Xanthene dyes containing guanidinium cations, and colored compositions, color filters, and color filter for color filters containing the same

Abstract

The present application relates to a xanthene dye containing a guanidinium cation, and a colored composition, a color filter colorant, and a color filter containing the xanthene dye. The conventional xanthene dye has high solubility in water or an aqueous alkali solution, and is easily eluted. A salt compound with a quaternary ammonium salt compound is not suitable for stable production on an industrial scale. The present application aims to provide a xanthene dye having excellent water resistance and alkali resistance, and a color filter colorant having good color characteristics by using the dye. A xanthene dye represented by the following general formula (1), a colored composition containing the dye, a color filter colorant, and a color filter. In formula (1), R 1 ~R 4 represents H, an alkyl group, or an aromatic hydrocarbon group, R 5 ~R 9 represents H, a halogen atom, SO3 ‑ , -SO3M, a sulfonyl group, -COO-, -COOM, a carbonyl group, or the like, Gu represents a guanidinium cation, and An represents an anion.

Description

Technical Field

[0001] The present invention relates to succinyl guanidine cations, coloring compositions containing the succinyl guanidine cations, colorants for filters containing the succinyl guanidine cations or the coloring compositions, and filters using the colorants. Background Technology

[0002] Color filters are used in liquid crystal display devices, organic electroluminescent (organic EL) display devices, and CCD and CMOS imaging elements. Color filters are manufactured by stacking colored layers such as pigment thin films and pigment-resin composite films on light-transmitting substrates such as glass and transparent resin using dyeing methods, pigment dispersion methods, printing methods, and electrodeposition methods.

[0003] Colorants used in color filters include pigments and dyes. However, since color filters are exposed to high temperatures above 200°C and ultraviolet radiation during manufacturing, pigments with excellent heat resistance and light resistance are usually used.

[0004] In recent years, there has been a trend towards more energy-efficient image display devices and higher brightness color filters to improve the utilization efficiency of backlights.

[0005] Pigments are generally insoluble in solvents and therefore exist in particulate form in color filters containing resins, etc. Thus, it can be understood that for color filters using pigments, transmitted light is reflected from the surface of the pigment particles. Scattering affects brightness and color purity, and the contrast ratio of color display devices is reduced due to the depolarization effect caused by reflection.

[0006] To address the issues of reduced brightness and contrast, methods have been proposed that use only dyes as colorants or a combination of dyes and pigments as colorants. Since dyes are soluble in solvents, color filters using dyes exhibit reduced depolarization compared to those using only pigments, resulting in superior spectral characteristics and the anticipated improvement in brightness and contrast.

[0007] Xanthones (or dyes) represented by the following formulas (E-1) to (E-3) are compounds used as colorants in filters and the like due to their vividness (Patent Documents 1 to 3, etc.). For example, by using xanthones such as CI Acid Red 289 (Formula (E-1)) and CI Acid Red 52 (Formula (E-2)) (CI is an abbreviation for dye index) in combination with azopyridone dyes, excellent red hues can be obtained (Patent Document 1).

[0008] [Chemical Formula 1]

[0009]

[0010] In equation (E-1), n ​​is 1 or 2, and any one or two H are "-SO3 - "Substitution. Formula (E-1) represents a mixture of these compounds." Patent Document 1: Japanese Patent Application Publication No. 2002-265834 Patent Document 2: Japanese Patent Application Publication No. 2013-41145 Patent Document 3: Japanese Patent Application Publication No. 2017-83852 Non-patent literature 1: Watanabe, supervised by the author, "Film-forming technology and chemicals for color filters", CMC Co., Ltd., February 1, 1998, pp. 8-9 Summary of the Invention Photolithography is currently the mainstream method for manufacturing color filters. In photolithography, a colored resist is coated onto a glass substrate with a black matrix, and after pre-baking to remove the solvent, it is exposed through a photomask. Next, an alkaline developer is used for cleaning. Remove the unexposed portion (development process), and then bake it to cure it (Non-Patent Document 1).

[0011] During the developing process, when dyes dissolve into the alkaline developing solution, there is a problem of wastewater staining during wastewater treatment. Acid red dyes, such as Acid Red 289 and Acid Red 52, have high solubility in alkaline aqueous solutions, making them prone to dissolution. To prevent this, it is necessary to reduce their solubility in water and alkaline aqueous solutions (i.e., improve their water resistance and alkali resistance).

[0012] Generally, as a method to reduce the water solubility of acid dyes, a salt-forming reaction with an ammonium cation having a long-chain alkyl group is known. For example, Patent Document 2 discloses that a salt-forming compound is obtained as a precipitate by adding dialkyl (alkyl group of C14 to C18) dimethyl ammonium chloride and distearate dimethyl ammonium chloride to an alkaline aqueous solution of Acid Red 289 and Acid Red 52 (Patent Document 2, paragraphs

[0154] to

[0159] ).

[0013] Research has been conducted on manufacturing high-performance color filters, as described in Patent Document 2. However, the salt-forming reaction with ammonium cations containing long-chain alkyl groups is not suitable for stable industrial-scale production. In the manufacturing process of the salt-forming compound, water is required to wash the compound in order to remove the acidic or alkaline components used in the salt-forming reaction. However, according to the inventors' research, the salt-forming compound with quaternary ammonium cations containing long-chain alkyl groups readily aggregates and becomes viscous in water. When the precipitate becomes viscous in water, it is difficult to remove the washed solid. Even when it can be removed, a crushing process is required, thus reducing production efficiency and increasing the burden, especially on an industrial scale.

[0014] The present invention provides a succinate pigment capable of suppressing wastewater coloring in wastewater treatment and capable of industrial production. Therefore, the objective of the present invention is to provide a succinate pigment with excellent water resistance and alkali resistance, and also to provide a colorant for filters with good color characteristics (color gamut, brightness, contrast ratio, etc.) by using a coloring composition containing the pigment.

[0015] This invention is the result of in-depth research to solve the above-mentioned problems, and its main points are as follows.

[0016] 1. A pyrithione pigment, represented by the following general formula (1).

[0017] [Chemical Formula 2]

[0018] In equation (1), R 1 ~R 4 Each can independently represent -H, a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms with optional substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms with optional substituents; R 1 With R 2 R 3 With R 4 Each element can be randomly selected to bond with the others to form a ring.

[0019] R 5 ~R 9 Each can be independently represented as -H, halogen atom, -OH, -CN, -NO2, -OR 10 -SO3 - -SO3M, optional sulfonyl groups with 0 to 30 carbon atoms having substituents, -COO - -COOM, a carbonyl group having 1 to 30 carbon atoms with a substituent, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms with a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, or an amino group having 0 to 30 carbon atoms with a substituent.

[0020] R 10 It indicates a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, optionally with a substituent.

[0021] M represents an inorganic cation, which, when multiple are present, can be chosen to be the same or different.

[0022] Among them, R 1 ~R 10 At least two of them have the option of being free-SO3 - -COO -The anionic groups in the group consisting of monosulfonamide anionic groups with 1 to 10 carbon atoms and bissulfonamide anionic groups with 0 to 10 carbon atoms may be the same or different.

[0023] Gu represents a guanidine cation represented by any of the following general formulas (2) to (5).

[0024] An represents anion.

[0025] a represents the number of xanthan pigment skeletons and is an integer from 1 to 4.

[0026] b represents the quantity of Gu and is an integer from 1 to 4.

[0027] c represents the quantity of An and is an integer from 0 to 3. [Chemical Formula 3]

[0028] In equation (2), R 11 ~R 13 Each of the following can be independently represented: -H, halogen atom, -CN, -NO2, a straight-chain, branched, or cyclic alkyl group with 1 to 30 carbon atoms optionally having a substituent, an aromatic hydrocarbon group with 6 to 30 carbon atoms optionally having a substituent, an aromatic heterocyclic group with 2 to 30 carbon atoms optionally having a substituent, an acyl group with 1 to 20 carbon atoms optionally having a substituent, an oxycarbonyl group with 1 to 20 carbon atoms optionally having a substituent, an aminocarbonyl group with 1 to 20 carbon atoms optionally having a substituent, a thiocarbonyl group with 1 to 20 carbon atoms optionally having a substituent, an oxythiocarbonyl group with 1 to 20 carbon atoms optionally having a substituent, an aminothiocarbonyl group with 1 to 20 carbon atoms optionally having a substituent, a sulfonyl group with 0 to 20 carbon atoms optionally having a substituent, or an amino group with 0 to 20 carbon atoms optionally having a substituent.

[0029] R 11 With R 12 R 12 With R 13 R 13 With R 11 Each element can be randomly selected to bond with the others to form a ring. [Chemical Formula 4]

[0030] In equation (3), R 14 ~R 17 R in general formula (2) 11 ~R 13 The same definition.

[0031] L represents a linking group, and indicates a combination of one or two to three groups selected from the group consisting of a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms with optional substituents, and a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms with optional substituents. [Chemical Formula 5]

[0032] In equation (4), R 18 ~R 21 R in general formula (2) 11 ~R 13 The same definition. [Chemical Formula 6]

[0033] In equation (5), R 22 ~R 27 R in general formula (2) 11 ~R 13 By the same definition, L represents the same definition as L in general formula (3). 2. The pyrrolizin according to 1., wherein, in the general formula (1), R 1 and R 3 Each is independently -H or optionally has a substituent and is a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms; R 2 and R 4 Each of the substituents is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0034] 3. The pyrrolizin according to 1 or 2, wherein, in the general formula (1), R 5 ~R 9 -H, -SO3 - -SO3H, optional sulfonyl groups with 0 to 10 carbon atoms having substituents, -COO - -COOH or optionally a carbonyl group with 1 to 10 carbon atoms having a substituent.

[0035] 4. The guanidine pigment according to any one of 1. to 3., wherein, in the general formula (1), Gu is a guanidine cation represented by general formula (2), and in general formula (2), R 11 ~R 13 Each of the following is independently -H, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms with a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, or an aromatic heterocyclic group having 6 to 30 carbon atoms with a substituent.

[0036] 5. The guanidine pigment according to any one of 1. to 3., wherein, in the general formula (1), Gu is a guanidine cation represented by general formula (3), and in general formula (3), R 14 ~R 17 Each is independently -H, -CN, or an aromatic hydrocarbon group with 6 to 30 carbon atoms that may have a substituent, and L is a straight-chain, branched, or cyclic alkylene group with 1 to 30 carbon atoms.

[0037] 6. The guanidine pigment according to any one of 1. to 3., wherein, in the general formula (1), Gu is a guanidine cation represented by general formula (4), and in general formula (4), R 18 ~R 21 Each is independently -H, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms optionally with substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms optionally with substituents, R 18 and R 21 At least one of them is an aromatic hydrocarbon group with 6 to 30 carbon atoms that may be substituted.

[0038] 7. The guanidine pigment according to any one of 1. to 3., wherein, in the general formula (1), Gu is a guanidine cation represented by general formula (5), and in general formula (5), R 22 ~R 27 Each is independently -H, a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms with a substituent, or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, and L is a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms.

[0039] 8. The xaton pigment according to any one of 1. to 7, wherein the solubility of the xaton pigment in a 0.04% by mass aqueous solution of potassium hydroxide at room temperature (23 to 27°C) is less than 1.0 by mass.

[0040] 9. A coloring composition comprising any one of the pyritin pigments described in 1 to 8 above.

[0041] 10. A colorant for a color filter, comprising the coloring composition described in 9. above.

[0042] 11. A color filter using the colorant for color filters described in 10.

[0043] The zeolite pigment of the present invention has excellent water resistance and alkali resistance, and the coloring composition containing the pigment is useful as a colorant for filter. Detailed Implementation

[0044] Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the spirit of the present invention. The xanthones pigment of the present invention comprises a xanthones pigment skeleton having anionic groups, a guanidine cation represented by Gu, and an anionic species optionally represented by An. First, the xanthones pigment skeleton represented by general formula (1) will be described.

[0045] Various xanthones can be used as the xanthones pigment in this invention. Moreover, in addition to xanthones, other pigments that can be combined with the guanidine cation of this invention include, for example, triarylmethane pigments having anionic groups, azo pigments having anionic groups, cyanine pigments having anionic groups, and phthalocyanine pigments having anionic groups.

[0046] The preferred succinate pigment used in this invention is the succinate pigment represented by the above general formula (1).

[0047] In general formula (1), as a result of R 1 ~R 10 The phrase "alkyl groups having 1 to 30 carbon atoms, either straight-chain, branched, or cyclic" in the expression "optionally having substituents, of 1 to 30 carbon atoms, either straight-chain, branched, or cyclic" can be specifically exemplified by: Straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; Branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isooctyl, and 2-ethylhexyl; Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and other cyclic alkyl groups (cycloalkyl groups), 1-adamantyl, 2-adamantyl.

[0048] In general formula (1), as a result of R 1 ~R 10 The "aromatic hydrocarbon group with 6 to 30 carbon atoms" in the phrase "articulate hydrocarbon group with 6 to 30 carbon atoms that may have a substituent" can specifically include phenyl, biphenyl, terphenyl, naphthyl, azulel, anthracenel, phenanthryl, fluorenyl, indene, pyrene, perylene, fluoranyl, triphenylene, etc. (The "aromatic hydrocarbon group" in this invention also includes aryl and fused polycyclic aromatic hydrocarbon groups).

[0049] In general formula (1), as a result of R 5 ~R 9 Examples of "halogen atoms" include fluorine, chlorine, bromine, or iodine atoms. Fluorine or chlorine atoms are preferred as "halogen atoms".

[0050] In general formula (1), R 5 ~R 9 The phrase "sulfonyl group with 0 to 30 carbon atoms" in the expression "optionally having substituents" represents "-S(=O)2-", including "-SO2-R". 28 (or "-S(=O)2-R") 28 The '-' indicates a monosubstituted sulfonyl group. Examples also include those represented by '-S(=O)2-NR'. 29 R 30 The "-S(=O)2-NR" indicates an aminosulfonyl group (sulfonamide group), which is composed of "-S(=O)2-NR". 29 -S(=O)2-R 28 The '-S' represents a sulfonylaminosulfonyl group (bissulfonylimide group) and is composed of '-S(=O)2-N'. - -S(=O)2-R 28 The symbol "" indicates a disulfonamide anionic group, etc. At this time, R 28 ~R 30 Applications with R 1 ~R 10 The "substituent" in the text refers to the same substituent. For example, R 28 ~R 30 It can be "a sulfonyl group with 0 to 30 carbon atoms that may have a substituent" or "a carbonyl group with 1 to 30 carbon atoms that may have a substituent".

[0051] In general formula (5), R 5 ~R 9 The phrase "carbonyl group with 1 to 20 carbon atoms, optionally having substituents" indicates "-(C=O)-", which includes the group consisting of "-(C=O)-R". 28 "" indicates a monosubstituted carbonyl group. For example, it also includes "-(C=O)-OR". 28 The "-(C=O)-NR" indicates an oxycarbonyl group (ester group), which is composed of "-(C=O)-NR". 29 R 30 The "-(C=O)-NR" indicates an amino carbonyl group (amide group), which is composed of "-(C=O)-NR". 29 -S(=O)2-R 30 The sulfonylaminocarbonyl group (sulfonylamide group) and the group represented by "-(C=O)-N - -S(=O)2-R 30 " indicates a monosulfonamide anionic group, etc. 28 ~R 30 Applications with R 1 ~R 10 The "substituent" in the text refers to the same substituent. For example, R 28 ~R 30It can be "a sulfonyl group with 0 to 30 carbon atoms that may have a substituent" or "a carbonyl group with 1 to 30 carbon atoms that may have a substituent".

[0052] In general formula (1), R 5 ~R 9 The phrase "amino group with 0 to 30 carbon atoms, optionally having a substituent" can optionally have or not have a substituent, and examples include unsubstituted amino groups (-NH2), monosubstituted amino groups, and disubstituted amino groups. The number of carbon atoms in a monosubstituted or disubstituted amino group can be, for example, 1 to 20, or 1 to 10. "Amino group with 0 to 30 carbon atoms, optionally having a substituent" can be a group bonded via -NH-, -N<, or -N=CH- to one of the aforementioned "linear, branched, or cyclic alkyl groups with 1 to 20 carbon atoms," "aromatic hydrocarbon groups with 6 to 30 carbon atoms," or "aromatic heterocyclic groups with 1 to 30 carbon atoms." Examples of monosubstituted amino groups include methylamino, ethylamino, butylamino, acetylamino, and phenylamino. Examples of disubstituted amino groups include dialkylamino groups with 2 to 20 carbon atoms, such as dimethylamino, diethylamino, dipropylamino, dibutylamino, and dihexylamino; dienylamino groups with 4 to 20 carbon atoms, such as diallylamino; and diphenylamino, N-acetyl-N-phenylamino, and N-butyl-N-phenylamino.

[0053] In general formula (1), the "inorganic cation" represented by "M" in "-SO3M" or "-COOM" can be: hydrogen ion; alkali metal ions such as lithium ion and sodium ion; alkaline earth metal ions such as magnesium ion, calcium ion and barium ion; transition metal ions such as nickel ion and cobalt ion.

[0054] In general formula (1), as a result of R 1 ~R 10 The "substituent" in "optionally a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms with substituents", "optionally an aromatic hydrocarbon group having 6 to 30 carbon atoms with substituents", "optionally a sulfonyl group having 0 to 30 carbon atoms with substituents", "optionally a carbonyl group having 1 to 30 carbon atoms with substituents", and "optionally an amino group having 0 to 30 carbon atoms with substituents" can specifically be exemplified as follows: Deuterium atom, hydroxyl group (-OH), thiol group (-SH), cyano group (-CN), nitro group (-NO2); Halogen atoms such as fluorine, chlorine, bromine, and iodine; Amino groups with 0 to 20 carbon atoms; -SO3 - -SO3M, sulfonyl group with 0 to 20 carbon atoms; -COO- -COOM, carbonyl groups with 1 to 20 carbon atoms; Alkyl groups having 1 to 20 carbon atoms, and which are straight-chain, branched, or cyclic. Alkenes with 2 to 20 carbon atoms, in the form of straight chains, branches, or rings; Alkyl groups consisting of 1 to 20 carbon atoms in straight-chain, branched, or cyclic forms; Acyl groups with 1 to 20 carbon atoms; Ether groups with 0 to 20 carbon atoms; Thioether groups with 0 to 20 carbon atoms; Aromatic hydrocarbon groups or fused polycyclic aromatic groups with 6 to 20 carbon atoms; Aromatic heterocyclic groups with 5 to 20 ring atoms; etc. Furthermore, when the "substituent" contains a carbon atom, that carbon atom is included in the categories of "1 to 30 carbon atoms," "6 to 30 carbon atoms," and "0 to 30 carbon atoms" mentioned above. These "substituents" may be singular or multiple, and when multiple are included, they may be identical or different. These "substituents" may further have the substituents exemplified above. Additionally, these substituents may form a ring by bonding with each other via single bonds, substituted or unsubstituted methylene groups, oxygen atoms (-O-), or sulfur atoms (-S-). Wherein, the R group described above... 1 ~R 10 The maximum number of substituents in each group is 10.

[0055] Furthermore, in general formula (1), when R 1 ~R 10 Among the above-mentioned groups having a "substituent" represented by any of the above, specifically regarding the "substituent" as "amino group with 0 to 20 carbon atoms", "sulfonyl group with 0 to 20 carbon atoms", "carbonyl group with 1 to 20 carbon atoms", "linear, branched, or cyclic alkyl group with 1 to 20 carbon atoms", "linear, branched, or cyclic alkenyl group with 2 to 20 carbon atoms", "linear, branched, or cyclic alkoxy group with 1 to 20 carbon atoms", "acyl group with 1 to 20 carbon atoms", "ether group with 0 to 20 carbon atoms", "thioether group with 0 to 20 carbon atoms", "aromatic hydrocarbon group or fused polycyclic aromatic group with 6 to 20 carbon atoms", or "aromatic heterocyclic group with 1 to 20 carbon atoms", examples include: Amino groups; monosubstituted or disubstituted amino groups such as methylamino, dimethylamino, diethylamino, ethylmethylamino, dipropylamino, di-tert-butylamino, hexamethyleneimino, diphenylamino, etc., having a straight-chain, branched, or cyclic alkyl group or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Aminosulfonyl (sulfonamide), sulfonylaminosulfonyl (bissulfonylimide), trifluoromethane bissulfonylimide anionic group (-SO2N) - -SO2CF3) and other bissulfonylimide anionic groups, methanesulfonyl group, p-toluenesulfonyl group and other sulfonyl groups with 0 to 20 carbon atoms (-S(=O)2-); oxycarbonyl (ester group), aminocarbonyl (amide group), sulfonylaminocarbonyl (sulfonylamide group), trifluoromethanesulfonylamide anionic group (-CON) - Groups with carbonyl groups (-CO-) having 1 to 20 carbon atoms, such as monosulfonamide anionic groups (-SO2CF3) and others; Alkyl groups with 1 to 20 carbon atoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl, nonyl, and decyl; cyclic alkyl groups with 3 to 20 carbon atoms, including cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl; 1-adamantyl and 2-adamantyl. Alkenes with 2 to 20 carbon atoms, including vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or a combination of these alkenyl groups; cyclic alkenyl groups with 2 to 20 carbon atoms, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cycloheptenyl. Alkoxy groups with 1 to 20 carbon atoms, including methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, and isooctoxy; cyclic alkoxy groups with 3 to 20 carbon atoms, including cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexoxy, cyclononoxy, and cyclodecoxy; 1-adamantoxy and 2-adamantoxy. Acyl groups with 1 to 20 carbon atoms, such as formyl, acetyl, propionyl, acryloyl, and benzoyl. Ether groups (-O-), aminooxy groups, ester groups represented by "-O-(C=O)-R" (where R is any alkyl or aromatic hydrocarbon group, etc.), phosphate groups, phosphate ester groups, and other groups containing ether groups (-O-) with 0 to 20 carbon atoms; Thioether groups (-S-), thioalkyl groups, and thioester groups represented by "-S-(C=O)-R" (where R is any alkyl or aromatic hydrocarbon group, etc.) contain thioether groups with 0 to 20 carbon atoms. Aromatic hydrocarbon groups or fused polycyclic aromatic groups with 6 to 20 carbon atoms, such as phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluorenyl, indene, pyrene, perylene, fluoranyl, and triphenylene; Aromatic heterocyclic groups with 2 to 20 carbon atoms, including pyridyl, pyrimidinyl, triazinyl, thiopheneyl, furanyl, pyrroloyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolinyl, naphridinyl, quinoxalinyl, acridineyl, phenanthrolinel, benzofuranyl, benzothiopheneyl, oxazolyl, indolyl, carbazolyl, benzooxazolyl, thiazolyl, benzothiazolyl, benzoimidazolyl, benzothiadiazolyl, pyrazolyl, dibenzofuranyl, dibenzothiopheneyl, and carbazolyl. Aryloxy groups with 6 to 19 carbon atoms, such as phenoxy, toluoxy, biphenyloxy, naphthoxy, anthraquinoneoxy, and phenanthreneoxy.

[0056] In general formula (1), R 1 ~R 4 Preferably, it is -H, or optionally a straight-chain, branched, or cyclic alkyl group having 1 to 8 carbon atoms with substituents, or an aromatic hydrocarbon group having 6 to 10 carbon atoms with substituents. R is preferred. 1 and R 2 Either of the following is "a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, optionally with a substituent," and more preferably, the other is "a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, optionally with a substituent" or "an aromatic hydrocarbon group having 6 to 10 carbon atoms, optionally with a substituent." R is preferred. 3 and R 4 Either of these is "a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, optionally with a substituent," and more preferably, the other is "a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms, optionally with a substituent" or "an aromatic hydrocarbon group having 6 to 10 carbon atoms, optionally with a substituent." For example, R is preferably... 1 and R 3 Each is independently a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms and optionally having a substituent, more preferably R 2 and R 4 Each is independently a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, optionally with substituents, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, optionally with substituents. R is a preferred embodiment. 1 ~R 4 Examples include hydrogen atom, methyl, ethyl, n-propyl, n-butyl, isobutyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methoxyphenyl, difluorophenyl, dichlorophenyl, dimethylphenyl, mesityleneyl (2,4,6-trimethylphenyl), 1-naphthyl, and 2-naphthyl. Furthermore, when R...1 ~R 4 When the "substituent" contains carbon atoms, it is not included in the above-mentioned "number of carbon atoms 1 to 8" and "number of carbon atoms 6 to 10". It is preferable that the number of "substituents" is at most 5, and the largest number of carbon atoms in each group is preferably "20", more preferably "12".

[0057] Preferred to make R 1 ~R 4 At least one of them has a "substituent". Preferred substituents are hydroxyl (-OH), cyano (-CN), nitro (-NO2), fluorine atom, chlorine atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, and -SO3. - -SO3H, -SO3M, -COO - -COOH, -COOM, -SO2-N - -SO2CF3 or -CO-N - -SO2CF3, more preferably methyl, ethyl, n-propyl, isopropyl, -SO3 - -SO3H, -SO3M.

[0058] In this application, -SO3H and -COOH are respectively included in -SO3M and -COOM according to the definition in this application, and the above-mentioned "-SO3H" and "-COOH" are used as R 1 ~R 4 The preferred substituents are explicitly described, and do not exclude groups other than -SO3M and -COOM.

[0059] In general formula (1), R 5 ~R 9 Preferably -H, -SO3 - -SO3H, -SO3M, optional sulfonyl groups with 0 to 10 carbon atoms having substituents, -COO - -COOH, -COOM, or optionally a carbonyl group having 1 to 10 carbon atoms with substituents, more preferably -H or -SO3 - -SO3H, -SO3M, or optionally a sulfonyl group with 0 to 10 carbon atoms having a substituent.

[0060] R 5 ~R 9 At least one of them is preferably selected from free-SO3 - -COO - One of the anionic groups in the group consisting of monosulfonamide anionic groups having 1 to 10 carbon atoms and bissulfonamide anionic groups having 0 to 10 carbon atoms, more preferably -SO3. -Or trifluoromethane disulfonylimide anionic group (-SO2N) - -SO2CF3). Furthermore, when R 5 ~R 9 When the "substituent" contains carbon atoms, it is not included in the above "number of carbon atoms 0 to 10" and "number of carbon atoms 1 to 10". It is preferable that the number of "substituents" is at most 5, and the largest number of carbon atoms in each group is preferably "20", more preferably "12".

[0061] In general formula (1), R 10 Preferably, it is a straight-chain or branched alkyl group having 1 to 10 carbon atoms with a substituent, or a phenyl group having 6 to 10 carbon atoms with a substituent.

[0062] In general formula (1), it is preferable to make R 1 ~R 10 At least two of them have the option of being free-SO3 - -COO - Monosulfonamide anionic groups with 1 to 10 carbon atoms (-(C=O)-N) - -S(=O)2-R 30 ) and bis(sulfonamide) anionic groups with 0 to 10 carbon atoms (-S(=O)2-N) - -S(=O)2-R 28 The anionic groups in the group consisting of R are more preferably made to be anionic groups. 1 ~R 9 Any two or three of the components contain the anionic group. Therefore, the xanthanid pigment skeleton as a whole is anionic, and its valence is preferably monovalent or divalent. The -SO3 group is preferred as the anionic group. - -COO - Monosulfonamide anionic groups with 1 to 10 carbon atoms (-(C=O)-N) - -S(=O)2-R 30 Or a disulfonamide anionic group with 0 to 10 carbon atoms (-S(=O)2-N) - -S(=O)2-R 28 (More preferably -SO3) - Or the trifluoromethanesulfonyl imide anionic group (-SO2N) - -SO2CF3), particularly preferred is -SO3 - The multiple anionic groups present may be identical or different, but from a manufacturing point of view, they are preferably identical. Here, in general formula (1), R 1 ~R 10 "Having anionic groups" indicates: R 5 ~R 9Any one of them can be the anionic group, R 1 ~R 10 The substituent can be the anionic group.

[0063] R having the above-mentioned anionic groups 1 ~R 10 In the middle, R 1 ~R 10 Each group preferably has one anionic group. That is, for example, when R 1 ~R 9 When either of the two components has anionic groups, for example, it is preferable to use R. 1 With R 3 R 1 With R 5 Or R 5 With R 7 Each has one anionic group. R, as an anionic group... 1 ~R 10 The combination of is preferably R 1 With R 3 R 1 With R 5 R 5 With R 7 Or R 1 With R 3 With R 5 .

[0064] In general formula (1), 'a' represents the number of xanthanin skeletons and is an integer from 1 to 4. The values ​​of 'a', along with the values ​​of 'b' and 'c' (described later), are selected to ensure that the xanthanin represented by general formula (1) is electrically neutral as a whole. That is, since the xanthanin skeleton is anionic, the value of 'a' is chosen so that the product of its valence and 'a', plus the sum of the valences of the anions represented by 'An' (described later), matches the sum of the cations in 'Gu'. For example, when the xanthanin does not contain 'An' but the xanthanin skeleton has two anionic groups, the product of the valence of the guanidine cation and 'b' matches 'a'. Similarly, when the xanthanin skeleton has three anionic groups, the product of the valence of the guanidine cation and 'b' matches twice the value of 'a'. The value of 'a' is preferably 1, 2, or 4, more preferably 1 or 2.

[0065] Examples of xanthones with anionic groups, such as CI Acid Red 52 and CI Acid Red 289, can be cited as the pigment skeleton of the xanthones represented by the above general formula (1). Hereinafter, specific examples of compounds preferred for the xanthones of the present invention are shown using the following structural formulas (X-1) to (X-42), but the present invention is not limited to these compounds. Furthermore, in the xanthones of the present invention, a portion of the xanthones skeleton is shown, omitting the guanidine cation portion represented by Gu and the anionic portion represented by An. In the following structural formula, a portion of hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included; a planar structural formula is described.

[0066] [Chemical Formula 7]

[0067] [Chemical Formula 8]

[0068] [Chemical Formula 9]

[0069] [Chemical Formula 10]

[0070] [Chemical Formula 11]

[0071] [Chemical Formula 12]

[0072] [Chemical Formula 13]

[0073] [Chemical Formula 14]

[0074] [Chemical Formula 15]

[0075] [Chemical Formula 16]

[0076] [Chemical Formula 17]

[0077] As the succinate pigment of the present invention, the succinate pigment may be selected as a single one or a combination of two or more different succinate pigments, preferably a single one or a combination of two to five succinate pigments exemplified above.

[0078] In general formula (1), Gu represents a guanidine cation, preferably a guanidine cation represented by general formulas (2) to (5).

[0079] In general formulas (2) to (5), as R 11 ~R 27 The term "halogen atom" specifically refers to R in general formula (1). 5 ~R 9 The specific example of "halogen atom" in the text is the same halogen atom.

[0080] In general formulas (2) to (5), as R 11 ~R 27 The phrase "a straight-chain or branched alkyl group having 1 to 30 carbon atoms, optionally having a substituent" or "an aromatic hydrocarbon group having 6 to 30 carbon atoms, optionally having a substituent" specifically refers to R in general formula (1). 1 ~R 10 The specific examples of "linear, branched or cyclic alkyl groups with 1 to 30 carbon atoms" or "aromatic hydrocarbon groups with 6 to 30 carbon atoms" are the same groups.

[0081] In general formulas (2) to (5), as R 11 ~R 27 The phrase "aromatic heterocyclic groups with 2 to 30 carbon atoms that may have substituents" specifically includes pyridyl, pyrimidinyl, triazine, thiophene, furanyl, pyrroloyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolinyl, naphthidyl, quinoxalinyl, acridineyl, phenanthrolinel, benzofuranyl, benzothiophene, oxazolyl, indolyl, carbazolyl, benzooxazolyl, thiazolyl, benzothiazolyl, benzoimidazolyl, benzothiadiazolyl, pyrazolyl, dibenzofuranyl, dibenzothiophene, carbazolyl, etc.

[0082] In general formulas (2) to (5), as R 11 ~R 27The phrases "acyl group with 1 to 20 carbon atoms (optionally having a substituent)," "oxycarbonyl group with 1 to 20 carbon atoms (optionally having a substituent)," or "aminocarbonyl group with 1 to 20 carbon atoms (optionally having a substituent)" specifically include: formyl, acetyl, propionyl, acryloyl, benzoyl, etc., acyl groups with 1 to 20 carbon atoms; methoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, 2-(trimethylmethoxycarbonyl) Silyl ethoxycarbonyl, tert-butoxycarbonyl, allyloxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethoxycarbonyl, etc., with 1 to 20 carbon atoms; unsubstituted aminocarbonyl (-CONH2); monosubstituted or disubstituted aminocarbonyl groups with 1 to 20 carbon atoms, such as methylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, ethylmethylaminocarbonyl, dipropylaminocarbonyl, di-tert-butylaminocarbonyl, hexamethyleneiminocarbonyl, diphenylaminocarbonyl, etc., consisting of straight-chain, branched, or cyclic alkyl groups or aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0083] In general formulas (2) to (5), as R 11 ~R 27 The terms "thiocarbonyl group with 1 to 20 carbon atoms (optionally having substituents)," "oxy-thiocarbonyl group with 1 to 20 carbon atoms (optionally having substituents)," or "amino-thiocarbonyl group with 1 to 20 carbon atoms (optionally having substituents)" specifically include: thioformyl (-C(=S)H), thioacetyl (-C(=S)CH3), phenylthioacetyl, thiobenzoyl, pyridylthiocarbonyl, etc., with 1 to 20 carbon atoms. Thiocarbonyl groups; oxy-thiocarbonyl groups with 1 to 20 carbon atoms, such as methoxythiocarbonyl, ethoxythiocarbonyl, 2-propoxythiocarbonyl, butoxythiocarbonyl, pentoxythiocarbonyl, and phenoxythiocarbonyl; unsubstituted aminothiocarbonyl groups (-C(=S)NH2), dimethylaminothiocarbonyl, diethylaminothiocarbonyl, dibutylaminothiocarbonyl, hexamethyleneiminothiocarbonyl, dibenzylaminothiocarbonyl, and phenylthiocarbonyl groups, which are monosubstituted or disubstituted aminothiocarbonyl groups with 1 to 20 carbon atoms in the form of straight-chain, branched, or cyclic alkyl groups or aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0084] In general formulas (2) to (5), as R 11 ~R 27The "sulfonyl group with 0 to 20 carbon atoms" or "amino group with 0 to 20 carbon atoms" in the phrase "optionally having a substituent" or "optionally having a substituent" specifically refers to the R in general formula (1). 5 ~R 9 The specific examples of "sulfonyl group with 0 to 30 carbon atoms" or "amino group with 0 to 30 carbon atoms" are the same groups.

[0085] In general formulas (3) and (5), the "linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms with substituents" or "divalent aromatic hydrocarbon group having 6 to 30 carbon atoms with substituents" represented by L, specifically include: methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl Straight-chain alkylene groups such as nonane-1,9-diyl and decane-1,10-diyl; branched alkylene groups such as propane-2,2-diyl, propane-1,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-2,2-diyl, octane-1,2-diyl, and 2-ethylhexane-1,6-diyl; cyclic alkylene groups such as cyclopentane-1,4-diyl; and divalent aromatic hydrocarbon groups with 6 to 30 carbon atoms such as phenylene, biphenylene, terphenylene, naphthylene, anthraceneylene, phenanthrene, fluoreneylene, indene, pyreneylene, perylene, fluorene-anthrene, and triphenylene.

[0086] In general formulas (2) to (4), as R 11 ~R 27The letter L represents "a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms (optionally substituents)", "an aromatic hydrocarbon group having 6 to 30 carbon atoms (optionally substituents)", "an aromatic heterocyclic group having 1 to 30 carbon atoms (optionally substituents)", "an acyl group having 1 to 20 carbon atoms (optionally substituents)", "an oxycarbonyl group having 1 to 20 carbon atoms (optionally substituents)", "an aminocarbonyl group having 1 to 20 carbon atoms (optionally substituents)", and "a thioacyl group having 1 to 20 carbon atoms (optionally substituents)". The "substituent" in "optionally an oxythiocarbonyl group with 1 to 20 carbon atoms having a substituent", "optionally an aminothiocarbonyl group with 1 to 20 carbon atoms having a substituent", "optionally a sulfonyl group with 0 to 20 carbon atoms having a substituent", "optionally an amino group with 0 to 20 carbon atoms having a substituent", "optionally a linear, branched, or cyclic alkylene group with 1 to 30 carbon atoms having a substituent", or "optionally a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms having a substituent", specifically, can be applied to R in general formula (1). 1 ~R 10 The specific examples of "aromatic hydrocarbon groups with 6 to 30 carbon atoms" are the same substituents.

[0087] In general formula (2), R 11 ~R 13 Preferably, it is -H, or optionally a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms with a substituent, or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, or an aromatic heterocyclic group having 6 to 30 carbon atoms with a substituent, more preferably -H or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, and particularly preferably -H or a phenyl group having a substituent.

[0088] In general formula (3), R 14 ~R 17 Preferably, it is an aromatic hydrocarbon group with 6 to 30 carbon atoms, having a substituent, such as -H, -CN, or optionally a phenyl group with a substituent. In general formula (3), L is preferably a straight-chain, branched, or cyclic alkylene group with 1 to 30 carbon atoms, having a substituent ...

[0089] In general formula (4), R 18 ~R 21Preferably, it is a -H, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms with a substituent, or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, more preferably -H or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, and particularly preferably -H or a phenyl group having a substituent.

[0090] R 18 ~R 21 At least one of them is preferably -H or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent.

[0091] In general formula (5), R 22 ~R 27 Preferably, it is a -H, a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms with a substituent, or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, more preferably -H or an aromatic hydrocarbon group having 6 to 30 carbon atoms with a substituent, and particularly preferably -H or a phenyl group having a substituent. In general formula (5), L is preferably a linear, branched, or cyclic alkylene group having 1 to 30 carbon atoms, more preferably a linear alkylene group having 1 to 10 carbon atoms with a substituent, and particularly preferably a linear alkylene group having 6 to 10 carbon atoms with a substituent.

[0092] In general formula (1), b represents the number of guanidine cations and is an integer from 1 to 4. The value of b is chosen such that the product of the valence of each guanidine cation represented by general formulas (2) to (4) and b, the product of the valence of the xanthanite skeleton and a, and the sum of the valence of the anion represented by An (described later) are matched. The value of b is preferably 1, 2, or 4, more preferably 1 or 2.

[0093] Specific examples of compounds preferred for the guanidine cations of the present invention, represented by general formulas (2) to (5), are shown, but the present invention is not limited to these compounds. The following formulas (G-2-1) to (G-5-11) represent the guanidine cation portion of the xaton pigment of the present invention, omitting the xaton pigment skeleton portion contained in the xaton pigment represented by general formula (1). In the following structural formulas, some hydrogen atoms are omitted, and all possible stereoisomers and tautomers are included; a planar structural formula is described.

[0094] [Chemical Formula 18]

[0095] [Chemical Formula 19]

[0096] [Chemical Formula 20]

[0097] [Chemical Formula 21]

[0098] [Chemical Formula 22]

[0099] [Chemical Formula 23]

[0100] [Chemical Formula 24]

[0101] [Chemical Formula 25]

[0102] [Chemical Formula 26]

[0103] [Chemical Formula 27]

[0104] [Chemical Formula 28]

[0105] [Chemical Formula 29]

[0106] [Chemical Formula 30]

[0107] [Chemical Formula 31]

[0108] [Chemical Formula 32]

[0109] [Chemical Formula 33]

[0110] [Chemical Formula 34]

[0111] [Chemical Formula 35]

[0112] [Chemical Formula 36]

[0113] [Chemical Formula 37]

[0114] [Chemical Formula 38]

[0115] [Chemical Formula 39]

[0116] In general formula (1), An represents any anion. When the total number of anions in the xanthanid pigment skeleton is less than the total number of cations of the guanidine cation represented by "Gu", that is, when the total charge of the xanthanid pigment skeleton and the guanidine cation as a whole is a cation with a charge of 1 or more, it can form a complex salt or complex with one or more anions represented by "An" in the form of a counterion. In this invention, the salt formation reaction of xanthanid pigment and guanidine cation can be carried out by mixing xanthanid pigment and guanidine compound with any acid, as described later, or by mixing xanthanid pigment with guanidine salt compound, or by mixing xanthanid pigment and guanidine salt compound with any acid. An in general formula (1) can be a counterion from any acid used for the salt formation reaction, or a counterion from a guanidine salt compound. The type of An is not particularly limited and can be any of organic anions or inorganic anions, but is preferably a monovalent or divalent anion. As a specific example, the preferred ions are chloride ions, bromide ions, sulfate ions, bisulfate ions, nitrate ions, acetate ions, aminosulfonate ions, phosphate ions, trifluoroacetate ions, methanesulfonate ions, trifluoromethanesulfonate ions, p-toluenesulfonate ions, bis(trifluoromethanesulfonyl)imine anions, thiocyanate ions, or gluconate ions; more preferably, they are chloride ions, sulfate ions, bisulfate ions, methanesulfonate ions, trifluoromethanesulfonate ions, toluenesulfonate ions, or bis(trifluoromethanesulfonyl)imine anions.

[0117] In general formula (1), c represents the quantity of An and is an integer from 0 to 3. In general formula (1), An can be included in the thiamethoxam pigment. That is, the value of c in general formula (1) can be 0. C is preferably 0 or 2, and particularly preferably 0.

[0118] The xanthones in this invention can also be obtained by known methods, for example, by a salt exchange reaction of any xanthone having the xanthone skeleton of the above general formula (1) with a guanidine compound or guanidine salt compound having the guanidine cation skeleton represented by Gu in general formula (1). An example of a method for manufacturing the compounds of this invention is described below, but the method of manufacturing the invention is not limited thereto.

[0119] The xatonite pigment of this invention is obtained by salting a xatonite pigment having the corresponding substituents with a guanidine compound or guanidine salt compound having the corresponding substituents. The chemical reaction in this manufacturing process can be carried out in the presence of an organic solvent or water, but preferably in the presence of methanol or water. Alternatively, it can be carried out in the presence of an acid or base, or under neutral conditions, as needed.

[0120] In the method for manufacturing the succinate pigment of the present invention, the acids used in the salt-forming reaction can be, for example, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid; organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and bis(trifluoromethanesulfonyl)imide; and inorganic bases such as sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and lithium hydroxide; and organic bases such as diisopropylethylamine, diazabicycloundecene, and 2,4,6-trimethylpyridine.

[0121] The guanidine salt compounds used in this invention can be prepared by mixing a guanidine compound having the corresponding substituents with the aforementioned acid. The guanidine salt compounds can be prepared by pre-mixing the aforementioned guanidine compound with the aforementioned acid, or by mixing the aforementioned thiamethoxam pigment and the aforementioned guanidine compound with the aforementioned acid during a salt-forming reaction.

[0122] The separation and purification of the products in the manufacturing method of this invention can be appropriately combined with methods commonly used in organic synthesis, such as purification using column chromatography; adsorption purification using silica gel, activated carbon, activated clay, etc.; and known methods such as recrystallization, crystallization, and dispersion washing using solvents. Furthermore, for the identification, analysis, optical properties, thermophysical properties, and other property evaluation of these compounds, nuclear magnetic resonance (NMR), absorbance measurement using a spectrophotometer, ultraviolet-visible absorption spectroscopy (UV-Vis), and thermogravimetric-differential calorimetry (TG-DTA) can be performed. These analytical methods can also be used to evaluate the solubility, color, and heat resistance of the obtained compounds.

[0123] The saxanthin pigments of the present invention can be used in combination (e.g., mixed) of two or more different molecular structures. When using two or more types, the mass concentration ratio of the least significant saxanthin pigment in the total saxanthin pigment is 0.1 to 50% by mass. Preferably, one or two types of saxanthin pigments are used.

[0124] For the pigment, coloring composition containing the pigment, and colorant for filter containing the pigment or coloring composition of the present invention, it is necessary to dissolve or disperse it well in an organic solvent containing resin or the like during the manufacturing process of the colorant and the filter. Therefore, the higher the solubility and dispersibility in the organic solvent, the better. As an organic solvent, no particular limitation is made, but examples include: aromatic hydrocarbons such as toluene and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, and 2-propanol; esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA); amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); and chloroform (trichloromethane). PGME, PGMEA, cyclohexanone, or DAA are preferred. From the viewpoint of balancing the solubility of the resin and the solubility of the triarylmethane pigment, PGME or PGMEA is particularly preferred. These solvents can be used alone or in combination of two or more.

[0125] The solubility of the xatonite pigment of the present invention in a solvent can be determined, for example, by the following method: The xatonite pigment and solvent are mixed in an appropriate ratio, subjected to ultrasonic treatment, and then visually confirmed at room temperature (hereinafter, room temperature refers to a temperature within the range of 25°C or approximately ±2°C, i.e., 23 to 27°C) to determine the presence of insoluble components. The solubility can be evaluated by visually confirming the presence of insoluble components. The solvent used in the solubility determination is not particularly limited; water, alkaline solvents, or organic solvents can be used. Alkaline solvents are not particularly limited; specifically, examples include aqueous solutions of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonia, and ammonium acetate; and alkaline organic solvents such as ammonia-methanol solution. As an organic solvent, it is not particularly limited, but specifically, examples include: aromatic hydrocarbons such as toluene and xylene; ethers such as propylene glycol monomethyl ether acetate (PGMEA), methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether (PGME); ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, and 3-heptanone; alcohols such as methanol, ethanol, and 2-propanol; esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, and methyl 3-methoxypropionate; diacetone alcohol (DAA); amides such as N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP); dimethyl sulfoxide (DMSO); chloroform (trichloromethane); etc.

[0126] The water resistance and alkali resistance of the xaton pigment of the present invention can be determined, for example, by the following method: The xaton pigment and solvent are mixed in an appropriate ratio, subjected to ultrasonic treatment, and left at room temperature for 24 hours. The mixture with a pigment concentration of 0.5% by mass is visually observed for the presence of insoluble components (pigment residue) agglomeration, thereby evaluating water resistance and alkali resistance. As a solvent used in evaluating water resistance, water is not particularly limited, but purified water, distilled water, or deionized water is preferred, and purified water is more preferred. As a solvent used in evaluating alkali resistance, any of the above-mentioned alkaline solvents can be used, but an aqueous solution of potassium hydroxide is preferred, and a 0.04% by mass potassium hydroxide aqueous solution is more preferred. In the present invention, agglomeration refers to the formation of agglomerates by primary or secondary agglomeration of pigment residue. In the present invention, agglomeration is classified into strong agglomeration and weak agglomeration according to the morphology of the agglomerates. In the present invention, strong agglomeration refers to the formation of coarse agglomerates requiring pulverization when pigment residue diffuses in the solvent, while weak agglomeration refers to the formation of agglomerates that can be diffused by mixing operations such as stirring and shaking. In this invention, viscous materialization refers to the softening state of aggregates formed due to strong coagulation.

[0127] The zeolite pigment of the present invention exhibits excellent water and alkali resistance. For example, its solubility (mass%) in water (purified water) at room temperature is preferably less than 1.0% by mass, more preferably less than 0.5% by mass. Furthermore, its solubility (mass%) relative to a 0.04% by mass potassium hydroxide aqueous solution at room temperature is preferably less than 1.0% by mass, more preferably less than 0.5% by mass.

[0128] The colorant for color filters of the present invention comprises: the succinate pigment of the present invention or a coloring composition containing at least one of the succinate pigments, and components commonly used in the manufacture of color filters. For a conventional color filter, for example, when using a photolithography process, it can be obtained by mixing a dye, pigment, or other pigment with a resin component (including monomers and oligomers) and a solvent to prepare a liquid, coating the liquid onto a substrate such as glass or resin, photopolymerizing it using a photomask to create a colored pattern of a pigment-resin composite film that is soluble / insoluble in the solvent, cleaning it, and then heating it. Additionally, in electrodeposition and printing methods, mixtures obtained by mixing pigments with resins and other components are also used to create colored patterns. Therefore, specific components of the colorant for color filters of the present invention include at least one succinate pigment of the present invention, other dyes, pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. Furthermore, these components can be selected from among others, and other components can be added as needed.

[0129] When the succinate pigment of the present invention or a coloring composition containing the succinate pigment is used as a colorant for a filter, it can be used for filters of various colors, but is preferably used as a colorant for blue or red filters.

[0130] The colorant for the color filter of the present invention can be used alone with one or more of the pigments of the present invention, or it can be further mixed with other known pigments such as dyes or pigments as described below in order to adjust the hue, that is, to adjust the spectral characteristics.

[0131] When used as a colorant for red filters, no particular limitation is made, and examples that do not belong to the red pigment family of this invention include: CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 269, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71, etc.; other red lake pigments that do not belong to the red pigment family of this invention; CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, etc., which do not belong to the yellow pigment family of this invention; CI Acid Red 88, CI Basic Violet 10, etc., which are red dyes that do not belong to the red pigment family of this invention; etc.

[0132] When used as a colorant for blue filters, the following are examples of basic dyes without particular limitation: CI Basic Blue 3, CI Basic Blue 7, CI Basic Blue 9, CI Basic Blue 54, CI Basic Blue 65, CI Basic Blue 75, CI Basic Blue 77, CI Basic Blue 99, CI Basic Blue 129, CI Basic Violet 10, etc.; acidic dyes such as CI Acid Blue 9, CI Acid Blue 74, CI Acid Red 52, CI Acid Red 289, etc.; disperse dyes such as Disperse Blue 3, Disperse Blue 7, Disperse Blue 377, etc.; spiroketone dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, indene, oxazine, dioxazine, azo, and xatonne pigments (not included in this invention); and other blue lake pigments, etc., of the blue or purple family.

[0133] When used as a colorant for green filters, no particular limitation is made, and examples include: green pigments such as CI Pigment Green 7, CI Pigment Green 10, CI Pigment Green 36, CI Pigment Green 47, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63; yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, and CI Pigment Yellow 185; spiroketone dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane (not included in this invention), indane, oxazine, dioxazine, azo, xaton, isoindoline, and quinophthalone pigments; and other lake pigments and other blue, yellow, or green dyes or pigments.

[0134] By using these pigments and the zetatin pigments belonging to this invention, red, blue, or green color filters with excellent brightness and contrast ratios can be obtained.

[0135] The mixing ratio of other pigments in the colorant for filters of the present invention is preferably 5 to 2000% by mass relative to the total of the pigments in the present invention (when there are two or more). More preferably, it is 10 to 1000% by mass. The mixing ratio of pigment components such as dyes in the liquid colorant for filters is preferably 0.5 to 70% by mass relative to the total colorant. More preferably, it is 1 to 50% by mass.

[0136] As the resin component in the colorant for color filters of the present invention, any resin component that has the properties required for the manufacturing method and use of the color filter resin film formed using these components can be used, such as the "adhesive resin (B1)" described in Patent Document 3 (Japanese Patent Application Publication No. 2017-83852), paragraph

[0229] Synthesis Example 23. Specifically, examples such as acrylic resins, olefin resins, styrene resins, polyimide resins, polyurethane resins, polyester resins, epoxy resins, vinyl ether resins, phenolic (phenolic varnish) resins, other transparent resins, photocurable resins, or thermocurable resins can be used, and monomer or oligomer components of these components can be used in combination. In addition, copolymers of these resins can also be used in combination. In the case of liquid colorants, the content of these components in the resin of the colorant for color filters is preferably 5 to 95% by mass, more preferably 10 to 50% by mass.

[0137] To improve the performance of the colorant for color filters, the coloring composition of the present invention may contain other components such as surfactants, dispersants, defoamers, leveling agents, antioxidants, ultraviolet absorbers, and other organic compounds mixed in the manufacture of the colorant for color filters. However, it is preferable to include these additives in the coloring composition at an appropriate level, preferably at a level that reduces or increases the solubility of the coloring composition in the solvent to a desired level without affecting the effect of other similar additives used in the manufacture of color filters. These additives can be added at any time during the preparation of the coloring composition.

[0138] Other additives in the colorant for color filters of the present invention include photopolymerization initiators, crosslinking agents, and other components required for the polymerization and curing of resins. Additionally, surfactants, dispersants, and other components required to stabilize the properties of the components in the liquid colorant for color filters can be included. These additives can all be known additives used in color filter manufacturing, and are not particularly limited. The mixing ratio of the total amount of these additives in the solid component of the colorant for color filters is preferably 5 to 60% by mass, more preferably 10 to 40% by mass.

[0139] Example Hereinafter, embodiments of the present invention will be specifically described using examples, but the present invention is not limited to the following examples. The reagents described in the synthesis examples are products manufactured by Tokyo Chemical Industry Co., Ltd., Sigma Aldrich, Alfa Aesar, etc. Furthermore, the reactions in the synthesis examples were all carried out under a nitrogen atmosphere using reaction vessels equipped with a condenser, a stirring device, and a thermometer, unless otherwise specified. In addition, the identification of the compounds in the following synthesis examples utilizes… 1 H-NMR analysis (Bruker Ascend nuclear magnetic resonance device, model: 1H-NMR) TM (400MHz) to be used.

[0140] [Synthesis Example 1] Synthesis of Dye (Xn1-1) To a 100 mL flask, add 61.6 g (91.0 mmol) of CI Acid Red 289 (E-1), 46.4 g (273 mmol) of 1-iodopropane, 37.7 g (273 mmol) of potassium carbonate, and 184 mL of n-BuOH. Stir at 100 °C for 3 hours under reflux. After the reaction solution has cooled to room temperature, wash with 184 mL of water and 92 mL of 6M hydrochloric acid. Remove the solvent from the organic layer by vacuum distillation, and dry the residue overnight at 110 °C under reduced pressure to obtain the dye (Xn1-0) (53.9 g, 80%) as a reddish-brown solid.

[0141] The obtained solid was subjected to NMR analysis, and the following 41 hydrogen signals were detected. In formula (Xn1-0), n represents 1 to 2, indicating that it is a mixture. In addition, when the functional group is written outside the bond parentheses as in formula (Xn1-0), it means that the functional group is bonded to any part of the structural formula within the parentheses that can bond.

[0142] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.10-6.89 (13H), 6.22-5.78 (2H), 3.91-3.48 (4H), 2.46-1.94 (12H), 1.82-1.50 (4H), 1.14-0.80 (6H).

[0143] [Chemical Formula 40]

[0144] Next, 5.0 g (6.8 mmol) of dye (Xn1-0), 0.7 g (7.4 mmol) of guanidine chloride, and 50 mL of water were added to a 100 mL flask, and the mixture was stirred at 80 °C for 1 hour. After cooling to room temperature, the mixture was filtered under reduced pressure. The residue was dried under reduced pressure at 80 °C overnight to obtain dye (Xn1-1) (4.0 g, 75%) as a brown solid.

[0145] The obtained solid was subjected to NMR analysis, and the following 47 hydrogen signals were detected. In formula (Xn1-1), n ​​represents 1 to 2, indicating that it is a mixture.

[0146] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.06-6.69 (19H), 6.18-5.78 (2H), 3.92-3.51 (4H), 2.44-1.92 (12H), 1.82-1.48 (4H), 1.11-0.69 (6H).

[0147] [Chemical Formula 41]

[0148] [Synthesis Example 2] Synthesis of Dye (Xn1-2) Add 5.0 g (6.8 mmol) of dye (Xn1-0), 1.6 g (7.4 mmol) of diphenylguanidine, 1.3 mL of 6M hydrochloric acid, and 50 mL of water to a 100 mL flask, and stir at 80 °C for 1 hour. After cooling to room temperature, filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-2) (6.0 g, 94%) as a red solid.

[0149] The obtained solid was subjected to NMR analysis, and the following 57.7 hydrogen signals were detected. In formula (Xn1-2), n represents 1 to 2, indicating that it is a mixture.

[0150] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.92 (2.3H), 8.14-6.86 (27.4H), 6.17-5. 78 (2H), 3.96-3.50 (4H), 2.44-1.92 (12H), 1.80-1.51 (4H), 1.12-0.69 (6H).

[0151] [Chemical Formula 42]

[0152] [Synthesis Example 3] Synthesis of Dye (Xn1-3) Add 5.0 g (6.8 mmol) of dye (Xn1-0), 1.8 g (7.4 mmol) of 1,3-di-o-tolylguanidine, 1.3 mL of 6M hydrochloric acid, and 50 mL of water to a 100 mL flask, and stir at 80 °C for 1 hour. After cooling to room temperature, filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-3) (6.3 g, 95%) as a reddish-brown solid.

[0153] The obtained solid was subjected to NMR analysis, and the following 55.7 hydrogen signals were detected. In formula (Xn1-3), n represents 1 to 2, indicating that it is a mixture.

[0154] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.34 (2.1H), 8.12-6.84 (24H), 6.18-5.75 (2H), 4.00-3.51 (4H), 2.46-1.92 (18.6H), 1.80-1.48 (4H), 1.12-0.70 (6H).

[0155] [Chemical Formula 43]

[0156] [Synthesis Example 4] Synthesis of Dye (Xn1-4) Add 5.0 g (6.8 mmol) of dye (Xn1-0), 2.2 g (7.4 mmol) of triphenylguanidine, 3.4 mL of 6M hydrochloric acid, and 50 mL of water to a 100 mL flask, and stir at 80 °C for 1 hour. After cooling to room temperature, filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-4) (7.1 g, 98%) as a red solid.

[0157] The obtained solid was subjected to NMR analysis, and the following 58.4 hydrogen signals were detected. In formula (Xn1-4), n represents 1 to 2, indicating that it is a mixture.

[0158] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 10.60 (3.4H), 8.06-6.91 (31H), 6.18-5. 79 (2H), 4.00-3.44 (4H), 2.46-1.92 (12H), 1.81-1.46 (4H), 1.11-0.70 (6H).

[0159] [Chemical Formula 44]

[0160] [Synthesis Example 5] Synthesis of Dye (Xn1-5) Add 5.0 g (6.8 mmol) of dye (Xn1-0), 0.5 g (3.4 mmol) of phenylguanidine, 3.4 mL of 6M hydrochloric acid, and 50 mL of water to a 100 mL flask, and stir at 80 °C for 1 hour. After cooling to room temperature, filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-5) (2.1 g, 84%) as a purple-red solid.

[0161] The obtained solid was subjected to NMR analysis, and the following 95 hydrogen signals were detected. In formula (Xn1-5), n represents 0 to 1, indicating that it is a mixture.

[0162] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.67 (1H), 8.40-6.61 (38H), 6.18-5.74 (4H), 4.00-3.44 (8H), 2.46-1.92 (24H), 1.80-1.48 (8H), 1.11-0.68 (12H).

[0163] [Chemical Formula 45]

[0164] [Synthesis Example 6] Synthesis of Dye (Xn1-6) Add 5.0 g (6.8 mmol) of dye (Xn1-0), 0.9 g (1.7 mmol) of chlorhexidine, 0.9 mL of concentrated hydrochloric acid, and 100 mL of methanol to a 100 mL flask, and stir under reflux for 1 hour. After removing the methanol by vacuum distillation, add 60 mL of water, disperse and wash for 1 hour, and then filter under vacuum. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-6) (5.6 g, 95%) as a reddish-brown solid.

[0165] The obtained solid was subjected to NMR analysis, and the following 198 hydrogen signals were detected. In formula (Xn1-6), n represents 0 to 1, indicating that it is a mixture.

[0166] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.88-8.50 (2H), 8.50-6.55 (72H), 6.21-5.78 (8H), 3.86-3.44 (16 H), 3.06 (4H), 2.46-1.94 (48H), 1.78-1.53 ​​(16H), 1.53-1.33 (4H), 1.33-1.12 (4H), 1.09-0.70 (24H).

[0167] [Chemical Formula 46]

[0168] [Synthesis Example 7] Add 5.0 g (6.8 mmol) of dye (Xn1-0), 0.9 g (1.7 mmol) of chlorhexidine, 0.9 mL of concentrated hydrochloric acid, and 50 mL of water to a 100 mL flask, and stir at 80 °C for 1 hour. After cooling to room temperature, filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-7) (3.5 g, 99%) as a reddish-brown solid.

[0169] The obtained solid was subjected to NMR analysis, and the following 108 hydrogen signals were detected. In formula (Xn1-7), n represents 0 to 1, indicating that it is a mixture.

[0170] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 10.40-8.82 (2H), 8.68-6.62 (46H), 6.20-5.76 (4H), 3.88-3.48 (8 H), 3.06 (4H), 2.48-1.94 (24H), 1.82-1.55 (8H), 1.55-1.35 (4H), 1.33-1.11 (4H), 1.09-0.74 (12H).

[0171] [Chemical Formula 47]

[0172] [Comparative Example 1] Synthesis of Dye (Xn1-8) Add 5.0 g (6.8 mmol) of dye (Xn1-0), 3.2 g (5.4 mmol) of dimethyl di(octadecyl)ammonium chloride, and 50 mL of methanol to a 100 mL flask, and stir at 50 °C for 1 hour. After removing the methanol by vacuum distillation, add 50 mL of water and ultrasonically clean for 30 minutes. Remove the water by decantation, recover it with methanol, and remove it by vacuum distillation. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn1-8) (7.5 g, 98%) as a reddish-brown solid.

[0173] The obtained solid was subjected to NMR analysis, and the following 121 hydrogen signals were detected. In formula (Xn1-8), n represents 0 to 1, indicating that it is a mixture.

[0174] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.09-6.89 (13H), 6.18-5.80 (2H), 3.96-3.54 (4H), 3. 19 (4H), 2.97 (6H), 2.48-1.94 (12H), 1.84-1.52 (8H), 1.51-1.05 (60H), 1.05-0.73 (12H).

[0175] [Chemical Formula 48]

[0176] [Example 1] (Evaluation of water resistance) Weigh 20 mg of compound (Xn1-1) obtained in Synthesis Example 2 and purified water into a 10 mL glass sample vial to prepare a mixture with pigment concentrations of 0.5% by mass, 1% by mass, 3% by mass, and 5% by mass. After ultrasonic treatment for 20 minutes, the mixture was left at room temperature (25°C) for 24 hours. The pigment solutions of each concentration were visually observed, and the highest pigment concentration (by mass%) where no insoluble components were observed was taken as the solubility. For the 0.5% by mass mixture, the presence of agglomeration and viscous physicochemical properties of insoluble components (pigment residue) was visually observed, and the agglomeration state was evaluated according to the following three levels. The results of solubility and agglomeration related to water resistance are shown in Table 1.

[0177] “A”: Non-cohesive to weakly cohesive "B": Strongly cohesive and non-viscous physical properties “C”: Strongly cohesive and viscous physical properties (Evaluation of alkali resistance) For the evaluation of water resistance, a 0.04% (w / w) potassium hydroxide aqueous solution was used instead of purified water. The same method was used to visually observe solubility, the presence of insoluble aggregates, and viscous physicochemical properties. The results of solubility and aggregates related to alkali resistance are shown in Table 1.

[0178] “A”: Non-cohesive to weakly cohesive "B": Strongly cohesive and non-viscous physical properties “C”: Strongly cohesive and viscous physical properties [Examples 2-7] In contrast to Example 1, the compounds shown in Table 1 were used instead of compound (Xn1-1), and the water resistance and alkali resistance were determined and evaluated using the same method. The results are summarized in Table 1.

[0179] [Comparative Examples 1-2] In contrast to Example 1, the compounds shown in Table 1 were used instead of compound (Xn1-1), and the water resistance and alkali resistance were determined and evaluated using the same method. The results are summarized in Table 1.

[0180] [Table 1]

[0181] As shown in Table 1, compared with conventional succinate pigments that do not contain guanidine cations, the succinate pigments containing guanidine cations in the embodiments of the present invention exhibit excellent water resistance and alkali resistance.

[0182] [Synthesis Example 8] Synthesis of Dye (Xn6-1) 15.0 g (22.2 mmol) of CI Acid Red 289, 9.6 g (66.5 mmol) of iodomethane, 8.8 g (66.5 mmol) of potassium carbonate, and 45 mL of n-BuOH were added to a 100 mL flask. The mixture was stirred at 100 °C for 3 hours under reflux. After the reaction solution was allowed to cool naturally to room temperature, it was washed with 45 mL of water and 23 mL of 6M hydrochloric acid. The solvent in the organic layer was removed by vacuum distillation, and the residue was dried under reduced pressure overnight at 110 °C to obtain the dye (Xn6-0) (11.8 g, 78%) as a reddish-brown solid.

[0183] The obtained solid was subjected to NMR analysis, and the following 23 hydrogen signals were detected. In the formula (Xn6-0), n represents 1 to 2, indicating that it is a mixture.

[0184] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.18-6.81 (13H), 6.22-5.80 (2H), 3.55-3.26 (6H), 2.45-1.92 (12H).

[0185] [Chemical Formula 49]

[0186] Add 1.6 g (5.8 mmol) of triphenylguanidine, 0.7 mL of concentrated hydrochloric acid, and 20 mL of methanol to a 100 mL flask and stir at 60 °C. Dissolve 4.0 g (7.0 mmol) of dye (Xn6-0) in 30 mL of methanol, then add the solution dropwise to the flask and stir for 1 hour. After removing the methanol by distillation, add 50 mL of water, disperse and wash for 1 hour, and then filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn6-1) (4.4 g, 87%) as a purple solid.

[0187] The obtained solid was subjected to NMR analysis, and the following 52.8 hydrogen signals were detected. In formula (Xn6-1), n ​​represents 1 to 2, indicating that it is a mixture.

[0188] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 10.6 (3.3H), 8.08-6.88 (29.5H), 6.22-5.78 (2H), 3.60-3.24 (4H), 2.46-1.92 (12H).

[0189] [Chemical Formula 50]

[0190] [Synthesis Example 9] Synthesis of Dye (Xn22-1) Add 2.3 g (7.8 mmol) of triphenylguanidine, 1.3 mL of 6M hydrochloric acid, and 20 mL of water to a 100 mL flask and stir at 80 °C. Dissolve 5.0 g (6.8 mmol) of dye (E-2) in 30 mL of water and add the solution dropwise to the flask, stirring for 1 hour. After cooling to room temperature, filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn22-1) (6.5 g, 98%) as a purple solid.

[0191] The obtained solid was subjected to NMR analysis, and the following 47 hydrogen signals were detected.

[0192] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 10.6 (3H), 8.27 (1H), 7.72 (1H), 7.45-7.10 (16H), 7.03 (4H), 6.91 (2H), 3.74-3.52 (8H), 1.39-1.00 (12H).

[0193] [Chemical Formula 51]

[0194] [Synthesis Example 10] Synthesis of Dye (Xn32-1) 25.0 g (61.7 mmol) of the following compound (M-1) and 125 mL of 2-propanol were added to a 100 mL flask and stirred in an ice bath at a temperature below 10 °C. 12.5 g (123.4 mmol) of di-n-propylamine was dissolved in 50 mL of 2-propanol and added dropwise to the flask. The mixture was then stirred overnight at room temperature. The reaction solution was added dropwise to 700 mL of water, and 6 M hydrochloric acid was added to adjust the pH to below 2. The residue was filtered under reduced pressure and dispersed and washed with 250 mL of a water:2-propanol (8:2) mixture. The residue was dried under reduced pressure at 60 °C overnight to give compound (M-2) (23.1 g, 83%) as a purple solid.

[0195] [Chemical Formula 52]

[0196] [Chemical Formula 53]

[0197] Next, 20.0 g (42.6 mmol) of compound (M-2) and 85 mL of N-methyl-2-pyrrolidone were added to a 100 mL flask, and the mixture was stirred at 120 °C. 14.4 g (89.4 mmol) of sodium N-methyltaurate (62-66% aqueous solution) was added dropwise, and the mixture was stirred at 120 °C for 3 hours. The reaction mixture was cooled to room temperature and added dropwise to a mixture of 600 mL acetone and 8.6 mL concentrated hydrochloric acid. The mixture was then allowed to stand, decanted, and the supernatant was removed. The residue was purified by column chromatography (support: silica gel, solvent: chloroform / methanol = 10 / 1 to 6 / 1 (volume ratio)), and the solvent was removed by vacuum distillation. The residue was dried under reduced pressure overnight at 80 °C to obtain a purple-red solid dye (Xn32-0) (4.6 g, 24%).

[0198] The obtained solid was subjected to NMR analysis, and the following 31 hydrogen signals were detected.

[0199] 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.99 (1H), 7.59 (2H), 7.21 (1H), 7.14-6.94 (5H), 6.89 (1H), 3.85 (2H), 3.55 (4H), 3.23 (3H), 1.63 (4H), 0.94 (6H).

[0200] [Chemical Formula 54]

[0201] Next, 1.7 g (5.8 mmol) of triphenylguanidine, 1.3 mL of concentrated hydrochloric acid, and 20 mL of methanol were added to a 100 mL flask, and the mixture was stirred at 80 °C. 4.0 g (7.0 mmol) of dye (Xn32-0) was dissolved in 30 mL of methanol and added dropwise to the flask, and the mixture was stirred at 80 °C for 1 hour. After removing the methanol by vacuum distillation, 50 mL of water was added, and the mixture was dispersed and washed for 1 hour, followed by vacuum filtration. The residue was dried under reduced pressure at 80 °C overnight to obtain dye (Xn32-1) (4.4 g, 87%) as a purplish-red solid.

[0202] The obtained solid was subjected to NMR analysis, and the following 49 hydrogen signals were detected.

[0203] 1 H-NMR (400MHz, DMSO-d6) (ppm) = 10.6 (3H), 8.00 (1H), 7.59 (2H), 7.41-7.24 (12H), 7.24-7.11 (4H), 7 .11-6.93 (5H), 6.88 (1H), 3.83 (2H), 3.55 (4H), 3.22 (3H), 2.79 (2H), 0.94 (6H), 1.63 (4H), 0.94 (6H).

[0204] [Chemical Formula 55]

[0205] [Synthesis Example 11] Synthesis of Dye (Xn35-1) 50.0 g (221.4 mmol) of 3-cyclohexylaminopropanesulfonic acid, 9.0 g (221.4 mmol) of sodium hydroxide, and 400 mL of methanol were added to a 500 mL pear-shaped flask and stirred at room temperature for 3 hours. After removing the methanol by distillation, the residue was dried under reduced pressure at 80 °C overnight to obtain compound (M-3) (54.6 g, 100%) as a white solid.

[0206] [Chemical Formula 56]

[0207] Next, 3.0 g (7.4 mmol) of compound (M-1), 5.4 g (22.2 mmol) of intermediate (M-3), and 20 mL of N-methyl-2-pyrrolidone were added to a 100 mL flask, and the mixture was stirred at 120 °C for 19 hours. After cooling to room temperature, the reaction mixture was added dropwise to 600 mL of saturated saline solution and 3.0 mL of concentrated hydrochloric acid. The mixture was filtered under reduced pressure, and the residue was dried under reduced pressure overnight at 80 °C. The residue was then purified by column chromatography (support: silica gel, solvent: dichloromethane / methanol = 5 / 1 to 2 / 1 (volume ratio)), and the solvent was removed by reduced pressure distillation. The residue was dried under reduced pressure overnight at 80 °C to obtain the dye (Xn35-0) (1.9 g, 49%) as a purple solid.

[0208] The obtained solid was subjected to NMR analysis, and the following 44 hydrogen signals were detected.

[0209] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.00 (1H), 7.58 (2H), 7.33-6.85 (7H), 4.04 (2H), 3.65 (4H), 2.57 (4H), 2.12-0.98 (24H) [Chemical Formula 57]

[0210] Next, 2.7 g (9.4 mmol) of triphenylguanidine, 1.0 mL of concentrated hydrochloric acid, and 20 mL of methanol were added to a 100 mL flask, and the mixture was stirred at 60 °C. 4.0 g (6.8 mmol) of dye (Xn35-0) was dissolved in 30 mL of methanol and added dropwise to the flask, and the mixture was stirred at 60 °C for 1 hour. The methanol in the reaction solution was removed by vacuum distillation, and 50 mL of water was added to disperse and wash for 1 hour, followed by vacuum filtration. The residue was dried under reduced pressure overnight at 80 °C to obtain dye (Xn35-1) (5.2 g, 74%) as a purple solid.

[0211] The obtained solid was subjected to NMR analysis, and the following 44 hydrogen signals were detected.

[0212] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 10.6 (3H), 7.99 (1H), 7.59 (2H), 7.41-6.95 (37H), 4.02 (2H), 3.63 (4H), 2.57 (4H), 2.12-0.94 (24H).

[0213] [Chemical Formula 58]

[0214] [Synthesis Example 12] Synthesis of Dye (Xn36-1) To a 100 mL flask, add 60.0 g (42.6 mmol) of compound (M-2), 57.4 g (235.9 mmol) of compound (M-3), and 225 mL of N-methyl-2-pyrrolidone, and stir at 120 °C for 5 hours. Cool the reaction mixture to room temperature, add 41 mL of concentrated hydrochloric acid, and then add dropwise to 450 mL of saturated saline solution. After standing, decantate to remove the supernatant. Purify the residue by column chromatography (support: silica gel, solvent: chloroform / methanol = 20 / 1 to 15 / 1 (v / v)), and remove the solvent by vacuum distillation. Dry the residue under reduced pressure overnight at 80 °C to obtain a purple-red solid dye (Xn3-0) (21.8 g, 30%).

[0215] The obtained solid was subjected to NMR analysis, and the following 41 hydrogen signals were detected.

[0216] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.00 (1H), 7.58 (2H), 7.33-6.85 (7H), 4.03 (1H), 3.86-3.42 (6H), 2.60 (2H), 2.21-1.07 (16H), 1.05-0.69 (6H) [Chemical Formula 59]

[0217] Next, 11.9 g (18.2 mmol) of dye (Xn36-0) and 75 mL of water were added to a 100 mL flask and stirred at 60 °C. 1.8 g (19.1 mmol) of guanidine hydrochloride was dissolved in 10 mL of water and added dropwise to the flask, and the mixture was stirred at 80 °C for 1 hour. After cooling, the mixture was decanted. 40 mL of water was added, and the mixture was ultrasonically cleaned and decanted again. The residue was dried under reduced pressure at 80 °C overnight to obtain dye (Xn36-1) (9.8 g, 76%) as a purple solid.

[0218] The obtained solid was subjected to NMR analysis, and the following 47 hydrogen signals were detected.

[0219] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 8.00 (1H), 7.58 (2H), 7.33-6.71 (13H), 4.03 (1H), 3.86-3.42 (6H), 2.60 (2H), 2.21-1.07 (16H), 1.05-0.69 (6H) [Chemical Formula 60]

[0220] [Synthesis Example 13] Synthesis of Dye (Xn36-2) Add 0.4 g (1.7 mmol) of 1,3-di-o-tolylguanidine, 0.2 mL of concentrated hydrochloric acid, and 30 mL of water to a 100 mL flask and stir at 80 °C. Dissolve 1.0 g (1.6 mmol) of dye (Xn36-0) in 10 mL of water and add the solution dropwise to the flask. Stir at 60 °C for 1 hour. After cooling, decant. Add 40 mL of water, clean with sonication, and filter under reduced pressure. Dry the residue under reduced pressure at 80 °C overnight to obtain dye (Xn36-2) (1.1 g, 78%) as a purple solid.

[0221] The obtained solid was subjected to NMR analysis, and the following 59 hydrogen signals were detected.

[0222] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 9.17 (2H), 8.00 (1H), 7.58 (2H), 7.41-6.87 (17H) , 4.01 (1H), 3.78-3.46 (6H), 2.58 (2H), 2.25 (6H), 2.03-1.07 (16H), 1.05-0.83 (6H) [Chemical Formula 61]

[0223] [Examples 7-12] In contrast to Example 1, compounds (Xn1-1) listed in Tables 2 to 6 were used instead of compound (Xn1-1). Otherwise, the water resistance and alkali resistance were determined and evaluated using the same method. The results are summarized in Tables 2 to 6.

[0224] [Comparative Examples 3-7] In contrast to Example 1, compounds (Xn1-1) listed in Tables 2 to 6 were used instead of compound (Xn1-1). Otherwise, the water resistance and alkali resistance were determined and evaluated using the same method. The results are summarized in Tables 2 to 6.

[0225] [Table 2]

[0226] [Table 3]

[0227] [Table 4]

[0228] [Table 5]

[0229] [Table 6]

[0230] As shown in Tables 2-6, compared with conventional succinate pigments that do not contain guanidine cations, the various succinate pigments containing guanidine cations in the compounds of the embodiments of the present invention exhibit excellent water resistance and alkali resistance.

[0231] Industrial availability The coloring composition containing thallium pigment disclosed in this invention exhibits excellent water and alkali resistance, and can be used as a pigment material for various applications, such as colorants for color filters. Furthermore, by using this coloring composition as a colorant for color filters, the wastewater problem caused by pigment leaching into the cleaning solution during filter manufacturing can be suppressed.

Claims

1. A pyrrolizin pigment, represented by the following general formula (1), [Chemical Formula 62] In equation (1), R 1 ~R 4 Each independently represents -H, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms optionally having substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms optionally having substituents; R 1 With R 2 R 3 With R 4 They can be arbitrarily bonded together to form a ring. R 5 ~R 9 Each can be independently represented as -H, halogen atom, -OH, -CN, -NO2, -OR 10 -SO3 - -SO3M, a sulfonyl group having 0 to 30 carbon atoms optionally having a substituent, -COO - -COOM, a carbonyl group having 1 to 30 carbon atoms optionally having a substituent, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms optionally having a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms optionally having a substituent, or an amino group having 0 to 30 carbon atoms optionally having a substituent, R 10 This refers to a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms, optionally with substituents, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, optionally with substituents. M represents an inorganic cation, and when multiple cations are present, they may optionally be the same or different. in, R 1 ~R 10 At least two of them have the option of being free-SO3 - -COO - The anionic groups in the group consisting of monosulfonamide anionic groups with 1 to 10 carbon atoms and bissulfonamide anionic groups with 0 to 10 carbon atoms may be multiple anionic groups that are optionally the same or different. Gu represents a guanidine cation represented by any of the following general formulas (2) to (5). An represents anion. 'a' represents the number of xanthan pigment skeletons and is an integer from 1 to 4. b represents the quantity of Gu and is an integer from 1 to 4. c represents the quantity of An and is an integer from 0 to 3. [Chemical Formula 63] In equation (2), R 11 ~R 13 Each of these groups independently represents -H, a halogen atom, -CN, -NO2, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms optionally having substituents, an aromatic hydrocarbon group having 6 to 30 carbon atoms optionally having substituents, an aromatic heterocyclic group having 2 to 30 carbon atoms optionally having substituents, an acyl group having 1 to 20 carbon atoms optionally having substituents, an oxycarbonyl group having 1 to 20 carbon atoms optionally having substituents, an aminocarbonyl group having 1 to 20 carbon atoms optionally having substituents, a thiocarbonyl group having 1 to 20 carbon atoms optionally having substituents, an oxythiocarbonyl group having 1 to 20 carbon atoms optionally having substituents, an aminothiocarbonyl group having 1 to 20 carbon atoms optionally having substituents, a sulfonyl group having 0 to 20 carbon atoms optionally having substituents, or an amino group having 0 to 20 carbon atoms optionally having substituents. R 11 With R 12 R 12 With R 13 R 13 With R 11 They can be arbitrarily bonded together to form a ring. [Chemical Formula 64] In equation (3), R 14 ~R 17 R in general formula (2) 11 ~R 13 The same definition, L represents a linking group, and represents one or a combination of two or three groups selected from the group consisting of a straight-chain, branched, or cyclic alkylene group having 1 to 30 carbon atoms optionally having substituents and a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms optionally having substituents. [Chemical Formula 65] In equation (4), R 18 ~R 21 R in general formula (2) 11 ~R 13 The same definition, [Chemical Formula 66] In equation (5), R 22 ~R 27 R in general formula (2) 11 ~R 13 By the same definition, L represents the same definition as L in general formula (3).

2. The pyrrolizin pigment according to claim 1, wherein, In the general formula (1), R 1 and R 3 Each is an alkyl group having 1 to 10 carbon atoms, which is independently -H or optionally has substituents; R 2 and R 4 Each is independently a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms optionally having a substituent, or an aromatic hydrocarbon group having 6 to 10 carbon atoms optionally having a substituent.

3. The pyrrolizin pigment according to claim 1, wherein, In the general formula (1), R 5 ~R 9 -H, -SO3 - -SO3H, a sulfonyl group having 0 to 10 carbon atoms optionally having a substituent, -COO - -COOH or a carbonyl group having 1 to 10 carbon atoms, optionally with substituents.

4. The pyrrolizin pigment according to claim 1, wherein, In the general formula (1), Gu is a guanidine cation represented by general formula (2), where R 11 ~R 13 Each of the following is independently -H, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms optionally having a substituent, an aromatic hydrocarbon group having 6 to 30 carbon atoms optionally having a substituent, or an aromatic heterocyclic group having 6 to 30 carbon atoms optionally having a substituent.

5. The pyrrolizin pigment according to claim 1, wherein, In the general formula (1), Gu is a guanidine cation represented by general formula (3), where R 14 ~R 17 Each is an aromatic hydrocarbon group with 6 to 30 carbon atoms, which is independently -H, -CN, or optionally has substituents, and L is a straight-chain, branched, or cyclic alkylene group with 1 to 30 carbon atoms.

6. The pyrrolizin pigment according to claim 1, wherein, In the general formula (1), Gu is a guanidine cation represented by general formula (4), where R 18 ~R 21 Each is independently -H, optionally having a substituent, and comprising a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms, or optionally having a substituent, and an aromatic hydrocarbon group having 6 to 30 carbon atoms; R 18 and R 21 At least one of them is an aromatic hydrocarbon group having 6 to 30 carbon atoms, optionally having a substituent.

7. The pyrrolizin pigment according to claim 1, wherein, In the general formula (1), Gu is a guanidine cation represented by general formula (5), where R 22 ~R 27 Each is independently -H, a straight-chain, branched, or cyclic alkyl group having 1 to 30 carbon atoms optionally having a substituent, or an aromatic hydrocarbon group having 6 to 30 carbon atoms optionally having a substituent, and L is a straight-chain, branched, or cyclic alkylene group having 1 to 30 carbon atoms.

8. The pyrrolizin pigment according to claim 1, wherein, The solubility of the zeaxanthin in a 0.04% by mass potassium hydroxide aqueous solution at room temperature (23℃~27℃) is less than 1.0 by mass.

9. A coloring composition comprising the pyrithione pigment as described in any one of claims 1 to 8.

10. A colorant for a color filter, comprising the coloring composition of claim 9.

11. A color filter using the colorant for a color filter as described in claim 10.

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