Xanthene-based compound, resin composition, and color filter

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 a xanthene compound, a resin composition, and a color filter, and in particular to a xanthene compound that is a salt-forming compound of an anion that forms a xanthene chromophore having an anionic functional group and a cation that is composed of an aromatic nitrogen ring compound, a resin composition containing this xanthene compound, and a color filter that contains a cured product of this resin composition. [Background technology]

[0002] CI Acid Red 289 (hereinafter sometimes abbreviated as Acid Red 289), a sodium salt of a xanthene compound, has been widely used for over 35 years, from textile dyeing to information electronics materials, and in particular, in recent years, its performance as a raw material for dyes for color filters has been discovered.

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

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

[0005] Patent Document 1 discloses an improved version of Acid Red 289, which is a compound containing a xanthene compound used in Acid Red 289 and a compound represented by the following general formula (a): [ka] (In the general formula (a), R1 to R4 each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two of R1, R2, R3, and R4 have 5 to 20 carbon atoms. Y -represents an inorganic or organic anion.

[0006] Patent Document 2 also discloses an improved version of Acid Red 289, which is a compound obtained by combining a xanthene compound used in Acid Red 289 with a compound represented by the following general formula (b): [ka] (In general formula (b), R 16 ~R 19 represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and R 16 and R 17 is a hydrogen atom, and R 18 and R 19 wherein at least one of the groups is a linear or branched alkyl group having 4 to 20 carbon atoms which may have a substituent. M represents an alkali metal atom, and n represents 1.

[0007] Patent Document 3 also discloses an improved version of Acid Red 289, which is a compound obtained by combining a xanthene compound used in Acid Red 289 with a compound represented by the following general formula (c): [ka] (In general formula (c), R 1 ~R 4 are each independently a hydrogen atom or an organic group. 1 ~R 4 At least one of R is an organic group, 1 ~R 4 The total number of carbon atoms in the organic groups constituting R is 5 to 50, 1 ~R 4 Two of the groups may be bonded to form a ring.) or general formula (d) [ka] (In general formula (d), R 5 ~R 10are each independently a hydrogen atom or an organic group. 5 ~R 10 Two of these may be bonded to form a ring. X represents a divalent linking group. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 4492760 [Patent Document 2] Patent No. 6246120 [Patent Document 3] Patent No. 6572990 Summary of the Invention [Problem to be solved by the invention]

[0009] However, according to the salt-forming compound described in Patent Document 1, when a colorant containing this salt-forming compound and a blue pigment is used, it is said that a blue coloring composition for color filters can be obtained, which will give a stable color filter that is excellent in color properties, heat resistance, etc. However, there is no mention of improving the coloring strength of Acid Red 289 itself. When the inventors checked the coloring strength 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 strength.

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

[0011] Patent Document 3 discloses that a cured film obtained from a composition containing the salt-forming compound has higher tinting strength and higher heat resistance than a cured film containing the salt-forming compound of Patent Document 1. However, when the inventors checked the tinting strength and color stability of the cured film after heat history of the cured film containing the salt-forming compound of Patent Document 3, they could not confirm sufficient improvement compared to Acid Red 289.

[0012] Therefore, there has been a demand for a salt-forming compound that has higher coloring strength and color stability after heat exposure compared to an improved version of the conventional Acid Red 289.

[0013] Furthermore, when a compound that exhibits red color is used in an application that involves exposure to light, such as a color filter, color stability after exposure to light is also required.

[0014] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a salt-forming compound which is a salt of a xanthene compound and has higher tinting strength and higher color stability after exposure to heat and light than conventional compounds, 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 object of the present invention is to General formula (1) [ka] In the general formula (1), R1 and R2 are each 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 may be substituted with R 13 represents a saturated hydrocarbon group having 1 to 6 carbon atoms (provided that a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom), R3~R 12are, independently of each other, hydrogen atoms or -SO3 - or a saturated hydrocarbon group having 1 to 6 carbon atoms, R1~R 12 Contains -SO3 - the number n is determined by the total number of substituents, and n is an integer of 1 or more), and an anion forming a xanthene chromophore having an anionic functional group represented by the formula: It has been found that this can be achieved by a xanthene compound, which is a salt-forming compound formed by a cation consisting of an aromatic nitrogen ring 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).

[0016] The cation consisting of the aromatic nitrogen ring compound is represented by the general formula (2): [ka] (In general formula (2), R 14 is a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (optionally containing an ether bond and / or an ester bond within the hydrocarbon group), R 15 ~R 19 are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R 14 ~R 19 at least one of the groups is the hydrocarbon group; m is 1 or 2), or a quaternary ammonium cation of a pyridine derivative represented by the general formula (3): [ka] (In general formula (3), R 20 , R 22 are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing an ether bond and / or an ester bond within the hydrocarbon group), R 21 , R 23 , R 24 are each independently 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 the groups is the hydrocarbon group; 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 above-mentioned object of the present invention can also be achieved by a curable resin composition containing 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 compound of the present invention exhibits higher coloring strength than conventional Acid Red 289 and its improved salt-forming compounds, and the cured product of the curable resin composition containing the xanthene compound of the present invention and the color filter containing this cured product have higher color stability after heat and light exposure than conventional products. DETAILED DESCRIPTION OF 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 that comprises an aromatic nitrogen ring 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). Because the cation of the xanthene compound comprises an aromatic nitrogen ring compound, color stability after exposure to heat and light can be improved. Furthermore, since the aromatic nitrogen ring compound has the aforementioned hydrocarbon group, compatibility with binder resins and solvents is improved. As a result, the tinting power of the xanthene compound can be enhanced.

[0020] [Anions forming xanthene-based chromophores with anionic functional groups] The anion forming the xanthene chromophore having an anionic functional group is represented by the general formula (1): [ka] In the general formula (1), R1 and R2 are each 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 may be substituted with R 13 represents a saturated hydrocarbon group having 1 to 6 carbon atoms (provided that a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom), R3~R 12 are, independently of each other, hydrogen atoms or -SO3 - or a saturated hydrocarbon group having 1 to 6 carbon atoms, R1~R 12 Contains -SO3 - The number n is determined by the total number of substituents, and n is an integer of 1 or more.

[0021] Regarding the anion forming the xanthene chromophore having an anionic functional group of the present invention, the anionic functional group is -SO3 - This refers to the base.

[0022] R1 and R2 are each independently preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms. Specifically, an example of an aromatic hydrocarbon group having 6 carbon atoms is a phenyl group, and an example of an aromatic hydrocarbon group having 10 carbon atoms is a naphthyl group.

[0023] R 13The saturated hydrocarbon group may have a straight chain, branched chain or cyclic structure as long as it has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 carbon atom.

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

[0025] R3~R 12 The saturated hydrocarbon groups having 1 to 6 carbon atoms as the substituents may each independently have a linear, branched, or cyclic structure, and may have 1 to 3 carbon atoms, or may have 1 carbon atom. Specific examples include aliphatic hydrocarbon groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, and hexyl group; and alicyclic hydrocarbon groups such as a cyclopentyl group and cyclohexyl group.

[0026] R3~R 12 are, independently of one another, preferably a hydrogen atom or -SO3 - It is a substituent. In general formula (1), n ​​is an integer of 1 or more, preferably an integer of 1 or more and 4 or less, and particularly preferably n is 1 or 2. [Cations consisting of aromatic nitrogen ring compounds] In the present invention, examples of the cations formed from the aromatic nitrogen ring compounds include cations formed from five- or six-membered aromatic nitrogen compounds containing one or two nitrogen atoms in the aromatic ring structure.

[0027] Examples of cations composed 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 them, a cation consisting of an aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group (optionally containing an ether bond and / or an ester bond in the hydrocarbon group) is represented by the general formula (2): [ka] (In general formula (2), R 14 is a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (optionally containing an ether bond and / or an ester bond within the hydrocarbon group), R 15 ~R 19 are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and R 14 ~R 19 at least one of the groups is the hydrocarbon group; m is 1 or 2), It is preferable that n in the general formula (1) is equal to m in the general formula (2). In the general formula (2), R 14 is a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and if the hydrocarbon group contains an ester bond (-C(=O)-O-), the one carbon atom constituting the ester bond is not included in the number of carbon atoms.

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

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

[0031] R 14 Examples of the case where an ether bond is contained in a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms include R 14 is represented by the following structural formula (5) [ka] In the case where the hydrocarbon group contains an ester bond, for example, R 14 is represented by the following structural formula (6) [ka] This is the case when

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

[0033] In addition, a cation consisting of an aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group (which may optionally contain an ether bond and / or an ester bond in the hydrocarbon group) can be represented by the general formula (3): [ka] (In general formula (3), R 20 , R 22 are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing an ether bond and / or an ester bond within the hydrocarbon group), R 21 , R 23 , R 24 are each independently 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 the groups is the hydrocarbon group; m is 1 or 2), It is preferable that n in the general formula (1) is equal to m in the general formula (3). In the general formula (3), R 20 , R 22 is a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, and if the hydrocarbon group contains an ester bond (-C(=O)-O-), the one carbon atom constituting the ester bond is not included in the number of carbon atoms.

[0034] R 20 , R 22 are preferably each independently a linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms (which may optionally contain an ether bond and / or an ester bond within the hydrocarbon group).

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

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

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

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

[0039] The xanthene compound 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 (optionally containing an ether bond and / or an ester bond within the hydrocarbon group).

[0040] Here, the derivative of Acid Red 289 is a compound having the following structure of Acid Red 289: [ka] in which the hydrogen atoms or methyl groups on the benzene ring are substituted with saturated hydrocarbon groups having 1 to 6 carbon atoms (provided that the hydrogen atoms contained in the saturated hydrocarbon groups may be substituted with halogen atoms), or with alkoxy groups having 1 to 6 carbon atoms (provided that the alkyl group 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 alkylation of the aromatic nitrogen ring compound. Quaternary ammonium salts of aromatic nitrogen ring compounds containing an ether bond can be obtained, for example, by 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 dehydration condensation of a quaternary ammonium salt of a pyridine derivative having a carboxy group with an alcohol.

[0042] In addition, when the anion of Acid Red 289 or a derivative thereof is, for example, a mixture of an anion where n=1 and an anion where n=2 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 a salt-forming compound where n=m=1 and a salt-forming compound where n=m=2, and such a mixture is also included in the xanthene compound of the present invention.

[0043] Specific examples of the xanthene compound of the present invention include 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 contains the xanthene compound of the present invention and a binder resin. The resin composition of the present invention may be in a liquid form or in the form of a dry film obtained by drying a liquid resin composition. The xanthene compound has already been described, and its description will be omitted here.

[0054] [Binder resin] The binder resin is a binding agent that is the main component of a cured product such as a cured film. The binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group is preferred, and an example thereof is a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer.

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

[0056] The crosslinking agent refers to a compound having two or more polymerizable functional groups, such as an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, or an N-alkoxymethylamino group.

[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, the photopolymerization initiator is a compound that generates active species that can initiate polymerization of the binder resin and crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far infrared light, or X-rays. Examples of such photopolymerization initiators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and O-acyloxime-based compounds.

[0058] [solvent] The resin composition of the present invention may be prepared as a liquid composition by adding a solvent, such as (poly)alkylene glycol monoalkyl ethers, ketoalcohols, (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 other than the xanthene compound of the present invention, pigments, thermal polymerization initiators, fillers, polymeric compounds, surfactants, antioxidants, ultraviolet absorbers, anti-aggregating agents, and the like.

[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 and 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 of the components through a separate filter. Methods for preparing such resin compositions are disclosed, for example, in JP-A-2008-58642 and JP-A-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 has a colored layer including a cured film of the resin composition of the present invention.

[0062] An example of a method for producing a color filter is described below. First, a light-shielding layer (black matrix) for partitioning areas where pixels are to be formed is formed on the surface of a substrate, if necessary. Next, a solution of the resin composition of the present invention (red coloring composition) is applied to the surface of the substrate on which the light-shielding layer has been formed, and the solvent is evaporated by pre-baking to form a coating film. The resulting 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. Then, by post-baking, a pixel array in which a red pixel pattern is arranged in a predetermined array can be obtained.

[0063] Next, using a green or blue radiation-sensitive resin composition, the resin composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as above, and a green resin array and a blue pixel array are sequentially formed on the same substrate, whereby a color filter of the present invention in which pixel arrays of red, green, and blue three primary colors are arranged on the substrate can be obtained.

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

Example

[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 compound) [Synthesis Example 1] ><Synthesis of AR289-1> 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, a solution prepared 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 compound by a 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 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, a solution prepared by dissolving 16.0 g of 1-(diethyl pentylmalonate)-3-methylimidazolium bromide 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 compound by the salt exchange reaction between C.I. Acid red 289 and 1-(diethyl pentylmalonate)-3-methylimidazolium bromide. 1 It was confirmed by 1H NMR spectrum measurement that the obtained compound was 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 AR289-2 is represented by the following formula.

[0071]

Chem.

[0072] [Synthesis Example 3] [Synthesis of AR289-3] 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, 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 filtered, washed with water, and dried to obtain 23 g of a salt-forming compound by the salt exchange reaction between C.I. Acid red 289 and 1-hexadecyl-4-methylpyridinium chloride. 1 By measuring the 1H NMR spectrum, it was confirmed that the obtained compound was 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 the above AR289-3 is represented by the following formula.

[0074]

Chem.

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

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

[0077] AR289 is CIAcid red 289 and is represented by the following formula:

[0078] [ka]

[0079] AR289-c2 is a salt-formed compound obtained by a salt exchange reaction between CI Acid red 289 and benzyltrimethylammonium chloride, and is represented by the following formula:

[0080] [ka]

[0081] AR289-c3 is a salt-formed compound obtained by a salt exchange reaction between CI Acid red 289 and tetrabutylphosphonium chloride, and is represented by the following formula:

[0082] [ka]

[0083] (2. Implementation of evaluation tests) The above salt-forming compounds were used to measure absorbance in the visible light region, measure solubility, and evaluate the color stability of the coating film after heat and light exposure, as described below. 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 (Cyclomer P (ACA) Z320, manufactured by Daicel Chemical Industries, Ltd.), and 0.5 g of propylene glycol methyl ether (PGME) solvent. The resulting resin composition solution was applied to a glass plate to a thickness of 2 μm and prebaked on a hot plate at 100°C for 3 minutes. The absorption spectrum of the prepared film was measured using a spectrophotometer (manufactured by JASCO Corporation, device name: V-570). Table 1 shows the absorption spectrum in the range of 350 to 700 nm.

[0085] [Solubility measurement] Each salt-forming compound was added to a 200 mL sample bottle in a propylene glycol methyl ether (PGME) solvent, and a stirrer was added. The mixture was stirred at 20°C for 15 minutes, then left at 25°C for 10 minutes, and the solution was visually observed to determine whether it had dissolved.

[0086] The criterion for judgment was whether, after the above operation, each salt-forming compound dissolved in the PGME solvent at a rate of more than 3 mass % or less than 3 mass % in terms of mass percentage relative to the total mass of the PGME solvent and the salt-forming compound.

[0087] [Evaluation of color stability of coating film after thermal history] Resin compositions were prepared by mixing 0.01 g of each salt-forming compound, 0.99 g of resin (Cyclomer P (ACA) Z320, manufactured by Daicel Chemical Industries, Ltd.), and propylene glycol methyl ether (PGME) solvent. The resulting resin composition solution was applied to a glass plate to a thickness of 2 μm and prebaked on a hot plate at 100°C for 3 minutes. After cooling, the chromaticity 1 (L*(1), a*(1), b*(1)) of the resulting coating film was measured using a spectrophotometer (Konica Minolta, Inc., "CM-5"). Furthermore, 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. The measured color difference values ​​were used to calculate the color difference ΔEab* according to 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 coating film after exposure to light] Test glass plates were prepared using the same procedure as in the evaluation of the color stability of the coating film after heat history, and the chromaticity (L*(1), a*(1), b*(1)) was measured using a spectrophotometer (Konica Minolta, Inc. "CM-5"). The glass plates were then placed in a lightfastness tester (TOYOSEIKI "SUNTESTCPS+") and measured at 60 W / m 2 The glass plate was then left at 60°C for 24 and 48 hours. After removing the glass plate, the chromaticity 2 (L*(2), a*(2), b*(2)) was measured, and the color difference ΔE*ab was calculated in the same manner as in the evaluation of the color stability of the coating film after heat history, to evaluate the color stability of the coating film after light history.

[0090] [Table 1]

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

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

[0093] The xanthene compound of the present invention can be used as a colorant or reagent for various industrial products, and can be particularly suitably used as a colorant for resin compositions for forming color filters.

Claims

1. General formula (1) 【Chemical 1】 (In general formula (1), R １ , R ２ are each 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 not —SO ３ － , -OR １３ , or R １３ may be substituted with R １３ represents a saturated hydrocarbon group having 1 to 6 carbon atoms (provided that a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom), R ３ ~R １２ are each independently a hydrogen atom or —SO ３ － or a saturated hydrocarbon group having 1 to 6 carbon atoms, R １ ~R １２ Included in -SO ３ － the number n is determined by the total number of substituents, and n is an integer of 1 or more; and A xanthene compound which is a salt-forming compound formed by a cation consisting of an aromatic nitrogen ring 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).

2. The cation consisting of the aromatic nitrogen ring compound is represented by the general formula (2) 【Chemistry 2】 (In general formula (2), R １４ is a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms (optionally containing an ether bond and / or an ester bond within the hydrocarbon group), R １５ ~R １９ are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The R １４ ~R １９ at least one of the groups is the hydrocarbon group; and m is 1 or 2), or a quaternary ammonium cation of a pyridine derivative represented by the general formula (3): 【Chemistry 3】 (In general formula (3), R ２０ , R ２２ are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (optionally containing an ether bond and / or an ester bond within the hydrocarbon group), R ２１ , R ２３ , R ２４ are each independently a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and The R ２０ ~R ２４ at least one of the groups is the hydrocarbon group; m is 1 or 2), The xanthene compound 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 the xanthene compound according to claim 1 or 2 and a binder resin.

4. A color filter comprising a cured product of the resin composition according to claim 3.

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