Colored curable resin composition, optical filter, and solid-state imaging element

Abstract

The present invention provides a colored curable resin composition capable of maintaining absorbance at the maximum absorption wavelength. The present invention relates to a colored curable resin composition comprising a colorant, a resin, a polymerization initiator, a polymerizable compound and a metal compound, the metal compound being at least one compound selected from the group consisting of formula (GI) and formula (GII). [MA and MB represent a Group 11 metal atom; rC represents a divalent hydrocarbon group having 1-20 carbon atoms, and RD represents a hydrocarbon group connecting a pyridine ring A and a pyridine ring B; xA and XB represent a halogen atom, a hydroxyl group, ORE, NHRE, or N (RE) 2].

Description

Technical Field

[0001] This invention relates to color-curable resin compositions, optical filters, and solid-state imaging elements. Background Technology

[0002] Optical filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state imaging elements such as CCDs and CMOS sensors, are manufactured from color-curable resin compositions (Patent Document 1, etc.). Furthermore, it is also known that by adding specific metal compounds to color-curable resin compositions, color difference (ΔE*ab) after illumination can be suppressed (Patent Documents 2-4).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2013-122577

[0006] Patent Document 2: Japanese Patent Application Publication No. 2011-118365

[0007] Patent Document 3: Japanese Patent Application Publication No. 2004-295116

[0008] Patent Document 4: Japanese Patent Application Publication No. 2007-249160 Summary of the Invention

[0009] For the above-mentioned color-curing resin composition, it is important not only to have a small color difference (ΔE*ab) after irradiation, but also to maintain absorbance at the maximum absorption wavelength after irradiation.

[0010] The objective of this invention is to provide a color-curable resin composition capable of maintaining absorbance at the maximum absorption wavelength.

[0011] The gist of this invention is as follows.

[0012] [1] A coloring curable resin composition comprising a colorant, a resin, a polymerization initiator, a polymerization compound and a metal compound, wherein the metal compound is at least one compound selected from the group represented by formula (GI) and formula (GII).

[0013]

[0014] In formulas (GI) and (GII), M A , and M B Each of them independently represents a Group 11 metal atom.

[0015] R A1 ~R A4 and RB1 ~R B6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms.

[0016] R C This refers to a hydrocarbon group with 1 to 20 divalent carbon atoms.

[0017] R D This indicates a hydrocarbon group connecting pyridine ring A and pyridine ring B, and R D The pyridine ring A and / or pyridine ring B can be bonded by single bonds, R D In the case of a ring structure portion, this ring structure portion can be bonded to pyridine ring A and / or pyridine ring B through ring condensation.

[0018] X A and X B Each independently represents a halogen atom, hydroxyl group, and OR. E NHR E 、or N(R) E 2. There are multiple X's. A and X B They can be different from each other.

[0019] R E Represents hydrocarbon groups with 1 to 10 carbon atoms and two R groups. E At that time, R E They can be different from each other.

[0020] n and m are each independently 1 or 2.

[0021] M A Between N and M B The dashed lines between N and N represent coordinate bonds.

[0022] [2] According to the coloring and curing resin composition of [1], wherein M A and M B They are copper atoms.

[0023] [3] The coloring curable resin composition according to [1] or [2], wherein the colorant comprises a compound represented by formula (II).

[0024]

[0025] In formula (II), R 1 ~R 4 Each can independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents. The -CH2- contained in the saturated hydrocarbon group can be -O-, -CO-, or -NR. 11 - Replace. R1 and R 2 They can form a ring containing nitrogen atoms, R 3 and R 4 They can form a ring containing nitrogen atoms together.

[0026] R 5 Represents -OH, -SO3 － -SO3H, -SO3 － Z + -CO2H, -CO2 － Z + -CO2R 8 -SO3R 8 or -SO2NR 9 R 10 .

[0027] R 6 and R 7 Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0028] m represents an integer from 0 to 5. When m is 2 or higher, multiple R... 5 They can be the same or different.

[0029] 'a' represents an integer that is either 0 or 1.

[0030] X represents a halogen atom.

[0031] Z + express + N(R 11 4. Na + or K + 4 Rs 11 They can be the same or different.

[0032] R 8 This indicates a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atoms can be replaced by halogen atoms.

[0033] R 9 and R 10 Each of the following groups independently represents a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents. The -CH2- group contained in this saturated aliphatic hydrocarbon group can be -O-, -CO-, -NH-, or -NR. 8 - Replacement, R 9 and R 10 They can bond with each other to form heterocycles containing nitrogen atoms, ranging from 3 to 10 members.

[0034] R 11 This refers to a monovalent saturated hydrocarbon group containing 1 to 20 carbon atoms, or an aralkyl group containing 7 to 10 carbon atoms.

[0035] [4] An optical filter formed from any one of [1] to [3].

[0036] [5] A solid-state imaging element comprising the optical filter described in [4].

[0037] According to the present invention, a color-curable resin composition capable of forming an optical filter with absorbance that maintains the maximum absorption wavelength can be provided. According to this invention, color difference (Δ*ab) can also be suppressed for a longer period. Detailed Implementation

[0038] The coloring-curing resin composition of the present invention comprises a colorant (hereinafter, sometimes referred to as colorant (A)), a resin (hereinafter, sometimes referred to as resin (B)), and a metal compound (hereinafter, sometimes referred to as metal compound (G)). The coloring-curing resin composition of the present invention sometimes further comprises a polymerizable compound (hereinafter, sometimes referred to as polymerizable compound (C)), a polymerization initiator (hereinafter, sometimes referred to as polymerization initiator (D)), and may also further comprise a polymerization initiation aid (hereinafter, sometimes referred to as polymerization initiation aid (D1)). The coloring-curing resin composition of the present invention may further contain one or more selected from solvents (hereinafter, sometimes referred to as solvent (E)), thiols (hereinafter, sometimes referred to as thiols (T)), leveling agents (hereinafter, sometimes referred to as leveling agents (F)).

[0039] It should be noted that, unless otherwise specified, the compounds exemplified as components in this specification may be used alone or in combination. Furthermore, in this specification, "a compound represented by formula α" is sometimes referred to as compound α (α represents a string that varies depending on the compound).

[0040] <Coloring Agent (A)>

[0041] The colorant (A) is not particularly limited, but preferably includes a compound represented by formula (II) (hereinafter sometimes referred to as "compound (II)"). Even though irradiation of compound (II) in the atmosphere may sometimes reduce the absorbance at the maximum absorption wavelength, the reduction in absorbance can be suppressed by combining compound (II) with the specific metal compound of the present invention.

[0042]

[0043] In formula (II), R 1 ~R 4Each can independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents. The -CH2- contained in the saturated hydrocarbon group can be -O-, -CO-, or -NR. 11 - Replace. R 1 and R 2 They can form a ring containing nitrogen atoms, R 3 and R 4 They can form a ring containing nitrogen atoms together.

[0044] R 5 Represents -OH, -SO3 － -SO3H, -SO3 － Z + -CO2H, -CO2 － Z + -CO2R 8 -SO3R 8 or -SO2NR 9 R 10 .

[0045] R 6 and R 7 Each can be independently represented as an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0046] m represents an integer from 0 to 5. When m is 2 or higher, multiple R... 5 They can be the same or different.

[0047] 'a' represents an integer that is either 0 or 1.

[0048] X represents a halogen atom.

[0049] Z + express + N(R 11 4. Na + or K + 4 Rs 11 They can be the same or different.

[0050] R 8 This indicates a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atoms can be replaced by halogen atoms.

[0051] R 9 and R 10 Each of the following groups independently represents a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents. The -CH2- group contained in this saturated aliphatic hydrocarbon group can be -O-, -CO-, -NH-, or -NR. 8 - Replacement, R 9 and R 10They can bond with each other to form heterocycles containing nitrogen atoms, ranging from 3 to 10 members.

[0052] R 11 This refers to a monovalent saturated hydrocarbon group containing 1 to 20 carbon atoms, or an aralkyl group containing 7 to 10 carbon atoms.

[0053] As R 1 ~R 4 and R 8 ~R 11 Examples of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

[0054] As R 1 ~R 4 The monovalent aromatic hydrocarbon group representing 6 to 20 carbon atoms includes, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, 3,5-di-tert-butylphenyl, and 3,5-di-tert-butylphenyl. -4-Methylphenyl, 4-Butylphenyl, 4-Pentylphenyl, 2,6-Bis(1-methylethyl)phenyl, 2,4,6-Tris(1-methylethyl)phenyl, 4-Cyclohexylphenyl, 2,4,6-Trimethylphenyl, 4-Octylphenyl, 4-(1,1,3,3-Tetramethylbutyl)phenyl, 1-Naphthyl, 2-Naphthyl, 6-Methyl-2-Naphthyl, 5,6,7,8-Tetrahydro-1-Naphthyl, 5,6,7,8-Tetrahydro-2-Naphthyl, Fluorenyl, Phenylenyl, Anthracite, 2-Dodecylphenyl, 3-Dodecylphenyl, 4-Dodecylphenyl, Perylyl, Benzyl and pyrene, etc.

[0055] R 1 ~R 4 The substituents of monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms or monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms can be halogen atoms, -OH, -OR. 8 -SO3 － -SO3H, -SO3 － Z + -CO2H, -CO2R 8、-SR 8 -SO2R 8 -SO3R 8 or -SO2NR 9 R 10 Of these substituents, -SO3 is preferred. － -SO3H, -SO3 － Z + and -SO2NR 9 R 10 At least one of them, more preferably selected from SO3 － Z + and -SO2NR 9 R 10 At least one of them. As in this case, -SO3 － Z + Preferred SO3 －+ N(R 11 4.

[0056] R 1 and R 2 It can form a nitrogen-containing ring with nitrogen atoms, R 3 and R 4 It can form a nitrogen-containing ring together with a nitrogen atom. Examples of such a nitrogen-containing ring include the following.

[0057]

[0058] As -OR 8 Examples include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, 2-ethylhexoxy, and eicosyloxy.

[0059] As a CO2R 8 Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexoxycarbonyl, and eicosyloxycarbonyl.

[0060] As -SR 8 Examples include methyl thio, ethyl thio, butyl thio, hexyl thio, decyl thio, eicosyl thio, etc.

[0061] As -SO2R 8 Examples include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, eicosylsulfonyl, etc.

[0062] As -SO3R 8 Examples include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexoxysulfonyl, eicosyloxysulfonyl, etc.

[0063] As -SO2NR 9 R 10 For example, the following can be cited:

[0064] Aminosulfonyl;

[0065] N-Methylaminosulfonyl, N-ethylaminosulfonyl, N-propylaminosulfonyl, N-isopropylaminosulfonyl, N-butylaminosulfonyl, N-isobutylaminosulfonyl, N-sec-butylaminosulfonyl, N-tert-butylaminosulfonyl, N-pentylaminosulfonyl, N-(1-ethylpropyl)aminosulfonyl, N-(1,1-dimethylpropyl)aminosulfonyl, N-(1,2-dimethylpropyl)aminosulfonyl, N-(2,2-dimethylpropyl)aminosulfonyl, N-(1-methylbutyl)aminosulfonyl, N-(2-methylbutyl)aminosulfonyl, N -(3-methylbutyl)aminosulfonyl, N-cyclopentylaminosulfonyl, N-hexylaminosulfonyl, N-(1,3-dimethylbutyl)aminosulfonyl, N-(3,3-dimethylbutyl)aminosulfonyl, N-heptylaminosulfonyl, N-(1-methylhexyl)aminosulfonyl, N-(1,4-dimethylpentyl)aminosulfonyl, N-octylaminosulfonyl, N-(2-ethylhexyl)aminosulfonyl, N-(1,5-dimethyl)hexylaminosulfonyl, N-(1,1,2,2-tetramethylbutyl)aminosulfonyl and other N-1 substituted aminosulfonyl groups;

[0066] N,N-dimethylaminosulfonyl, N,N-ethylmethylaminosulfonyl, N,N-diethylaminosulfonyl, N,N-propylmethylaminosulfonyl, N,N-isopropylmethylaminosulfonyl, N,N-tert-butylmethylaminosulfonyl, N,N-butylethylaminosulfonyl, N,N-bis(1-methylpropyl)aminosulfonyl, N,N-heptylmethylaminosulfonyl and other N,N-2-substituted aminosulfonyl groups.

[0067] Additionally, R 9 and R 10 The substituents of the monovalent saturated hydrocarbon group representing 1 to 20 carbon atoms can be -OH or halogen atoms, and the -CH2- contained in the saturated hydrocarbon group can be -O-, -CO-, -NH- or -NR. 8 -replace.

[0068] R 9 and R 10 They can bond with each other to form heterocycles with nitrogen atoms to form 3- to 10-membered rings. Examples of such heterocycles include the following.

[0069]

[0070] As a representation of R 6 and R 7Alkyl groups having 1 to 6 carbon atoms include the straight-chain alkyl groups and branched alkyl groups mentioned above that have 1 to 6 carbon atoms.

[0071] As a representation of R 11 Aryl groups with 7 to 10 carbon atoms include benzyl, phenylethyl, and phenylbutyl.

[0072] Z + for + N(R 11 4. Na + or K + Preferred + N(R 11 4.

[0073] As mentioned above + N(R 11 )4, preferably 4 R 11 At least two of them are monovalent saturated hydrocarbon groups with 5 to 20 carbon atoms. In addition, there are four R... 11 The total number of carbon atoms is preferably 20 to 80, more preferably 20 to 60.

[0074] m is preferably 1 to 4, more preferably 1 or 2.

[0075] Compound (II) is more preferably a compound represented by formula (IIa) (hereinafter sometimes referred to as "compound (IIa)").

[0076]

[0077] In formula (IIa), R 21 ~R 24 Each can independently represent a hydrogen atom, or an aromatic hydrocarbon group with 6 to 20 carbon atoms that can have monovalent substituents. R 21 and R 22 It can form a nitrogen-containing ring with nitrogen atoms, R 23 and R 24 It can form a ring containing nitrogen atoms together with nitrogen atoms.

[0078] R 25 Indicates -SO3 － -SO3H, -SO3 － Z1 + Or -SO2NHR 26 .

[0079] m1 represents an integer from 0 to 5. When m1 is an integer greater than 2, multiple R... 25 They can be the same or different.

[0080] a1 represents an integer that is either 0 or 1.

[0081] X1 represents a halogen atom.

[0082] R 26 A monovalent saturated hydrocarbon group representing 1 to 20 carbon atoms.

[0083] Z1 + express + N(R 27 4. Na + or K + .

[0084] R 27 Each group independently represents a monovalent saturated hydrocarbon group or a benzyl group with 1 to 20 carbon atoms.

[0085] As R 21 ~R 24 The monovalent aromatic hydrocarbon group representing 6 to 10 carbon atoms can be exemplified by the R group mentioned above. 1 ~R 4 The same group as those mentioned above as aromatic hydrocarbon groups. The substituent of this aromatic hydrocarbon group can be -SO3. － -SO3H, -SO3 － Z1 + -SO3R 26 Or -SO2NHR 26 .

[0086] As R 21 ~R 24 The combination of R is preferred. 22 and R 23 For hydrogen atoms, R 21 and R 24 It is a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms, R 25 SO3 - -SO3H, -SO3 - Z1 + -SO3R 26 Or -SO2NHR 26 A more preferred combination is R. 22 and R 23 For hydrogen atoms, R 21 and R 24 It is a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms, R 25 SO3 - -SO3 - Z1 + Or -SO2NHR 26 .

[0087] Additionally, R 21 and R 22It can form aliphatic heterocycles containing nitrogen atoms together with nitrogen atoms, and R 23 and R 24 It can form aliphatic heterocycles containing nitrogen atoms together with nitrogen atoms.

[0088] Examples of aliphatic heterocycles mentioned above include the following aliphatic heterocycles.

[0089]

[0090] As a representation of R 26 and R 27 Monovalent saturated hydrocarbon groups with 1 to 20 carbon atoms can be cited as examples related to R. 8 ~R 11 The same group as the saturated hydrocarbon group mentioned above.

[0091] Z1 + Preferred + N(R 27 4. Na + or K + More preferably + N(R 27 4.

[0092] As mentioned above + N(R 27 )4, preferably 4 R 27 At least two of them are monovalent saturated hydrocarbon groups with 5 to 20 carbon atoms. In addition, there are four R... 27 The total number of carbon atoms is preferably 20 to 80, more preferably 20 to 60.

[0093] m1 is preferably 1 to 4, more preferably 1 or 2.

[0094] As compounds (IIa), for example, compounds represented by formulas (1-1) to (1-25) can be cited. It should be noted that in the formulas, R... 26 The group represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. Among these, sulfonamides of CI Acid Red 289, quaternary ammonium salts of CI Acid Red 289, sulfonamides of CI Acid Violet 102, or quaternary ammonium salts of CI Acid Violet 102 are preferred. Examples of such compounds include those represented by formulas (1-1) to (1-8), (1-11), and (1-12).

[0095]

[0096]

[0097]

[0098] In addition, compound (II) preferably includes compounds represented by formula (IIIa) (hereinafter sometimes referred to as "compound (IIIa)").

[0099]

[0100] In formula (IIIa), R 32 and R 33 Each can be independently represented as an alkyl group having 1 to 4 hydrogen atoms or carbon atoms.

[0101] R 31 and R 34 Each can be independently represented as an alkyl group having 1 to 4 carbon atoms, an alkyl thio group having 1 to 4 carbon atoms, or an alkyl sulfonyl group having 1 to 4 carbon atoms.

[0102] R 31 and R 32 It can form a nitrogen-containing ring with nitrogen atoms, R 33 and R 34 It can form a ring containing nitrogen atoms together with nitrogen atoms.

[0103] p and q each independently represent integers from 0 to 5. When p is 2 or higher, multiple R... 31 They can be the same or different; when q is 2 or higher, multiple Rs are allowed. 34 They can be the same or different.

[0104] As R 31 R 32 R 33 and R 34 Alkyl groups representing 1 to 4 carbon atoms include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc.

[0105] As R 31 and R 34 Examples of alkyl thio groups representing 1 to 4 carbon atoms include methyl thio, ethyl thio, propyl thio, butyl thio, and isopropyl thio.

[0106] As R 31 and R 34 Examples of alkyl sulfonyl groups representing 1 to 4 carbon atoms include methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, butyl sulfonyl, and isopropyl sulfonyl.

[0107] R 32 and R 33 Each is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. R 31 and R 34Preferably, it is an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0108] p and q are each preferably integers from 0 to 2, more preferably 1 or 2.

[0109] Examples of compounds (IIIa) include those represented by formulas (1-26) to (1-36). Among these, compounds represented by formulas (1-26) to (1-32) and (1-36) are preferred in terms of excellent solubility in organic solvents, and compounds represented by formulas (1-26) are more preferred (also referred to as compounds represented by formula (II-1) below).

[0110]

[0111]

[0112] Colorant (A) may also contain colorants different from those represented by formula (II).

[0113] Examples of different coloring agents include dyes (A1) and pigments (A2), with pigments (A2) being preferred. These can be used alone or in combination of two or more.

[0114] The dye (A1) is not particularly limited; well-known dyes can be used, such as solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as dyes in color indexes (published by The Society of Dyers and Colourists) and well-known dyes listed in dyeing guides (for dyeing companies). Additionally, based on chemical structure, examples include azo dyes, cyanide dyes, triphenylmethane dyes, xanthones, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methylene dyes, azomethyl base dyes, and squaric acid. Dyes, including acridine dyes, styrene dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, quinoline dyes, and isoindoline dyes. Among these, organic solvent-soluble dyes are preferred.

[0115] Specifically, examples of dyes with the following color index (CI) numbers can be cited.

[0116] CI Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

[0117] CI Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

[0118] CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

[0119] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0120] CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 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;

[0121] CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; and other CI solvent dyes;

[0122] 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, 15 7, 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;

[0123] 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, 182 183, 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;

[0124] CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

[0125] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0126] 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, 123, 1 26, 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, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;

[0127] 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; and other CI acid dyes;

[0128] CI direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

[0129] 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;

[0130] CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0131] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0132] 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, 87, 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, 1 67, 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;

[0133] CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; and other CI direct dyes;

[0134] CI Disperse Yellow 51, 54, 76;

[0135] CI Disperse Violet 26, 27;

[0136] CI disperse blue 1, 14, 56, 6; 0 and other CI disperse dyes;

[0137] CI Basic Red 1, 10;

[0138] 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;

[0139] CI Basic Violet 2;

[0140] CI Basic Red 9;

[0141] CI Basic Green 1; and other CI basic dyes;

[0142] CI Active Yellow 2, 76, 116;

[0143] CI Active Orange 16;

[0144] CI Reactive Red 36; and other CI reactive dyes;

[0145] CI mediator yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0146] CI-mediated redness 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;

[0147] CI-mediated orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0148] CI Mordant Purple 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;

[0149] 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;

[0150] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; and other CI mordant dyes;

[0151] CI Reduced Green 1; and other CI reduced dyes, etc.

[0152] These dyes can be selected appropriately based on the spectroscopic spectrum of the desired optical filter.

[0153] As a pigment (A2), well-known pigments can be used; for example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists) can be cited. Additionally, based on chemical structure, azo pigments, cyanine pigments, triphenylmethane pigments, xanthannaquinone pigments, anthraquinone pigments, naphthoquinone pigments, quinone imine pigments, methine pigments, azomethyl alkali pigments, and squaric acid pigments can be cited. Pigments include acrylidine-based pigments, styrene-based pigments, coumarin-based pigments, quinoline-based pigments, nitro-based pigments, phthalocyanine-based pigments, perylene-based pigments, quinoline-based pigments, and isoindoline-based pigments. Among these, phthalocyanine-based pigments, quinoline-based pigments, and isoindoline-based pigments are preferred.

[0154] As pigments classified as pigments, examples include CI pigments yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, and 231.

[0155] CI pigments include orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, and other orange pigments;

[0156] CI pigments include red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291, and other red pigments;

[0157] CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

[0158] CI pigments include purple 1, 19, 23, 29, 32, 36, 38, and other purple pigments;

[0159] CI pigments include green 7, 36, 58, 59, 62, and 63, among other green pigments.

[0160] CI pigments, such as brown 23 and 25, are tea-colored pigments.

[0161] CI pigments include black 1, 7, 31, 32, and other black pigments; etc.

[0162] These pigments can be selected appropriately based on the spectroscopic spectrum of the desired optical filter.

[0163] The content of compound (II) in the total amount of colorant is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0164] When a coloring-curing resin composition contains a solvent (E), a liquid containing the colorant (A) and the solvent (E) can be prepared in advance, and the coloring-curing resin composition can be prepared using this liquid. When the colorant (A) is not soluble in the solvent (E), for example, when the colorant (A) contains a pigment (A2), the liquid containing the colorant can be prepared by dispersing the colorant (A) in the solvent (E) and mixing. The liquid containing the colorant may contain part or all of the solvent (E) contained in the coloring-curing resin composition.

[0165] The content of solid components in the liquid containing colorant is less than 100% by mass relative to the total amount of liquid containing colorant, preferably 1% to 80% by mass, more preferably 2% to 70% by mass, and even more preferably 5% to 65% by mass.

[0166] The content of colorant (A) in the liquid containing colorant is less than 100% by mass relative to the total amount of solid components in the liquid containing colorant, preferably 0.5% to 80% by mass, more preferably 1% to 70% by mass, and even more preferably 2.5% to 65% by mass.

[0167] The colorant (A) can be subjected to various treatments as needed, such as rosin treatment, surface treatment using derivatives with introduced acidic or basic groups, grafting treatment of the surface of the colorant (A) using polymeric compounds, micronization treatment based on sulfuric acid micronization, salt milling, etc., cleaning treatment based on organic solvents, water, etc. to remove impurities, and removal treatment based on ion exchange, etc., for ionic impurities. Preferably, the particle size of the colorant (A) is substantially uniform.

[0168] Colorant (A) can be dispersed in a solution by containing a dispersant and undergoing dispersion treatment. When two or more colorants (A) are used in combination, they can be dispersed individually or mixed together for dispersion treatment.

[0169] As dispersants, examples include surfactants, which can be cationic, anionic, nonionic, or amphoteric surfactants. Specifically, examples include polyester-based, polyamine-based, and acrylic surfactants. These dispersants can be used alone or in combination of two or more. Examples of dispersants by trade name include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Corporation), AJISPER (registered trademark) (manufactured by Ajinomoto Fine Chemicals Co., Ltd.), and Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.). Additionally, the resin (B) described later can also be used as a dispersant.

[0170] When using a dispersant, the amount of the dispersant (solid component) used is typically 1 to 10,000 parts by mass relative to 100 parts by mass of the colorant (A) in the liquid containing the colorant, preferably 5 to 5,000 parts by mass, more preferably 10 to 1,000 parts by mass, and even more preferably 15 to 800 parts by mass. When the amount of the dispersant used is within the above range, there is a tendency to obtain a more uniformly dispersed liquid containing the colorant (hereinafter, sometimes referred to as a colorant dispersion or pigment dispersion).

[0171] When preparing a colorant-containing liquid containing colorant (A) and solvent (E) in advance, and then using the colorant-containing liquid to prepare a color-curing resin composition, the colorant-containing liquid may pre-contain part or all, preferably part, of the resin (B) contained in the color-curing resin composition. By pre-containing resin (B), the dispersion stability of the colorant-containing liquid can be further improved.

[0172] When the liquid containing colorant contains resin (B), the content of resin (B) is 10 parts by mass to 10,000 parts by mass, preferably 20 parts by mass to 5,000 parts by mass, and more preferably 25 parts by mass to 2,500 parts by mass, relative to 100 parts by mass of colorant (A) in the liquid containing colorant.

[0173] The content of colorant (A) in the total solid components of the coloring curable resin composition is preferably 1% to 93% by mass, more preferably 10% to 91% by mass, even more preferably 15% to 89% by mass, and even more preferably 18% to 87% by mass. When the content of colorant (A) is within the above range, the color concentration is sufficient when making optical filters, and the composition contains the required amount of resin (B), thus enabling the formation of patterns with sufficient mechanical strength, which is therefore preferred.

[0174] Here, "total solids" in this specification refers to the amount obtained by removing the solvent content from the total amount of the coloring and curing resin composition. The total solids and the content of each component relative to that total solids can be determined, for example, using known analytical methods such as liquid chromatography or gas chromatography.

[0175] <Resin (B)>

[0176] The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of resin (B) include resins [K1] to [K6], and at least one selected from resins [K1] to [K6] is preferred.

[0177] Resin [K1]: A copolymer having structural units derived from at least one monomer (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)"); and structural units derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an olefinic unsaturated bond (hereinafter sometimes referred to as "(b)");

[0178] Resin [K2]: A copolymer having structural units from (a) and (b) as described above, and structural units from monomer (c) that can copolymerize with (a) (wherein, it is different from (a) and (b). (Hereinafter referred to as "(c)").);

[0179] Resin [K3]: A copolymer having the structural units from (a) and (c) described above;

[0180] Resin [K4]: is a copolymer having a structural unit obtained by adding the above (b) with the structural unit from (a) and the structural unit from (c), and is a copolymer containing the structural unit from (a) without the addition of (b);

[0181] Resin [K4']: is a copolymer having structural units obtained by adding the above (b) with the structural units from (a) and the structural units from (c), and is a copolymer that does not contain structural units from (a) to which (b) has not been added;

[0182] Resin [K5]: A copolymer having structural units obtained by adding the structural units from (a) and (b) to the structural units from (c) and the structural units from (c) (may contain structural units from (b) without addition of (a), but preferably not).

[0183] Resin [K6]: A copolymer having structural units obtained by adding the structural units from (b) to (a) and then to carboxylic anhydride, and structural units from (c).

[0184] As for (a), specifically, examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid;

[0185] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, zeaxanthin, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid.

[0186] 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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc., are bicyclic unsaturated compounds containing carboxyl groups;

[0187] Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic acid bicyclic [2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides;

[0188] Unsaturated mono[(meth)acryloyloxyethyl] esters of di- or higher polycarboxylic acids, such as mono[2-(meth)acryloyloxyethyl] ester of succinate and mono[2-(meth)acryloyloxyethyl] ester of phthalate;

[0189] Unsaturated (meth)acrylates such as α-(hydroxymethyl)(meth)acrylic acid, which contain both hydroxyl and carboxyl groups in the same molecule.

[0190] Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferred, considering both the copolymerization reactivity and the solubility of the resulting resin in alkaline aqueous solutions.

[0191] (b) is a polymeric compound having, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of an oxecyclopropane ring, an oxecyclobutane ring, and a tetrahydrofuran ring) and an olefinic unsaturated bond. (b) Preferably, it is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0192] It should be noted that in this specification, "(meth)acrylic acid" refers to at least one selected from acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0193] Examples of monomers (b) include monomers having oxetyl and olefinic unsaturated bonds (hereinafter sometimes referred to as "monomer (b1)"), monomers having oxetyl and olefinic unsaturated bonds (hereinafter sometimes referred to as "monomer (b2)"), monomers having tetrahydrofuranyl and olefinic unsaturated bonds (hereinafter sometimes referred to as "monomer (b3)"), etc.

[0194] As (b1), for example, monomers having a structure of epoxidized aliphatic unsaturated hydrocarbons in the form of straight or branched chains (b1-1) (hereinafter sometimes referred to as "(b1-1)") and monomers having a structure of epoxidized alicyclic unsaturated hydrocarbons (b1-2) (hereinafter sometimes referred to as "(b1-2)") can be cited.

[0195] Examples of (b1-1) include, for instance, 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)acrylate, glycidyl ether, β-methyl-o-vinylbenzyl glycidyl ether, β-methyl-m-vinylbenzyl glycidyl ether, β-methyl-p-vinylbenzyl glycidyl ether, β-methyl-di(glycidyl)acrylate, β-methyl-di(vinyl)benzyl glycidyl ether ... Glyceryl oxymethyl styrene, 2,4-bis(glyceryl oxymethyl)styrene, 2,5-bis(glyceryl oxymethyl)styrene, 2,6-bis(glyceryl oxymethyl)styrene, 2,3,4-tris(glyceryl oxymethyl)styrene, 2,3,5-tris(glyceryl oxymethyl)styrene, 2,3,6-tris(glyceryl oxymethyl)styrene, 3,4,5-tris(glyceryl oxymethyl)styrene, 2,4,6-tris(glyceryl oxymethyl)styrene, etc.

[0196] Examples of compounds (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), methyl 3,4-epoxycyclohexyl(meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), methyl 3,4-epoxycyclohexyl(meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0197]

[0198] In equations (BI) and (BII), R e and R f It refers to an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, wherein the hydrogen atoms in the alkyl group may be replaced by hydroxyl groups.

[0199] X e and X f Indicates a single bond, *-R g -、*-R g -O-、*-R g -S- or *-R g -NH-.

[0200] R g It represents alkyl diols with 1 to 6 carbon atoms.

[0201] * indicates a bonding site with O.

[0202] Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl.

[0203] Examples of alkyl groups in which hydrogen atoms are replaced by hydroxyl groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, and 4-hydroxybutyl.

[0204] As R e and R f Examples of preferred elements include hydrogen atoms, methyl groups, hydroxymethyl groups, 1-hydroxyethyl groups, and 2-hydroxyethyl groups; examples of more preferred elements include hydrogen atoms and methyl groups.

[0205] Examples of alkyl dimethyl groups include methylene, ethylene, propane-1,2-dimethyl, propane-1,3-dimethyl, butane-1,4-dimethyl, pentane-1,5-dimethyl, and hexane-1,6-dimethyl.

[0206] As Xe and X f Preferred examples include single bonds, methylene, ethylene, *-CH2-O- and *-CH2CH2-O-, and more preferably single bonds and *-CH2CH2-O- (* indicates the bonding site with O).

[0207] Examples of compounds represented by formula (BI) include compounds represented by any of formulas (BI-1) to (BI-15). Among these, compounds represented by formulas (BI-1), (BI-3), (BI-5), (BI-7), (BI-9), or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9), or (BI-15) are more preferred.

[0208]

[0209] Examples of compounds represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15). Among these, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9), or (BII-15) are more preferred.

[0210]

[0211] The compounds represented by formula (BI) and formula (BII) can be used individually or in combination of two or more. When the compounds represented by formula (BI) and formula (BII) are used together, their content ratio [compound represented by formula (BI): compound represented by formula (BII)] is preferably 5:95 to 95:5 on a molar basis, more preferably 20:80 to 80:20.

[0212] As (b2), monomers having oxetyl and (meth)acryloyloxy groups are more preferred. Examples of (b2) include 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, etc.

[0213] As (b3), monomers having a tetrahydrofuran group and a (meth)acryloyloxy group are more preferred. Specifically, examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

[0214] As for (b), (b1) is preferred in terms of further improving the reliability of the obtained optical filter, such as its heat resistance and reagent resistance. Furthermore, (b1-2) is more preferred in terms of excellent storage stability of the coloring and curing resin composition.

[0215] Examples of (c) include (meth)acrylate monomers, unsaturated carboxylic acid esters such as unsaturated dicarboxylic acid esters, and vinyl monomers having unsaturated aliphatic hydrocarbon rings, unsaturated heterocycles, or aromatic rings.

[0216] Examples of (meth)acrylate monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, and cyclopentyl methacrylate, which are (meth)acrylates having straight-chain or branched aliphatic saturated hydrocarbon groups.

[0217] Allyl methacrylate, propargyl methacrylate, and other (meth)acrylates containing straight-chain or branched aliphatic unsaturated hydrocarbon groups;

[0218] Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0] 2，6 Decane-8-yl (meth)acrylate (in this technical field, it is commonly referred to as "(meth)acrylate dicyclopentyl ester". In addition, it is sometimes called "(meth)acrylate tricyclodecyl ester"), isobornyl (meth)acrylate, adamantyl (meth)acrylate, and other (meth)acrylates with cyclic saturated hydrocarbon groups;

[0219] Three Rings [5.2.1.0] 2，6 Decen-8-yl(meth)acrylate (in this technical field, it is commonly referred to as "(meth)acrylate dicyclopentenyl)acrylate"), dicyclopentoxyethyl(meth)acrylate, and other (meth)acrylates having cyclic unsaturated aliphatic hydrocarbon groups;

[0220] (Meth)acrylates such as phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, and phenoxybenzyl methacrylate have aromatic rings.

[0221] (Meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0222] Examples of unsaturated dicarboxylic acid esters include diethyl maleate, diethyl fumarate, and diethyl itaconic acid.

[0223] Among these unsaturated carboxylic acid esters, methyl methacrylate and 2-ethylhexyl acrylate are preferred. 1－10 Alkyl (meth)acrylates; tricyclic [5.2.1.0] 2，6 [Decan-8-yl(meth)acrylates and other (meth)acrylates with cyclic saturated hydrocarbon groups; tricyclic [5.2.1.0] 2，6 [Decene-8-yl(meth)acrylate and other (meth)acrylates with cyclic unsaturated aliphatic hydrocarbon groups; benzyl (meth)acrylate, phenoxybenzyl (meth)acrylate and other (meth)acrylates with aromatic rings, etc.]

[0224] Examples of vinyl monomers with unsaturated aliphatic hydrocarbon rings include bicyclo[2.2.1]hept-2-ene (or 2-norbornene), 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, 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, and 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene. .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- Bicyclic unsaturated compounds such as tert-butoxycarbonylbicyclo[2.2.1]hept-2-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.

[0225] Examples of dicarbonyl imide derivatives that are vinyl monomers with unsaturated heterocycles include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, and N-(9-acridyl)maleimide.

[0226] Examples of vinyl monomers with aromatic rings include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene.

[0227] Other vinyl monomers include: acrylonitrile, methacrylonitrile and other nitrile monomers; vinyl chloride, vinylidene chloride and other halogen-containing monomers; acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0228] Among these vinyl monomers, from the perspective of copolymerization reactivity and heat resistance, styrene-based monomers such as styrene and vinyltoluene, dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide, and bicyclic unsaturated compounds such as bicyclic [2.2.1]hept-2-ene (or 2-norbornene) are preferred.

[0229] The structural unit obtained by adding (b) to a structural unit from (a) refers to a unit formed by adding (b) to a structural unit from (a) constituting the main chain of the copolymer, and having a side-chain unsaturated group from (b). In this structural unit, (a) can be any of the examples described above, and (b) can also be any of the examples described above. As (a), unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred. As (b), a monomer (b1) having an oxacyclopropyl and olefinic unsaturated bond is preferred, and a monomer (b1-1) having a structure obtained by epoxidation of a straight-chain or branched aliphatic unsaturated hydrocarbon is more preferred.

[0230] The structural unit obtained by adding (a) to a structural unit from (b) refers to a unit formed by adding (a) to a structural unit from (b) constituting the main chain of the copolymer, and having a side-chain unsaturated group from (a). In this structural unit, (b) can be any of the examples described above, and (a) can also be any of the examples described above. As (b), a monomer (b1) having an oxacyclopropyl and olefinic unsaturated bond is preferred, and a monomer (b1-1) having a structure obtained by epoxidation of a straight-chain or branched aliphatic unsaturated hydrocarbon is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0231] The structural unit obtained by adding (a) to a structural unit from (b), and then to a carboxylic anhydride, refers to a structural unit synthesized by adding (a) to a structural unit from (b) that is bonded to the main chain of the copolymer, resulting in the half-esterification of a hydroxyl group with a carboxylic anhydride, and having a side-chain carboxyl group from the carboxylic anhydride and a side-chain unsaturated group from (a). In this structural unit, (b) can be any of the examples described above, and (a) can also be any of the examples described above. As (b), a monomer (b1) having an oxacyclopropyl and olefinic unsaturated bond is preferred, and a monomer (b1-1) having a structure obtained by epoxidation of a straight-chain or branched aliphatic unsaturated hydrocarbon is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0232] Examples of carboxylic anhydrides include saturated aliphatic polycarboxylic anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxylic bicyclic [2.2.1]hept-2-ene anhydride.

[0233] In resin [K1], the ratio of structural units from each unit is preferably 2 to 60 mol% from structural units from (a) and 40 to 98 mol% from structural units from (b) among all structural units constituting resin [K1], more preferably 10 to 50 mol% from structural units from (a) and 50 to 90 mol% from structural units from (b).

[0234] In addition, it is preferable that the structure does not actually contain any structural units from (c).

[0235] The total of the structural units from (a) and the structural units from (b) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all structural units constituting resin [K1].

[0236] When the ratio of the structural units of resin [K1] is within the above range, there is a tendency for the color curable resin composition to have excellent storage stability, developability when forming a color pattern, and solvent resistance of the resulting optical filter.

[0237] The resin [K1] can be manufactured, for example, by referring to the method described in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Dojin, 1st Edition, 1st Printing, March 1, 1972) and the references described in that document.

[0238] Specifically, the following method can be used: A specified amount of (a) and (b), the polymerization initiator, and the solvent are loaded into a reaction vessel. For example, a deoxygenated atmosphere is created by replacing oxygen with nitrogen. The mixture is stirred while being heated and kept at a constant temperature. It should be noted that the polymerization initiator and solvent used herein are not particularly limited; commonly used polymerization initiators and solvents in this field can be used. For example, as polymerization initiators, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) and organic peroxides (benzoyl peroxide, etc.). As solvents, any solvent capable of dissolving the monomers is acceptable; examples include solvents described later as solvent (E) for the coloring and curing resin composition of the present invention.

[0239] It should be noted that the obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or from a substance extracted in solid (powder) form by methods such as reprecipitation. In particular, by using the solvent contained in the coloring and curing resin composition of the present invention as a solvent during the polymerization, the reaction solution can be directly used to prepare the coloring and curing resin composition of the present invention, thus simplifying the manufacturing process of the coloring and curing resin composition of the present invention.

[0240] In resin [K2], the ratio of structural units from each unit is preferably 1-70 mol% from (a), 1-60 mol% from (b), and 20-95 mol% from (c) among all structural units constituting resin [K2]. More preferably, the ratio is 3-50 mol% from (a), 3-40 mol% from (b), and 30-90 mol% from (c). Even more preferably, the ratio is 5-40 mol% from (a), 5-30 mol% from (b), and 40-80 mol% from (c).

[0241] The total of the structural units from (a), (b), and (c) constitutes, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% of all structural units constituting resin [K2].

[0242] When the ratio of the structural units of resin [K2] is within the above range, there is a tendency for the color curable resin composition to have excellent storage stability, developability when forming color patterns, and excellent solvent resistance, heat resistance and mechanical strength of the obtained optical filter.

[0243] In resin [K2], (a) unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred. As (b), monomers having oxetine propyl and olefinic unsaturated bonds (b1) are preferred, and monomers having an alicyclic unsaturated hydrocarbon epoxidized structure (b1-2) are more preferred. As (c), (meth)acrylates having cyclic unsaturated aliphatic hydrocarbon groups, (meth)acrylates having aromatic rings, and dicarbonylimide derivatives are preferred.

[0244] Resin [K2] can be manufactured, for example, in the same manner as the method described in the manufacturing method of resin [K1].

[0245] In resin [K3], the ratio of structural units from each unit is preferably 2 to 60 mol% from (a) and 40 to 98 mol% from (c) among all structural units constituting resin [K3]. More preferably, the ratio is 10 to 50 mol% from (a) and 50 to 90 mol% from (c). Even more preferably, the ratio is 35 to 45 mol% from (a) and 55 to 65 mol% from (c).

[0246] In addition, it is preferable that the structure does not actually contain any structural units from (b).

[0247] The total of the structural units from (a) and the structural units from (c) in all structural units constituting resin [K3] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0248] In resin [K3], (a) unsaturated monocarboxylic acids such as (meth)acrylic acid are preferred. (c) (meth)acrylates having an aromatic ring are preferred.

[0249] Resin [K3] can be manufactured, for example, in the same manner as the method described in the manufacturing method of resin [K1].

[0250] In resin [K4], the ratio of structural units from each unit is preferably 1 to 60 mol% of structural units from (a) (unadded (b)), 1 to 50 mol% of structural units obtained by adding (b) to structural units from (a), and 30 to 90 mol% of structural units from (c). More preferably, the ratio is 5 to 50 mol% of structural units from (a) (unadded (b)), 5 to 40 mol% of structural units obtained by adding (b) to structural units from (a), and 35 to 80 mol% of structural units from (c). Even more preferably, the ratio is 10 to 40 mol% of structural units from (a) (unadded (b)), 10 to 25 mol% of structural units obtained by adding (b) to structural units from (a), and 40 to 75 mol% of structural units from (c).

[0251] The total of the structural units from (a) (without addition (b)), the structural units obtained by adding (b) and the structural units from (a), and the structural units from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all structural units constituting resin [K4].

[0252] As the structural unit from (a) (without addition (b)), it is preferably a structural unit from an unsaturated monocarboxylic acid such as (meth)acrylic acid. As the structural unit obtained by adding (b) to the structural unit from (a), it is preferably a structural unit obtained by adding the structural unit from an unsaturated monocarboxylic acid such as (meth)acrylic acid to a monomer (b1-1) having a structure of linear or branched aliphatic unsaturated hydrocarbons that have been epoxidized. As the structural unit from (c), it is preferably one or more selected from (meth)acrylates having linear or branched aliphatic saturated hydrocarbon groups, (meth)acrylates having cyclic saturated hydrocarbon groups, (meth)acrylates having aromatic rings, bicyclic unsaturated compounds, and styrene monomers, more preferably two or more. When (c) has two constituent units from (c), (c) is preferably selected from two unsaturated carboxylic acid esters such as (meth)acrylates, (meth)acrylates having cyclic saturated hydrocarbon groups, and (meth)acrylates having aromatic rings, and preferably selected from two or more vinyl monomers such as bicyclic unsaturated compounds and styrene monomers.

[0253] The resin [K4] can be manufactured by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic anhydride in (a).

[0254] First, the copolymer of (a) and (c) is manufactured in the same manner as described in the method for manufacturing resin [K1]. In this case, the ratio of structural units from each unit is preferably the same as the ratio mentioned in resin [K3].

[0255] Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride from (a) in the copolymer described above.

[0256] Following the production of the copolymer of (a) and (c), the atmosphere inside the flask is replaced with air instead of nitrogen, and (b), a reaction catalyst (e.g., tris(dimethylaminomethyl)phenol) and a polymerization inhibitor (e.g., hydroquinone) are placed inside the flask. The reaction is carried out, for example, at 60–130°C for 1–10 hours, thereby producing resin [K4].

[0257] The amount of (b) used relative to 100 moles of (a) is preferably 5 to 80 moles, more preferably 10 to 75 moles. By setting it within this range, there is a tendency for the color-curing resin composition to achieve a good balance in terms of storage stability, developability when forming a pattern, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern.

[0258] The amount of the above-mentioned reaction catalyst used is preferably 0.001 to 5 parts by mass relative to the total mass of (a), (b), and (c) 100 parts by mass. The amount of the above-mentioned polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to the total mass of (a), (b), and (c) 100 parts by mass.

[0259] The reaction conditions, such as the feeding method, reaction temperature, and time, can be appropriately adjusted taking into account the manufacturing equipment and the calorific value of polymerization. It should be noted that the feeding method and reaction temperature can be appropriately adjusted, similarly to the polymerization conditions, taking into account the manufacturing equipment and the calorific value of polymerization.

[0260] In resin [K4'], the ratio of structural units from each unit is preferably 5 to 95 mol% of the structural units obtained by adding structural units from (a) to (b), and 5 to 95 mol% of the structural units from (c), more preferably 15 to 90 mol% of the structural units obtained by adding structural units from (a) to (b), and 10 to 85 mol% of the structural units from (c), and even more preferably 20 to 80 mol% of the structural units obtained by adding structural units from (a) to (b), and 20 to 80 mol% of the structural units from (c).

[0261] In addition, it does not actually contain structural units from (a) and is a structural unit without addition (b).

[0262] The total of the structural units obtained by adding (b) to the structural units from (a) and the structural units from (c) in all structural units constituting resin [K5'] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0263] As the structural unit obtained by adding (b) to the structural unit from (a), it is preferable to obtain the structural unit obtained by adding a structural unit from an unsaturated monocarboxylic acid such as (meth)acrylic acid to a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized. As the structural unit from (c), it is preferably selected from one or more of (meth)acrylates having a straight-chain or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, more preferably two or more.

[0264] The resin [K4'] can be manufactured according to the above-described method for manufacturing resin [K4], and the amount of (b) used is preferably 100 moles relative to 100 moles of (a).

[0265] In resin [K5], the ratio of structural units from each unit is preferably 0 to 30 mol% of structural units from (b) (unadded (a)), 5 to 95 mol% of structural units obtained by adding (a) and structural units from (b), and 5 to 95 mol% of structural units from (c). More preferably, the ratio of structural units from (b) (unadded (a)) is 0 to 10 mol%, 15 to 90 mol% of structural units obtained by adding (a) and structural units from (b), and 10 to 85 mol% of structural units from (c). Even more preferably, the ratio of structural units from (b) (unadded (a)) is 0 to 5 mol%, 20 to 80 mol% of structural units obtained by adding (a) and structural units from (b), and 20 to 80 mol% of structural units from (c).

[0266] The total of the structural units from (b) (without addition to (a)), the structural units obtained by adding (a) to the structural units from (b), and the structural units from (c) is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol% in all structural units constituting resin [K5].

[0267] As the structural unit from (b) (without addition (a)), it is preferably a structural unit from a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized. As the structural unit obtained by adding (a) to a structural unit from (b), it is preferably a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to a structural unit from a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized. As the structural unit from (c), it is preferably one or more selected from (meth)acrylates having a straight-chain or branched aliphatic saturated hydrocarbon group and (meth)acrylates having a cyclic saturated hydrocarbon group, more preferably two or more.

[0268] For resin [K5], as a first stage, the same method as for manufacturing resin [K1] described above is used to obtain copolymers (b) and (c). Similarly, for the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance extracted in solid (powder) form using methods such as reprecipitation can be used.

[0269] The ratio of structural units from (b) and (c) relative to the total molar number of all structural units constituting the copolymer is preferably 5-95 mol% from (b) and 5-95 mol% from (c), more preferably 10-90 mol% from (b) and 10-90 mol% from (c).

[0270] Furthermore, under the same conditions as the manufacturing method of resin [K4] or resin [K4'], the carboxylic acid or carboxylic anhydride contained in (a) is reacted with the cyclic ether from (b) contained in the copolymer of (b) and (c), thereby obtaining resin [K5].

[0271] The amount of (a) reacting with the above copolymer is preferably 5 to 100 moles relative to 100 moles of (b). Since cyclic ethers are highly reactive, unreacted (b) is less likely to remain. Therefore, (b1) is preferred as (b) used in resin [K5], and (b1-1) is even more preferred.

[0272] In resin [K6], the ratio of structural units from each unit is preferably 0-30 mol% for structural units from (b) (unadded (a)), 20-85 mol% for structural units obtained by adding (a) to structural units from (b) (unadded carboxylic anhydride), 2-40 mol% for structural units obtained by adding (a) to structural units from (b) and then to carboxylic anhydride, and 10-60 mol% for structural units from (c). More preferably, the ratio of structural units from (b) (unadded (a)) to structural units obtained by adding (a) to structural units from (b) is 0-10 mol%. The structural unit (unadded carboxylic anhydride) is 40-80 mol%, the structural unit obtained by adding (a) to the structural unit from (b) and then to the carboxylic anhydride is 3-30 mol%, the structural unit from (c) is 15-50 mol%, and more preferably the structural unit (unadded (a)) from (b) is 0-5 mol%, the structural unit (unadded carboxylic anhydride) obtained by adding (a) to the structural unit from (b) is 50-70 mol%, the structural unit obtained by adding (a) to the structural unit from (b) and then to the carboxylic anhydride is 5-20 mol%, and the structural unit from (c) is 20-40 mol%.

[0273] The total of the structural units from (b) (unadded to (a)), the structural units obtained by adding (a) to the structural units from (b) (unadded carboxylic anhydride), the structural units obtained by adding (a) to the structural units from (b) and then to the carboxylic anhydride, and the structural units from (c) in all structural units constituting resin [K6] is, for example, 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 100 mol%.

[0274] As a structural unit from (b) (without addition (a)), a structural unit from a monomer (b1-1) having a structure of a straight-chain or branched aliphatic unsaturated hydrocarbon that has been epoxidized is preferred. As a structural unit obtained by adding (a) to a structural unit from (b) (without addition carboxylic anhydride), a structural unit obtained by adding an unsaturated monocarboxylic acid such as (meth)acrylic acid to a structural unit from a monomer (b1-1) having a structure of a straight-chain or branched aliphatic unsaturated hydrocarbon that has been epoxidized is preferred. As a structural unit obtained by adding (a) to a structural unit from (b) and then to a carboxylic anhydride, a structural unit obtained by adding a structural unit from a monomer (b1-1) having a structure of a straight-chain or branched aliphatic unsaturated hydrocarbon that has been epoxidized to an unsaturated monocarboxylic acid such as (meth)acrylic acid and then to a saturated aliphatic polycarboxylic anhydride such as succinic anhydride is preferred. As the structural unit from (c), it is preferably selected from one or more of (meth)acrylates having straight-chain or branched aliphatic saturated hydrocarbon groups and (meth)acrylates having cyclic saturated hydrocarbon groups, more preferably two or more.

[0275] For resin [K6], as a first stage, the same method as for manufacturing resin [K1] described above is used to obtain copolymers (b) and (c). Similarly, for the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used, or a substance extracted in solid (powder) form using methods such as reprecipitation can be used.

[0276] The ratio of structural units from (b) and (c) relative to the total molar number of all structural units constituting the copolymer is preferably 5 to 95 mol% from (b) and 5 to 95 mol% from (c), more preferably 10 to 90 mol% from (b) and 10 to 90 mol% from (c).

[0277] Furthermore, under the same conditions as the manufacturing method of resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) is reacted with the cyclic ether from (b) contained in the copolymer of (b) and (c). The amount of (a) used is preferably 80 to 100 moles relative to (b).

[0278] The carboxylic anhydride is reacted with the hydroxyl group produced by the reaction of the above-mentioned cyclic ether with the carboxylic acid or carboxylic anhydride contained in (a).

[0279] The amount of carboxylic anhydride used relative to the amount of (a) used relative to 1 mole (in other words, 1 mole of hydroxyl group generated by using (a)) is preferably 0.05 to 1 mole, more preferably 0.10 to 0.8 moles, and even more preferably 0.13 to 0.7 moles.

[0280] As for resin (b), specifically, examples include:

[0281] 3,4-Epoxycyclohexylmethyl methacrylate / (meth)acrylate copolymer, 3,4-Epoxytricyclic methacrylate [5.2.1.0] 2,6 [K1] decyl ester / (meth)acrylic acid copolymer and other resins;

[0282] (Meth)glyceryl acrylate / (meth)benzyl acrylate / (meth)acrylic acid copolymer, (meth)glyceryl acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0] 2,6 ] Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxy tricyclic acrylate [5.2.1.0] 2,6 ] Decyl ester / (meth)acrylic acid / N-cyclohexylmaleimide / (meth)acrylic acid tricyclic [5.2.1.0] 2,6 ] Decene-8-yl ester copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0] 2,6 ] Decyl acrylate / (meth)acrylate / (meth)acrylate benzyl acrylate copolymer, 3,4-epoxy tricyclic acrylic acid [5.2.1.0] 2,6 Resins such as decyl ester / (meth)acrylic acid / (meth)acrylic acid phenoxybenzyl ester copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer [K2];

[0283] Resins such as benzyl methacrylate / methacrylic acid copolymer and styrene / methacrylic acid copolymer [K3];

[0284] Resins obtained by adding a portion of the carboxylic acid group of (meth)acrylate and benzyl (meth)acrylate / (meth)acrylate copolymer, resins obtained by adding a portion of the carboxylic acid group of (meth)acrylate and tricyclodecyl (meth)acrylate / styrene / (meth)acrylate copolymer, resins obtained by adding a portion of the carboxylic acid group of (meth)acrylate and tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylate copolymer, resins obtained by adding a portion of the carboxylic acid group of (meth)acrylate and norbornene / vinyltoluene / (meth)acrylate copolymer, resins obtained by adding a portion of the carboxylic acid group of (meth)acrylate and norbornene / styrene / (meth)acrylate copolymer, etc. [K4];

[0285] Resins such as [K4'] obtained by reacting glyceryl methacrylate with a copolymer of tricyclodecyl methacrylate / methacrylic acid, and resins obtained by reacting glyceryl methacrylate with a copolymer of tricyclodecyl methacrylate / styrene / methacrylic acid.

[0286] Resins obtained by reacting a copolymer of (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester / (meth)acrylic acid glyceryl ester, and resins obtained by reacting a copolymer of (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester / styrene / (meth)acrylic acid glyceryl ester, etc. [K5];

[0287] The resin obtained by reacting a copolymer of (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester / (meth)acrylic acid glyceryl ester with tetrahydrophthalic anhydride, the resin obtained by reacting a copolymer of (meth)acrylic acid and (meth)acrylic acid 2-ethylhexyl ester / (meth)acrylic acid tricyclodecyl ester / (meth)acrylic acid glyceryl ester with succinic anhydride, the resin obtained by reacting a copolymer of (meth)acrylic acid and (meth)acrylic acid methyl ester / (meth)acrylic acid 2-ethylhexyl ester / (meth)acrylic acid tricyclodecyl ester / (meth)acrylic acid glyceryl ester with succinic anhydride, and the resin obtained by reacting a copolymer of (meth)acrylic acid and (meth)acrylic acid methyl ester / (meth)acrylic acid 2-ethylhexyl ester / (meth)acrylic acid tricyclodecyl ester / (meth)acrylic acid glyceryl ester with succinic anhydride, etc. [K6]

[0288] Resins [K1] to [K6] can be one type or a combination of two or more types. Preferred combinations include, for example, a combination of resins [K2] and [K6]. When resins [K2] and [K6] are combined, the amount of resin [K2] relative to a total of 100 parts by weight of resins [K2] and [K6] is, for example, 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight.

[0289] The weight-average molecular weight of the polystyrene-converted 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, there is a trend of increased hardness of the optical filter, high residual film rate, good solubility of the unexposed portion in the developer, and improved resolution of the colored pattern.

[0290] The dispersion of resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6, more preferably 1.2 to 4.

[0291] The acid value of resin (B), converted from solid content, is preferably 20 to 170 mg-KOH / g, more preferably 25 to 150 mg-KOH / g, and even more preferably 30 to 135 mg-KOH / g. Here, the acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1g of resin (B), and can be obtained, for example, by titration using an aqueous solution of potassium hydroxide.

[0292] The content of resin (B) relative to the total amount of solid components is preferably 2 to 65% by mass, more preferably 3 to 60% by mass, and even more preferably 5 to 55% by mass. When the content of resin (B) is within the above range, a colored pattern can be formed, and there is a trend of increasing the resolution of the colored pattern and the residual film rate.

[0293] <Polymerizing Compound (C)>

[0294] The polymerizable compound (C) is a compound that can be polymerized by active free radicals and / or acids generated by a polymerization initiator (D). Examples include compounds with polymerizable olefinic unsaturated bonds, preferably (meth)acrylate compounds.

[0295] Examples of polymeric compounds having one olefinic unsaturated bond include, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the monomers (a), (b), and (c) described above.

[0296] Examples of polymeric compounds having two olefinic unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentyl glycol di(meth)acrylate.

[0297] The polymerizable compound (C) is preferably a polymerizable compound having three or more olefinic unsaturated bonds. Examples of such polymerizable compounds include, for instance, trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylates (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylates (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylates (e.g., tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylates (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, and alkyl-oxidized pentaerythritol poly(meth)acrylates (e.g., ethoxylated pentaerythritol tri(meth)acrylate). Acrylates, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, alkyl-oxidized pentaerythritol poly(meth)acrylates (e.g., ethoxylated pentaerythritol penta(meth)acrylate, ethoxylated pentaerythritol hexa(meth)acrylate, propoxylated pentaerythritol penta(meth)acrylate, propoxylated pentaerythritol hexa(meth)acrylate), caprolactone-modified pentaerythritol poly(meth)acrylates (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified pentaerythritol poly(meth)acrylates (e.g., caprolactone-modified pentaerythritol penta(meth)acrylate, caprolactone-modified pentaerythritol hexa(meth)acrylate), etc.

[0298] Preferably, it contains at least one selected from trimethylolpropane tri(meth)acrylate and dipentaerythritol poly(meth)acrylate, more preferably, it contains at least one selected from trimethylolpropane triacrylate and dipentaerythritol polyacrylate.

[0299] The weight-average molecular weight of the polymeric compound (C) is preferably 50 to 4000, more preferably 70 to 3500, even more preferably 100 to 3000, even more preferably 150 to 2900, and particularly preferably 250 to 1500.

[0300] The content of the polymeric compound (C) relative to the total amount of solid components in the coloring and curing resin composition can be, for example, 1% to 99% by mass, preferably 3% to 90% by mass, more preferably 5% to 80% by mass, and even more preferably 7% to 70% by mass.

[0301] <Polymerization Initiator (D)>

[0302] Polymerization initiator (D) can be any compound that can generate active free radicals, acids, etc. under the action of light and heat to initiate polymerization.

[0303] Examples of polymerization initiators (D) include O-acyl oxime compounds, alkyl phenyl ketone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0304] The above-mentioned O-acyl oxime compounds are compounds having a partial structure represented by formula (d-1). In the formula, * represents a bonding site.

[0305]

[0306] Examples of the aforementioned O-acyl oxime compounds include, for instance, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetoxy-1-[9-ethyl-6-{2-methyl-4-( 3,3-Dimethyl-2,4-dioxanepentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, etc. Commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine), Irgacure OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine) (all manufactured by BASF) and N-1919 (manufactured by ADEKA) can also be used. The O-acyl oxime compound is preferably selected from N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and... At least one of N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, more preferably N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine. When these O-acyl oxime compounds are used, there is a tendency to obtain high-brightness optical filters.

[0307] The alkyl phenyl ketone compounds described above are compounds having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3). In these partial structures, the benzene ring may have substituents. In the formulas, * denotes a bonding site.

[0308]

[0309] Examples of compounds having a partial structure represented by formula (d-2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can also be used.

[0310] Examples of compounds having a partial structure represented by formula (d-3) include, for example, oligomers of 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyladimethyl ketal.

[0311] In terms of sensitivity, compounds having a partial structure represented by formula (d-2) are preferred as alkyl phenyl ketone compounds.

[0312] Examples of the aforementioned triazine compounds include, for instance, 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-piperyl-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0313] Examples of the aforementioned acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by BASF) can be used.

[0314] Examples of the aforementioned biimidazole compounds include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (e.g., see Japanese Patent Application Publication Nos. 6-75372, 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carbonylalkoxy group (e.g., see Japanese Patent Application Publication No. 7-10913, etc.). Among these, compounds represented by the following formulas and mixtures thereof are preferred.

[0315]

[0316] In addition, examples of polymerization initiators (D) include benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as methyl benzoyl peroxybenzoate, 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-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzoyl, methyl benzoylformate, and titanium dioxide compounds. These are preferably used in combination with polymerization initiators (D1) (especially amines) described later.

[0317] Examples of polymerization initiators that generate acids include, for example, 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzyl sulfonium hexafluoroantimonate, triphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, and diphenyl iodide. p-Toluenesulfonate, diphenyliodine Hexafluoroantimonates, etc. Salts, nitrobenzyl toluenesulfonates, benzoin toluenesulfonates, etc.

[0318] As a polymerization initiator (D), it is preferred to include a polymerization initiator selected from at least one of alkyl phenyl ketone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds, more preferably a polymerization initiator including O-acyl oxime compounds and / or biimidazole compounds, and even more preferably a polymerization initiator including O-acyl oxime compounds.

[0319] The content of polymerization initiator (D) relative to the total mass of resin (B) and polymerizable compound (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the content of polymerization initiator (D) is within the above range, there is a tendency to increase sensitivity and shorten the exposure time, thereby improving the productivity of optical filters.

[0320] <Polymerization Initiator (D1)>

[0321] A polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound (C) initiated by a polymerization initiator (D). When a polymerization initiator (D1) is present, it is usually used in combination with the polymerization initiator (D).

[0322] Examples of polymerization initiators (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0323] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Mischel ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, with 4,4'-bis(diethylamino)benzophenone being a preferred example. Additionally, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used as amine compounds.

[0324] Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0325] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0326] Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0327] When using these polymerization initiators (D1), their content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of all resins (B) and polymeric compounds (C) contained in the coloring and curing resin composition.

[0328] <Metal Compound (G)>

[0329] The coloring and curing resin composition of the present invention contains a metal compound (G), which includes one or both of a compound represented by formula (GI) (hereinafter sometimes referred to as "compound (GI)") or a compound represented by formula (GII) (hereinafter sometimes referred to as "compound (GII)"). When compound (GI) or compound (GII) is contained, absorbance at the maximum absorption wavelength after irradiation of the colorant (preferably compound (II)) is maintained.

[0330]

[0331] In formulas (GI) and (GII), M A , and M B Each of them independently represents a Group 11 metal atom.

[0332] R A1 ~R A4 , and R B1 ~R B6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms.

[0333] R C This refers to a hydrocarbon group with 1 to 20 divalent carbon atoms.

[0334] R D This indicates a hydrocarbon group connecting pyridine ring A and pyridine ring B, and R D The pyridine ring A and / or pyridine ring B can be bonded by single bonds, R D In the case of a ring structure portion, the ring structure portion and pyridine ring A and / or pyridine ring B can be bonded together by ring condensation.

[0335] X A and X B Each independently represents a halogen atom, hydroxyl group, and OR. ENHR E 、or N(R) E 2. There are multiple X's. A and X B They can be different from each other.

[0336] R E Represents hydrocarbon groups with 1 to 10 carbon atoms and two R groups. E At that time, R E They can be different from each other. n and m are each independently 1 or 2.

[0337] M A Between N and M B The dashed lines between N and N represent coordinate bonds.

[0338] As R A1 ~R A4 R B1 ~R B6 and R E The hydrocarbon group represented by carbon atoms of 1 to 10 can be exemplified by aliphatic hydrocarbon groups of 1 to 10 carbon atoms or aromatic hydrocarbon groups of 6 to 10 carbon atoms.

[0339] The aliphatic hydrocarbon group having 1 to 10 carbon atoms can be either saturated or unsaturated, preferably saturated. Furthermore, the aliphatic hydrocarbon group having 1 to 10 carbon atoms can be any of straight-chain, branched, or cyclic, preferably straight-chain or branched.

[0340] Examples of straight-chain or branched aliphatic hydrocarbons with 1 to 10 carbon atoms include straight-chain aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, vinyl, 1-propenyl, and 2-propenyl (allyl); and branched aliphatic hydrocarbon groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl. The aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 4.

[0341] The cyclic aliphatic hydrocarbon group can be monocyclic or polycyclic. Examples of such cyclic aliphatic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 8, more preferably 3 to 6.

[0342] Examples of aromatic hydrocarbon groups with 6 to 10 carbon atoms include phenyl, xylyl, trimethylphenyl, and naphthyl. More preferably, the aromatic hydrocarbon group has 6 to 15 carbon atoms, even more preferably 6 to 12, and still more preferably 6 to 9.

[0343] R A1 ~R A4 R B1 ~R B6 and R EThe hydrocarbon group with 1 to 10 carbon atoms may have substituents, such as carboxyl groups; halogen atoms such as fluorine, chlorine, and iodine; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; hydroxyl groups; aminosulfonyl groups; alkoxycarbonyl groups with 1 to 10 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; etc.

[0344] As R C Examples of divalent hydrocarbon groups representing 1 to 20 carbon atoms that make the above R A1 ~R A4 R B1 ~R B6 and R E The group represented by the substituent (which may be a hydrocarbon group with 11 to 20 carbon atoms) contains one hydrogen atom as a bonding site, preferably R. C It also makes R A1 ~R A4 R B1 ~R B6 and R E The preferred hydrocarbon group represents a group in which one hydrogen atom serves as the bonding site. As R C Preferably, it is a divalent aliphatic hydrocarbon group with 1 to 15 carbon atoms, more preferably a divalent aliphatic hydrocarbon group with 1 to 10 carbon atoms, and even more preferably an alkylene group with 1 to 6 carbon atoms.

[0345] As R D The hydrocarbon group represented includes divalent hydrocarbon groups with 1 to 20 carbon atoms; for example, R... C The divalent hydrocarbon group is represented. Additionally, in R... D When the represented hydrocarbon group has a cyclic structure portion, this cyclic structure portion can be bonded to pyridine ring A and / or pyridine ring B through ring condensation. As R having the above-mentioned cyclic structure portion... D The structure formed by bonding pyridine ring A and pyridine ring B in the form of a condensed ring can be exemplified by the following structure.

[0346]

[0347] M A and M B The group 11 metal atoms represented are copper atoms, silver atoms, and gold atoms, preferably copper atoms and silver atoms, and more preferably copper atoms.

[0348] X A and X B The halogen atom represented is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

[0349] As compound (GI), the compound represented by formula (GIa) is preferred, and as compound (GII), the compound represented by formula (GIIa) is preferred.

[0350]

[0351] In equations (GIa) and (GIIa), M Aa and M Ba They represent copper atoms,

[0352] R A1a ~R A4a and R B1a ~R B6a Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms.

[0353] R Ca This indicates a straight-chain aliphatic hydrocarbon group with 1 to 6 divalent carbon atoms.

[0354] R Da For groups that, together with pyridine ring A and pyridine ring B, form a condensed ring structure represented by formula (GIIIa), (GIIIb), or (GIIIc),

[0355] X Aa and X Ba Each halogen atom represents itself independently.

[0356] na and ma are each independently 1 or 2.

[0357] M Aa Between N and M Ba The dashed lines between N and N represent coordinate bonds.

[0358]

[0359] Examples of compounds represented by formula (GIa) include compounds (GII-1) to (GII-36) in which each group in formula (GIa) is a combination shown in Tables 1 and 2. Examples of compounds represented by formula (GIIa) include compounds (GII-1) to (GII-12) in which each group in formula (GIIa) is a combination shown in Table 3.

[0360] [Table 1]

[0361] Table 1

[0362] compound na <![CDATA[X Aa ]]> <![CDATA[R A1a 、R A3a ]]> <![CDATA[R A2a 、R A4a ]]> <![CDATA[R Ca ]]> GI-1 1 Cl H H <![CDATA[-CH2CH2-]]> GI-2 1 Br H H <![CDATA[-CH2CH2-]]> GI-3 1 Cl H <![CDATA[CH3]]> <![CDATA[-CH2CH2-]]> GI-4 1 Br H <![CDATA[CH3]]> <![CDATA[-CH2CH2-]]> GI-5 1 Cl H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2-]]> GI-6 1 Br H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2-]]> GI-7 1 Cl H H <![CDATA[-CH2CH2CH2-]]> GI-8 1 Br H H <![CDATA[-CH2CH2CH2-]]> GI-9 1 Cl H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-10 1 Br H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-11 1 Cl H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-12 1 Br H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-13 1 Cl H H <![CDATA[-CH2CH2CH2CH2-]]> GI-14 1 Br H H <![CDATA[-CH2CH2CH2CH2-]]> GI-15 1 Cl H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2CH2-]]> GI-16 1 Br H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2CH2-]]> GI-17 1 Cl H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2CH2-]]> GI-18 1 Br H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2CH2-]]>

[0363] [Table 2]

[0364] Table 2

[0365] compound na <![CDATA[X Aa ]]> <![CDATA[R A1a 、R A3a ]]> <![CDATA[R A2a 、R A4a ]]> <![CDATA[R Ca <!-- 32 -->]]> GI-19 2 Cl H H <![CDATA[-CH2CH2-]]> GI-20 2 Br H H <![CDATA[-CH2CH2-]]> GI-21 2 Cl H <![CDATA[CH3]]> <![CDATA[-CH2CH2-]]> GI-22 2 Br H <![CDATA[CH3]]> <![CDATA[-CH2CH2-]]> GI-23 2 Cl H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2-]]> GI-24 2 Br H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2-]]> GI-25 2 Cl H H <![CDATA[-CH2CH2CH2-]]> GI-26 2 Br H H <![CDATA[-CH2CH2CH2-]]> GI-27 2 Cl H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-28 2 Br H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-29 2 Cl H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-30 2 Br H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2-]]> GI-31 2 Cl H H <![CDATA[-CH2CH2CH2CH2-]]> GI-32 2 Br H H <![CDATA[-CH2CH2CH2CH2-]]> GI-33 2 Cl H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2CH2-]]> GI-34 2 Br H <![CDATA[CH3]]> <![CDATA[-CH2CH2CH2CH2-]]> GI-35 2 Cl H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2CH2-]]> GI-36 2 Br H <![CDATA[CH2CH3]]> <![CDATA[-CH2CH2CH2CH2-]]>

[0366] [Table 3]

[0367] Table 3

[0368] compound ma <![CDATA[X Ba ]]> <![CDATA[R B1a ~R B6a ]]> <![CDATA[R Da Fused ring structure formed with pyridine rings A and B]]> GII-1 1 Cl H GIIIa GII-2 1 Br H GIIIa GII-3 1 Cl H GIIIb GII-4 1 Br H GIIIb GII-5 1 Cl H GIIIc GII-6 1 Br H GIIIc GII-7 1 Cl H GIIIa GII-8 1 Br H GIIIa GII-9 1 Cl H GIIIb GII-10 1 Br H GIIIb GII-11 1 Cl H GIIIc GII-12 1 Br H GIIIc

[0369] The content of the metal compound (G) relative to 100 parts by mass of the colorant is preferably 0.1 to 75 parts by mass, more preferably 1 to 50 parts by mass, further preferably 2 to 40 parts by mass, and even more preferably 3 to 30 parts by mass.

[0370] The content of the metal compound (G) in 100% by mass of the solids component of the coloring and curing resin composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, further preferably 1 to 15% by mass, and even more preferably 2 to 10% by mass.

[0371] Solvent (E)

[0372] The solvent (E) is not particularly limited and can be any solvent commonly used in this field. Examples of solvents (E) include ester solvents (solvents containing -COO- but not -O-), ether solvents (solvents containing -O- but not -COO-), ether ester solvents (solvents containing both -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO-), alcohol solvents (solvents containing OH- but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more of these solvents may be used in combination.

[0373] Examples of ester solvents include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0374] Examples of ether solvents 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, and 1,4-di(ethylene glycol monomethyl ether). Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole, etc.

[0375] Examples of 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-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, 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, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0376] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0377] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0378] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0379] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0380] As solvent (E), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and cyclohexanone are preferred, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferred.

[0381] When solvent (E) is present, the content of solvent (E) relative to the total amount of the color-curing resin composition is typically 99.99% by mass or less, preferably 40% to 99% by mass, more preferably 50% to 97% by mass, even more preferably 70% to 96% by mass, and even more preferably 73% to 95% by mass. In other words, the total amount of solid components in the color-curing resin composition is typically 0.01% by mass or more, preferably 1% to 60% by mass, more preferably 3% to 50% by mass, even more preferably 4% to 30% by mass, and even more preferably 5% to 27% by mass. When the content of solvent (E) is within the above range, there is a tendency for the flatness during coating to become better, and for the display properties to become better because the color concentration is not insufficient when forming an optical filter.

[0382] <Thiols (T)>

[0383] The coloring and curing resin composition of the present invention may contain a thiol compound (T). The thiol compound (T) is a compound having a sulfur group (-SH) in its molecule.

[0384] As a compound having one sulfanyl group within its molecule, an example is 2-sulfanyl. 2-Thiothiazole, 2-Thiobenzimidazole, 2-Thiobenzothiazole, 2-Thiobenzo[] Azole, 2-thionicotinic acid, 2-thiopyridine, 2-thiopyridine-3-ol, 2-thiopyridine-N-oxide, 4-amino-6-hydroxy-2-thiopyrimidine, 4-amino-6-hydroxy-2-thiopyrimidine, 4-amino-2-thiopyrimidine, 6-amino-5-nitroso-2-thiopyrimidine, 4,5-diamino-6-hydroxy-2-thiopyrimidine, 4,6-diamino-2-thiopyrimidine, 2,4-diamino-6-thiopyrimidine, 4,6- Dihydroxy-2-thiopyrimidine, 4,6-dimethyl-2-thiopyrimidine, 4-hydroxy-2-thio-6-methylpyrimidine, 4-hydroxy-2-thio-6-propylpyrimidine, 2-thio-4-methylpyrimidine, 2-thiopyrimidine, 2-thioureapyrimidine, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-thioimidazole, 2-thio-1-methylimidazole, 4-amino-3-hydrazino-5-thio-1,2,4- Triazole, 3-amino-5-thio-1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 3-thio-1H-1,2,4-triazole-3-thiol, 2-amino-5-thio-1,3,4-thiadiazole, 5-amino-1,3,4-thiadiazole-2-thiol, 2,5-dithio-1,3,4-thiadiazole, (furan-2-yl)methanethiol 2-Thio-5-thiazolidinone, 2-Thiothiazoline, 2-Thio-4(3H)-quinazolinone, 1-Phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-Thio-5-methylbenzimidazole, 2-Thio-5-nitrobenzimidazole, 6-Amino-2-thiobenzothiazole, 5-Chloro-2-thiobenzothiazole, 6-Ethoxy-2-thiobenzothiazole, 6-Nitro-2-thiobenzothiazole, 2-Thionaphthemidazole, 2-Thionaphthemidazole Zyridine, 3-thio-1,2,4-triazole, 4-amino-6-thiopyrazolo[2,4-d]pyridine, 2-amino-6-purine thiol, 6-thiopurine, 4-thio-1H-pyrazolo[2,4-d]pyrimidine, etc.

[0385] Examples of compounds having two or more sulfur groups in their molecules include hexanedithiol, decandithiol, 1,4-bis(methylthio)benzene, butanediol bis(3-thiopropionate), butanediol bis(3-thioacetate), ethylene glycol bis(3-thioacetate), trimethylolpropane tri(3-thioacetate), butanediol bis(3-thiopropionate), trimethylolpropane tri(3-thiopropionate), trimethylolpropane tri(3-thioacetate), pentaerythritol tetra(3-thiopropionate), pentaerythritol tetra(3-thioacetate), trihydroxyethyl tri(3-thiopropionate), pentaerythritol tetra(3-thiobutyrate), and 1,4-bis(3-thiobutoxy)butane.

[0386] The content of the thiol compound (T) relative to 100 parts by mass of the polymerization initiator (D) is preferably 0.5 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass. When the content of the thiol compound (T) is within this range, there is a tendency for the sensitivity to increase and the developability to improve.

[0387] <Leveling Agent (F)>

[0388] Examples of leveling agents (F) include silicone surfactants, fluorinated surfactants, and silicone surfactants containing fluorine atoms. They may have polymerizable groups on their side chains.

[0389] Examples of organosilicon surfactants include surfactants with intramolecular siloxane bonds. Specifically, examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

[0390] As fluorinated surfactants, examples include surfactants with intramolecular fluorocarbon chains. Specifically, examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Corporation), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, and Surflon... SC105 (manufactured by AGC Corporation) and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.), etc.

[0391] Organosilicon surfactants containing fluorine atoms include surfactants with siloxane bonds and fluorocarbon chains within their molecules. Specifically, examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0392] When leveling agent (F) is included, the content of leveling agent (F) relative to the total amount of the coloring and curing resin composition is preferably 0.0005% to 1% by mass, more preferably 0.001% to 0.5% by mass, and even more preferably 0.005% to 0.1% by mass. It should be noted that this content does not include the content of pigment dispersant. When the content of leveling agent (F) is within the above range, the flatness of the optical filter can be improved.

[0393] <Other Ingredients>

[0394] Coloring and curing resin compositions may contain fillers, other polymer compounds, adhesion promoters, quenchers, antioxidants, light stabilizers, chain transfer agents, and other additives known in the art, as needed.

[0395] Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane. 3-Mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane, etc.

[0396] <Method for manufacturing coloring and curing resin compositions>

[0397] Colored curable resin compositions can be prepared by mixing a colorant (A), a metal compound (G), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and, as needed, a polymerization initiation aid (D1), a solvent (E), a leveling agent (F), and other components. Mixing can be carried out using known or conventional apparatus and conditions.

[0398] The colorant (A) can be premixed with a portion or all of the solvent (E) and dispersed using a bead mill or similar device until the average particle size is about 0.2 μm or less, and then used in the form of a liquid containing the colorant, preferably in the form of a liquid containing the colorant. At this time, a portion or all of the dispersant and resin (B) can be added as needed. By mixing the remaining components into the liquid containing the colorant obtained in this way at a predetermined concentration, a target-colored curable resin composition can be prepared.

[0399] In addition, when the dye is used as a colorant (A), the dye can be pre-dissolved in part or all of the solvent (E) to prepare a solution. Preferably, the solution is filtered using a filter with a pore size of about 0.01 to 1 μm.

[0400] <Manufacturing Method of Optical Filters (Color Filters)>

[0401] Optical filters (color filters) can be formed from the color-curing resin composition of the present invention. Methods for manufacturing the color pattern include photolithography, inkjet printing, and printing. Photolithography is preferred. Photolithography involves coating the aforementioned color-curing resin composition onto a substrate, drying it to form a color composition layer, and then exposing and developing the color composition layer through a photomask. In photolithography, by not using a photomask and / or not performing development during exposure, a color coating film, which is a cured product of the aforementioned color composition layer, can be formed. The color pattern and color coating film thus formed constitute the optical filter (color filter) of the present invention.

[0402] The film thickness of the optical filter (color filter) is not particularly limited and can be appropriately adjusted according to the purpose, application, etc. For example, it is 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 4.5 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0403] As substrates, various types of glass can be used, including quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass with a silica-coated surface, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and substrates on which aluminum, silver, or silver / copper / palladium alloy thin films are formed. Other optical filter layers (color filter layers), resin layers, transistors, circuits, etc., can be formed on these substrates. Alternatively, substrates treated with HMDS (hexamethyldisilazane) on a silicon substrate can also be used.

[0404] The formation of individual color pixels based on photolithography can be carried out using known or conventional apparatus and conditions. For example, it can be fabricated as follows.

[0405] First, the coloring curable resin composition is coated onto a substrate and then subjected to heat drying (pre-baking) and / or vacuum drying to remove volatile components such as solvents and achieve a smooth coloring composition layer. Examples of coating methods include spin coating, slot coating, and a combination of slot and spin coating. The preferred temperature for heat drying is 30°C to 120°C, more preferably 50°C to 110°C. The preferred heating time is 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

[0406] When performing vacuum drying, it is preferable to carry out the process under a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C. The film thickness of the coloring composition layer is not particularly limited, but can be appropriately selected according to the film thickness of the target optical filter (color filter).

[0407] Next, the coloring composition layer is exposed through a photomask used to form the target coloring pattern. The pattern on the photomask is not particularly limited; a pattern appropriate for the intended use can be used. Furthermore, in order to uniformly illuminate the entire exposure surface with parallel light and to accurately align the photomask with the substrate on which the coloring composition layer is formed, exposure apparatus such as a mask aligner and a stepper is preferably used. In the case of forming a coloring coating, exposure without using a photomask is acceptable.

[0408] As the light source used in exposure, a light source that produces light with wavelengths of 250 nm to 450 nm is preferred. For example, light with wavelengths less than 350 nm can be cut off using a filter that cuts off that wavelength region, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength regions. Specifically, examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0409] The exposed coloring composition layer is developed by contacting a developing solution, thereby forming a colored coating (colored pattern) on the substrate. The unexposed portions of the coloring composition layer are dissolved in the developing solution and removed during development. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferred. 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 developing solution may contain a surfactant. The developing method can be any of the paddle method, immersion method, or spray method. Furthermore, the substrate can be tilted at any angle during development.

[0410] The substrate after development is preferably washed with water.

[0411] Preferably, the obtained colored pattern or colored coating is further subjected to post-baking. The post-baking temperature is preferably 80°C to 250°C, more preferably 100°C to 245°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 2 minutes to 30 minutes.

[0412] The resulting colored patterns and coatings are useful as optical filters (color filters).

[0413] Display devices, solid-state imaging elements

[0414] The aforementioned optical filters (color filters) are useful as optical filters (color filters) used in display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[0415] Example

[0416] The present invention will be described in more detail below with examples, but the present invention is not limited to the following examples. Of course, it can be implemented by appropriate modifications within the scope suitable for the above and following spirit, and all such modifications are included within the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" refers to "parts by mass" and "%" refers to "% by mass".

[0417] In the following examples, the structure of the compounds was determined by mass spectrometry (LC; Agilent 1200, MASS; Agilent LC / MSD6130). 1 Confirmed by H-NMR (Varian 400-MR).

[0418] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polystyrene resin were determined by GPC under the following conditions.

[0419] Device: HLC-8120GPC (manufactured by Tosoh Corporation)

[0420] Column: TSK-GELG2000HXL

[0421] Column temperature: 40℃

[0422] Solvent: Tetrahydrofuran

[0423] Flow rate: 1.0 mL / min

[0424] The concentration of solid components in the analytical sample was 0.001–0.01% by mass.

[0425] Injection volume: 50 μL

[0426] Detector: RI

[0427] Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0428] The ratio of the weight-average molecular weight to the number-average molecular weight (Mw / Mn) of the polystyrene obtained above is used as the dispersity.

[0429] <Synthesis example 1>

[0430] 40.5 parts of the compound represented by formula (II-X) and 60.5 parts of 2,6-dimethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions and stirred at 150°C for 8 hours in 200 parts of N-methylpyridinone. The resulting reaction solution was cooled to room temperature and added to a mixture of 1200 parts of water and 75 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, resulting in crystal precipitation. The precipitated crystals were collected as a residue by vacuum filtration, washed with 100 parts of methanol, and dried under reduced pressure at 60°C for 12 hours to obtain 49 parts of the compound represented by formula (II-1). The yield was 85%.

[0431]

[0432] Identification of compounds represented by formula (II-1)

[0433] (Mass spectrometry) Ionization mode = ESI+: m / z = [M+H] + 575

[0434] Exact Mass: 574

[0435] <Synthesis example 2>

[0436] A suitable amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen. 340 parts of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 80°C while stirring. Next, 57 parts of acrylic acid and 3,4-epoxytricyclic acrylic acid [5.2.1.0] were added dropwise over 5 hours. 2,6 ] Decane-8-yl ester and 3,4-epoxy tricyclic acrylate [5.2.1.0] 2 ,6 A mixture of decane-9-yl esters (containing 54 parts in a molar ratio of 1:1), 239 parts benzyl methacrylate, and 73 parts propylene glycol monomethyl ether acetate was prepared. Meanwhile, a solution was prepared by dropwise addition of 40 parts of polymerization initiator 2,2-azobis(2,4-dimethylpentanonitrile) dissolved in 197 parts propylene glycol monomethyl ether acetate over 6 hours. After the addition of the initiator solution was completed, the solution was maintained at 80°C for 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution with a viscosity of 127 mPas and a solid content of 37.0% by weight, as measured by a type B viscometer (23°C). The weight-average molecular weight (Mw) of the resulting copolymer was 9.4 × 10⁻⁶. 3 The dispersion is 1.89, and the acid value converted from solids is 114 mg-KOH / g. Resin (B-1) has the following structural units.

[0437]

[0438] <Synthesis Example 3>

[0439] 276.8 parts of propylene glycol monomethyl ether acetate were taken into a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and heated to 120°C while undergoing nitrogen purging. Then, over 2 hours, a solution containing 35.3 parts of tert-butyl peroxide (polymerization initiator) was added dropwise to the flask from a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentyl methacrylate. After the addition was complete, the mixture was stirred further at 120°C for 30 minutes to induce a copolymerization reaction, generating an addition copolymer. Then, the flask was purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst), and 0.8 parts of methylquinone (polymerization inhibitor) were added to the above-mentioned addition copolymer solution. The reaction was continued at 110°C for 10 hours. During this process, polymerizable unsaturated bonds were introduced into the polymer side chains through the reaction of epoxy groups from glycidyl methacrylate with acrylic acid, causing epoxy group cracking. Next, 24.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued at 110°C for 1 hour. This allowed the hydroxyl groups generated from the epoxy group cracking to react with the succinic anhydride, introducing carboxyl groups into the side chains, thus obtaining the polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate were added to the reaction solution to obtain a polymer (resin (B-2)) solution with a polymer solids content of 40%. The weight-average molecular weight (Mw) of the resulting copolymer (polymer; resin (B-2)) was 6.3 × 10⁻⁶. 3 The acid value calculated from the solid components is 34 mg-KOH / g.

[0440]

[0441] <Example 1>

[0442] (1) Preparation of coloring dispersion 1

[0443] 80.0 parts of compound (II-1), 29.1 parts of dispersant (BYK LPN-6919, manufactured by BYK Corporation) (solids content conversion), 29.1 parts of resin B-1 (solids content conversion), 861.8 parts of propylene glycol monomethyl ether acetate, and 1500 parts of 0.2 mm zirconia beads were mixed and shaken for 1 hour using a paint conditioner (LAU Corporation). The zirconia beads were then removed by filtration to obtain colored dispersion 1.

[0444] (2) Preparation of coloring and curing resin composition 1

[0445] Colored curable resin composition 1 is obtained by mixing the following components.

[0446] Colorant (A): 1,407.1 parts of coloring dispersion

[0447] Metal compound (G): 5.3 parts of bis(1,3-propanediamine)copper(II) dichloride.

[0448]

[0449] Resin (B): 51.8 parts of resin (B-2) obtained in Synthesis Example 3 (converted to solid content).

[0450] Polymerizable compound (C): (Dipentaerythritol polyacrylate: trade name A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (converted to solid content) 42.5 parts

[0451] Polymerization initiator (D): N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine: Trade name TR-PBG327 (manufactured by Changzhou Qiangli Electronic New Materials) 9.0 parts

[0452] Solvent (E): 484.2 parts of propylene glycol monomethyl ether acetate

[0453] Leveling agent (F): 0.1 parts of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

[0454] (3) Preparation of colored coating

[0455] The obtained colored curable resin composition 1 was coated onto a 5 cm square glass substrate (EAGLE2000; manufactured by Corning) using a spin coating method, and then pre-baked at 100°C for 3 minutes to obtain an optical filter. Then, it was baked in an oven at 230°C for 20 minutes to obtain the colored coating film 1.

[0456] (4) Lightfastness test

[0457] An ultraviolet cutoff filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Corporation; cuts off light below 380nm) was placed on the obtained colored coating film 1, and the film was irradiated with xenon lamps for 67 hours in the atmosphere using a lightfastness tester (SUNTEST CPS+: manufactured by Toyo Seiki Co., Ltd.) to obtain the cured film 1.

[0458] (5) Absorbance measurement

[0459] For the cured film 1 on the obtained glass substrate, the absorption spectrophotometer (OSP-SP-200; manufactured by Olympus Corporation) was used to measure the absorption spectrophotometry before and after the lightfastness test, and the absorbance retention rate was calculated. It should be noted that the absorbance retention rate in this test refers to the value obtained by setting the absorbance at the maximum absorption wavelength of the colored coating 1 before the lightfastness test to 100%. A higher absorbance retention rate indicates better lightfastness. Furthermore, if the colored coating 1 has good lightfastness, then the colored pattern made from the same coloring and curing resin composition 1 can also be said to have good lightfastness. The results are shown in Table 4.

[0460] <Example 2>

[0461] Using copper(II) dichloro(1,10-phenanthroline) as shown below instead of bis(1,3-propanediamine)copper(II) dichloride as the metal compound (G), the colored resin composition 2 was obtained in the same manner as in Example 1, and the colored coating film 2 was prepared. The composition and lightfastness test results of each example are shown in Table 4.

[0462]

[0463] <Comparative Example 1>

[0464] The bis(1,3-propanediamine)copper(II) dichloride of Example 1 was not used, but the same procedure as in Example 1 was followed to obtain the colored resin composition 3, and a colored coating film 3 was prepared. The composition and lightfastness test results of each example are shown in Table 4.

[0465] [Table 4]

[0466]

[0467] Industrial availability

[0468] The curable composition of the present invention is useful for optical filters and display devices equipped with such optical filters (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.), solid-state imaging elements, etc.

Claims

1. A coloring-curing resin composition comprising a colorant, a resin, a polymerization initiator, a polymerizable compound, and a metal compound, wherein the metal compound is at least one compound selected from the group represented by formula (GI) and formula (GII). In equations (GI) and (GII), M A and M B Each of them independently represents a Group 11 metal atom. R A1 ~R A4 and R B1 ~R B6 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms. R C This refers to a hydrocarbon group with 1 to 20 divalent carbon atoms. R D This indicates a hydrocarbon group connecting pyridine ring A and pyridine ring B, and R D The pyridine ring A and / or pyridine ring B can be bonded by single bonds, R D In the case of a ring structure portion, this ring structure portion can be bonded to pyridine ring A and / or pyridine ring B through ring condensation. X A and X B Each independently represents a halogen atom, hydroxyl group, and OR. E NHR E 、or N(R) E 2. There are multiple X's. A and X B They can be different from each other. R E Represents hydrocarbon groups with 1 to 10 carbon atoms and two R groups. E At that time, R E They can be different from each other. n and m are each independently 1 or 2. M A Between N and M B The dashed lines between N and N represent coordinate bonds.

2. The coloring and curing resin composition according to claim 1, wherein, M A and M B They are copper atoms.

3. The coloring and curing resin composition according to claim 1, wherein, The colorant contains the compound represented by formula (II). In equation (II), R 1 ~R 4 Each can independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents, or a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms that may have substituents. The -CH2- contained in the saturated hydrocarbon group can be -O-, -CO-, or -NR. 11 - Replacement, R 1 and R 2 They can form a ring containing nitrogen atoms, R 3 and R 4 They can form a ring containing nitrogen atoms together. R 5 Represents -OH, -SO3 － -SO3H, -SO3 － Z + -CO2H, -CO2 － Z + -CO2R 8 -SO3R 8 or -SO2NR 9 R 10 , R 6 and R 7 Each can independently represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. m represents an integer from 0 to 5. When m is 2 or higher, multiple R... 5 They can be the same or different. a represents an integer that is either 0 or 1. X represents a halogen atom. Z + express + N(R 11 4. Na + or K + 4 Rs 11 They can be the same or different. R 8 This indicates a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, in which the hydrogen atoms can be replaced by halogen atoms. R 9 and R 10 Each of the following groups independently represents a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms that may have substituents. The -CH2- group contained in this saturated aliphatic hydrocarbon group can be -O-, -CO-, -NH-, or -NR. 8 - Replacement, R 9 and R 10 They can bond with each other to form heterocycles containing nitrogen atoms, ranging from 3 to 10 members. R 11 It represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms.

4. An optical filter formed from the composition of claim 1.

5. A solid-state imaging element comprising the optical filter of claim 4.

Images