon group). R １５ ~R １９ These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The aforementioned R １４ ~R １９ At least one of them is the hydrocarbon group, A quaternary ammonium cation of a pyridine derivative represented by the general formula (3), where m is 1 or 2. 【Transformation 3】 (In general formula (3), R ２０ , R ２２ These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing ether and / or ester bonds within the hydrocarbon group), R ２１ , R ２３ , R ２４ These are, independently of each other, a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The aforementioned R ２０ ~R ２４ At least one of them is the hydrocarbon group, A quaternary ammonium cation of an imidazole derivative represented as m is 1 or 2, The colorant according to claim 1, wherein n in the general formula (1) is equal to m in the general formula (2) or (3).

3. A resin composition comprising a colorant according to claim 1 or 2 and a binder resin.

4. A color filter having a cured product of the resin composition described in claim 3.

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