Dye, coloring composition, color filter and solid-state imaging element

Abstract

To provide a dye and a coloring composition having excellent coloring power, transmittance, heat resistance and light resistance.SOLUTION: There is provided a dye (A) which is a salt-forming product of a cationic moiety represented by the general formula (1) and an anionic moiety selected from the general formulas (2-1) to (2-4). (R1 to R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent and in which a divalent organic group may be introduced between these carbon atoms, R1 and R2, and R3 and R4 may be linked together to form a ring and a divalent organic group may be introduced in forming the ring.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dye having a specific structure, a coloring composition containing the dye, a color filter, and a solid-state imaging device. [Background technology]

[0002] Conventionally, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 62, CI Pigment Green 63, squarylium dyes, etc. have been mainly used as green pigments. Although all of them have relatively excellent transmittance, CI Pigment Green 36 and CI Pigment Green 58 do not have sufficient coloring power for recent applications such as color filters, which require thin films, and squarylium dyes, etc. are required to have improved heat resistance and light fastness in order to be used in various applications such as color filters and printing inks. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2013-079301 A [Patent Document 2] JP 2007-284589 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a dye and a coloring composition which are excellent in coloring strength, transmittance, heat resistance, and light fastness. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that a dye (A) having a specific structure can solve the above problems, and have completed the present invention.

[0006] [1] A dye (A) which is a salt formed between a cationic moiety represented by the following general formula (1) and a specific anionic moiety selected from the general formulae (2-1) to (2-4): General formula (1) [ka] (R 1 ~R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these groups; 1 and R 2 , R 3 and R 4 may be linked to each other to form a ring, and a divalent organic group may be inserted between the rings. R 5 ~R 9 each independently represents a hydrogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, a sulfo group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an alkylcarboxy group, a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group, an aryl group having 6 to 20 carbon atoms, -SO 2 -OR 111 , or -SO 2 -NH-R 112 R 111 , R 112 each independently represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, a divalent organic group may be inserted between the carbon atoms thereof, adjacent two of these may be linked to each other to form a ring, and a divalent organic group may be inserted between the rings formed. X is -SiR 31 R 32 -, -P(=O)R 33 - or -SO 2 - represents R 31 ~R 33each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these groups; 31 and R 32 may be linked to each other to form a ring. General formula (2-1) [(R 21 ) c P-Hal (6-c) ] - (R 21 represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, R 21 When a plurality of Hal are present, they may be the same or different. c represents an integer of 0 to 6. General formula (2-2) [(R 22 ) d B -Hal (4-d) ] - (R 22 represents a halogenated hydrocarbon group, a cyano group, a phenyl group substituted with a nitro group, or a phenyl group substituted with a cyano group; B represents a boron atom; Hal represents a halo group; R 22 When a plurality of Hal are present, they may be the same or different. d represents an integer of 0 to 4. General formula (2-3) R 23 -N - -R 24 (R 23 and R 24 each independently represents a halogenated hydrocarbon group, N - Halogenated hydrocarbon group having a sulfonyl group at the bond to FSO, cyano group or FSO 2 R 23 and R 24 Both are halogenated hydrocarbon groups, N -When R is a halogenated hydrocarbon group having a sulfonyl group at the bonding site, they may be bonded to each other to form a ring. 23 and R 24 At least one of the halogenated hydrocarbon groups, N - or a cyano group. General formula (2-4) R 25 -SO 3 - (R 25 represents a halogenated hydrocarbon group which may be linked via a linking group having a nitrogen atom or an oxygen atom.

[0007] [2] A coloring composition comprising the dye (A) and a resin.

[0008] [3] The coloring composition according to [2], further comprising a yellow pigment.

[0009] [4] The coloring composition according to [2] or [3], further comprising a photopolymerization initiator.

[0010] [5] The coloring composition according to any one of [2] to [4], further comprising a photopolymerizable monomer.

[0011] [6] A color filter having a film formed on a substrate from the coloring composition of any one of [2] to [5].

[0012] [7][6] A solid-state imaging element having a color filter. Effect of the Invention

[0013] According to the present invention, by using a dye (A) which is a salt formed between a cationic moiety represented by the following general formula (1) and an anionic moiety selected from the following general formulae (2-1) to (2-4), it is possible to provide a coloring composition excellent in coloring power, transmittance, heat resistance and light fastness, and a color filter and a sensor using the same. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with a color filter of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is used, it means "acryloyl and / or methacryl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" in this invention means Color Index (CI). Colorants include dyes (A) and other colorants.

[0016] <Dye (A)> The dye (A) in the present invention is a salt formed between a cationic moiety represented by the following general formula (1) and an anionic moiety selected from the following general formulas (2-1) to (2-4). The dye (A) can provide a coloring composition excellent in coloring power, transmittance, and heat resistance. The dye (A) may be in the form of green, blue, etc., depending on its structure, but is not limited thereto.

[0017] General formula (1) [ka] (R 1 ~R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these groups; 1 and R 2 , R 3 and R 4may be linked to each other to form a ring, and a divalent organic group may be inserted between the rings. R 5 ~R 9 each independently represents a hydrogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, a sulfo group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an alkylcarboxy group, a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group, an aryl group having 6 to 20 carbon atoms, -SO 2 -OR 111 , or -SO 2 -NH-R 112 R 111 , R 112 each independently represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, a divalent organic group may be inserted between the carbon atoms thereof, adjacent two of these may be linked to each other to form a ring, and a divalent organic group may be inserted between the rings formed. X is -SiR 31 R 32 -, -P(=O)R 33 - or -SO 2 - represents R 31 ~R 33 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these groups; 31 and R 32 may be linked to each other to form a ring.

[0018] Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, and a stearyl group, and examples of the alkyl group having a substituent include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, and a dimethylcyclohexyl group.

[0019] Examples of alkenyl groups having 2 to 20 carbon atoms include vinyl groups, 1-propenyl groups, 2-propenyl groups, 2-butenyl groups, 3-butenyl groups, isopropenyl groups, isobutenyl groups, 1-pentenyl groups, 2-pentenyl groups, 3-pentenyl groups, 4-pentenyl groups, 1-hexenyl groups, 2-hexenyl groups, 3-hexenyl groups, 4-hexenyl groups, and 5-hexenyl groups.

[0020] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, a 4-methylphenyl group, and a 3,5-dimethylphenyl group, and examples of those having a substituent include a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, and a 4-cyanophenyl group.

[0021] Examples of the alkoxy group, alkoxycarbonyl group, and alkylcarboxy group include groups containing the above-mentioned alkyl group having 1 to 20 carbon atoms as the alkyl group.

[0022] Examples of the alkenyloxy group include groups containing the above-mentioned alkenyl groups having 2 to 20 carbon atoms.

[0023] Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group, an acyloxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group, an aryloxycarbonyl group, a chloro group, a fluoro group, a bromo group, and a group containing an iodo group.

[0024] Examples of the divalent organic group include groups containing an alkylene group having 1 to 20 carbon atoms, an alkylenedioxy group, an alkenylene group having 2 to 20 carbon atoms, an alkylenedicarbonyl group or an alkylenedicarboxy group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene dioxy group, an arylene dicarbonyl group or an arylene dicarboxyl group.

[0025] Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, and an octadecylene group. Examples of the alkylenedioxy group having 1 to 20 carbon atoms include a methylenedioxy group, an ethylenedioxy group, a propylenedioxy group, a hexylenedioxy group, a dodecylenedioxy group, and an octadecylenedioxy group. Examples of the alkenylene group having 2 to 20 carbon atoms include an ethynylene group, a propenylene group, and a butyrenylene group. Examples of the alkylene dicarbonyl group having 3 to 20 carbon atoms include a methylene dicarbonyl group, an ethylene dicarbonyl group, a butylene dicarbonyl group, and a dodecylene dicarbonyl group. Examples of the alkylene dicarboxy group having 3 to 20 carbon atoms include an ethylene dicarboxy group and a butylene dicarboxy group. Examples of the arylene group having 6 to 20 carbon atoms include a phenylene group and a xylenylene group. Examples of the arylene dioxy group having 6 to 20 carbon atoms include a phenylenedioxy group and a xylenylenedioxy group. Examples of the arylene dicarboxyl group having 6 to 20 carbon atoms include a phenylenedicarboxy group and a xylenylenedicarboxy group.

[0026] R 1 ~R 4 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group from the viewpoint of coloring power, and more preferably an ethyl group or an isopropyl group from the viewpoint of solubility. R 5 ~R 9 is preferably an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and from the viewpoint of coloring power, is preferably a methyl group or a hydrogen atom. The dye (A) may be, for example, a compound in which X is -SiR 31 R 32 -, it tends to show blue color, and X is -P(=O)R 33 - or -SO 2-, but is not limited thereto.

[0027] General formula (2-1) [(R 21 ) c P-Hal (6-c) ] - (R 21 represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, R 21 When a plurality of Hal are present, they may be the same or different. c represents an integer of 0 to 6.

[0028] Examples of Hal in the general formula (2-1) include a fluoro group, a chloro group, a bromo group, and an iodo group, and a fluoro group is preferable.

[0029] R in general formula (2-1) 21 The halogenated hydrocarbon group in is preferably an alkyl group substituted with a halogen atom or an aryl group substituted with a halogen atom, more preferably a fluorinated alkyl group or a fluorinated aryl group, further preferably a fluorinated aryl group, and particularly preferably a pentafluorophenyl group.

[0030] Representative examples of the anion represented by the general formula (2-1) include, for example, (CF 3 ) 3 PF 3 - , (C 2 F 5 ) 2 PF 4 - , (C 2 F 5 ) 3 PF 3 - , [(CF 3 ) 2 CF] 2 PF 4 - , [(CF 3 ) 2 CF] 3 PF 3- , (n-C 3 F 7 ) 2 PF 4 - , (n-C 3 F 7 ) 3 PF 3 - , (n-C 4 F 9 ) 3 PF 3 - , (C 2 F 5 )(CF 3 ) 2 PF 3 - , [(CF 3 ) 2 CFCF 2 ) 2 PF 4 - , [(CF 3 ) 2 CFCF 2 ) 3 PF 3 - , (n-C 4 F 9 ) 2 PF 4 - , (n-C 4 F 9 ) 3 PF 3 - , (C 2 F 4 H)(CF 3 ) 2 PF 3 - , (C 2 F 3 H 2 ) 3 PF 3 - , (C 2 F 5 )(CF 3 ) 2 PF 3 - etc. can be mentioned. Among them, PF 6 - , (C 2 F 5 ) 2PF 4 - , (C 2 F 5 ) 3 PF 3 - , (n-CF 7 ) 3 PF 3 - , (nC 4 F 9 ) 3 PF 3 - , [(CF 3 ) 2 CF] 3 PF 3 - , [(CF 3 ) 2 CF] 2 PF 4 - , [(CF 3 ) 2 CFCF 2 ] 3 PF 3 - , [(CF 3 ) 2 CFCF 2 ] 2 PF 4 - is preferred, and PF 6 - is more preferred.

[0031] General formula (2-2) [(R 22 ) d B -Hal (4-d) ] - (R 22 represents a halogenated hydrocarbon group, a cyano group, a phenyl group substituted with a nitro group, or a phenyl group substituted with a cyano group; B represents a boron atom; Hal represents a halo group; R 22 When a plurality of Hal are present, they may be the same or different. d represents an integer of 0 to 4.

[0032] Hal in the general formula (2-2) has the same meaning as Hal in the above general formula (2-1).

[0033] R in general formula (2-2) 22 The halogenated hydrocarbon group in the above formula (2-1) is R 21 R has the same meaning as the halogenated hydrocarbon group. 22 is preferably a halogenated hydrocarbon group, and more preferably a fluorinated alkyl group or a fluorinated aryl group.

[0034] Representative examples of the anionic moiety represented by the general formula (2-2) include, for example, (CF 3 ) 4 B - , C.F. 3 ) 3 BF - , (CF 3 ) 2 BF 2 - , (CF 3 )B.F. 3 - , (C 2 F 5 ) 4 B - , (C 2 F 5 ) 3 BF - , (C 2 F 5 )B.F. 3 - , (C 2 F 5 ) 2 BF 2 - , (CF 3 )(C 2 F 5 ) 2 BF - , (C 6 F 5 ) 4 B - , [(CF 3 ) 2 C 6 H 3 ] 4 B - , (CF 3 C 6 H 4 ) 4 B - , (C 6F 5 ) 2 BF 2 - 、(C 6 F 5 )BF 3 - 、(C 6 H 3 F 2 ) 4 B - 、B(CN) 4 - 、B(CN)F 3 - 、B(CN) 2 F 2 - 、B(CN) 3 F - 、(CF 3 ) 3 B(CN) - 、(CF 3 ) 2 B(CN) 2 - 、(C 2 F 5 ) 3 B(CN) - 、(C 2 F 5 ) 2 B(CN) 2 - 、(nC 3 F 7 ) 3 B(CN) - 、(nC 4 F 9 ) 3 B(CN) - 、(nC 4 F 9 ) 2 B(CN) 2 - 、(nC 6 F 13 ) 3 B(CN) - ,(CHF 2 ) 3 B(CN) - ,(CHF 2 ) 2 B(CN) 2 - 、(CH 2 CF 3 )3 B(CN) - , (CH 2 CF 3 ) 2 B(CN) 2 - , (CH 2 C 2 F 5 ) 3 B(CN) - , (CH 2 C 2 F 5 ) 2 B(CN) 2 - , (CH 2 CH 2 C 3 F 7 ) 2 B(CN) 2 - , (nC 3 F 7 CH 2 ) 2 B(CN) 2 - , (C 6 H 5 ) 3 B(CN) - Among them, BF 4 - , B(CN) 3 F - , (CF 3 ) 4 B - , (C 6 F 5 ) 4 B - (tetrakis(pentafluorophenyl)borate anion), [(CF 3 ) 2 C 6 H 3 ] 4 B - is preferred.

[0035] General formula (2-3) R 23 -N - -R 24 (R 23 and R 24each independently represents a halogenated hydrocarbon group, N - Halogenated hydrocarbon group having a sulfonyl group at the bond to FSO, cyano group or FSO 2 R 23 and R 24 Both are halogenated hydrocarbon groups, N - When R is a halogenated hydrocarbon group having a sulfonyl group at the bonding site, they may be bonded to each other to form a ring. 23 and R 24 At least one of the halogenated hydrocarbon groups, N - or a cyano group.

[0036] R in general formula (2-3) 23 and R 24 The halogenated hydrocarbon group in the above formula (2-1) is R 1 The halogenated hydrocarbon group in R 23 and R 24 R may form a cyclic structure of an aliphatic saturated hydrocarbon. 23 and R 24 are each independently N - A halogenated hydrocarbon group having a sulfonyl group at the bonding site with the halogenated hydrocarbon group is preferred, and a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group is more preferred, which provides particularly excellent heat resistance.

[0037] Representative examples of the anionic moiety represented by the general formula (2-3) include, for example, [(FSO 2 ) 2 N] - , [(FSO 2 )N(CF 3 SO 2 )] - , [(FSO 2 )N(CF 3 CF 2 SO 2 )] - , [(FSO 2 )N{(CF 3 ) 2 CFSO 2}] -,[(FSO 2 )N(CF 3 CF 2 CF 2 I AM 2 )] - ,[(FSO 2 )N(CF 3 CF 2 CF 2 CF 2 I AM 2 )] - ,[(FSO 2 )N{(CF 3 ) 2 CFCF 2 I AM 2}] - ,[(FSO 2 )N{CF 3 CF 2 (CF 3 )CFSO 2}] - ,[(FSO 2 )N{(CF 3 ) 3 CSO 2}] - ,[(CF 3 I AM 2 ) 2 [No] - ,[(CF 3 CF 2 I AM 2 ) 2 [No] - ,[(CF 3 CF 2 CF 2 I AM 2 ) 2 [No] - 、(CF 3 CF 2 CF 2 CF 2 I AM 2 ) 2 [No] - ,[{(CF 3 ) 2 CFCF 2 I AM 2} 2 [No] - [[{CF 3 CF 2 (CF 3 )CFSO 2}2 N] - , [{(CF 3 ) 3 CSO 2} 2 N] - or the following structure. Among them, [(CF 3 SO 2 ) 2 N] - , [(nC 4 F 9 SO 2 ) 2 N] - The following structure is preferred:

[0038] [ka]

[0039] General formula (2-4) R 25 -SO 3 - (R 25 represents a halogenated hydrocarbon group which may be linked via a linking group having a nitrogen atom or an oxygen atom.

[0040] R in general formula (2-4) 25 The halogenated hydrocarbon group in the above formula (2-1) is R 21 The halogenated hydrocarbon group may be linked via -O-, -CO-, -COO-, -CO-NH-, or the like. R 25 is preferably a halogenated hydrocarbon group, more preferably a fluorinated alkyl group or a fluorinated aryl group, which is particularly excellent in heat resistance.

[0041] Specific examples of the anionic moiety represented by formula (2-4) are shown below. [ka] [ka]

[0042] Among them, CF 3 SO 3 - is preferred.

[0043] As the anionic moiety selected from the general formulae (2-1) to (2-4), an anionic moiety represented by the general formula (2-2) or (2-3) is preferable.

[0044] <Method for producing dye (A)> The dye (A) can be produced by synthesizing a dye (a) that is a salt formed between a cationic moiety represented by general formula (1) and an appropriate anion, and then forming a salt with a compound (b) having an anionic moiety selected from general formulae (2-1) to (2-4), but the production method is not limited to this method.

[0045] (Pigment (a)) An example of a method for producing the dye (a) is shown below.

[0046] [ka]

[0047] (Y - represents an anion such as a halogen.) Reaction 1 involves nitration with concentrated nitric acid under acidic conditions. Reaction 2 involves reduction of the nitro group with Pd / C catalyst and hydrazine monohydrate. Reaction 3 involves alkylation of the amino group with an alkyl halide. Reaction 4 involves construction of a ketone structure using formaldehyde. Reaction 5 involves coupling with a benzaldehyde analogue using paratoluenesulfonic acid and chloranil to obtain the desired dye structure.

[0048] The dye (a) may, for example, have the following structure: [ka] [ka]

[0049] (Compound (b) Having an Anionic Site) The compound (b) having an anionic moiety includes salts formed between an anionic moiety selected from the general formulae (2-1) to (2-4) and a metal or the like.

[0050] In one example of the manufacturing process of dye (A), dye (a) is dissolved in water or water containing a hydrophilic organic solvent, and a solution of a compound (b) having one anionic moiety selected from the general formulae (2-1) to (2-4) dissolved in water or water containing a hydrophilic organic solvent is gradually added, and the precipitate is filtered off. The precipitate is then dried to obtain dye (A) which is a salt.

[0051] <Uses of dye (A)> The colorant (A) of the present invention can be used in various applications, such as printing inks, paints, colorants for plastics, and color filters. In addition, the dye (A) of the present invention has a characteristic of emitting strong fluorescence of 650 to 800 nm when irradiated with light of 650 to 750 nm. Therefore, for example, by giving a site that interacts with a specific site of a living body to the dye (A) of the present invention, it can be used as a fluorescent dye for a living body. Since a living body has strong absorption in the wavelength region of 400 to 650 nm, which is almost the same as visible light, and does not transmit light in this region, even if visible light is emitted inside the living body, it cannot be detected from the outside, but has a characteristic of transmitting light of 650 to 1000 nm. Therefore, when the dye (A) of the present invention interacts with a specific site of a living body, it is possible to irradiate light of 650 to 750 nm from the outside of the living body and detect the emitted light of 650 to 800 nm outside the living body. In addition, a fluorescent dye needs to have high light resistance because it is irradiated with light, and since the dye (A) has high light resistance because it is a salt formed with a specific anionic site, it is useful as a fluorescent dye.

[0052] <Other colorants> The coloring composition of the present invention may contain, in addition to the colorant (A), various conventionally known pigments, dyes, etc., as other coloring materials. Representative pigments and dyes that can be used in the present invention are listed below.

[0053] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 1 01, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 22 0, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, 295, 296, etc.

[0054] As orange pigments which function similarly to red pigments, for example, orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 73, etc. can be used.

[0055] Red dyes include CI Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 108, 109, 109, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 3, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 1 28, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 24 9, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

[0056] Also, CI Direct Red 1, 2, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26:1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 102, 103, 104, 105, 106, 107, 108, 109, 109, 102, 103, 104, 105, 106, 107, 108, 10 9, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114 , 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, Also included are 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, and the like.

[0057] Further examples include CI Solvent Red 52, 135, 146, 149, 168, 179, 207, and the like.

[0058] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0059] Purple dyes include CI Acid Violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, and the like.

[0060] Further examples include CI Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, and 97.

[0061] The coloring composition of the present invention may contain a yellow colorant. The yellow colorant refers to a yellow pigment and a yellow dye.

[0062] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, 234, and the pigments described in JP-A-2012-226110.

[0063] Yellow dyes include CI Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66 , 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

[0064] Further examples include CI Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, and 134.

[0065] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and 80.

[0066] Blue dyes include CI Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. , 53, 54, 55, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 11 0, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203 , 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, etc.

[0067] Also, CI Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, Also included are 130:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, and 263.

[0068] The coloring composition of the present invention may contain a green colorant. The green colorant refers to a green pigment and a green dye.

[0069] Examples of green pigments include, but are not limited to, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and pigments described in JP-A-2017-111398. Among these, from the viewpoint of transmittance, CI Pigment Green 7, 36, 58, 59, 62, 63, and pigments described in JP-A-2017-111398 are preferred.

[0070] Examples of green dyes include CI Solvent Green 3, 20, and 28, CI Acid Green 25, 27, 36, 37, 38, 41, 42, and 44, and CI Bat Green 3, 6, and 8.

[0071] The green coloring composition for forming the green filter segment can be a mixture of yellow pigments such as CI Pigment Yellow 138, 139, 150, 185, 231, 233, 234 and the pigments described in JP 2012-226110 A, and / or green pigments such as CI Pigment Green 7, 36, 58, 59, 62, 63 and the pigments described in JP 2017-111398 A.

[0072] In the cyan coloring composition for forming the cyan filter segment, blue pigments such as CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, and 81 can be used alone or in combination.

[0073] The magenta coloring composition for forming the magenta filter segment can be made of a single or mixed purple pigment and a red pigment, such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81, etc. The magenta coloring composition can be made of a yellow pigment.

[0074] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between saturation and brightness.

[0075] <Minification of pigments> When a pigment is used as a colorant, it is preferable to mix it with other raw materials after the fine-graining treatment. Examples of the method of the fine-graining treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after the fine-graining treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the film. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0076] The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0077] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0078] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0079] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0080] <Metal Removal> If the coloring composition contains a large amount of specific metal elements as impurities other than the colorant components, it may hinder the dispersion stability over time, and may cause a decrease in heat resistance or a decrease in sensitivity. In addition, a color filter made using the composition may have foreign matter, which may result in a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the coloring composition is preferably 500 mass ppm or less.

[0081] The total amount of specific metal elements contained in the coloring composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less.The lower limit of the total amount of specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more.Within the above range, it is possible to obtain a coloring composition that can form a color filter that can suppress costs, has excellent storage stability, and has little generation of foreign matter and little decrease in brightness.

[0082] The amount of each specific metal element contained in the coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0083] Also, it is better that the metals constituting the colorant, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, and impurities that do not function effectively are small, and they can be removed in the same manner as the specific metal elements by the following method. Furthermore, it is preferable that Mn, Cs, Ti, Co, Si, Pd, etc., which are mixed in by materials (for example, catalysts) used in the manufacturing process of various raw materials of the coloring composition, are low in concentration.

[0084] Methods for removing colorants or metals that have become mixed in from equipment during the manufacturing process include methods using water washing as described in JP 2010-83997 A, JP 2018-36521 A, JP 7-198928 A, JP 8-333521 A, JP 2009-7432 A, etc., and methods such as removing magnetic foreign matter using a magnet as described in JP 2011-48736 A, and these methods can be used alone or in combination as appropriate.

[0085] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0086] <Resin> The coloring composition of the present invention contains a resin. The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region when a coating film having a thickness of 2 μm is formed. Examples of the resin include a binder resin and a resin-type dispersant.

[0087] (binder resin) The coloring composition of the present invention preferably contains a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin may be, for example, a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin. The active energy ray curable resin may have an active energy ray reactive functional group in the thermoplastic resin or the thermosetting resin. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali solubility is for imparting development solubility in an alkali development step during the production of a color filter, and an acidic group is required.

[0088] The binder resins can be used alone or in combination of two or more kinds.

[0089] The content of the binder resin is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, relative to 100 parts by mass of the colorant. When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0090] ≪Thermoplastic resin≫ Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0091] <<Active energy ray-curable alkali-soluble resin>> The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the following methods (i) and (ii). When cured with active energy rays, the resin is three-dimensionally crosslinked, increasing the crosslink density and improving chemical resistance.

[0092] [Method (i)] In the method (i), for example, an ethylenically unsaturated monomer having an epoxy group is copolymerized with another monomer to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction with the side chain epoxy group of the copolymer.Then, a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0093] Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0094] Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0095] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. If necessary, for example, to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

[0096] Examples of other monomers include the following: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol, and the like. (meth)acrylates such as ethylene glycol (meth)acrylate or ethoxy polyethylene glycol (meth)acrylate; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide or acryloylmorpholine; styrenes such as styrene or α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate or vinyl propionate.

[0097] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of the polyimide include N-substituted maleimides such as imidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0098] As a method similar to the method (i), for example, there is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0099] [Method (ii)] Method (ii) is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0100] Examples of the ethylenically unsaturated monomer having a hydroxyl group include hydroxyalkyl methacrylates such as 2-hydroxyethyl(meth)acrylate, 2- or 3-hydroxypropyl(meth)acrylate, 2-, 3- or 4-hydroxybutyl(meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl(meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and / or poly(12-hydroxystearic acid). From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use a compound having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0101] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0102] Examples of other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0103] As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already explained can be used.

[0104] The phosphate group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0105] <Alkali-soluble resin having no ethylenically unsaturated double bond> The coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating.

[0106] The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 to 40,000, preferably 3,000 to 30,000, more preferably 4,000 to 20,000, in order to impart alkali development solubility. The value of Mw / Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, making it difficult to leave an exposed pattern. If it exceeds 40,000, the alkali development solubility decreases, residues are generated, and the linearity of the pattern deteriorates. The acid value of the alkali-soluble resin in the present invention is 50 to 200 (KOH mg / g) in order to impart solubility in alkaline development, preferably 70 to 180, more preferably 90 to 170. If the acid value is less than 50, the solubility in alkaline development decreases, residues are generated, and linearity of the pattern deteriorates. If the acid value exceeds 200, adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

[0107] Each of the raw materials used in the synthesis of the binder resin can be used alone or in combination of two or more kinds.

[0108] (Resin-type dispersant) The resin-type dispersant has a pigment-affinity portion that has the property of adsorbing to the added pigment, and a portion that is compatible with the colorant carrier, and functions to adsorb to the added colorant and stabilize the dispersion in the colorant carrier. Examples of resin-type dispersants include polyurethane, polyacrylate and other polycarboxylate esters, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and their salts, oil-based dispersants, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters. These can be used alone or in combination of two or more, but are not necessarily limited to these.

[0109] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, and 2155 manufactured by BYK Japan. Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, 6919, Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 440 manufactured by BASF Japan Ltd. 2, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0110] The blending amount of the resin type dispersant is preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, based on 100 parts by mass of the colorant. When an appropriate amount is used, the film-forming property is further improved.

[0111] <Dispersion aid> The coloring composition of the present invention may use a dispersing aid such as a dye derivative, a surfactant, etc. The dispersing aid is excellent in dispersing the coloring agent and has a large effect of preventing the coloring agent from re-aggregating after dispersion, so that when a coloring composition in which the coloring agent is dispersed in a coloring agent carrier using the dispersing aid is used, a film with high transmittance can be obtained.

[0112] (Pigment Derivatives) The dye derivative is a compound having a structure in which a part of the dye skeleton is substituted with an acidic group, a basic group, or a phthalimidomethyl group. As the dye derivative, a dye derivative having an acidic group or a basic group is preferable from the viewpoint of dispersibility and dispersion stability. As the acidic group possessed by the dye derivative, sulfonic acid, carboxylic acid and quaternary ammonium salts thereof are preferable, carboxylic acid group and sulfonic acid group are more preferable, and sulfonic acid group is more preferable. As the basic group possessed by the dye derivative, an amino group is preferable, and a tertiary amino group is more preferable. The dye derivative may be contained alone or in combination of two or more kinds.

[0113] (Surfactant) Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in a mixture of two or more, but are not necessarily limited to these.

[0114] When a surfactant is added, the blending amount is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. If the blending amount of the surfactant is less than 0.1 part by mass, it is difficult to obtain the effect of adding the surfactant, and if the blending amount is more than 55 parts by mass, it may have an adverse effect on the dispersion stability.

[0115] <Photopolymerizable monomer> The coloring composition of the present invention can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer of the present invention includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to produce a transparent resin, and these can be used alone or in combination of two or more kinds. The amount of the monomer is preferably 5 to 50 parts by mass relative to 100 parts by mass of the colorant, and more preferably 10 to 30 parts by mass from the viewpoint of photocurability and developability.

[0116] Examples of monomers and oligomers that harden when exposed to ultraviolet light, heat, or the like to form a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl. Examples of the acrylic acid esters and methacrylic acid esters include, but are not limited to, ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0117] <Photopolymerization initiator> When the coloring composition of the present invention is cured by ultraviolet irradiation to form a filter segment by photolithography, a photopolymerization initiator and the like can be added to prepare the coloring composition in the form of a solvent-developable or alkali-developable coloring resist material. When using a photopolymerization initiator, the blending amount is preferably 5 to 200 parts by mass relative to 100 parts by mass of the coloring agent, and more preferably 10 to 150 parts by mass from the viewpoints of photocurability and developability.

[0118] The photoinitiator may be 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethylamino. acetophenone compounds such as 1-(4-morpholinophenyl)-butan-1-one; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperphenyl)sulfide. benzophenone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, triazine-based compounds such as 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; titanocene compounds; etc. may be used.

[0119] These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. The amount of these photopolymerization initiators is preferably 5 to 200 parts by mass, and more preferably 10 to 150 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition, from the viewpoints of photocurability and developability.

[0120] <Sensitizer> Furthermore, the coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0121] Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are used.

[0122] More specifically, examples of sensitizers include, but are not limited to, those described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), "Tokushu No Futoshi Zairyo" edited by Chuzo Ikemori et al., and "Tokushu No Futoshi Zairyo" (CMC, 1986). In addition, the photosensitive layer may contain a sensitizer that absorbs light in the ultraviolet to near infrared range.

[0123] The sensitizers can be used alone or in combination of two or more kinds.

[0124] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0125] <Thiol-based chain transfer agents> The coloring composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen in polymerization, so that the obtained coloring composition has high sensitivity.

[0126] Also preferred is a polyfunctional aliphatic thiol having two or more thiol groups bonded to an aliphatic group such as a methylene or ethylene group. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and curing can be achieved from the surface of the pattern to the vicinity of the substrate.

[0127] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, ... Examples of the thiopropionate include tris(2-hydroxyethyl)trimercaptopropionic acid, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Of these, preferred are ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0128] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0129] The content of the thiol chain transfer agent is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the nonvolatile content of the colored composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0130] <Polymerization inhibitor> The colored composition of the present invention may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern with a desired shape.

[0131] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n- alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucine.

[0132] The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the colored composition. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles in the coating, pattern resolution, etc. are improved.

[0133] <Ultraviolet absorbing agent> The coloring composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

[0134] The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. This allows a high degree of compatibility between photosensitivity and resolution. When the coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

[0135] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, adhesion may be weakened and pixel peeling may occur, whereas if it is more than the above, the sensitivity may become excessively high and the resolution may deteriorate.

[0136] Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl esters. mixture of esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, reaction products of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl) 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, etc. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

[0137] Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. In addition, oligomer and polymer type compounds having a triazine structure can also be used.

[0138] Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

[0139] Examples of the salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

[0140] <Antioxidants> The coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the coloring composition from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and therefore can improve the transmittance of the coating. In particular, when the coloring composition has a high colorant concentration, the amount of the coating crosslinking component is reduced, and therefore a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, resulting in a phenomenon in which yellowing during the thermal process is intensified. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a film with high transmittance can be obtained.

[0141] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0142] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred. The antioxidants can be used alone or in combination of two or more kinds.

[0143] Furthermore, when the content of the antioxidant is 0.5 to 5.0% by mass relative to 100% by mass of the solid content of the colored composition, the transmittance, spectral characteristics, and sensitivity are excellent, which is more preferable.

[0144] <Amine compounds> The coloring composition of the present invention may contain an amine compound for reducing dissolved oxygen. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

[0145] <Leveling agent> The coloring composition of the present invention may contain a leveling agent to improve the leveling property of the coloring composition during coating. The leveling agent is preferably, for example, dimethylsiloxane having a polyether structure or polyester structure in the main chain. Examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie. Examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the non-volatile content of the coloring composition.

[0146] The leveling agent is, for example, a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and is a compound that has a hydrophilic group but has low solubility in water and can reduce surface tension. As the leveling agent, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit is, for example, a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

[0147] The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

[0148] The leveling agent may contain an anionic, cationic, nonionic or amphoteric surfactant as a supplement. Two or more types of surfactants may be mixed together.

[0149] Examples of the anionic surfactant added auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

[0150] Examples of cationic surfactants to be added to the leveling agent as an auxiliary include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants to be added to the leveling agent as an auxiliary include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicon-based surfactants.

[0151] <Storage stabilizer> The coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the coloring composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer may be used in an amount of 0.1 to 10% by mass in 100% by mass of the coloring agent.

[0152] <Adhesion improver> The coloring composition of the present invention can contain an adhesion improver such as a silane coupling agent in order to improve adhesion to a substrate. By improving adhesion with the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

[0153] Examples of the adhesion improver include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane, epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane and N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition. Within this range, the effect is large, and a good balance of adhesion, resolution, and sensitivity is achieved, which is more preferable.

[0154] <Organic solvent> The coloring composition of the present invention may contain an organic solvent in order to facilitate the sufficient dispersion and penetration of the colorant into the colorant carrier and the application of the composition onto a substrate such as a glass substrate to form a filter segment.

[0155] Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, and 3-methoxy-3-methylbutyl acetate. acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, gamma-butyrolactone, isobutyl alcohol, isophorone , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate,Dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0156] Among these, 3-methoxy-1-butanol, ethyl lactate, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferably used because they provide good dispersion and dissolution of the pigment. In particular, from the viewpoints of safety and hygiene and low viscosity, it is more preferable to use 3-methoxy-1-butanol or propylene glycol monomethyl ether acetate (PGMAc).

[0157] These organic solvents can be used alone or in combination of two or more. When a mixed solvent of two or more kinds is used, it is preferable that the above-mentioned preferred organic solvent is contained in an amount of 65 to 95 parts by mass per 100 parts by mass of the organic solvent.

[0158] The organic solvent is preferably used in an amount of 800 to 4000 parts by mass per 100 parts by mass of the colorant, since it adjusts the viscosity of the coloring composition to an appropriate level and enables the formation of a film with a desired uniform thickness.

[0159] <Method of producing colored composition> The coloring composition of the present invention can be prepared by mixing the above-mentioned components. In the preparation, the components may be mixed at once, or may be mixed successively after dissolving or dispersing the components in an organic solvent. For example, a colorant, a dispersing aid, a resin, an organic solvent, etc. are added and a dispersion treatment is performed. Then, if necessary, a photopolymerizable compound, a photopolymerization initiator, etc. are mixed and mixed to produce the coloring composition. The timing of mixing the components is arbitrary. The dispersion treatment can also be performed multiple times.

[0160] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0161] The average dispersed particle size (secondary particle size) of the particles in the coloring composition is preferably from 30 to 200 nm, more preferably from 40 to 200 nm. If the particles have an appropriate particle size, a coloring composition having high dispersion stability is easily obtained.

[0162] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

[0163] The coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0164] <Removal of large particles> The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0165] <Water content in color composition> The coloring composition of the present invention preferably has a water content of 2% by mass or less. When the water content of the coloring composition is within the above range, the coloring composition has excellent dispersion stability and sensitivity even after storage over time. The water content in the colored composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. If the water content is sufficiently low within this range, problems are unlikely to occur in dispersion stability and sensitivity even after storage over time.

[0166] The method for controlling the water content is not particularly limited, and a known method can be used. For example, a method of producing a colored composition while blowing in a dry inert gas, a method of dehydrating the colored composition by adding molecular sieves after production, etc. are included. Among them, the method of producing the colored composition while blowing in a dry inert gas is preferred. The water content can be measured by a known method such as the Karl Fischer method.

[0167] <Amount of toluene in colored composition> The coloring composition of the present invention may contain toluene, and when it does contain toluene, the content of toluene is preferably 0.1 to 10 mass ppm. The upper limit of the toluene content is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and even more preferably 0.4 mass ppm or more.

[0168] <Membrane> The coloring composition of the present invention can be used for optical filters and the like by forming a film (also called a coating film). The film can be used in a state of being laminated on a substrate, or the film can be peeled off from the substrate. The film can be either a flat film or a film having a pattern formed thereon, but a film having a pattern formed thereon is preferred.

[0169] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced through a step of coating the colored composition of the present invention on a substrate.

[0170] The substrate may be, for example, a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on the substrate. An imaging element such as a CCD or CMOS may be formed on the substrate. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the substrate surface.

[0171] The coating method may be a known method, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0172] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0173] Next, a pattern is formed. Examples of a method for forming a pattern include a photolithography method and a dry etching method. When the film is used as a flat film, the step of forming a pattern is not necessary, and the film is dried as necessary after coating.

[0174] The method for forming the pattern will now be described in detail.

[0175] (When forming patterns using photolithography) When forming a pattern by photolithography, a layer formed by applying the coloring composition of the present invention on a substrate is dried (pre-baked) as necessary, and then exposed to light in a pattern through a mask (exposure step), and the unexposed parts are removed by alkaline development (development step), and the pattern is then heat-treated (post-bake step) as necessary.

[0176] [Exposure process] In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF (wavelength 193 nm). In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure).

[0177] [Development process] Next, an alkali development process is carried out, whereby the unexposed portions of the layer are dissolved in an aqueous alkali solution, and only the hardened portions remain, yielding a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0178] [Post-bake process] After development, a heat treatment (post-baking) can be carried out as necessary, which improves the resistance of the film. The temperature is preferably 80 to 300° C. The time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the substrate or when an organic electroluminescence element is used as the light source, the temperature is preferably 150° C. or less, and more preferably 130° C. or less.

[0179] (When forming patterns using dry etching) When forming a pattern by dry etching, for example, the coloring composition of the present invention is applied onto a substrate, and the layer formed is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then the patterned photoresist layer is used as a mask to perform dry etching on the cured film using an etching gas. For pattern formation by dry etching, the method described in JP2013-064993A can be referred to.

[0180] <Optical filters> The film can be used as an optical filter. The optical filter can be used as, for example, a color filter which is a component of a liquid crystal display device, a solid-state imaging device, an organic EL display device, etc., or an infrared cut filter, an infrared transmission filter, etc. which is a component of an infrared sensor, etc. <Color filters> The color filter includes a red filter segment, a green filter segment, and a blue filter segment, and may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0181] <Manufacturing method for color filters> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film with a light-shielding agent dispersed therein.

[0182] A color LCD is manufactured by laminating the color filter to the opposing substrate using a sealant, injecting liquid crystal through the injection port provided in the seal, sealing the injection port, and laminating a polarizing film or retardation film on the outside of the substrate as necessary. This color LCD can be used in LCD display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0183] The color filter of the present invention can be used for applications such as solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays, in addition to liquid crystal displays.

[0184] <Liquid crystal display device> A liquid crystal display device equipped with the color filter of the present invention will now be described. The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFL) and white LEDs, but in the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and liquid crystal LC is sealed between them.

[0185] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), etc. A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0186] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0187] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0188] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0189] The white LED light source may be one in which a fluorescent filter is formed on the surface of a blue LED, or one in which a fluorescent material is contained in the resin package of a blue LED, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. In particular, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0190] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0191] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0192] <Solid-state imaging element> The film of the present invention can be used for a solid-state imaging device. The form of the solid-state imaging device used is not particularly limited, but for example, a substrate is provided with a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and a transfer electrode made of polysilicon or the like, a light-shielding film is provided on the photodiodes and the transfer electrode with only the light receiving portion of the photodiodes being opened, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a filter is provided on the device protection film. Furthermore, the device protection film may have a configuration in which a light-collecting means (e.g., a microlens, etc., the same below) is provided on the device protection film and below the filter (the side closer to the substrate), or a configuration in which a light-collecting means is provided on the filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned, for example, in a lattice shape, by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used for various purposes such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), vehicle-mounted cameras, surveillance cameras, sensors, etc. EXAMPLES

[0193] The present invention will be described below based on examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0194] (Mass average molecular weight of resin (Mw)) The mass average molecular weight (Mw) of the resin is the polystyrene-equivalent mass average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as the developing solvent.

[0195] (Method of identifying dye (a)) The dye (a) was identified by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation. The molecular ion peak of the mass spectrum was measured using Waters ACQUITY UPLC H-Class (UPLC) (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm × 50 mm) / Ms TAP XEVO TQD.

[0196] (Column Chromatography) Column chromatography was performed using neutral silica gel PSQ100B (Fuji Silysia Chemical Ltd.) or silica gel 60 (Kanto Chemical Co., Ltd.).

[0197] <Production method of binder resin> (Preparation of binder resin 1) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 196 parts by mass of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 37.2 parts by mass of n-butyl methacrylate, 12.9 parts by mass of 2-hydroxyethyl methacrylate, 12.0 parts by mass of methacrylic acid, 20.7 parts by mass of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts by mass of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts by mass of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare binder resin 1. The mass average molecular weight (Mw) was 26,000.

[0198] (Preparation of binder resin 2) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts by mass of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts by mass of methacrylic acid, 20 parts by mass of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts by mass of methyl methacrylate, 8.5 parts by mass of 2-hydroxyethyl methacrylate and 1.33 parts by mass of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. The total amount of the obtained copolymer solution was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 parts by mass of 2-methacryloyloxyethyl isocyanate (Karens MOI manufactured by Showa Denko K.K.), 0.08 parts by mass of dibutyltin laurate, and 26 parts by mass of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution synthesized earlier so that the non-volatile content was 20 mass% to prepare binder resin 2. The mass average molecular weight (Mw) was 18,000.

[0199] <Production of resin-type dispersant>

[0200] (Preparation of Resin-Type Dispersant 1) A flask equipped with a cooling tube and a stirrer was charged with 1.0 parts by mass of AIBN (2,2'-azobisisobutyronitrile) and 186 parts by mass of propylene glycol monomethyl ether acetate, followed by 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate, and 3.6 parts by mass of cumyl dithiobenzoate, and substituted with nitrogen for 30 minutes. After that, the temperature of the reaction solution was raised to 60 ° C. with gentle stirring, and this temperature was maintained for 24 hours to carry out living radical polymerization. Next, a solution of 1.0 parts by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate dissolved in 70 parts by mass of propylene glycol monomethyl ether acetate and substituted with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was carried out at 60 ° C. for 24 hours to obtain a solution of a block copolymer. To the obtained block copolymer solution, 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether were added, and the reaction was carried out at 80°C for 2 hours, and the solid content concentration was adjusted to 40% by mass, thereby obtaining a resin-type dispersant 1. The resin-type dispersant 1 is a block copolymer consisting of an A block having repeating units derived from methacryloyloxyethyl benzyl dimethyl ammonium chloride and dimethylaminoethyl methacrylate, and a B block having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloyloxyethyl benzyl dimethyl ammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate = 34 / 4 / 18 / 18 / 14 / 12 (mass ratio).

[0201] <Production of dye (a)> (Synthesis of dye (a1)) The dye (a1) was synthesized according to the following synthesis sequence. [ka]

[0202] 10 parts by mass of the starting material 4,4'-diaminodiphenylmethane (a1-1) was dissolved in 30% by mass of oleum H 2 SO 4 SO 3 The mixture was dissolved in 50 parts by mass of a 50% NaOH solution and stirred at 80°C for 3 hours. After confirming the disappearance of the raw materials by UPLC, the reaction was quenched by adding an appropriate amount of 0.5M NaOH aqueous solution under ice cooling until the pH of the system reached about 9.0. The mixture was extracted three times with 200 parts by mass of ethyl acetate, washed once with saturated saline, and washed with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 The filtrate was filtered off and concentrated under reduced pressure to obtain 11.5 parts by mass of compound (a1-2) as white-pink crystals (yield 87.6%). 0.4 parts by mass of the obtained compound (a1-2) was dissolved in 15 parts by mass of acetonitrile, and K 2 CO 3 After adding 0.9 parts by mass of allyl bromide and 1.0 part by mass of allyl bromide, the mixture was stirred at 80° C. for 7 hours. After that, 1.0 part by mass of allyl bromide was added again, and the mixture was stirred at 80° C. for 7 hours. After confirming the disappearance of the raw materials by UPLC, excess saturated NH 4 The reaction was quenched by adding aqueous Cl. After dilution with ethyl acetate, the organic layer was successively washed with saturated NH 4 Wash once with Cl solution and once with saturated saline, then with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column chromatography (1 / 1 ethyl acetate / toluene) to obtain 0.4 parts by mass of compound (a1-3) as white-pink crystals (yield 61.9%). 0.2 parts by mass of the obtained compound (a1-3) was dissolved in 5.5 parts by mass of 1,2-dichloroethane, 0.2 parts by mass of p-chloranil was added, and the mixture was stirred at room temperature for 7 hours. After confirming the disappearance of the raw material by UPLC, the mixture was cooled with ice and then stirred with excess saturated NaHCO 3 The reaction was quenched by adding aqueous solution of ethyl acetate. After dilution with ethyl acetate, the organic layer was successively washed with saturated NH 4Wash once with Cl solution and once with saturated saline, then with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column gel chromatography (1 / 1 ethyl acetate / toluene) to obtain 0.1 parts by mass of compound (a1-4) (yield 48.4%). 0.1 parts by mass of the obtained compound (a1-4) was dissolved in 4.6 parts by mass of THF, and 3.5 parts by mass of a 0.1 M solution of phenylmagnesium bromide in THF was added, followed by stirring at room temperature for 4 hours. After confirming the disappearance of the raw materials by UPLC, the reaction was quenched by adding an excess of 2N aqueous HCl solution under ice cooling. After stirring for 2 hours, the mixture was diluted with ethyl acetate, and the organic layer was washed once with saturated saline and then washed with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column chromatography (1 / 1 ethyl acetate / toluene) to obtain 0.02 parts by mass of dye (a1) as a green oil (yield 16.4%). Pigment (a1) [ka]

[0203] (Synthesis of dye (a2)) In the synthesis of dye (a1), except that 2.0 parts by mass of iodoethyl were used instead of 2.0 parts by mass of allyl bromide, 0.05 parts by mass of dye (a2) was obtained as a green oil (yield 17.5%) in the same manner as in the synthesis of dye (a1). Pigment (a2) [ka]

[0204] (Synthesis of dye (a3)) The dye (a3) ​​was synthesized according to the following synthesis sequence. [ka]

[0205] 8.0 parts by mass of methyl(diphenyl)phosphine oxide (a3-1) as a starting material was dissolved in a mixed solution of 20 parts by mass of concentrated sulfuric acid and 5 parts by mass of concentrated nitric acid under ice cooling, and stirred for 3 hours under ice cooling. After confirming the disappearance of the raw materials by UPLC, the reaction solution was dropped into 500 parts by mass of ion-exchanged water under ice cooling to quench the reaction. Extraction was performed with 300 parts by mass of ethyl acetate. The extracted organic layer was sequentially washed with saturated NaHCO 3 Wash once with aqueous solution and once with saturated saline, then rinse with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 The extract was filtered off and concentrated under reduced pressure to obtain 14.2 parts by mass of compound (a3-2) as a yellow solid. 1.5 parts by mass of the obtained compound (a3-2) was dissolved in 20 parts by mass of ethanol, and 0.2 parts by mass of palladium carbon catalyst and 2.5 parts by mass of hydrazine monohydrate were added, followed by stirring at 90°C for 4 hours. After confirming the disappearance of the raw materials by UPLC, the reaction solution was filtered through Celite with ethyl acetate, and the eluate was purified by filtration using anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 The extract was filtered off and concentrated under reduced pressure to obtain 5.1 parts by mass of compound (a3-3) as a brown liquid. 4.5 parts by mass of the obtained compound (a3-3) was dissolved in 60 parts by mass of THF, and 11.6 parts by mass of NaH was gradually added under ice cooling, and the mixture was stirred for 30 minutes under ice cooling. Then, 3.0 parts by mass of iodoethane was added, and the mixture was stirred at 60°C for 5 hours. Then, 11.6 parts by mass of NaH was gradually added again under ice cooling, and the mixture was stirred for 30 minutes under ice cooling, and then 3.0 parts by mass of iodoethane was added, and the mixture was stirred again at 60°C for 3 hours. After confirming the disappearance of the raw materials by UPLC, excess saturated NH 4 The reaction was quenched by adding aqueous Cl solution. After dilution with ethyl acetate, the organic layer was washed once with saturated aqueous NH4Cl solution, once with saturated saline, and then washed with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4After filtering and concentrating under reduced pressure, the product was purified by silica gel chromatography (ethyl acetate / toluene=2 / 1) to obtain 1.0 part by mass of compound (a3-4) as white-pink crystals (yield 15.8%). 0.2 parts by mass of the obtained (a3-4) was added to 1.0 part by mass of benzaldehyde, 0.1 parts by mass of paratoluenesulfonic acid was added, and the mixture was heated at 140°C for 8 hours. After confirming the production of the target product by UPLC, 2 parts by mass of methanol and 0.1 parts by mass of chloranil were added, and the mixture was stirred at 50°C overnight. Thereafter, the chloranil was filtered off using a cotton plug, and then the mixture was subjected to stirring at 50°C for 1 hour. 2 Cl 2 After diluting to 10 parts by mass, the organic layer was washed once with 2N HCl aqueous solution, once with saturated saline, and then with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column chromatography (methanol) to obtain 0.04 parts by mass of dye (a3) ​​as a green oil (yield 15.0%). Pigment (a3) [ka]

[0206] (Synthesis of dye (a4)) A green oily dye (a4) (0.03 part by mass) was obtained in the same manner as in the synthesis of dye (a3), except that methoxymethyl bromide was used instead of iodoethane (a3) ​​(yield: 12.5%). pigment (a4) [ka]

[0207] (Synthesis of dye (a5)) The dye (a5) was synthesized according to the following synthesis sequence. [ka]

[0208] 2 parts by mass of 3-bromoaniline (a5-1) as the starting material was dissolved in 38 parts by mass of acetonitrile, and K 2 CO 3 After adding 6.4 parts by mass of iodoethane and 9.1 parts by mass of iodoethane, the mixture was stirred at 80° C. for 7 hours. After adding 9.1 parts by mass of iodoethane, the mixture was stirred at 80° C. for 7 hours. After confirming the disappearance of the raw materials by UPLC, excess saturated NH 4 The reaction was quenched by adding aqueous Cl. After dilution with ethyl acetate, the organic layer was successively washed with saturated NH 4 Wash once with Cl solution and once with saturated saline, then with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column chromatography (1 / 1 = ethyl acetate / toluene) to obtain 2.0 parts by mass of compound (a5-2) (yield 75.4%). 2.0 parts by mass of the obtained (a5-2) was dissolved in 30 parts by mass of THF, and 6.6 parts by mass of a 1.6 M hexane solution of n-butyllithium was added at -78 ° C over 10 minutes, and stirred at the same temperature for 1 hour. Subsequently, 0.7 parts by mass of dichlorodimethylsilane was added at -78 ° C, and stirred at the same temperature for 1 hour. After confirming the disappearance of the raw materials by UPLC, the temperature was raised to room temperature, and excess saturated NH 4 The reaction was quenched by adding aqueous Cl. After dilution with ethyl acetate, the organic layer was successively washed with saturated NH 4 Wash once with Cl solution and once with saturated saline, then with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column chromatography (1 / 1 ethyl acetate / toluene) to obtain 3.9 parts by mass of compound (a5-3) (yield 80.0%). 0.2 parts by mass of the obtained (a5-3) was added to 1.0 part by mass of benzaldehyde, 0.1 parts by mass of paratoluenesulfonic acid was added, and the mixture was heated at 140°C for 8 hours. After confirming the production of the target product by UPLC, 2 parts by mass of methanol and 0.1 parts by mass of chloranil were added, and the mixture was stirred overnight at 50°C. Thereafter, the chloranil was filtered off using a cotton plug, and then the mixture was subjected to stirring at 50°C for 1 hour. 2 Cl2 After diluting to 10 parts by mass, the organic layer was washed once with 2N HCl aqueous solution, once with saturated saline, and then with anhydrous Na 2 SO 4 Dried in anhydrous Na 2 SO 4 After filtering and concentrating under reduced pressure, the product was purified by column chromatography (methanol) to obtain 0.2 parts by mass of dye (a5) as a blue oil (yield 74.3%). Pigment (a5) [ka]

[0209] (Synthesis of dye (a6)) In the synthesis of dye (a5), except that 19.0 parts by mass of benzyl bromide was used instead of 18.2 parts by mass of iodoethane, 0.3 parts by mass of dye (a6) was obtained as a blue oil (yield 69.3%) in the same manner as in the synthesis of dye (a5). Pigment (a6) [ka]

[0210] (Synthesis of dye (a7)) In the synthesis of dye (a3), 0.2 parts by mass of the obtained (a3-4) was mixed with 1.5 parts by mass of 2-methoxybenzaldehyde and 1.0 part by mass of N,N-dimethylformamide, to which 0.1 parts by mass of paratoluenesulfonic acid was added, and then the mixture was heated at 140° C. for 8 hours. In the same manner as in the synthesis of dye (a3), 0.03 parts by mass of dye (a7) was obtained as a blue oil (yield 14.5%). Pigment (a7) [ka]

[0211] (Synthesis of dye (a8)) In the synthesis of dye (a7), except that 1.7 parts by mass of 2,6-dimethoxybenzaldehyde was used instead of 1.5 parts by mass of 2-methoxybenzaldehyde, 0.05 parts by mass of dye (a8) was obtained as a green oil (yield 18.0%) in the same manner as in the synthesis of dye (a7). Pigment (a8) [ka]

[0212] (Synthesis of dye (a9)) In the synthesis of dye (a7), 0.02 parts by mass of dye (a9) was obtained as a green oil (yield 15.8%) in the same manner as in the synthesis of dye (a7), except that 1.5 parts by mass of 2,6-dimethylbenzaldehyde was used instead of 1.5 parts by mass of 2-methoxybenzaldehyde. Pigment (a9) [ka]

[0213] (Synthesis of dye (a10)) In the synthesis of dye (a7), except that 2.0 parts by mass of 2-chlorobenzaldehyde was used instead of 1.5 parts by mass of 2-methoxybenzaldehyde, 0.02 parts by mass of dye (a10) was obtained as a green oil (yield 14.0%) in the same manner as in the synthesis of dye (a7). Pigment (a10) [ka]

[0214] (Synthesis of dye (a11)) In the synthesis of dye (a7), except that 2.1 parts by mass of 2,6-dichlorobenzaldehyde was used instead of 1.5 parts by mass of 2-methoxybenzaldehyde, 0.02 parts by mass of dye (a11) was obtained as a green oil (yield 15.0%) in the same manner as in the synthesis of dye (a7). Pigment (a11) [ka]

[0215] (Synthesis of dye (a12)) In the synthesis of dye (a7), except that 2.1 parts by mass of 2,6-dibromobenzaldehyde was used instead of 1.5 parts by mass of 2-methoxybenzaldehyde, 0.03 parts by mass of dye (a12) was obtained as a green oil (yield 13.4%) in the same manner as in the synthesis of dye (a7). Pigment (a12) [ka]

[0216] <Production of dye (A)>

[0217] [Example A1] (Production of Dye (A-1)) 180 parts by mass of water and 20 parts by mass of methanol were added to 5.3 parts by mass of dye (a1), and the mixture was stirred at room temperature to dissolve the dye. An aqueous solution of 2.9 parts by mass of lithium bis(trifluoromethanesulfonyl)imide dissolved in 50 parts of water as a compound (b) having an anionic site was added dropwise over 30 minutes. Stirring was continued for 90 minutes, and the reaction solution was dropped onto filter paper. The point at which bleeding ceased was regarded as the end point, and it was determined that a salt was obtained. After that, suction filtration was performed, and the salt remaining on the filter paper was dried by removing moisture in a dryer after washing with water, to obtain 2.9 parts by mass of dye (A-1), which is a salt formed between the cationic site of dye (a) and the compound (b) having an anionic site.

[0218] [Examples A2 to A18] (Production of dyes (A-2) to (A-18)) As shown in Table 1, dyes (A-2) to (A-18) were produced in the same manner as for dye (A-1).

[0219] [Table 1]

[0220] <Production of fine yellow pigment> (Production of Yellow Micropigment (PY-1)) 200 parts by mass of isoindoline-based yellow pigment CI Pigment Yellow 138 (BASF "Paliotol Yellow K0961HD"), 1400 parts by mass of sodium chloride, and 360 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8000 parts by mass of warm water, and stirred for 2 hours while heating to 80°C to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain a yellow fine pigment (PY-1).

[0221] (Production of Yellow Micropigment (PY-2)) 200 parts by mass of isoindoline-based yellow pigment CI Pigment Yellow 150 (CLARIANT's "Hostaperm Yellow HN4G"), 1400 parts by mass of sodium chloride, and 360 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded mixture was added to 8000 parts by mass of warm water and stirred for 2 hours while heating to 80°C to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain a yellow fine pigment (PY-2).

[0222] (Production of Yellow Micropigment (PY-3)) 200 parts by mass of isoindoline-based yellow pigment CI Pigment Yellow 185 (BASF "Paliotol Yellow D 1155"), 1400 parts by mass of sodium chloride, and 360 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8000 parts by mass of warm water, and stirred for 2 hours while heating to 80°C to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain a yellow fine pigment (PY-3).

[0223] (Production of Yellow Micropigment (PY-4)) 200 parts by mass of isoindoline-based yellow pigment CI Pigment Yellow 139 (BASF "Paliotol Yellow L 2146HD"), 1400 parts by mass of sodium chloride, and 360 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8000 parts by mass of warm water, and stirred for 2 hours while heating to 80°C to form a slurry. This slurry was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain a yellow fine pigment (PY-4).

[0224] <Production of finely divided green pigment> (Production of Green Micropigment (PG-1)) 200 parts by mass of phthalocyanine green pigment CI Pigment Green 36 (Clariant's "Green 8G"), 1400 parts by mass of sodium chloride, and 360 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded mixture was added to 8000 parts by mass of warm water, heated to 80° C. and stirred for 2 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. for one day to obtain a finely divided green pigment (PG-1).

[0225] (Production of Green Micropigment (PG-2)) 200 parts by mass of phthalocyanine green pigment CI Pigment Green 58 (DIC Corporation "FASTOGEN GREEN A110"), 1400 parts by mass of sodium chloride, and 360 parts by mass of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded mixture was added to 8000 parts by mass of warm water and stirred for 2 hours while heating to 80° C. to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried at 85° C. for a day and night to obtain a finely divided green pigment (PG-2).

[0226] <Production of Colored Composition> [Example 1] (Production of Coloring Composition (G-1)) The mixture having the following composition was stirred and mixed to a uniform state to prepare a colored composition (G-1). Dye (A-1) 10.0 parts by mass Binder resin 2 50.0 parts by mass 3-Methoxy-1-butanol 40.0 parts by mass

[0227] [Examples 2 to 19, Comparative Examples 1 to 3] (Production of Colored Compositions (G-2) to (G-19), (GG-1) to (GG-3)) As shown in Table 2, green colored compositions (G-2) to (G-19) and (GG-1) to (GG-3) were prepared in the same manner as the green colored composition (G-1), except that the types of dye (A) and binder resin were changed.

[0228] [Comparative Example 4] (Production of Coloring Composition (GG-4)) The mixture of the following composition was stirred and mixed until homogeneous, and then dispersed for 5 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (GG-4). Green fine pigment (PG-1) 10.0 parts by weight Resin-type dispersant 1 25.0 parts by mass PGMAc 65.0 parts by mass

[0229] [Comparative Example 5] (Production of Coloring Composition (GG-5)) As shown in Table 3, except that the types of the green fine pigment and the resin-type dispersant were changed, a colored composition (GG-5) was prepared in the same manner as the colored composition (GG-4).

[0230] [Table 2]

[0231] [Table 3]

[0232] The coloring compositions (G-1) to (G-19) and (GG-1) to (GG-5) were applied to a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater under conditions such that the film thickness would be 0.5 μm, and then dried at 70 ° C for 20 minutes to obtain a film, and the absorption spectrum of the film was measured using a spectrophotometer (Hitachi "U-4100").

[0233] (Evaluation of coloring strength) The maximum absorbance value of the above film was determined in the range of 600 to 700 nm. The criteria for evaluation were as follows: 2.0 or above: 〇+ 1.6 or more but less than 2.0: 〇 1.3 or more and less than 1.6: △ Less than 1.3: ×

[0234] (Evaluation of heat resistance) A heat resistance test was carried out on the above-mentioned film by performing a heat treatment at 230° C. for 20 minutes. The change in the maximum absorbance at 600 to 700 nm was evaluated as follows. Decrease rate less than 5%: 〇+ Decrease rate is between 5% and 10%: Yes Decrease rate is 10% or more: ×

[0235] (Evaluation of light resistance) The substrate on which the above-mentioned film was formed was measured using a xenon weather meter and found to have a radiation intensity of 60 W / m2 at 300 to 400 nm. 2 The light resistance test was conducted by exposing the sample to an illumination intensity of 1000 for 20 hours. The change in maximum absorbance at 600 to 700 nm was evaluated as follows. Decrease rate less than 5%: 〇+ Decrease rate is between 5% and 10%: Yes Decrease rate is 10% or more: ×

[0236] (Transmittance evaluation) Next, the colored compositions (G-1) to (G-19), (GG-1) to (GG-5) were applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater under conditions such that the maximum absorbance at 600 to 700 nm was 2.0, and then dried at 70°C for 20 minutes, and the transmission spectrum was measured using a spectrophotometer (Hitachi's "U-4100") to determine the transmittance at 550 nm. The criteria for evaluation are as follows. Over 97%: 〇+ Over 95%: Yes Less than 95%: × The absorbance Trs (%) and transmittance Abs of the coating film are expressed by the following formula: Trs / 100 = 0.1 (Abs) In a certain wavelength region, at the wavelength where the absorbance is maximum, the transmittance at that wavelength is minimum within that region. That is, when the absorbance value is 2.0 at wavelength X where the absorbance is maximum in the range of 600 to 700 nm, the transmittance at that wavelength X is 1%, which is the minimum value in the range of 600 to 700 nm.

[0237] <Production of Yellow Colored Composition> (Production of Yellow Colored Composition (Y-1)) The mixture of the following composition was stirred and mixed to make it uniform, and then dispersed for 5 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to prepare a yellow colored composition (Y-1). Yellow fine pigment (PY-1) 10.0 parts Resin type dispersant 1 25.0 parts PGMAc 65.0 parts

[0238] (Production of Yellow Colored Compositions (Y-2) to (Y-4)) Yellow colored compositions (Y-2) to (Y-4) were obtained as shown in Table 4 in the same manner as in the production of the yellow fine pigment (PY-1), except that the type of the yellow fine pigment was changed.

[0239] [Table 4]

[0240] <Production of Green Colored Composition> [Example 20] (Production of Green Colored Composition (GY-1)) The following composition was mixed and stirred until homogeneous to prepare a green colored composition (GY-1). Coloring composition (G-1) 80.0 parts Yellow coloring composition (Y-1) 20.0 parts

[0241] [Examples 21 to 38, Comparative Examples 6 to 10] (Production of Green Colored Compositions (GY-2) to (GY-19), (GGY-1) to (GGY-5)) As shown in Table 5, green colored compositions (GY-2) to (GY-19), (GGY-1) to (GGY-5) were produced in the same manner as the green colored composition (GY-1), except that the types of the colored composition and the yellow fine pigment were changed.

[0242] [Table 5]

[0243] The green colored compositions (GY-2) to (GY-19), (GGY-1) to (GGY-5) were applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater under conditions such that the maximum absorbance at 600 to 700 nm was 2.0, and then dried at 70°C for 20 minutes to obtain a film.

[0244] (Evaluation of coloring strength) The thickness of the obtained film was measured, and the coloring strength was evaluated. Since the maximum absorbance value at 600 to 700 nm was 2.0 for all films, the thinner the film, the higher the coloring strength of the colorant. Less than 0.63μm: 〇+ 0.63μm or more and less than 0.8μm: 〇 0.8μm or more and less than 1.0μm: △ 1.0μm or more: ×

[0245] (Evaluation of heat resistance) A heat resistance test was carried out on the above-mentioned film by performing a heat treatment at 230° C. for 20 minutes. The change in the maximum absorbance at 600 to 700 nm was evaluated as follows. Decrease rate less than 5%: 〇+ Decrease rate is between 5% and 10%: Yes Decrease rate is 10% or more: ×

[0246] (Evaluation of light resistance) The substrate on which the above-mentioned film was formed was measured using a xenon weather meter and found to have a radiation intensity of 60 W / m2 at 300 to 400 nm. 2 The light resistance test was performed by exposing the sample to an illuminance of 1000 nm for 20 hours. The change in the maximum absorbance at 600 to 700 nm was evaluated as follows. Decrease rate less than 5%: 〇+ Decrease rate is between 5% and 10%: Yes Decrease rate is 10% or more: ×

[0247] (Transmittance evaluation) The transmittance of the above substrate at 550 nm was measured and evaluated in the same manner as above. Over 93%: 〇+ Over 92%: Yes Less than 92%: ×

[0248] <Production of Photosensitive Green Coloring Composition> [Example 39] (Production of Photosensitive Green Coloring Composition (GR-1)) A mixture of the following composition was stirred and mixed to be homogeneous, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive green colored composition (GR-1). Green coloring composition (GY-1) 100.0 parts Photopolymerizable monomer (Toagosei Co., Ltd. "Aronix M-306") 4.0 parts Photopolymerization initiator (ADEKA "ADEKA Arcles NCI-831E") 1.0 part PGMAc 20.0 parts

[0249] [Examples 40 to 57, Comparative Examples 11 to 15] (Production of Photosensitive Green Coloring Compositions (GR-2) to (GR-19), (GGR-1) to (GGR-5)) As shown in Table 6, photosensitive green coloring compositions (GR-2) to (GR-19), (GGR-1) to (GGR-5) were prepared in the same manner as the photosensitive green coloring composition (GR-1), except that the type of the green coloring composition was changed.

[0250] [Table 6]

[0251] The photosensitive green coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater under conditions such that the maximum absorbance at 600 nm to 700 nm was 2.0, and then dried at 70°C for 20 minutes. Then, using an ultra-high pressure mercury lamp, the composition was exposed to 300 mJ / cm 2The film was exposed to ultraviolet light at 40° C. and developed with an alkaline developer at 23° C. The alkaline developer used was composed of 1.5% by mass of sodium carbonate, 0.5% by mass of sodium bicarbonate, 8.0% by mass of an anionic surfactant ("Perilex NBL" manufactured by Kao Corporation), and 90% by mass of water. The film was then heated at 70° C. for 30 minutes to obtain a dried film.

[0252] (Evaluation of coloring strength) The thickness of the obtained film was measured, and the coloring strength was evaluated. Since the maximum absorbance value at 600 to 700 nm was 2.0 for all films, the thinner the film, the higher the coloring strength of the colorant. Less than 0.77μm: 〇+ 0.77μm or more and less than 1.0μm: 〇 1.0μm or more and less than 1.25μm: △ 1.25μm or more:×

[0253] (Evaluation of heat resistance) The film was subjected to a heat treatment at 230° C. for 20 minutes to carry out a heat resistance test. The change in the maximum absorbance value from 600 to 700 nm was evaluated as follows. Decrease rate less than 5%: 〇+ Decrease rate is 5% or more but less than 10%: 〇 Decrease rate is 10% or more: ×

[0254] (Evaluation of light resistance) The substrate on which the above-mentioned film was formed was measured using a xenon weather meter and found to have a radiation intensity of 60 W / m2 at 300 to 400 nm. 2 The light resistance test was conducted by exposing the sample to an illumination intensity of 1000 for 20 hours. The change in maximum absorbance at 600 to 700 nm was evaluated as follows. Decrease rate less than 5%: 〇+ Decrease rate is 5% or more but less than 10%: 〇 Decrease rate is 10% or more: ×

[0255] (Transmittance evaluation) The transmittance of the above substrate at 550 nm was measured and evaluated in the same manner as above. Over 93%: 〇+ Over 92%: Yes Less than 92%: ×

[0256] Furthermore, by using these coloring compositions, green coloring compositions, and photosensitive green coloring compositions, it is possible to provide a color filter for an image sensor and a solid-state imaging device that are thin and have improved color resolution and color reproducibility. [Explanation of symbols]

[0257] 10 LCD display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC Liquid Crystal

Claims

1. A dye (A) which is a salt formed between a cationic moiety represented by the following general formula (1) and an anionic moiety selected from the general formulae (2-1) to (2-4): General formula (1) 【Chemistry 1】 (R １ ~R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these groups; １ and R ２ , R 3 and R 4 may be linked to each other to form a ring, and a divalent organic group may be inserted between the rings. R ５ ~R ９ each independently represents a hydrogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, a sulfo group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an alkylcarboxy group, a halogen atom, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group, an aryl group having 6 to 20 carbon atoms, -SO ２ -O-R １１１ , or -SO ２ -NH-R １１２ represents R １１１ , R １１２ each independently represents an alkyl group having 1 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these carbon atoms, and two adjacent ones of these may be linked to each other to form a ring, and a divalent organic group may be inserted between the rings formed. X is -SiR ３１ R ３２ -, -P(=O)R ３３ - or -SO ２ - represents R ３１ ~R ３３ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have a substituent, and a divalent organic group may be inserted between the carbon atoms of these groups; ３１ and R ３２ may be linked to each other to form a ring.) General formula (2-1) <h2 style=";text-align:left;direction:ltr">[(R<h2 style=";text-align:left;direction:ltr"> ２１ <h2 style=";text-align:left;direction:ltr"> )<h2 style=";text-align:left;direction:ltr"> ｃ <h2 style=";text-align:left;direction:ltr"> P -Hal<h2 style=";text-align:left;direction:ltr"> （６－ｃ） <h2 style=";text-align:left;direction:ltr"> ]<h2 style=";text-align:left;direction:ltr"> － (R ２１ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, R ２１ When a plurality of Hal are present, they may be the same or different. c represents an integer of 0 to 6. General formula (2-2) <h2 style=";text-align:left;direction:ltr">[(R<h2 style=";text-align:left;direction:ltr"> ２２ <h2 style=";text-align:left;direction:ltr"> )<h2 style=";text-align:left;direction:ltr"> ｄ <h2 style=";text-align:left;direction:ltr"> B-Hal<h2 style=";text-align:left;direction:ltr"> （４－ｄ） <h2 style=";text-align:left;direction:ltr"> ]<h2 style=";text-align:left;direction:ltr"> － (R ２２ represents a halogenated hydrocarbon group, a cyano group, a phenyl group substituted with a nitro group, or a phenyl group substituted with a cyano group; B represents a boron atom; Hal represents a halo group; R ２２ When a plurality of Hal are present, they may be the same or different. d represents an integer of 0 to 4. General formula (2-3) R ２３ -N － -R ２４ (R ２３ and R ２４ each independently represents a halogenated hydrocarbon group, N － A halogenated hydrocarbon group having a sulfonyl group at the bond to FSO ２ R ２３ and R ２４ are both halogenated hydrocarbon groups, N － When R is a halogenated hydrocarbon group having a sulfonyl group at the bonding site, they may be bonded to each other to form a ring. ２３ and R ２４ At least one of the groups is a halogenated hydrocarbon group, N － or a cyano group. General formula (2-4) R ２５ -SO ３ － (R ２５ represents a halogenated hydrocarbon group which may be linked via a linking group having a nitrogen atom or an oxygen atom.

2. A coloring composition comprising the dye (A) according to claim 1 and a resin.

3. The coloring composition of claim 2 , further comprising a yellow pigment.

4. The colored composition according to claim 2 or 3, further comprising a photopolymerization initiator.

5. The colored composition according to claim 2 or 3, further comprising a photopolymerizable monomer.

6. A color filter having a film formed from the coloring composition according to claim 2 or 3 on a substrate.

7. A solid-state imaging device comprising the color filter according to claim 6 .

Images