Xanthene-based compound, resin composition, and color filter

Abstract

The invention relates to a xanthene compound, a resin composition and a color filter. Provided are: a salt-forming compound which is a salt of a xanthene-based compound and has higher tinting strength and color development stability after a thermal / optical process than conventional salt-forming compounds; a resin composition containing the salt-forming compound; and a color filter containing a cured product of the resin composition. The present invention is a xanthene-based compound which is represented by general formula (1) and which is obtained by reacting an anion that forms a xanthene-based chromophore having an anionic functional group with a linear or branched saturated or unsaturated hydrocarbon group (wherein R1 represents a hydrogen atom or a hydrogen atom). And a salt-forming compound of a cation formed by an aromatic nitrogen ring compound in which an ether bond and / or an ester bond is optionally included in the hydrocarbon group). In addition, the present invention also provides a resin composition containing the xanthene-based compound of the present invention, and a color filter having a cured product of the resin composition.

Description

Technical Field

[0001] The present invention relates to xanthene compounds, resin compositions and color filters, and in particular to xanthene compounds that are salt-forming compounds of cations formed by anions of xanthene chromophores having anionic functional groups and aromatic nitrogen ring compounds, resin compositions containing the xanthene compounds, and color filters containing cured products of the resin compositions. Background Art

[0002] CIAcid red 289 (hereinafter sometimes referred to as Acid red 289), a sodium salt of a xanthene-based compound, has been widely used for dyeing fibers and information and electronic materials for over 35 years. In recent years, its performance as a raw material for color filter dyes has been particularly recognized.

[0003] A color filter is a filter made by forming a pattern of three colors of color resist: red (R), green (G), and blue (B) on a translucent substrate such as glass. Light passes through the color filter, providing color information to the light.

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

[0005] Patent Document 1 discloses, as an improved product of Acid red 289, a salt compound formed by a xanthene-based compound used in Acid red 289 and a quaternary ammonium salt compound represented by the following general formula (a):

[0006]

[0007] (In the general formula (a), R1 to R4 each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, and the number of carbon atoms in at least two of R1, R2, R3, and R4 is 5 to 20. Y - represents an inorganic or organic anion. ).

[0008] Patent Document 2 discloses, as an improved product of Acid red 289, a salt compound formed by the xanthene compound used in Acid red 289 and a quaternary ammonium salt compound represented by the following general formula (b):

[0009]

[0010] (In general formula (b), R 16 ~R 19represents a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, R 16 and R 17 is a hydrogen atom, R 18 and R 19 At least one of them is a linear or branched alkyl group having 4 to 20 carbon atoms and optionally having a substituent. M represents an alkali metal atom, and n represents 1.).

[0011] Patent Document 3 discloses, as an improved product of Acid red 289, a salt compound formed by the xanthene compound used in Acid red 289 and a phosphonium cation represented by the following general formula (c) or (d):

[0012]

[0013] (In general formula (c), R 1 ~R 4 Each of R represents independently a hydrogen atom or an organic group. 1 ~R 4 At least one of them is an organic group, and constitutes R 1 ~R 4 The total number of carbon atoms in the organic group is 5 to 50, R 1 ~R 4 Two of them are optionally bonded to form a ring.)

[0014]

[0015] (In general formula (d), R 5 ~R 10 Each of R represents a hydrogen atom or an organic group independently of the other. 5 ~R 10 Two of them are optionally bonded to form a ring. X represents a divalent linking group. ).

[0016] Prior art literature

[0017] Patent Literature

[0018] Patent Document 1: Japanese Patent No. 4492760

[0019] Patent Document 2: Japanese Patent No. 6246120

[0020] Patent Document 3: Japanese Patent No. 6572990 BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a graph showing the results of measurement of absorbance in the visible light region, measurement of solubility, and evaluation of color stability of the coating film after heat / light history. Summary of the Invention

[0022] Problems to be solved by the invention

[0023] However, according to the salt-forming compound described in Patent Document 1, when a colorant containing the salt-forming compound and a blue pigment is used, a blue coloring composition for a color filter is obtained that produces a stable color filter with excellent color properties and heat resistance. However, there is no mention of improving the tinting power of Acid Red 289 itself. The inventors confirmed the tinting power of cured films containing the salt-forming compound contained in the invention disclosed in Patent Document 1, but found that the salt-forming compound itself could not have sufficient tinting power.

[0024] The salt compound described in Patent Document 2 provides a color filter with excellent heat resistance and good solubility in organic solvents of a color filter colorant containing the salt compound. However, there is no description of the tinting power of the salt compound itself compared to conventional Acid Red 289.

[0025] Patent Document 3 discloses that a cured film obtained from a composition containing the salt-forming compound has higher tinting power and higher heat resistance than a cured film containing the salt-forming compound of Patent Document 1. However, the inventors examined the tinting power and color stability of the cured film after a heat history of the salt-forming compound described in Patent Document 3 and found no sufficient improvement compared to Acid Red 289.

[0026] Therefore, a salt-forming compound having higher tinting strength and color stability after heat history than the conventional improved product of Acid Red 289 is sought.

[0027] Furthermore, when a red compound is used in an application exposed to light, such as a color filter, color development stability after light exposure is also required.

[0028] The present invention has been made in view of the above-mentioned problems, and its object is to provide: a salt-forming compound which is a salt of a xanthene-based compound and has higher tinting power than before and higher color stability after heat / light treatment, a resin composition containing the salt-forming compound, and a color filter containing a cured product of the resin composition.

[0029] Solutions for solving problems

[0030] It has been found that the aforementioned object of the present invention is achieved by the following xanthene-based compound, which is a salt-forming compound of an anion of a xanthene-based chromophore having an anionic functional group represented by the general formula (1) and a cation formed by an aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond),

[0031]

[0032] (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, wherein the hydrogen atom contained in the aromatic hydrocarbon group is optionally replaced by -SO3 - 、-OR 13 or R 13 replaced by

[0033] R 13 is a saturated hydrocarbon group having 1 to 6 carbon atoms (wherein hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms),

[0034] R3~R 12 are independently a hydrogen atom, or -SO3 - or a saturated hydrocarbon group having 1 to 6 carbon atoms,

[0035] According to R1~R 12 -SO3 contained in - The number of n is limited by the total number of substituents, and n is an integer greater than or equal to 1).

[0036] In addition, it is preferred that the cation formed by the aromatic nitrogen ring compound is a quaternary ammonium cation of a pyridine derivative represented by the general formula (2), or a quaternary ammonium cation of an imidazole derivative represented by the general formula (3).

[0037] (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 (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond),

[0038] R 15 ~R 19 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and

[0039] The aforementioned R 14 ~R 19 At least one of them is the aforementioned hydrocarbon group,

[0040] m is 1 or 2),

[0041]

[0042] (In general formula (3), R 20 、R 22 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (wherein the hydrocarbon group may optionally contain an ether bond and / or an ester bond),

[0043] R 21 、R 23 、R 24 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and

[0044] R 20 ~R 24 At least one of them is the aforementioned hydrocarbon group,

[0045] m is 1 or 2),

[0046] n in the aforementioned general formula (1) is equal to m in the aforementioned general formula (2) or (3).

[0047] Furthermore, the aforementioned object of the present invention can also be achieved by a curable resin composition comprising the xanthene-based compound of the present invention and a binder resin, and a color filter having a cured product of the curable resin composition.

[0048] Effects of the Invention

[0049] The xanthene-based compounds of the present invention exhibit higher tinting strength than conventional Acid red 289 and its improved salt compounds. Cured products of curable resin compositions containing the xanthene-based compounds of the present invention and color filters containing the cured products have higher color stability after heat / light treatment than conventional ones. DETAILED DESCRIPTION

[0050] <Xanthene compounds>

[0051] The xanthene compound of the present invention is a salt-forming compound of a cation formed by an anion of a xanthene chromophore having an anionic functional group and an aromatic nitrogen ring compound having a straight or branched, saturated or unsaturated hydrocarbon group (wherein, ether bonds and / or ester bonds are arbitrarily included in the hydrocarbon group). The cation of the xanthene compound is formed by an aromatic nitrogen ring compound, and therefore, the color stability after heat / light history can be improved. In addition, the aromatic nitrogen ring compound improves the compatibility with the binder resin and the solvent by having the above-mentioned hydrocarbon group. As a result, the tinting power of the xanthene compound can be improved.

[0052] [Anion forming a xanthene-based chromophore having an anionic functional group]

[0053] The anion forming the xanthene-based chromophore having an anionic functional group is an anion represented by the general formula (1),

[0054]

[0055] (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, wherein the hydrogen atom contained in the aromatic hydrocarbon group is optionally replaced by -SO3 - 、-OR 13 or R 13 replaced by

[0056] R 13 is a saturated hydrocarbon group having 1 to 6 carbon atoms (wherein the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms),

[0057] R3~R 12 are independently a hydrogen atom, or -SO3 - or a saturated hydrocarbon group having 1 to 6 carbon atoms,

[0058] According to R1~R 12 -SO3 contained in - The number of n is limited by the total number of substituents, and n is an integer greater than or equal to 1).

[0059] Regarding the anion forming the xanthene-based chromophore having an anionic functional group of the present invention, the anionic functional group is -SO3 - base.

[0060] R1 and R2 are preferably each independently an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms. Specifically, the aromatic hydrocarbon group having 6 carbon atoms includes phenyl, and the aromatic hydrocarbon group having 10 carbon atoms includes naphthyl.

[0061] R 13 The saturated hydrocarbon group may have any structure, such as linear, branched, or cyclic, as long as it has 1 to 6 carbon atoms. The saturated hydrocarbon group preferably has 1 to 3 carbon atoms, and more preferably 1 carbon electrode.

[0062] As R 13 Specific examples of the saturated hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl; linear or branched aliphatic hydrocarbon groups; and cyclopentyl and cyclohexyl alicyclic hydrocarbon groups.

[0063] As R3~R 12The saturated hydrocarbon groups having 1 to 6 carbon atoms may independently have any linear, branched or cyclic structure, and may have 1 to 3 carbon atoms, or 1 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl aliphatic hydrocarbon groups; and cyclopentyl and cyclohexyl alicyclic hydrocarbon groups.

[0064] R3~R 12 Preferably, each independently is a hydrogen atom, or -SO3 - substituent.

[0065] In the general formula (1), n ​​is an integer of 1 or greater, preferably an integer of 1 or greater and 4 or less, and particularly preferably 1 or 2.

[0066] [Cations formed by aromatic nitrogen ring compounds]

[0067] In the present invention, examples of the cation formed by the aromatic nitrogen ring compound include cations formed by 5-membered or 6-membered aromatic nitrogen compounds containing one or two nitrogen atoms in their aromatic ring structure.

[0068] Examples of the cation formed by such an aromatic nitrogen compound 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.

[0069] Among them, it is preferred that the cation formed by the aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond) is a quaternary ammonium cation of a pyridine derivative represented by the general formula (2),

[0070]

[0071] (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 (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond),

[0072] R 15 ~R 19 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and

[0073] The aforementioned R 14 ~R 19 At least one of them is the aforementioned hydrocarbon group,

[0074] m is 1 or 2),

[0075] n in the general formula (1) is equal to m in the general formula (2).

[0076] It should be noted that in the above general formula (2), R 14 It is a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. When the hydrocarbon group contains an ester bond (—C(═O)—O—), one carbon atom constituting the ester bond is not included in the aforementioned carbon number.

[0077] R 14 Preferably, it is a linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond), and more preferably, it is a linear or branched saturated hydrocarbon group having 8 to 18 carbon atoms (wherein the hydrocarbon group optionally contains an ester bond).

[0078] R 14 Specific examples of the linear or branched saturated hydrocarbon group having 8 to 18 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and branched saturated hydrocarbon groups thereof (2-ethylhexyl, 2-methyloctyl, 8,8-dimethylnonyl, 3-methylundecyl, 2-ethylundecyl, 1-methyl-11-methyldodecyl, 2-methyltetradecyl, 3-ethyltetradecyl).

[0079] As R 14 In the case where the linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms contains an ether bond, for example, R 14 According to the following structural formula (5),

[0080]

[0081] When the hydrocarbon group contains an ester bond, for example, R 14 According to the following structural formula (6),

[0082]

[0083] R 15 ~R 19 They are preferably independently a hydrogen atom or a linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms, and more preferably independently a hydrogen atom or a methyl group.

[0084] In addition, it is preferred that the cation formed by the aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond) is a quaternary ammonium cation of an imidazole derivative represented by the general formula (3),

[0085]

[0086] (In general formula (3), R 20 、R22 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms (wherein the hydrocarbon group may optionally contain an ether bond and / or an ester bond),

[0087] R 21 、R 23 、R 24 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, and

[0088] The aforementioned R 20 ~R 24 At least one of them is the aforementioned hydrocarbon group,

[0089] m is 1 or 2),

[0090] n in the general formula (1) is equal to m in the general formula (3).

[0091] It should be noted that in the above general formula (3), R 20 、R 22 It is a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms. When the hydrocarbon group contains an ester bond (—C(═O)—O—), one carbon atom constituting the ester bond is not included in the aforementioned carbon number.

[0092] R 20 、R 22 Preferably, each is independently a linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond).

[0093] R 20 、R 22 Specific examples of the linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and branched saturated hydrocarbon groups thereof (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).

[0094] R 20 、R 22 The case where the linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms contains an ether bond refers to the case represented by the above structural formula (5). As the case where the hydrocarbon group contains an ester bond, for example, R 20 、R 22 The situation shown by the above structural formula (6).

[0095] In particular, R is more preferably 20 、R 22 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 (wherein the hydrocarbon group optionally contains an ester bond).

[0096] R 21 、R 23 、R 24 They are preferably independently a hydrogen atom or a saturated hydrocarbon group having 1 to 3 carbon atoms, more preferably independently a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0097] The xanthene compounds of the present invention can be obtained, for example, by a salt exchange reaction of Acid red 289 or its derivatives with a quaternary ammonium salt of an aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group (wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond).

[0098] Here, the derivative of Acid red 289 refers to the following structural part of Acid red 289

[0099]

[0100] The hydrogen atom or methyl group of the benzene ring is substituted by a saturated hydrocarbon group having 1 to 6 carbon atoms (wherein the hydrogen atoms contained in the saturated hydrocarbon group are optionally substituted by halogen atoms), or by an alkoxy group having 1 to 6 carbon atoms (wherein the alkyl part 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 are optionally substituted by halogen atoms).

[0101] Quaternary ammonium salts of aromatic nitrogen ring compounds can be obtained by reacting an aromatic nitrogen ring compound with a compound having a hydrocarbon group, such as an alkylation reaction of the aromatic nitrogen ring compound. Furthermore, quaternary ammonium salts of aromatic nitrogen ring compounds containing ether bonds 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 ester bonds can be obtained, for example, by dehydration condensation of a quaternary ammonium salt of a pyridine derivative having a carboxyl group with an alcohol.

[0102] It should be noted that the anions of Acid red 289 or its derivatives are, for example, as follows: In the general formula (1) of the present invention, in the case of a mixture of anions with n=1 and anions with n=2, the oxygen-anthene compound of the present invention obtained by the salt exchange reaction becomes a mixture of a salt-forming compound with n=m=1 and a salt-forming compound with n=m=2, but such a mixture is also included in the oxygen-anthene compound of the present invention.

[0103] Specific examples of the xanthene-based compound of the present invention include compounds having the following structures: Among these, the xanthene-based compound of the present invention is preferably at least one of Compounds 1 to 4.

[0104] Compound 1

[0105]

[0106] Compound 2

[0107]

[0108] Compound 3

[0109]

[0110] Compound 4

[0111]

[0112] Compound 5

[0113]

[0114] Compound 6

[0115]

[0116] Compound 7

[0117]

[0118] Compound 8

[0119]

[0120] Compound 9

[0121]

[0122] <Resin composition>

[0123] The resin composition of the present invention comprises the xanthene-based 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 formed by drying the liquid resin composition. The xanthene-based compound has been described above and its description is omitted here.

[0124] [Binder resin]

[0125] The binder resin is a bonding agent that is the main element of a cured product such as a cured film. While the binder resin is not particularly limited, resins having acidic functional groups such as carboxyl groups and phenolic hydroxyl groups are preferred. Among these, polymers having carboxyl groups are preferred, and examples thereof include copolymers of ethylenically unsaturated monomers having one or more carboxyl groups and other copolymerizable ethylenically unsaturated monomers.

[0126] [Crosslinking agent]

[0127] 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.

[0128] The crosslinking agent is a compound having two or more polymerizable functional groups. Examples of the polymerizable functional group include an ethylenically unsaturated group, an oxirane group, an oxetane group, and an N-alkoxymethylamino group.

[0129] [Photopolymerization initiator]

[0130] The resin composition of the present invention may contain a photopolymerization initiator. A photopolymerization initiator imparts radiation sensitivity to the resin composition of the present invention. Specifically, a photopolymerization initiator is a compound that generates an active substance capable of initiating 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 compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

[0131] [Solvent]

[0132] The resin composition of the present invention can also be prepared as a liquid composition by adding a solvent. Examples of the solvent include (poly)alkylene glycol monoalkyl ethers, ketone alcohols, (poly)alkylene glycol monoalkyl ether acetates, ketones, aromatic hydrocarbons such as toluene and xylene, and ethyl acetates.

[0133] [Other ingredients]

[0134] The resin composition of the present invention may optionally contain dyes, pigments, thermal polymerization initiators, fillers, polymer compounds, surfactants, antioxidants, ultraviolet absorbers, deflocculants, and the like in addition to the xanthene-based compound of the present invention.

[0135] 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 dyes and pigments other than the xanthene compound through separate filters to remove minute foreign matter, and / or filtering the resin composition mixed / kneaded with all components through another filter. Methods for preparing such resin compositions are disclosed, for example, in Japanese Patent Application Publication Nos. 2008-58642 and 2010-132874.

[0136] Color Filters

[0137] The color filter of the present invention comprises a cured product of the resin composition of the present invention. Specifically, the color filter of the present invention comprises a colored layer comprising a cured film of the resin composition of the present invention.

[0138] Below, an example of the manufacture method of color filter is described. First, on the substrate surface, a light-shielding layer (black matrix) for dividing the part forming pixels is formed as needed. Then, a solution of the resin composition of the present invention (red coloring composition) is applied on the substrate surface formed with the light-shielding layer, and the solvent is evaporated by pre-baking to form a coating. The obtained coating is exposed through a photomask, developed with an alkaline developer, and the unexposed portion of the coating is dissolved and removed. Afterwards, formal baking is carried out to obtain a pixel array configured with a red pixel pattern in a specified arrangement.

[0139] Next, using a green or blue radiation-sensitive resin composition, the resin composition is coated, pre-baked, exposed, developed, and baked in the same manner as described above, and a green resin array and a blue pixel array are sequentially formed on the same substrate. Thus, the color filter of the present invention can be obtained, in which a pixel array of the three primary colors of red, green, and blue is arranged on the substrate.

[0140] The order of forming the pixel arrays of each color is not limited to the above-mentioned order, and the color filter of the present invention may be any coloring layer as long as the red pixel array is a colored layer containing the cured product of the resin composition of the present invention.

[0141] Example

[0142] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0143] (1. Synthesis of Xanthene Compounds)

[0144] [Synthesis example 1]

[0145] Synthesis of AR289-1

[0146] In a 300ml flask, add 24.0g (35.5mmol) of CIAcid red 289 and 240g of ion exchange water and dissolve them at room temperature. To this solution, add 5.2g of 1-dodecylpyridinium chloride dissolved in 60g of ion exchange water. After stirring at room temperature for 1 hour, the precipitated crystals are filtered, washed with water and dried to obtain 23g of a salt compound based on the salt exchange reaction of CIAcid red 289 and 1-dodecylpyridinium chloride. 1 H NMR spectroscopy confirmed that the obtained compound was a compound represented by the following formula.

[0147] 1 H 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- (CH2)9 -), 0.80(pyridine-(CH2) 11 - CH3 )

[0148] It should be noted that the synthesis of the above-mentioned AR289-1 is represented by the following formula.

[0149]

[0150] [Synthesis example 2]

[0151] Synthesis of AR289-2

[0152] In a 300ml flask, add 24.0g (35.5mmol) of CIAcid red 289 and 240g of ion exchange water and dissolve them at room temperature. To this solution, add a solution in which 16.0g of 1-(pentylmalonic acid diethyl)-3-methylimidazolium bromide is dissolved in 60g of ion exchange water. After stirring at room temperature for 1 hour, the precipitated crystals are filtered, washed with water and dried to obtain 23g of a salt-forming compound based on the salt exchange reaction of CIAcid red 289 and 1-(pentylmalonic acid diethyl)-3-methylimidazolium bromide. According to 1 H NMR spectroscopy confirmed that the obtained compound was a compound represented by the following formula.

[0153] 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- (CH2)4 -, 1.12(O-CH2- CH3 )

[0154] It should be noted that the synthesis of the above-mentioned AR289-2 is represented by the following formula.

[0155]

[0156] [Synthesis example 3]

[0157] Synthesis of AR289-3

[0158] In a 300ml flask, add 24.0g (35.5mmol) of CIAcid red 289 and 240g of ion exchange water and dissolve them at room temperature. To this solution, add a solution in which 14.5g of 1-hexadecyl-4-methylpyridinium chloride is dissolved in 60g of ion exchange water. After stirring at room temperature for 1 hour, the precipitated crystals are filtered, washed with water and dried to obtain 23g of a salt-forming compound based on the salt exchange reaction of CIAcid red 289 and 1-hexadecyl-4-methylpyridinium chloride. According to 1 H NMR spectroscopy confirmed that the obtained compound was a compound represented by the following formula.

[0159] 1 H 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- CH2 -), 1.18(pyridine-CH2-CH2- (CH2) 13 -), 0.80(pyridine-(CH2) 15 - CH3 )

[0160] It should be noted that the synthesis of the above-mentioned AR289-3 is represented by the following formula.

[0161]

[0162] These AR289-1, AR289-2, and AR289-3 were designated as salt-forming compounds of Examples 1 to 3, respectively.

[0163] The salt-forming compounds of the comparative examples are AR289 (Comparative Example 1), AR289-c2 (Comparative Example 2), and AR289-c3 (Comparative Example 3).

[0164] AR289 is CIAcid red 289 and is represented by the following formula.

[0165]

[0166] AR289-c2 is a salt-forming compound formed by a salt exchange reaction between CIAcid red 289 and benzyltrimethylammonium chloride, and is represented by the following formula.

[0167]

[0168] AR289-c3 is a salt-forming compound formed by a salt exchange reaction between CIAcid red 289 and tetrabutylphosphine chloride, and is represented by the following formula.

[0169]

[0170] (2. Implementation of evaluation test)

[0171] Using the above-mentioned salt-forming compound, the absorbance in the visible light region, the solubility, and the color stability of the coating film after heat / light history were measured as follows. The results are shown in Figure 1 .

[0172] [Measurement of absorbance in the visible light region]

[0173] A resin composition was prepared by mixing 0.01 g of each salt-forming compound, 0.99 g of a resin (CYCLOMER P(ACA)Z320 manufactured by Daicel Corporation), and 0.5 g of a propylene glycol methyl ether (PGME) solvent. The resulting resin composition solution was applied to a glass plate to a thickness of 2 μm and baked on a hot plate at 100°C for 3 minutes. The absorption spectrum of the prepared film was measured using a spectrophotometer (V-570 manufactured by JASCO Corporation). Figure 1 The absorption spectrum at 350 to 700 nm is shown in FIG.

[0174] [Determination of solubility]

[0175] In a 200 mL sample bottle, each salt-forming compound was added to propylene glycol methyl ether (PGME) solvent, a stirring bar was added, and the mixture was stirred at 20°C for 15 minutes. The mixture was then allowed to stand at 25°C for 10 minutes, and the dissolution was visually observed and judged.

[0176] It should be noted that the judgment criteria are as follows: after the above operation, whether each salt-forming compound is dissolved in the PGME solvent at a ratio exceeding 3% by mass, or whether each salt-forming compound is dissolved at only less than 3% by mass, measured as a mass percentage relative to the total mass of the PGME solvent and the salt-forming compound.

[0177] [Evaluation of Color Stability of Coating Films after Heat History]

[0178] 0.01 g of each salt-forming compound, 0.99 g of a resin (CYCLOMER P(ACA)Z320 manufactured by Daicel Corporation) and a propylene glycol methyl ether (PGME) solvent were mixed to prepare a resin composition. The resulting solution of the resin composition was applied to a glass plate with a thickness of 2 μm and baked on a hot plate at 100°C for 3 minutes. After natural cooling, the chromaticity 1 (L*(1), a*(1), b*(1)) of the resulting coating was measured using a spectrophotometer ("CM-5" manufactured by Konica Minolta, Inc.). Subsequently, as a heat resistance test, the coating was heated in an oven at 230°C for 2 hours, and the chromaticity 2 (L*(2), a*(2), b*(2)) was measured. The color difference ΔE*ab was calculated using the measured color difference value according to the following calculation formula.

[0179] ΔE*ab=√((L*(2)-L*(1)) 2 +(a*(2)-a*(1)) 2 +(b*(2)-b*(1)) 2 )

[0180] [Evaluation of color stability of coating film after light history]

[0181] A test glass plate was prepared in the same manner as in the evaluation of the color stability of the coating film after the above-mentioned heat history, and the chromaticity 1 (L*(1), a*(1), b*(1)) was measured using a spectrophotometer ("CM-5" manufactured by Konica Minolta, Inc.). The glass plate was then placed in a light resistance tester ("SUNTESTCPS+" manufactured by TOYOSEIKI) and the light was tested at 60 W / m 2 The coating was placed at 40°C and 60°C for 24 and 48 hours. After the glass plate was removed, 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 the heat history, and the color stability of the coating film after the light history was evaluated.

[0182] As Figure 1 Comparison of Examples 1 to 3 with Comparative Examples 1 to 3 shows that the xanthene-based compounds of the present invention exhibit higher tinting strength (referring to the absorption spectrum (350 to 700 nm)) than the existing Acid Red 289 and its improved products. Comparison of a*(1) values ​​shows that the xanthene-based compounds of the present invention have a deeper red color. In addition, the color stability of the coating film after a heat treatment is as good as or slightly better than that of the conventional coating film, and the color stability after a light treatment is higher than that of the conventional coating film.

[0183] Furthermore, it was found that the xanthene-based compound of the present invention exhibits higher solubility in solvents than conventional Acid Red 289 and its improved products.

[0184] Industrial applicability

[0185] The xanthene-based 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 a resin composition for forming a color filter.

Claims

1. A xanthene compound, which is a salt-forming compound of an anion forming a xanthene chromophore having an anionic functional group and a cation formed by an aromatic nitrogen ring compound having a linear or branched, saturated or unsaturated hydrocarbon group, represented by the general formula (1), wherein: The hydrocarbon group optionally contains ether bonds and / or ester bonds, 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, wherein the hydrogen atom contained in the aromatic hydrocarbon group is optionally replaced by -SO3 - 、-OR 13 or R 13 replaced by R 13 is a saturated hydrocarbon group having 1 to 6 carbon atoms, wherein the hydrogen atoms contained in the saturated hydrocarbon group are optionally substituted by halogen atoms, R3~R 12 are independently a hydrogen atom, or -SO3 - or a saturated hydrocarbon group having 1 to 6 carbon atoms, According to R1~R 12 -SO3 contained in - The number n is defined by the total number of substituents, and n is an integer greater than or equal to 1.

2. The xanthene compound according to claim 1, wherein The cation formed by the aromatic nitrogen ring compound is a quaternary ammonium cation of a pyridine derivative represented by the general formula (2), or a quaternary ammonium cation of an imidazole derivative represented by the general formula (3). In the 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, wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond, R 15 ~R 19 are 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 is the hydrocarbon group, m is 1 or 2, In the general formula (3), R 20 、R 22 are independently a hydrogen atom, or a linear or branched saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, wherein the hydrocarbon group optionally contains an ether bond and / or an ester bond, R 21 、R 23 、R 24 are 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 is the hydrocarbon group, m is 1 or 2, 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. A color filter comprising a cured product of the resin composition according to claim 3.

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