Colored curable resin composition

Abstract

To provide a colored curable resin composition that can suppress a decrease of maximum absorption in a visible light region even in a deposition process such as an exposure step and a post-baking step.SOLUTION: A colored curable resin composition contains a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant. The colorant contains a squarylium dye having maximum absorption in the visible light region, and the antioxidant contains a phenolic antioxidant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a colored curable resin composition. [Background technology]

[0002] Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, are produced from colored curable resin compositions. Squarylium dyes are known as colorants used in such colored curable resin compositions (Patent Documents 1, 2, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-86379 A [Patent Document 2] JP 2015-86380 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the above-mentioned colored curable resin composition containing a squarylium dye, when post-baking is performed after exposure, the maximum absorption in the visible light region may decrease. Therefore, an object of the present invention is to provide a colored curable resin composition that can suppress the decrease in the maximum absorption in the visible light region even in the film formation process such as the exposure process and the post-baking process. [Means for solving the problem]

[0005] The gist of the present invention is as follows. [1] A composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant; the colorant comprises a squarylium dye having a maximum absorption in the visible light region; The colored curable resin composition, wherein the antioxidant comprises a phenol-based antioxidant. [2] The colored curable resin composition according to [1], wherein the phenol-based antioxidant is a compound having no vinyl group and no ethene-1,1-diyl group. [3] The colored curable resin composition according to [1] or [2], wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group, and a hydrogen atom or an alkyl group is bonded to the other carbon atom. [4] The colored curable resin composition according to any one of [1] to [3], wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group, and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom. [5] The colored curable resin composition according to any one of [1] to [4], wherein a mass ratio of the antioxidant to the squarylium dye (antioxidant / squarylium dye) is 0.8 or more. [6] The colored curable resin composition according to any one of [1] to [5], wherein the squarylium dye is a compound represented by formula (AI): [ka] [In formula (AI), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. R 5 ~R 8 each independently represents a hydrogen atom or a hydroxy group. Ar 1 and Ar 2 each independently represents a group represented by formula (i). [ka] [In formula (i), R 12 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m represents an integer of 0 to 5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, multiple R 12 may be the same or different. * represents a bond to a nitrogen atom.] R 9 and R 10 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by formula (i). A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.] [7] The colored curable resin composition according to any one of [1] to [6], wherein the squarylium dye is a compound represented by formula (AII): [ka] [In formula (AII), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. R 5 ~R 8 each independently represents a hydrogen atom or a hydroxy group. Ar 1 and Ar 2 each independently represents a group represented by formula (i). [ka] [In formula (i), R 12represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m represents an integer of 0 to 5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, multiple R 12 may be the same or different. * represents a bond to a nitrogen atom.] R 13 and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which has a hydroxyl group or a carboxyl group, and a methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.] [8] A color filter formed from the colored curable resin composition according to any one of [1] to [7]. [9] A display device comprising the color filter according to [8]. Effect of the Invention

[0006] According to the present invention, it is possible to provide a colored curable resin composition capable of suppressing a decrease in maximum absorption in the visible light region even during a film formation process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] <Colored curable resin composition> The colored curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as colorant (A)), a resin (hereinafter, sometimes referred to as resin (B)), a polymerizable compound (hereinafter, sometimes referred to as polymerizable compound (C)), a polymerization initiator (hereinafter, sometimes referred to as polymerization initiator (D)), and an antioxidant (hereinafter, sometimes referred to as antioxidant (E)), in which the colorant (A) contains a squarylium dye having a maximum absorption in the visible light region, and the antioxidant (E) contains a phenol-based antioxidant. In this specification, the compounds exemplified as each component can be used alone or in combination, unless otherwise specified.

[0008] <Colorant (A)> The colorant (A) contains a squarylium dye having a maximum absorption in the visible light region. The visible light region here refers to a wavelength region of 380 nm or more and 780 nm or less. The squarylium dye is preferably a compound having a maximum absorption at 390 nm or more (preferably 400 nm or more) and less than 700 nm (preferably 650 nm or less).

[0009] The squarylium dye is not particularly limited as long as it is a compound having a maximum absorption in the visible light region, and any known squarylium dye can be used, and is preferably a compound represented by formula (AI).

[0010] [ka]

[0011] [In formula (AI), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. R 5 ~R 8 each independently represents a hydrogen atom or a hydroxy group. Ar 1 and Ar 2 each independently represents a group represented by formula (i). [ka] [In formula (i), R 12 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m represents an integer of 0 to 5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, multiple R12 may be the same or different. * represents a bond to a nitrogen atom.] R 9 and R 10 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by formula (i). A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.]

[0012] R 1 ~R 4 The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0013] R 1 ~R 4 , R 9 , R 10 , and R 12 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include linear alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups having 3 to 20 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and adamantyl groups.

[0014] Substituents of these saturated hydrocarbon groups include halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; hydroxy groups; carboxy groups; -NR a R b (R a and R bare each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxycarbonyl group having 1 to 10 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like. Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a substituent include groups represented by the following formula: In the following formula, * represents a bond.

[0015] [ka]

[0016] Examples of the saturated hydrocarbon group in which the methylene group is substituted with -O- or -S- include groups represented by the following formula: In the following formula, * represents a bond.

[0017] [ka]

[0018] R 12 Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

[0019] The substituent of the unsaturated hydrocarbon group may be a halogen atom such as a fluorine atom, a chlorine atom, or an iodine atom; a hydroxy group; a carboxy group; c R d (R c and R d are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group or an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like.

[0020] R 1 ~R 4is preferably a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a hydroxy group, or a methyl group, and even more preferably a hydrogen atom.

[0021] R 5 ~R 8 At least one of R is preferably a hydroxy group. 5 and R 6 At least one of R is a hydroxy group. 7 and R 8 More preferably, at least one of R is a hydroxy group. 5 and R 6 is a hydroxy group, and R 7 and R 8 It is more preferable that one of the groups is a hydroxy group.

[0022] R 9 and R 10 As the alkyl group, a linear alkyl group having 1 to 20 carbon atoms which may have a substituent or a branched alkyl group having 3 to 20 carbon atoms which may have a substituent is preferable, a linear alkyl group having 1 to 10 carbon atoms which may have a substituent or a branched alkyl group having 3 to 10 carbon atoms which may have a substituent is more preferable, and a linear alkyl group having 1 to 5 carbon atoms which has a hydroxy group at its terminal, a linear alkyl group having 1 to 5 carbon atoms which has a carboxy group at its terminal, or a branched alkyl group having 3 to 10 carbon atoms.

[0023] R 12 As the alkyl group, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferable, and a linear alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable.

[0024] m is preferably 1-5, and more preferably 1-3.

[0025] Ar 1 and Ar 2 is preferably a group represented by formula (ii).

[0026] [ka]

[0027] [In formula (ii), R 15 represents a hydroxy group, a carboxy group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxy group or a carboxy group, and p represents an integer of 0 to 5. A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When p is 2 or more, a plurality of R 15 may be the same or different. R 16 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, and q represents an integer of 0 to 5, provided that p+q represents an integer of 0 to 5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When q is 2 or more, multiple R 16 may be the same or different. * represents a bond to the nitrogen atom.

[0028] R 15 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include those exemplified above as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Among them, a linear alkyl group having 1 to 20 carbon atoms is preferred, a linear alkyl group having 1 to 10 carbon atoms is more preferred, and a linear alkyl group having 1 to 5 carbon atoms is even more preferred.

[0029] The hydroxyl group or carboxyl group contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the molecular chain terminal of the saturated hydrocarbon group.

[0030] Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxyl group include groups represented by the following formula: In the following formula, * represents a bond.

[0031] [ka]

[0032] R 15 is preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group. 15 It is preferable that at least one of the methylene groups constituting the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by the following formula is substituted with -O-. 15 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, represented by the formula (I) in which at least one of the methylene groups constituting the group is substituted with -O- include groups represented by the formula (I), in which * represents a bond.

[0033] [ka]

[0034] R 16 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, represented by the formula (I), include the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent described above. Among these, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferred, a linear alkyl group having 1 to 5 carbon atoms which may have a substituent, a linear alkyl group having 1 to 3 carbon atoms which may have a substituent, and a methyl group is particularly preferred.

[0035] p is preferably an integer of 0 to 3, more preferably an integer of 0 to 1, and particularly preferably 1.

[0036] q is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

[0037] Among the compounds represented by formula (AI), the compound represented by formula (AII) is more preferable. When the squarylium dye is a compound represented by formula (AII), the decrease in maximum absorption during the film formation process can be further suppressed, and the color change during the film formation process can also be further suppressed.

[0038] [ka]

[0039] [In formula (AII), R 1 ~R 8 , Ar 1 and Ar 2 is the same as above. R 13 and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which has a hydroxy group or a carboxy group, and a methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.]

[0040] R 13 and R 14 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include those exemplified above as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Among them, a linear alkyl group having 1 to 20 carbon atoms is preferred, a linear alkyl group having 1 to 10 carbon atoms is more preferred, and a linear alkyl group having 1 to 5 carbon atoms is even more preferred.

[0041] The hydroxyl group or carboxyl group contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the molecular chain terminal of the saturated hydrocarbon group.

[0042] Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group or a carboxyl group include groups represented by the following formula: In the following formula, * represents a bond.

[0043] [ka]

[0044] R in formula (AII) 1 ~R 8 , Ar 1 and Ar 2 The preferred aspects of are the same as those described above.

[0045] Examples of the compound represented by formula (AI) include compounds represented by formulae (AI-1) to (AI-60) shown in Tables 1 and 2, and among them, from the viewpoint of availability of raw materials, compounds represented by formulae (AI-1) to (AI-20) are preferred. The compound represented by formula (AI) is more preferably a compound represented by formula (AI-1) to formula (AI-5) and formula (AI-11) to formula (AI-20). More preferably, the compound is represented by formula (AI-11) to formula (AI-20), The compounds represented by formulae (AI-11) to (AI-15) are even more preferred.

[0046] [Table 1]

[0047] [Table 2]

[0048] In Tables 1 and 2, x-1 to x-4 represent groups represented by the following formulae (* represents a bond).

[0049] [ka]

[0050] In Tables 1 and 2, y-1 to y-5 represent groups represented by the following formulae (* represents a bond).

[0051] [ka]

[0052] The compound represented by formula (AI) can be produced, for example, by reacting a compound represented by formula (pt1), a compound represented by formula (pt2), and a compound represented by formula (pt3). In this reaction, the total amount of the compound represented by formula (pt1) and the compound represented by formula (pt2) used is preferably 1.5 to 2.5 mol per mol of the compound represented by formula (pt3).

[0053] [ka]

[0054] In the formula, R 1 ~R 10 , Ar 1 and Ar 2 have the same meanings as above.

[0055] The reaction temperature is preferably 30° C. to 180° C., more preferably 80° C. to 140° C. The reaction time is preferably 1 hour to 12 hours, more preferably 3 hours to 8 hours.

[0056] From the viewpoint of yield, the reaction is preferably carried out in an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitrohydrocarbon solvents such as nitrobenzene; ketone solvents such as methyl isobutyl ketone; and amide solvents such as 1-methyl-2-pyrrolidone. These may be used in combination. Among these, a mixed solvent of butanol and toluene is preferred. The amount of the organic solvent used is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 30 parts by mass or more and 150 parts by mass or less, relative to 1 part by mass of the total of the compound represented by formula (pt1) and the compound represented by formula (pt2).

[0057] The method of extracting the target compound represented by formula (AI) from the reaction mixture is not particularly limited, and various known methods can be used. For example, the method of distilling off the solvent from the reaction solution to obtain the target product, or the method of cooling after the reaction is completed and filtering out the precipitated crystals, is mentioned. The filtered crystals are preferably washed with water and then dried. If necessary, the crystals may be further purified by known methods such as column chromatography and recrystallization.

[0058] The content of the squarylium dye in the colorant (A) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, and may be 95% by mass or more, or may be 100% by mass.

[0059] The colorant (A) may contain, in addition to the squarylium dye, a colorant other than the squarylium dye, and the colorant other than the squarylium dye may be either a dye (hereinafter, sometimes referred to as dye (A1)) or a pigment (hereinafter, sometimes referred to as pigment (A2)). The colorant other than the squarylium dye may contain one or both of the dye (A1) and the pigment (A2).

[0060] The dye (A1) is not particularly limited, and any known dye can be used, as long as it does not include the squarylium dye, and examples of such dyes include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha). In addition, examples of dyes that can be used according to chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

[0061] Specifically, CI Solvent Yellow 4 (hereinafter, the notation CI Solvent Yellow will be omitted and only the numbers will be listed), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 1 82, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 1 23, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; CI Acid Dyes such as CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Dyes such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Dyes such as CI Disperse Blue 1, 14, 56, 60, etc. CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic Red 9; CI Basic dyes such as CI Basic Green 1, CI Reactive Yellow 2,76,116; CI Reactive Orange 16; CI Reactive dyes such as CI Reactive Red 36, CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI Mordant dyes such as CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, Examples of such dyes include CI Vat dyes such as CI Vat Green 1. These dyes may be appropriately selected according to the optical spectrum of the desired color filter.

[0062] The pigment (A2) is not particularly limited and any known pigment can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Pigments include, for example, yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; Blue pigments such as CI Pigment Blue 15:6, 60; Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; Green pigments such as CI Pigment Green 7, 36, 58; Brown pigments such as CI Pigment Brown 23, 25; Examples of black pigments include CI Pigment Black 1 and 7.

[0063] The pigment may be subjected, as necessary, to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, or the like, a grafting treatment onto the pigment surface using a polymer compound or the like, a particle size reduction treatment using a sulfuric acid atomization method or the like, a washing treatment using an organic solvent or water for removing impurities, a removal treatment of ionic impurities using an ion exchange method or the like, or the like. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment in the presence of a pigment dispersant, it is possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.

[0064] Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include trade names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWRENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Corporation), EFKA (manufactured by CIBA Corporation), AJISPER (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie). When a pigment dispersant is used, the amount of the pigment dispersant used is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 50% by mass, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

[0065] The content of the colorant (A) in the colored curable resin composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, and even more preferably 1% by mass or more and 50% by mass or less, based on the total amount of solids. When the content of the colorant (A) is within the above range, the color density when made into a color filter is sufficient, and the composition can contain the necessary amounts of the resin (B) and the polymerizable compound (C), so that a pattern with sufficient mechanical strength can be formed.

[0066] Here, the "total amount of solids" in this specification refers to the amount obtained by subtracting the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

[0067] <Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6]. Resin [K1]: a copolymer having a structural unit derived from at least one member (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; Resin [K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, sometimes referred to as "(c)"); Resin [K3]: a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: a copolymer having a structural unit derived from (a) to which (b) has been added, and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (b) to which (a) has been added, and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride, and a structural unit derived from (c).

[0068] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the standpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkaline solution.

[0069] (b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0070] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

[0071] Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

[0072] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples of such styrene include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0073] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (I) and compounds represented by formula (II).

[0074] [ka]

[0075] [In formula (I) and formula (II), R a and R b represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X a and X b is a single bond, *-Rc -, *-R c -O-, *-R c -S- or *-R c -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0076] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. R a and R b Preferred examples of the alkyl group include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0077] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. X a and X b Preferred examples of the group include a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O-, and more preferred examples include a single bond and *-CH2CH2-O- (* represents a bond to O).

[0078] The compound represented by formula (I) includes compounds represented by any one of formulas (I-1) to (I-15), etc. Among them, compounds represented by formulas (I-1), (I-3), (I-5), (I-7), (I-9) or (I-11) to (I-15) are preferred, and compounds represented by formulas (I-1), (I-7), (I-9) or (I-15) are more preferred.

[0079] [ka]

[0080] [ka]

[0081] The compound represented by formula (II) includes compounds represented by any one of formulas (II-1) to (II-15), etc. Among them, compounds represented by formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) are preferred, and compounds represented by formulas (II-1), (II-7), (II-9) or (II-15) are more preferred.

[0082] [ka]

[0083] [ka]

[0084] The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, the content ratio thereof [compound represented by formula (I): compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0085] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like can be mentioned.

[0086] As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0087] As (b), (b1) is preferable in that the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter can be improved. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

[0088] (c) may be, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decan-8-yl(meth)acrylate (commonly known in the art as "dicyclopentanyl(meth)acrylate" and sometimes called "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.02,6 ](meth)acrylic acid esters such as decene-8-yl (meth)acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene chloro[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, bicyclounsaturated compounds such as ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Among these, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferred from the standpoint of copolymerization reactivity and heat resistance.

[0089] In the resin [K1], the ratio of the structural units derived from each of them is as follows among all the structural units constituting the resin [K1]: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that: When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the obtained color filter.

[0090] Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the cited references described in said literature.

[0091] Specifically, a method is exemplified in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, and the atmosphere is deoxygenated by, for example, replacing oxygen with nitrogen, and the mixture is heated and kept warm while stirring. The polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used. For example, the polymerization initiator includes an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide, etc.), and the solvent may be any one that dissolves each monomer, and examples of the solvent include the solvent described below as the solvent (F) of the colored curable resin composition of the present invention.

[0092] The copolymer obtained may be used as it is in the form of a solution after the reaction, or may be used after being concentrated or diluted, or may be used after being extracted as a solid (powder) by a method such as reprecipitation. In particular, by using a solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, and therefore the manufacturing process of the colored curable resin composition of the present invention can be simplified.

[0093] In the resin [K2], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K2]: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% It is preferred that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that: When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained color filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.

[0094] Resin [K2] can be produced, for example, in the same manner as described above as the method for producing resin [K1].

[0095] In the resin [K3], the ratio of structural units derived from each of them is as follows among all structural units constituting the resin [K3]: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that: Resin [K3] can be produced, for example, in the same manner as described above as the method for producing resin [K1].

[0096] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].

[0097] Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b). Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130°C for 1 to 10 hours to produce the resin [K4]. The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By adjusting the amount within this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to be good. Since the reactivity of the cyclic ether is high and unreacted (b) is unlikely to remain, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.

[0098] Resin [K5] is produced in the first step by the same method as the above-mentioned resin [K1] to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as it is in the form of a solution after the reaction, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively, Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0099] Furthermore, under the same conditions as in the manufacturing method of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) for use in resin [K5], and (b1-1) is more preferred.

[0100] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with the carboxylic acid anhydride. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of the amount of (a) used.

[0101] Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl(meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid copolymer resin [K1]; glycidyl (Meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, etc. [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, etc. [K3]; benzyl (meth)acrylate / (meth)acrylic acid copolymer to which glycidyl (meth)acrylate has been added, tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer to which glycidyl (meth)acrylate has been added, tricyclodecyl Resins such as [K4] in which glycidyl (meth)acrylate is added to a (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer; resins such as [K5] in which a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer is reacted with (meth)acrylic acid, and resins such as [K6] in which a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer is reacted with (meth)acrylic acid and further reacted with tetrahydrophthalic anhydride; and the like. Among these, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K1] is particularly preferable.

[0102] The polystyrene-equivalent weight average molecular weight of resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern tends to be improved.

[0103] The dispersity of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.

[0104] The acid value of the resin (B) is preferably 30 to 170 mg-KOH / g, more preferably 40 to 150 mg-KOH / g, and further preferably 50 to 135 mg-KOH / g, calculated as solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0105] The content of resin (B) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and further preferably 17 to 55 mass%, based on the total amount of solids. When the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved.

[0106] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.

[0107] Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tri ... Examples of the acrylates include 2-(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, and caprolactone modified dipentaerythritol hexa(meth)acrylate. Of these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

[0108] The content of the polymerizable compound (C) is preferably 1 to 65 mass % based on the total amount of solids, more preferably 5 to 60 mass %, and further preferably 10 to 55 mass %. When the content of the polymerizable compound (C) is within the above range, the residual film rate during color pattern formation and the chemical resistance of the color filter tend to be improved.

[0109] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.

[0110] Examples of the O-acyloxime compound include O-acyloxime compounds having a diphenyl sulfide skeleton such as N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine; N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-one-2-imine; imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, and other O-acyloxime compounds having a carbazole skeleton; and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime, and other O-acyloxime compounds having a fluorene skeleton. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all manufactured by BASF), N-1919 (manufactured by ADEKA), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and PBG-327 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) may also be used.Among them, the O-acyloxime compound is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyloxime. These O-acyloxime compounds tend to provide a high brightness color filter.

[0111] Examples of the alkylphenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF) may also be used.

[0112] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0113] The acylphosphine oxide compound may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0114] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

[0115] Examples of the polymerization initiator that generates an acid include onium salts such as 4-hydroxyphenyl dimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0116] Further examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

[0117] The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

[0118] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

[0119] <Antioxidants (E)> The antioxidant (E) includes a phenol-based antioxidant. When the colored curable resin composition of the present invention contains a phenol-based antioxidant, a decrease in maximum absorption in the film formation step can be suppressed.

[0120] As the phenol-based antioxidant, a known phenol-based antioxidant can be used. For example, Irganox (registered trademark) 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Ltd.), Irganox (registered trademark) 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF Ltd.), Irganox (registered trademark) 1330: 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol ... ox(registered trademark) 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF), Irganox(registered trademark) 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by BASF), Irganox(registered trademark) 1035: thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF), Irganox(registered trademark) 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoate C7-C9 side chain alkyl ester (manufactured by BASF), Irganox (registered trademark) 1520L: 4,6-bis(octylthiomethyl)-o-cresol (manufactured by BASF), Irganox (registered trademark) 3125 (manufactured by BASF), Irganox (registered trademark) 565: 2,4-bis(n-octylthio)-6-(4-hydroxy3',5'-di-tert-butylanilino)-1,3,5-triazine (manufactured by BASF), Irganox (registered trademark) 1726: 1,3,5-tris[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxy]ethyl]hexahydro-1,3,5-triazine-2,4,6-trione (manufactured by BASF), ADK STAB (registered trademark) AO-80: 3,9-Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (manufactured by ADEKA Corporation), ADK STAB (registered trademark) AO-20: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by ADEKA Corporation), ADK STAB (registered trademark) AO-30: 4,4',4''-(1-methyl propanylidene)tris(6-tert-butyl-m-cresol) (manufactured by ADEKA CORPORATION), ADK STAB (registered trademark) AO-40: 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol (manufactured by ADEKA CORPORATION), ADK STAB (registered trademark) AO-50: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (manufactured by ADEKA CORPORATION), ADK STAB (registered trademark) AO-60: pentaerythritol tetrakis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate] (manufactured by ADEKA Corporation), Adeka STAB® AO-330: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene (manufactured by ADEKA Corporation), Sumilizer® BHT: 2,6-di-tert-butyl-p-cresol (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer® GA-80: 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (manufactured by ADEKA Corporation), Sumilizer® GP: 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol (Sumitomo Chemical Co., Ltd.), Sumilizer® GS: 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,Examples of the acrylates include 6-di-tert-pentylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer (registered trademark) GM: 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Cytec Co., Ltd.), and Vitamin E (manufactured by Eisai Co., Ltd.).

[0121] The phenol-based antioxidant is preferably a compound having no vinyl group or ethene-1,1-diyl group. By using a phenol-based antioxidant, the decrease in maximum absorption during the film formation process can be suppressed, but there are cases where the color change (ΔEab*) becomes large. However, by using a compound having no vinyl group or ethene-1,1-diyl group as the phenol-based antioxidant, not only the decrease in maximum absorption during the film formation process can be suppressed, but also the color change can be suppressed.

[0122] The number of phenolic hydroxyl groups per molecule of the phenol-based antioxidant is preferably 1-5, more preferably 1-4, and further preferably 2-4.

[0123] Among the phenol-based antioxidants, hindered phenol-based antioxidants are preferred. The hindered phenol-based antioxidant is preferably a compound in which a tertiary alkyl group is bonded to at least one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group; More preferably, it is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of the phenolic hydroxyl group, and a hydrogen atom or an alkyl group is bonded to the other carbon atom; More preferably, it is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of the phenolic hydroxyl group, and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom; Particularly preferred is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of the phenolic hydroxyl group, and a hydrogen atom or a methyl group is bonded to the other carbon atom. In addition, the hindered phenol-based antioxidant is preferably a compound having two or more phenolic hydroxyl groups in the molecule, in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of the phenolic hydroxyl groups, and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom.

[0124] Alkyl groups include methyl groups, primary alkyl groups, secondary alkyl groups, and tertiary alkyl groups.

[0125] Examples of the primary alkyl group include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and a 2-ethylhexyl group, with an ethyl group and an n-propyl group being preferred. Examples of the secondary alkyl group include an isopropyl group and an isobutyl group. Examples of the tertiary alkyl group include a tert-butyl group, a tert-pentyl group, a tert-hexyl group, and a thexyl group, with a tert-butyl group and a tert-pentyl group being preferred, and a tert-butyl group being more preferred.

[0126] Specific examples of the hindered phenol-based antioxidants include Irganox® 1010, Irganox® 1076, Irganox® 1330, Irganox® 3114, Irganox® 3790, Irganox® 1035, Irganox® 1135, Irganox® 3125, Irganox® 565, ADK STAB® AO-80, ADK STAB® AO-20, ADK STAB® AO-30, ADK STAB® AO-40, ADK STAB® AO-50, ADK STAB® AO-60, ADK STAB® AO-330, Sumilizer® BHT, Sumilizer® GA-80, Sumilizer® GP, Sumilizer® GM, Cyanox 1790, etc., in which a tert-butyl group is bonded to at least one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group, Irganox® 1010, Irganox® 1076, Irganox® 1330, Irganox® 3114, Irganox® 3790, Irganox® 1035, Irganox® 1135, Irganox® 3125, Irganox® 565, ADK STAB® AO-80, ADK STAB® AO-20, ADK STAB® AO-30, ADK STAB® AO-40, ADK STAB® AO-50, ADK STAB® AO-60, ADK STAB® AO-330, Sumilizer® BHT, Sumilizer® GA-80, Sumilizer® GP, Cyanox More preferably, it is a compound in which a tert-butyl group is bonded to one of the carbon atoms at the ortho-position of the phenolic hydroxyl group, such as 1790, and a hydrogen atom, a methyl group, or a tert-butyl group is bonded to the other carbon atom, More preferred are compounds in which a tert-butyl group is bonded to one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group and a hydrogen atom or a methyl group is bonded to the other carbon atom, such as Irganox (registered trademark) 3790, Adeka STAB (registered trademark) AO-80, Adeka STAB (registered trademark) AO-30, Adeka STAB (registered trademark) AO-40, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GP, and Cyanox 1790, Particularly preferred are compounds having two or more phenolic hydroxyl groups, such as Irganox (registered trademark) 3790, Adeka STAB (registered trademark) AO-80, Adeka STAB (registered trademark) AO-30, Adeka STAB (registered trademark) AO-40, Sumilizer (registered trademark) GA-80, and Cyanox 1790, in which a tert-butyl group is bonded to one of the carbon atoms at the two ortho positions of the phenolic hydroxyl group and a hydrogen atom or a methyl group is bonded to the other carbon atom.

[0127] The antioxidant (E) may be a phenol-based antioxidant and other antioxidants in combination. Examples of other antioxidants that can be used include phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based antioxidants.

[0128] The content of the phenol-based antioxidant in the antioxidant (E) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, and may be 95% by mass or more, or may be 100% by mass.

[0129] The mass ratio of the antioxidant (E) to the squarylium dye (antioxidant (E) / squarylium dye) is preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.5 or more, and particularly preferably 2.0 or more, and is preferably 13 or less, more preferably 10 or less, and even more preferably 8 or less.

[0130] The content of the antioxidant (E) is preferably from 0.5 to 20 mass %, more preferably from 1 to 17 mass %, and further preferably from 1.5 to 15 mass %, based on the total amount of solids.

[0131] <Solvent (F)> The colored curable resin composition of the present invention preferably further contains a solvent (F). The solvent (F) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (a solvent containing OH in the molecule and not containing -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide can be mentioned.

[0132] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0133] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

[0134] The ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methyl ... Examples of the alkyl ether acetates include ethyl methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0135] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone (hereinafter sometimes referred to as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0136] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0137] Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0138] Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0139] Among the above solvents, from the viewpoint of coatability and drying property, preferred are organic solvents having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Preferred solvents are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol and N,N-dimethylformamide, and more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diacetone alcohol, ethyl lactate and ethyl 3-ethoxypropionate.

[0140] The content of the solvent (F) is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid content of the colored curable resin composition is preferably 5 to 30 mass%, more preferably 8 to 25 mass%. When the content of the solvent (F) is within the above range, the flatness during coating is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics tend to be good.

[0141] <Leveling agent (G)> The colored curable resin composition of the present invention may further contain a leveling agent (G). Examples of the leveling agent (G) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain. Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).

[0142] The fluorine-based surfactant may include surfactants having a fluorocarbon chain in the molecule.Specific examples include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.).

[0143] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0144] The content of the leveling agent (G) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, and even more preferably 0.005% by mass or more and 0.2% by mass or less, based on the total amount of the colored curable resin composition. This content does not include the content of the dispersant. When the content of the leveling agent (G) is within the above range, the flatness of the color filter can be improved.

[0145] <Other ingredients> The colored curable resin composition of the present invention may contain additives known in the technical field, such as a polymerization initiator aid, a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as necessary.

[0146] <Method for producing colored curable resin composition> The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), an antioxidant (E), and, as necessary, a solvent (F), a leveling agent (G), and other components.

[0147] <Manufacturing method of color filters> Examples of methods for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among these, the photolithography method is preferred. The photolithography method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and / or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention. The thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted depending on the purpose or application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0148] The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate, silicon, or a substrate having a thin film of aluminum, silver, or a silver / copper / palladium alloy formed thereon. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may be formed.

[0149] The formation of each color pixel by photolithography can be carried out using known or conventional devices and conditions. For example, the pixel can be produced as follows. First, a colored curable resin composition is applied onto a substrate, and then dried by heating and drying (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth colored composition layer. Examples of the coating method include spin coating, slit coating, and slit and spin coating. The temperature when drying by heating is preferably 30 to 120° C., more preferably 50 to 110° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying is carried out under reduced pressure, it is preferable to carry out the drying under a pressure of 50 to 150 Pa and at a temperature in the range of 20 to 25°C. The thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the intended thickness of the color filter.

[0150] Next, the coloring composition layer is exposed to light to form a colored coating film. When forming a colored pattern, the coloring composition layer is exposed to light through a photomask. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, around 408 nm, and around 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specifically, mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. may be mentioned. It is preferable to use an exposure device such as a mask aligner or a stepper, since it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to accurately align the photomask with the substrate on which the colored composition layer is formed.

[0151] The colored composition layer after exposure is brought into contact with a developer for development, thereby forming a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in the developer and removed by development. The developer is preferably, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant. The developing method may be any of a puddle method, a dipping method, a spray method, etc. Furthermore, the substrate may be inclined at an arbitrary angle during the developing. After development, it is preferable to wash with water.

[0152] Furthermore, it is preferable to perform post-baking on the obtained colored coating film or colored pattern. The post-baking temperature is preferably 150 to 250° C., more preferably 160 to 235° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0153] According to the present invention, it is possible to provide a colored curable resin composition having high suitability in a film-forming process. A color filter produced from the colored curable resin composition is useful as a color filter for use in a display device (e.g., a liquid crystal display device, an organic EL display device, electronic paper, etc.) and a solid-state imaging device. EXAMPLES

[0154] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples, and can be modified as long as it satisfies the purpose described above and below, and all of these are included in the technical scope of the present invention. In the examples, % and parts indicating the content or amount used are based on mass unless otherwise specified.

[0155] [Colorant synthesis example 1] 10.0 parts of 2,4-dimethylaniline (Tokyo Chemical Industry Co., Ltd.), 17.0 parts of 2-ethylhexane bromide (Tokyo Chemical Industry Co., Ltd.), and 44.0 parts of tetrabutylammonium bromide (Wako Chemical Industry Co., Ltd.) were mixed. The resulting mixture was stirred at 90°C for 8 hours. After the reaction was completed, 50 parts of 10% sodium bicarbonate water was added, and then 100 parts of ethyl acetate was added and the aqueous layer was discarded. The operation of washing with water and 10% hydrochloric acid was repeated twice, and the solvent was distilled off. The obtained oil was dried under reduced pressure at 60°C for 24 hours to obtain 9.3 parts of a compound represented by the following formula (a-1).

[0156] [ka]

[0157] The compound represented by formula (a-1) 1 H-NMR (270MHz, δ value (ppm, TMS Standard), DMSO-d6 δ 0.85(m,6H), 1.23-1.42(br,8H), 1.59(br,1H), 2.04(s,3H), 2.12(s,3H), 2.91(d,2H), 4.37(br,1H), 6.38(d,1H), 6.75(s,1H), 6.77(d,1H)

[0158] 3.0 parts of the compound represented by formula (a-1) obtained above, 2.2 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.015 parts of palladium acetate, 3.2 parts of sodium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.055 parts of tri-tert-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.6 parts of toluene were mixed and stirred at 100 ° C. for 15 hours. 30 parts of ethyl acetate and 100 parts of water were added to the obtained mixture, and the aqueous layer was discarded. After repeating the operation of washing with water twice, the solvent was distilled off. The residue was purified by silica gel chromatography (chloroform / hexane = 1 / 1), and the obtained oil was dried under reduced pressure at 60 ° C. for 24 hours, and 1.9 parts of a compound represented by the following formula (a-2) was obtained.

[0159] [ka]

[0160] The compound represented by formula (a-2) 1 H-NMR (270MHz, δ value (ppm, TMS standard), DMSO-d6) δ 0.85(m,6H), 1.23-1.42(br,8H), 1.55(br,1H), 1.94(s,3H), 2.27(s,3H), 2.90 (d,2H), 6.37(d,1H), 6.75(s,1H), 6.76(d,1H), 6.92-7.14(m,4H), 8.93(s,1H)

[0161] 4.4 parts of the compound represented by formula (a-2) obtained above, 0.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 90.0 parts of 1-butanol, and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125°C for 3 hours while removing the water generated using a Dean-Stark tube. After the reaction was completed, the solvent was distilled off, 15 parts of acetic acid was added, and then dropped into 100 parts of 18% saline, and the precipitated solid was filtered off. The filtered solid was washed with hexane. The obtained solid was dried under reduced pressure at 60°C for 24 hours, and 4.9 parts of the compound represented by formula (AI-1) was obtained.

[0162] [ka]

[0163] The compound represented by formula (AI-1) 1 H-NMR (270MHz, δ value (ppm, TMS standard), DMSO-d6) δ 0.87(m,12H), 1.21-1.57(m,16H), 1.72(br,2H), 2.05(s,6H), 2.36(s,6H), 3.37(br,2H), 3. 78(br,2H), 6.00(br,4H), 6.97-7.12(m,6H), 7.77-7.95(m,2H), 11.35(s,1H), 12.06(s,1H)

[0164] [Colorant synthesis example 2] 50 parts of m-bromophenol (Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 parts of dichloromethane (Kanto Chemical Co., Ltd.) and cooled to 0°C, and then 48 parts of tert-butyldimethylchlorosilane (Tokyo Chemical Industry Co., Ltd.) were added dropwise. After the dropwise addition, the temperature was raised to 23°C and stirred for 16 hours. After the reaction was completed, water was added to extract the organic layer, and the solvent was concentrated and then separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by formula (1-10). In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[0165] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 287.0 Exact Mass:+286.0

[0166] [ka]

[0167] 45 parts of 4-amino-3,5-xylenol (Tokyo Chemical Industry Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (Kanto Chemical Co., Ltd.). 127 parts of di-tert-butyl dicarbonate (Tokyo Chemical Industry Co., Ltd.) was added to this solution and dissolved. The mixture was stirred at 23°C for 16 hours to react. After the reaction was completed, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was stirred and purified in a mixed solvent of 90 parts of ethyl acetate (Kanto Chemical Co., Ltd.) and 272 parts of n-hexane (Kanto Chemical Co., Ltd.) at 23°C for 2 hours to obtain 47 parts of a compound represented by formula (1-33).

[0168] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 238.3 Exact Mass:+237.1

[0169] [ka]

[0170] 20 parts of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 333 parts of dichloromethane (manufactured by Kanto Chemical Industry Co., Ltd.). 32.4 parts of triethylamine (manufactured by Kanto Chemical Industry Co., Ltd.) and 0.156 parts of 4-dimethylaminopyridine (manufactured by Kanto Chemical Industry Co., Ltd.) were added to this solution, and 28.95 parts of tert-butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved while stirring. The mixture was reacted by stirring at 23°C for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of a compound represented by formula (1-34).

[0171] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 239.1 Exact Mass:+238.0

[0172] [ka]

[0173] 47 parts of the compound represented by formula (1-33) were dissolved in 141.5 parts of the bromo compound represented by formula (1-34) and 447 parts of dimethylformamide (Kanto Chemical Co., Ltd.). 138.2 parts of potassium carbonate (Kanto Chemical Co., Ltd.) were added to this solution and reacted with stirring at 70°C for 16 hours. After the reaction was completed, the solvent was distilled off and extraction with an organic solvent was performed to obtain 49 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 41 parts of a compound represented by formula (1-35).

[0174] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+Ht-Bu + ] + 339.2Exact Mass:+395.3

[0175] [ka]

[0176] 41 parts of the compound represented by formula (1-35) was dissolved in 424 parts of 1,4-dioxane (Kanto Chemical Co., Ltd.), and 263 parts of hydrogen chloride (about 4 mol / L 1,4-dioxane solution) (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 23°C for 1 hour to perform deprotection. After the reaction was completed, the solvent was distilled off to obtain 36 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 22 parts of the compound represented by formula (1-36).

[0177] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 182.2 Exact Mass:+181.1

[0178] [ka]

[0179] 22 parts of the compound represented by formula (1-36) were dissolved in 293 parts of dichloromethane (Kanto Chemical Co., Ltd.). 10.8 parts of imidazole (Kanto Chemical Co., Ltd.) and 22 parts of tert-butyldimethylsilyl chloride (Tokyo Chemical Industry Co., Ltd.) were added to this solution and dissolved. The mixture was stirred at 23°C for 16 hours to react. The solvent was distilled off to obtain 23 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of the compound represented by formula (1-37).

[0180] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 296.3 Exact Mass:+295.2

[0181] [ka]

[0182] 15 parts of the compound represented by formula (1-10) was dissolved in 14.5 parts of the compound represented by formula (1-37) and 130 parts of toluene (Kanto Chemical Co., Ltd.), and this solution was mixed with 5.7 parts of potassium hydroxide (Kanto Chemical Co., Ltd.), 15 parts of water, 2 parts of tetrabutylammonium bromide (Tokyo Chemical Industry Co., Ltd.), and 0.26 parts of bis(tri-tert-butylphosphine)palladium(0) (Tokyo Chemical Industry Co., Ltd.). After heating to 90°C and stirring for 20 minutes, the organic layer was extracted and the solvent was distilled off to obtain 15 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 12 parts of a compound represented by formula (1-38).

[0183] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 502.4 Exact Mass:+501.3

[0184] [ka]

[0185] 12 parts of the compound represented by formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 41.6 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) were mixed and heated with stirring at 90° C. for 1 hour. After the reaction was completed, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of the compound represented by formula (1-39).

[0186] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 616.3 Exact Mass:+615.3

[0187] [ka]

[0188] 5.9 parts of the compound represented by formula (1-39) was dissolved in 52.4 parts of tetrahydrofuran (Kanto Chemical Co., Ltd.) and cooled to 0°C, and then 11 parts of tetrabutylammonium fluoride 1M tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd.) was added dropwise, and after the completion of the dropwise addition, the mixture was stirred for 2 hours at 23°C. After the reaction was completed, water was added, and the tetrahydrofuran solvent was distilled off to obtain a crude product, which was subjected to an extraction operation with an organic solvent and concentrated to obtain 4.3 parts of the compound represented by formula (1-40).

[0189] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 388.2 Exact Mass:+387.2

[0190] [ka]

[0191] 4.3 parts of the compound represented by formula (1-40), 56.4 parts of borane 1M tetrahydrofuran solution (Kanto Chemical Co., Ltd.), and 38.2 parts of tetrahydrofuran (Kanto Chemical Co., Ltd.) were mixed at 0°C, heated to 23°C, and stirred for 16 hours. After completion of the reaction, water was added to quench the reaction, and the mixture was extracted with an organic solvent. The solvent was distilled off, and the resulting crude product was purified by silica gel column chromatography to obtain 2.3 parts of the compound represented by formula (1-41).

[0192] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 346.3 Exact Mass:+345.2

[0193] [ka]

[0194] 2.3 parts of the compound represented by formula (1-41) and 0.38 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 80 parts of toluene (manufactured by Kanto Chemical Industries, Ltd.) and 19 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.), and the mixture was heated with stirring at 120° C. for 4 hours. After completion of the reaction, the solvent was distilled off, and the resulting crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by formula (AI-15).

[0195] Identification: (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 769.8 Exact Mass:+768.4

[0196] [ka]

[0197] [Resin synthesis example] A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixture of 289 parts of a mixture of decan-9-yl acrylate (mixing ratio 1:1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a mixture of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the flask was kept at 80°C for 4 hours and then cooled at room temperature to obtain a copolymer (resin (B-1)) solution with a B-type viscosity (23°C) of 125 mPa·s and a solid content of 35.1%. The weight average molecular weight Mw of the resulting copolymer was 9200, the dispersity was 2.08, and the solid acid value was 77 mg-KOH / g. Resin (B-1) has the following structural units.

[0198] [ka]

[0199] [Examples 1 to 15, Comparative Examples 1 to 3] [Preparation of Colored Curable Resin Composition] Colored curable resin compositions were obtained by mixing the components so as to obtain the compositions shown in Table 3. In Table 3, the unit of the content of each component is "parts."

[0200] [Table 3]

[0201] In Table 3, each component represents the following compound. Colorant (A-1): A compound represented by formula (AI-1) Colorant (A-2): Compound represented by formula (AI-15) Resin (B-1): Resin (B-1) (solid content conversion) Polymerizable compound (C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (PBG-327; oxime compound; Changzhou Strong Electronic New Materials Co., Ltd.) Antioxidant (E-1): 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) (ADEKA STAB® AO-30; manufactured by ADEKA Corporation) Antioxidant (E-2): 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol (ADEKA STAB® AO-40; manufactured by ADEKA Corporation) Antioxidant (E-3): 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (Sumilizer® GA-80; manufactured by Sumitomo Chemical Co., Ltd.) Antioxidant (E-4): Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA STAB® AO-60; manufactured by ADEKA Corporation) Antioxidant (E-5): 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (ADEKA STAB® AO-20; manufactured by ADEKA Corporation) Antioxidant (E-6): 2-tert-butyl-6-methyl-4-{3-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl}phenol (Sumilizer® GP; manufactured by Sumitomo Chemical Co., Ltd.) Antioxidant (E-7): 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Sumilizer® GS; manufactured by Sumitomo Chemical Co., Ltd.) Antioxidant (E-8): 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (ADEKA STAB® LA82; manufactured by ADEKA Corporation) Antioxidant (E-9): 2,2,6,6-tetramethyl-4-piperidyl methacrylate (ADEKA STAB® LA87; manufactured by ADEKA Corporation) Solvent (F-1): Diacetone alcohol Solvent (F-2): Propylene glycol monomethyl ether acetate Leveling agent (G-1): Polyether modified silicone oil (Toray Silicone SH8400 manufactured by Toray Dow Corning Co., Ltd.)

[0202] [Preparation of colored coating film] A colored curable resin composition was applied by spin coating onto a 5 cm square glass substrate (Eagle 2000; Corning Incorporated) so that the film thickness after post-baking would be 2.0 μm, and then pre-baked at 100° C. for 3 minutes to form a colored composition layer. After cooling, the colored composition layer was exposed to light at 100 mJ / cm 2 in the air using an exposure machine (TME-150RSK; Topcon Corporation). 2 The colored composition layer was irradiated with light at an exposure amount (based on 365 nm) of 1000 nm, and then post-baked in an oven at 230° C. for 30 minutes to obtain a colored coating film.

[0203] [evaluation] 1. Absorbance retention rate After pre-baking and post-baking, the maximum absorbance in the visible light region was obtained from the spectrum measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the retention rate of the maximum absorbance was calculated according to the following formula. The results are shown in Table 4. Absorbance retention rate (ΔAbs.Max) = Maximum absorbance after post-bake / Maximum absorbance after pre-bake A higher absorbance retention rate means a higher suitability for the film formation process.

[0204] 2. Color change (ΔEab*) After pre-baking and post-baking, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) and stimulus value Y in the CIE XYZ color system were measured using the characteristic function of the C light source. From the measured values, the color difference ΔEab* was calculated according to the method described in JIS Z 8730:2009 (7. Calculation method of color difference), and the results are shown in Table 4. The smaller ΔEab* means the smaller the color change.

[0205] [Table 4] [Industrial Applicability]

[0206] INDUSTRIAL APPLICABILITY According to the present invention, a colored curable resin composition having high suitability in a film-forming process can be provided, and therefore the colored curable resin composition is useful as a colored curable resin composition used in color filters of display devices and solid-state imaging devices.

Claims

1. The composition includes a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant, the colorant comprises a squarylium dye having a maximum absorption in the visible light region; the antioxidant comprises a phenolic antioxidant; A colored curable resin composition, wherein a mass ratio of the antioxidant to the squarylium dye (antioxidant / squarylium dye) is 0.8 or more.

2. 2. The colored curable resin composition according to claim 1, wherein the phenol-based antioxidant is a compound having no vinyl group and no ethene-1,1-diyl group.

3. 3. The colored curable resin composition according to claim 1, wherein the phenolic antioxidant is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group, and a hydrogen atom or an alkyl group is bonded to the other carbon atom.

4. The colored curable resin composition according to any one of claims 1 to 3, wherein the phenol-based antioxidant is a compound in which a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of a phenolic hydroxyl group, and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom.

5. The colored curable resin composition according to claim 1 or 2, wherein the phenolic antioxidant is a compound having two or more phenolic hydroxyl groups in the molecule, and a tertiary alkyl group is bonded to one of the carbon atoms at the two ortho positions of the phenolic hydroxyl groups, and a hydrogen atom, a methyl group, or a primary alkyl group is bonded to the other carbon atom.

6. The colored curable resin composition according to any one of claims 1 to 5, wherein the squarylium dye is a compound represented by formula (AI): 【Chemistry 1】 [In formula (AI), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. R 5 ~R 8 each independently represents a hydrogen atom or a hydroxy group. Ar 1 and Ar 2 each independently represents a group represented by formula (i). 【Chemistry 2】 [In formula (i), R 12 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m represents an integer of 0 to 5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, multiple R 12 may be the same or different. * represents a bond to a nitrogen atom.] R 9 and R 10 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by formula (i). A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.]

7. The colored curable resin composition according to any one of claims 1 to 6, wherein the squarylium dye is a compound represented by formula (AII): 【Chemistry 3】 [In formula (AII), R 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. A methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. R 5 ~R 8 each independently represents a hydrogen atom or a hydroxy group. Ar 1 and Ar 2 each independently represents a group represented by formula (i). 【Chemistry 4】 [In formula (i), R 12 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have a substituent, a hydroxy group, or a carboxy group, and m represents an integer of 0 to 5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, multiple R 12 may be the same or different. * represents a bond to a nitrogen atom.] R 13 and R 14 each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which has a hydroxyl group or a carboxyl group, and a methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-.]

8. A color filter formed from the colored curable resin composition according to any one of claims 1 to 7.

9. A display device comprising the color filter according to claim 8.

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