Colored resin composition, cured product, color filter, and image display device

Abstract

Provided is a colored resin composition having a high dissolution rate in a developer even when a pre-baking temperature is low. This colored resin composition contains (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, the colored resin composition being characterized in that the coloring agent (A) contains a yellow colorant and a phthalocyanine compound having a specific chemical structure, and the content ratio for the phthalocyanine compound in the (A) colorant is a specific ratio.

Description

[Technical Field]

[0001] The present invention relates to a colored resin composition, a cured product, a color filter, and an image display device. This application claims priority based on Japanese Patent Application No. 2022-040964, filed in Japan on March 16, 2022, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Conventionally, methods for manufacturing color filters used in liquid crystal display devices and the like include pigment dispersion, dyeing, electrodeposition, and printing. Among these, pigment dispersion is the most widely adopted method because it generally exhibits superior characteristics in terms of spectral properties, durability, pattern shape, and precision.

[0003] In recent years, there has been a growing demand for higher brightness, higher contrast, and wider color gamut in color filters. While pigments are generally used as colorants to determine the color of color filters due to their heat resistance, lightfastness, and other factors, pigments are no longer able to meet market demands, particularly for high brightness. As a result, there is a growing interest in using dyes as colorants instead of pigments. For example, studies are being conducted on using phthalocyanine-based dyes for green pixel applications (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2020 / 171060 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present inventors conducted an investigation and found that, in the colored resin composition described in Patent Document 1, the solubility in the developer solution changes significantly depending on the content ratio of the phthalocyanine dye in the colorant, and that when the content ratio of the phthalocyanine dye is low, the dissolution rate in the developer solution slows down. In particular, it was found that this tendency is more pronounced when the pre-bake temperature is relatively low. Furthermore, it was found that, depending on the ratio of the phthalocyanine-based dye in the coloring agent, the colored resin composition described in Patent Document 1 may result in the generation of residue after development and may also result in inferior contrast of the resulting green pixels.

[0006] Therefore, the present invention aims to provide a colored resin composition that dissolves quickly in a developer solution even at relatively low pre-bake temperatures and has high production efficiency. Furthermore, the present invention aims to provide a colored resin composition that suppresses the generation of residue and produces green pixels with excellent contrast. [Means for solving the problem]

[0007] As a result of diligent research by the present inventors, we discovered that the above problem can be solved by setting the content ratio of a specific phthalocyanine compound in the coloring agent to a specific ratio or higher, leading to the present invention. In other words, the present invention has the following configuration.

[0008] [1] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, The aforementioned (A) coloring agent comprises a phthalocyanine compound having a chemical structure represented by the following general formula (1) and a yellow coloring agent, A colored resin composition characterized in that the content of the phthalocyanine compound in the colorant (A) is 65% by mass or more and 90% by mass or less.

[0009] [ka]

[0010] (In formula (1), A 1 ~A 16 each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 ~A 16 represents a fluorine atom, and one or more of A 1 ~A 16 represents a group represented by the following general formula (2).)

[0011] [Chemical formula]

[0012] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.) [2] The colored resin composition according to [1], wherein the content ratio of the phthalocyanine compound in the (A) colorant is 70% by mass or more and 90% by mass or less. [3] The colored resin composition according to [1] or [2], wherein the halogen atom in A 1 ~A 16 in formula (1) is a fluorine atom. [4] Among A 1 ~A 4 in formula (1), one or more are fluorine atoms, among A 5 ~A 8 one or more are fluorine atoms, among A 9 ~A 12 one or more are fluorine atoms, and among A 13 ~A 16 one or more are fluorine atoms. The colored resin composition according to any one of [1] to [3].[[]END]] [5] The colored resin composition according to any one of [1] to [4], wherein the benzene ring in formula (2) has an alkoxycarbonyl group. [6] The colored resin composition according to any one of [1] to [5], wherein X in formula (2) is an oxygen atom. [7] In formula (1), A 1 ~A 4One or more of these are groups represented by formula (2), and A 5 ~A 8 One or more of these are groups represented by formula (2), and A 9 ~A 12 One or more of these are groups represented by formula (2), and A 13 ~A 16 A colored resin composition of any of [1] to [6], wherein one or more of the groups are represented by formula (2). [8] A colored resin composition according to any of [1] to [7], wherein the yellow colorant is at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 185, and a nickel azo complex represented by the following formula (i).

[0013] [ka]

[0014] [9] The colored resin composition of [1], wherein the content of the yellow colorant in the colorant of (A) is 10% by mass or more and 35% by mass or less.

[10] A colored resin composition according to any of [1] to [9], wherein the content of the colorant (A) in the total solid content of the colored resin composition is 10% by mass or more and 80% by mass or less. A cured product obtained by curing any of the colored resin compositions

[11] [1] to

[10] . A color filter comprising pixels created using one of the colored resin compositions

[12] [1] to

[10] . An image display device having color filters

[13]

[12] . [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a colored resin composition that dissolves quickly in a developer solution and has high production efficiency, even when the pre-bake temperature is relatively low. Furthermore, according to the present invention, it is possible to provide a colored resin composition that suppresses the generation of residue and has excellent contrast in the resulting green pixels. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of an organic EL element having a color filter according to the present invention. [Modes for carrying out the invention]

[0017] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) calculated on a polystyrene basis by GPC (gel permeation chromatography). In this invention, "total solids" refers to all components in the colored resin composition other than the solvent. Even if components other than the solvent are liquid at room temperature, they are not included in the solvent and are included in the total solids. In this invention, unless otherwise specified, "amine value" refers to the amine value on an effective solids basis, and is a value expressed by the amount of base and the equivalent amount of KOH per gram of solids of the dispersant. In this invention, "CI" means color index.

[0018] [1] Colored resin composition The colored resin composition of the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer. Furthermore, other additives besides the above components may be included if necessary.

[0019] [1-1](A) Colorants The coloring agent (A) contained in the colored resin composition of the present invention includes a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter sometimes referred to as "phthalocyanine compound (1)") and a yellow coloring agent. The content of phthalocyanine compound (1) in the coloring agent (A) is 65% by mass or more and 90% by mass or less.

[0020] [ka]

[0021] In formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, A 1 ~A 16 One or more of these represent a fluorine atom, and A 1 ~A 16 One or more of these represent a group represented by the following general formula (2).

[0022] [ka]

[0023] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituents. * represents a bond.

[0024] The coloring agent (A) contained in the colored resin composition of the present invention contains a phthalocyanine compound (1), and the content of the phthalocyanine compound (1) in the coloring agent (A) is 65% by mass or more and 90% by mass or less. The phthalocyanine compound (1) has one or more hydrogen atoms constituting the phthalocyanine skeleton substituted with fluorine atoms, which have a smaller atomic radius. This structure does not easily inhibit the association of phthalocyanine compounds (1) with each other. Therefore, when the intermolecular distance is reduced by heating during pre-baking, an aggregate is formed, and the alkali-soluble resin (C) contained in the colored resin composition of the present invention wraps around it, forming a complex. This is thought to result in a faster dissolution rate compared to when phthalocyanine compound (1) is used alone. At this time, if the pre-baking temperature is low, association of phthalocyanine compounds (1) is less likely to occur. On the other hand, when the content of phthalocyanine compound (1) is 65% by mass or more, the association of phthalocyanine compound (1) molecules is less likely to be inhibited by other colorants, and even at low pre-bake temperatures, the regular formation of aggregates of phthalocyanine compound (1) progresses, making local aggregation less likely. This improves transmittance and increases contrast, and as the molecular weight of the aggregates increases, alkali-soluble resins can more easily wrap around them, thus increasing the dissolution rate and suppressing the generation of residues during development.

[0025] (A 1 ~A 16 ) In the above formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, A 1 ~A 16 One or more of these represent a fluorine atom, and A 1 ~A 16 One or more of these represent a group represented by the following general formula (2).

[0026] [ka]

[0027] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituents. * represents a bond.

[0028] A1 ~A 16 Examples of halogen atoms in this product include fluorine, chlorine, and bromine atoms. Fluorine atoms are preferred from the viewpoint of increasing brightness. Also, A 1 ~A 16 Preferably, one or more of these atoms are fluorine atoms, more preferably six or more, even more preferably seven or more, and particularly preferably eight or more. Furthermore, the number of fluorine atoms is 15 or less, preferably 12 or less, and more preferably 10 or less. Setting the value above the lower limit tends to improve the stability of the phthalocyanine compound (1), and setting it below the upper limit tends to improve the affinity with dispersants and solvents in the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, A 1 ~A 16 The number of substituents representing fluorine atoms is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and even more preferably 8 to 10.

[0029] (X) In formula (2), X represents a divalent linking group. The divalent linking group is not particularly limited, but for example, it could be an oxygen atom, a sulfur atom, or -N(R a1 )-group(R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples include ). From the viewpoint of stability during calcination, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0030] (Substituents that the benzene ring may have) The benzene ring in formula (2) may have any substituent. The substituent is not particularly limited, but for example, a halogen atom, an alkyl group (-R A (-OR) group, alkoxy group (-OR) A Base (however, R A represents an alkyl group. )), alkoxycarbonyl group (-COOR A Base (however, R A )), aryl group (-R B (-OR) group, aryloxy group (-OR) B Base (however, RB represents an aryl group. )), aryloxycarbonyl group (-COOR B Base (however, R B represents an aryl group. )) are examples. From the viewpoint of developability and brightness, an alkoxycarbonyl group is preferred.

[0031] These groups are alkyl groups (R A The alkyl group may be linear, branched, or cyclic, but a linear alkyl group is preferred from the viewpoint of affinity with organic solvents. Alkyl(R) A The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 5 or less, and still preferably 4 or less. Setting it above the lower limit tends to suppress aggregation and foreign matter, while setting it below the upper limit tends to improve solvent affinity and stability over time. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, and still preferably 2 to 4. Alkyl(R) A Examples of these groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. From the viewpoint of suppressing aggregation, methyl or ethyl groups are preferred, and ethyl groups are more preferred.

[0032] These groups include the aryl group (R B ) may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Aryl group (R B The number of carbon atoms in the aryl group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting it above the lower limit tends to suppress aggregation due to steric repulsion, and setting it below the upper limit tends to improve solvent affinity and stability over time. The above upper and lower limits can be arbitrarily combined, for example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0033] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monoring or a fused ring. Examples of aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, pentalene rings, indene rings, azulene rings, and heptalene rings, all of which have one free valence atom. The aromatic heterocyclic group may be a monocyclic or fused ring. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thiopyran rings, pyridine rings, 1,3-oxazole rings, isoxazole rings, 1,3-thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazan rings, pyrazine rings, pyrimidine rings, pyridazine rings, 1,3,5-triazine rings, and benzofuran rings, all of which have one free valence atom. Examples include 2-benzofuran rings, benzothiophene rings, 2-benzothiophene rings, 1H-pyrrolidine rings, indole rings, isoindole rings, indidine rings, 2H-1-benzopyran rings, 1H-2-benzopyran rings, quinoline rings, isoquinoline rings, 4H-quinoridine rings, benzimidazole rings, 1H-indazole rings, quinoxaline rings, quinazoline rings, sinnoline rings, phthalazine rings, 1,8-naphthyridine rings, purine rings, and pteridine rings.

[0034] When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited, but from the viewpoint of improving heat resistance through π-π stacking among dye molecules and suppressing the decrease in brightness due to the decomposition of the dye, it is preferable that there is one substitution per benzene ring. If the benzene ring in formula (2) has any substituent, the substitution position may be at the ortho-, meta-, or para-position, but the para-position is preferred from the viewpoint of enabling stacking in a close-packed structure.

[0035] A 1 ~A 16 One or more of these represent a fluorine atom. From the viewpoint of improving brightness by forming an intermolecular aggregate of phthalocyanine compound (1), A 1 ~A 4 One or more of them are fluorine atoms, A5 ~A 8 One or more of them are fluorine atoms, and A 9 ~A 12 One or more of them are fluorine atoms, and moreover, A 13 ~A 16 It is preferable that one or more of them are fluorine atoms; A 1 ~A 4 Two or more of them are fluorine atoms, and A 5 ~A 8 Two or more of them are fluorine atoms, and A 9 ~A 12 Two or more of them are fluorine atoms, and moreover, A 13 ~A 16 It is more preferable that two or more of them are fluorine atoms.

[0036] In formula (1), A 1 ~A 16 One or more of them represent a group represented by formula (2). From the viewpoints of solubility in an organic solvent and luminance, A 1 ~A 4 One or more of them are a group represented by formula (2), and A 5 ~A 8 One or more of them are a group represented by formula (2), and A 9 ~A 12 One or more of them are a group represented by formula (2), and moreover, A 13 ~A 16 It is preferable that one or more of them are a group represented by formula (2); A 1 ~A 4 Two or more of them are a group represented by formula (2), and A 5 ~A 8 Two or more of them are a group represented by formula (2), and A 9 ~A 12 Two or more of them are a group represented by formula (2), and moreover, A 13 ~A 16 It is more preferable that two or more of them are a group represented by formula (2). From the viewpoint that luminance decrease is suppressed by efficient stacking, A 2 、A 3 、A 6 、A 7 、A 10, A 11 , A 14 , and A 15 is a base represented by formula (2), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 It is preferable that it is a halogen atom; A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 is a base represented by formula (2), and A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 It is particularly preferable that the atom is a fluorine atom.

[0037] Examples of phthalocyanine compounds (1) include the following compounds.

[0038] [ka]

[0039] In the above formula, Et represents an ethyl group.

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] A known method can be used to produce the phthalocyanine compound (1), for example, the method described in Japanese Patent Publication No. 05-345861 can be used.

[0044] In the colored resin composition of the present invention, the content of phthalocyanine compound (1) in colorant (A) is 65% by mass or more, preferably 70% by mass or more, and 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less, relative to the total solid content of colorant (A). Setting the content above the lower limit tends to increase the dissolution rate even at low pre-bake temperatures and tends to improve adhesion to the substrate. Furthermore, it tends to increase contrast and suppress residue. Furthermore, by keeping the value below the upper limit, it tends to be possible to ensure the chromaticity required for the color filter. The above upper and lower limits can be combined arbitrarily. For example, the content of phthalocyanine compound (1) in the (A) colorant in the colored resin composition is 65 to 90% by mass of the total solid content of the (A) colorant, preferably 70 to 90% by mass, more preferably 70 to 85% by mass, and even more preferably 70 to 80% by mass.

[0045] (A) The coloring agent contains a yellow coloring agent in addition to the phthalocyanine compound (1). (A) When the coloring agent contains a yellow colorant in addition to the phthalocyanine compound (1), it tends to be possible to achieve the color reproduction required for green pixels. Examples of yellow colorants include yellow pigments and yellow dyes.

[0046] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 8 1, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 15 4, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196 Examples include compounds obtained by inserting other compounds into a 1:1 complex of azobarbituric acid represented by formula (i) below with nickel, or its interchangeable isomer (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

[0047] [ka]

[0048] Other compounds that can be inserted into the nickel azo complex represented by formula (i) include, for example, the compound represented by the following formula (ii).

[0049] [ka]

[0050] From the viewpoint of high brightness and wide color gamut, CI Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and nickel azo complex represented by formula (i) are preferred, and CI Pigment Yellow 83, 138, 139, 180, 185 and nickel azo complex represented by formula (i) are more preferred.

[0051] Examples of yellow dyes include barbiturate azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples include the compounds described in Japanese Patent Publication No. 2010-168531. As for yellow dyes, among those classified as dyes in the Color Index, examples of CI solvent dyes include CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163. Examples of CI acid dyes include CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109, and 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, and 128. Examples include 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and their derivatives. Examples of CI direct dyes include CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141. Examples of CI modant dyes include CI Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65.Preferably, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, 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, 1 Examples include 57, 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, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243, and their derivatives. From the viewpoint of suppressing dye decomposition during firing, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163 are preferred.

[0052] (A) As for the yellow colorant included in the colorant, from the viewpoint of the color reproducibility required for green pixels, CI Pigment Yellow 138, 185, and nickel azo complex represented by formula (i) are preferred, with CI Pigment Yellow 138 being more preferred.

[0053] (A) The coloring agent may contain other coloring agents in addition to the phthalocyanine compound (1) and the yellow coloring agent. Examples of other coloring agents include pigments and dyes. When the colored resin composition of the present invention is used for green pixel applications, it is preferable to use a green coloring agent such as a green pigment or green dye. Examples of green pigments include CI Pigment Green 7, 36, 58, 59, 62, and 63, with CI Pigment Green 58 being preferred from the viewpoint of brightness. As for green dyes, among those classified as dyes in the color index, examples of CI solvent dyes include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. As for CI acid dyes, examples of CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. From the viewpoint of suppressing dye decomposition during heat firing, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred.

[0054] The average primary particle size of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.04 μm or less. For the micronization of the pigment, for example, the solvent salt milling method is suitably used.

[0055] The content of colorant (A) in the colored resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 30% by mass or more, and also preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. Setting it above the lower limit tends to allow for the reproduction of a wide range of hues, and setting it below the upper limit tends to ensure stability over time. The above upper and lower limits can be combined arbitrarily. For example, the content of colorant (A) in the colored resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, even more preferably 20 to 60% by mass, even more preferably 25 to 50% by mass, and particularly preferably 30 to 40% by mass, based on the total solid content of the colored resin composition.

[0056] The content of phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Setting it above the lower limit tends to improve brightness, and setting it below the upper limit tends to ensure stability over time. The above upper and lower limits can be arbitrarily combined. For example, the content of phthalocyanine compound (1) in the colored resin composition is more preferably 3 to 50% by mass, even more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, based on the total solid content of the colored resin composition.

[0057] The amount of yellow pigment in the total solid content of the colored resin composition of the present invention is preferably 2% by mass or more, more preferably 4% by mass or more, even more preferably 6% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. Setting the amount above the lower limit tends to reproduce the color required for the green pixels, and setting it below the upper limit tends to increase the dissolution rate and further increase the contrast. The above upper and lower limits can be combined arbitrarily. For example, if the colored resin composition contains a yellow pigment as another coloring agent, the content of the yellow pigment is preferably 2 to 25% by mass, more preferably 4 to 20% by mass, and even more preferably 6 to 10% by mass in the total solid content of the colored resin composition.

[0058] The content of the yellow pigment in the (A) colorant is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more. Also, 35% by mass or less is preferred, and 30% by mass or less is more preferred. Setting it above the lower limit tends to reproduce the color required for the green pixels, and setting it below the upper limit tends to increase the dissolution rate and further increase the contrast. The above upper and lower limits can be combined arbitrarily. For example, if the (A) colorant contains a yellow pigment, the content of the yellow pigment in the (A) colorant is preferably 5 to 35% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass.

[0059] The mass-based content ratio of phthalocyanine compound (1) to yellow colorant (phthalocyanine compound (1) / yellow colorant) is preferably 1.8 or higher, more preferably 2 or higher, even more preferably 2.3 or higher, and also preferably 9 or lower, more preferably 7 or lower, and even more preferably 6 or lower. Setting it above the lower limit tends to increase the dissolution rate, and setting it below the upper limit tends to reproduce the color required for the green pixels. The above upper and lower limits can be combined arbitrarily. For example, if (A) the colorant contains a yellow colorant, the mass-based content ratio of phthalocyanine compound (1) to yellow colorant (phthalocyanine compound (1) / yellow colorant) is preferably 1.8 to 9, more preferably 1.8 to 7, even more preferably 1.8 to 6, and even more preferably 2 to 6.

[0060] When the colored resin composition of the present invention contains other colorants, the content ratio is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass or more, and also preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Setting it above the lower limit tends to allow for the reproduction of a wide range of hues, and setting it below the upper limit tends to ensure stability over time. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains other colorants, the content ratio of the other colorants is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, even more preferably 5 to 25% by mass, even more preferably 7 to 25% by mass, and particularly preferably 10 to 20% by mass, in the total solid content of the colored resin composition.

[0061] [1-2](B) Solvent (B) The solvent has the function of dissolving or dispersing (A) the colorant, (C) the alkali-soluble resin, (D) the photopolymerization initiator, (E) the photopolymerizable monomer, and other components in the colored resin composition and pigment dispersion of the present invention, and adjusting the viscosity. (B) The solvent can be any solvent that can dissolve or disperse each component.

[0062] (B) Examples of solvents include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0063] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0064] Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, and methoxymethylpentanone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0065] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain-like or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Examples include nitriles such as acetonitrile and benzonitrile.

[0066] Examples of commercially available solvents include mineral spirits, Balsol #2, Apco #18 solvent, Apco thinner, Socal solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and Digrime (all trade names). These solvents may be used individually or in combination of two or more.

[0067] When forming pixels of a color filter by photolithography, (B) a solvent with a boiling point of 100 to 200°C (under a pressure of 1013.25 [hPa]; the same applies to all boiling points hereafter) is preferred. More preferably, the solvent has a boiling point of 120 to 170°C. Glycol alkyl ether acetates are preferred because they offer a good balance of applicability and surface tension, and the solubility of their constituent components in the composition is relatively high.

[0068] Glycol alkyl ether acetates may be used alone or in combination with other solvents. Glycol monoalkyl ethers are particularly preferred as solvents to be used in combination. Propylene glycol monomethyl ether is preferred from the viewpoint of solubility of the components in the composition. Glycol monoalkyl ethers are highly polar, and if added in excessive amounts, the pigment tends to aggregate, leading to a decrease in storage stability, such as an increase in the viscosity of the resulting colored resin composition. Therefore, when using glycol monoalkyl ethers in combination, the proportion of glycol monoalkyl ethers in solvent (B) is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass.

[0069] In another embodiment, a solvent having a boiling point of 150°C or higher can be used in combination. By using a solvent having a boiling point of 150°C or higher, the colored resin composition becomes less likely to dry, but it has the effect of making it less likely for the interrelationships of the constituent components in the pigment dispersion to be destroyed by rapid drying. When using a solvent having a boiling point of 150°C or higher, the content of the solvent having a boiling point of 150°C or higher in (B) solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. Setting it above the lower limit tends to make it easier to avoid, for example, the precipitation and solidification of colorant components at the tip of the slit nozzle, which can cause foreign matter defects, and setting it below the upper limit tends to make it easier to avoid problems such as poor cycle time in the vacuum drying process or pin marks from pre-baking, as the drying speed of the composition slows down. The solvent with a boiling point of 150°C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether; in this case, it is not necessary to include a solvent with a boiling point of 150°C or higher separately. Preferred solvents with a boiling point of 150°C or higher include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin.

[0070] When forming pixels of a color filter by the inkjet method, (B) the solvent is preferably one with a boiling point of 130°C to 300°C, more preferably 150°C to 280°C. Setting the boiling point above the lower limit tends to result in better uniformity of the resulting coating film, while setting it below the upper limit tends to reduce residual solvent during firing. From the viewpoint of uniformity of the resulting coating film, the vapor pressure of the solvent should preferably be 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 1 mmHg or less.

[0071] In the inkjet manufacturing of color filters, the ink emitted from the nozzle is very fine, ranging from a few to tens of pL. Therefore, the solvent tends to evaporate and concentrate the ink before it lands around the nozzle opening or within the pixel bank. To avoid this, it is preferable that solvent (B) contains a solvent with a high boiling point, specifically, a solvent with a boiling point of 180°C or higher. It is more preferable that it contains a solvent with a boiling point of 200°C or higher, and particularly preferable that it contains a solvent with a boiling point of 220°C or higher. When a solvent with a boiling point of 180°C or higher is included, the content ratio of the solvent with a boiling point of 180°C or higher in solvent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. Setting it above the lower limit tends to ensure that the effect of preventing solvent evaporation from droplets is sufficiently exhibited.

[0072] Examples of solvents with a boiling point of 180°C or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin. To adjust the viscosity of the colored resin composition and the solubility of the solids, a solvent with a boiling point lower than 180°C may be included. Such solvents are preferably low viscosity, highly soluble, and low surface tension, such as ethers, esters, and ketones. For example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferred.

[0073] If the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. When alcohols are used in combination, (B) the alcohol content in the solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0074] The content of solvent (B) in the colored resin composition of the present invention is not particularly limited, but its upper limit is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. Setting it below the upper limit tends to make it easier to form a coated film. On the other hand, the lower limit of the solvent content is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, taking into consideration viscosity suitable for coating. The above upper and lower limits can be arbitrarily combined. For example, the content of solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and even more preferably 80 to 85% by mass.

[0075] [1-3](C) Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curing by photopolymerization and solubility with a developer. (C) As the alkali-soluble resin, for example, known polymer compounds described in Japanese Patent Publication No. 7-207211, Japanese Patent Publication No. 8-259876, Japanese Patent Publication No. 10-300922, Japanese Patent Publication No. 11-140144, Japanese Patent Publication No. 11-174224, Japanese Patent Publication No. 2000-56118, and Japanese Patent Publication No. 2003-233179 can be used. Preferably, the following resins (C-1) to (C-5) are used. (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, or by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction, and which is an alkali-soluble resin (hereinafter sometimes referred to as "resin (C-1)"). (C-2): A linear alkali-soluble resin containing carboxyl groups in its main chain (hereinafter sometimes referred to as "resin (C-2)"). (C-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as "resin (C-3)"). (C-4): (Meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)"). (C-5): Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)"). Particularly preferred is resin (C-1).

[0076] The resins (C-2) to (C-5) only need to be so soluble in an alkaline developer that the desired developing process can be carried out. Preferably, each resin is one of those described in the same section of Japanese Patent Publication No. 2009-025813.

[0077] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, or by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction, thereby obtaining an alkali-soluble resin. One preferred embodiment of resin (C-1) is "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups in a copolymer of 5 to 90 mol% epoxy group-containing (meth)acrylate and 10 to 95 mol% of another radical polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups produced by the addition reaction."

[0078] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Glycidyl (meth)acrylate is preferred among these. These epoxy group-containing (meth)acrylates may be used individually or in combination of two or more.

[0079] As other radical polymerizable monomers copolymerized with epoxy group-containing (meth)acrylates, mono(meth)acrylates having the structure represented by the following general formula (V) are preferred.

[0080] [ka]

[0081] In formula (V), R 91 ~R 98 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 96 and R 98 , or R 95 and R 97 These elements may be connected to each other to form a ring. In equation (V), R 96 and R 98 , or R 95 and R 97 The ring formed by the linkage of these elements is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

[0082] Among these, the structures represented by formula (V) are preferably those represented by the following general formulas (Va), (Vb), or (Vc). By introducing these structures into an alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition is improved, and the intensity of pixels formed using the colored resin composition tends to increase.

[0083] A mono(meth)acrylate having the structure represented by formula (V) may be used alone or in combination of two or more types.

[0084] [ka]

[0085] As a mono(meth)acrylate having the structure represented by formula (V), various known mono(meth)acrylates can be used as long as they have the structure represented by formula (V), but mono(meth)acrylates represented by the following general formula (VI) are particularly preferred.

[0086] [ka]

[0087] In formula (VI), R 89 R represents a hydrogen atom or a methyl group. 90 This represents the structure expressed by equation (V).

[0088] In a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, if repeating units derived from mono(meth)acrylate represented by formula (VI) are included, the content of repeating units derived from mono(meth)acrylate represented by formula (VI) is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%, of the repeating units derived from the other radical polymerizable monomer.

[0089] Other radical polymerizable monomers besides mono(meth)acrylates represented by formula (VI) are not particularly limited, but include, for example, vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-propyl (meth)acrylate. -Butyl, (meth)acrylate-sec-butyl, (meth)acrylate-tert-butyl, (meth)acrylate-pentyl, (meth)acrylate-neopentyl, (meth)acrylate-isoamyl, (meth)acrylate-hexyl, (meth)acrylate-2-ethylhexyl, (meth)acrylate-lauryl, (meth)acrylate-dodecyl, (meth)acrylate-cyclopentyl, (meth)acrylate-cyclohexyl, (meth)acrylate-2-methylcyclohexyl, (meth)acrylate-dicyclohexyl, (meth)acrylate- (Meth) Isobolonyl acrylate, Adamantyl methacrylate, Propagel methacrylate, Phenyl methacrylate, Naphthyl methacrylate, Anthracenyl methacrylate, Anthraninonyl methacrylate, Piperonyl methacrylate, Salicylic methacrylate, Furyl methacrylate, Furfuryl methacrylate, Tetrahydrofuryl methacrylate, Pyranyl methacrylate, Benzyl methacrylate, Phenethyl methacrylate (meth)acrylic acid esters such as cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate;Examples include (meth)acrylamides such as (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-diisopropylamide, and (meth)acrylate anthracenylamide; vinyl compounds such as (meth)acrylate anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

[0090] Among these other radically polymerizable monomers, styrene, benzyl (meth)acrylate, and monomaleimide are preferred from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition. In a copolymer of epoxy group-containing (meth)acrylate and another radical polymerizable monomer, if any repeating units derived from styrene, benzyl (meth)acrylate, or monomaleimide are included, the total content of repeating units derived from styrene, benzyl (meth)acrylate, and monomaleimide among the repeating units derived from the other radical polymerizable monomer is preferably 1 to 70 mol%, and more preferably 3 to 50 mol%.

[0091] For copolymerization reactions between epoxy group-containing (meth)acrylates and other radically polymerizable monomers, known solution polymerization methods can be applied. The solvent used is not particularly limited as long as it is inert to radical polymerization; commonly used organic solvents can be used. Solvents used in solution polymerization include, for example, ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetic acid esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, and butyl carbitol. Examples include diethylene glycol dialkyl ethers such as 1,4-dioxane and tetrahydrofuran; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; and dimethylformamide and N-methylpyrrolidone. These solvents may be used individually or in combination of two or more.

[0092] The amount of solvent used in the solution polymerization method is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, per 100 parts by mass of the resulting copolymer. By keeping the amount of solvent used within this range, it tends to be easier to control the molecular weight of the copolymer. The radical polymerization initiator used in copolymerization reactions is not particularly limited as long as it can initiate radical polymerization; commonly used organic peroxide catalysts and azo compound catalysts can be used. Examples of organic peroxide catalysts include those classified as known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

[0093] Examples of radical polymerization initiators used in copolymerization reactions include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-bis(t-butyl peroxy)hexyl-3,3-isopropyl Examples include hydroperoxides, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.

[0094] Examples of azo compound catalysts include azobisisobutyronitrile and azobiscarbamide. From these, one or more radical polymerization initiators with appropriate half-lives are used depending on the polymerization temperature. The amount of radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the total monomers used in the copolymerization reaction.

[0095] The copolymerization reaction may be carried out by dissolving the monomers and radical polymerization initiators used in the copolymerization reaction in a solvent and raising the temperature while stirring; or by adding the monomers to which the radical polymerization initiator has been added dropwise to a heated and stirred solvent; or by adding the radical polymerization initiator to a solvent and raising the temperature, then adding the monomers dropwise. The reaction conditions can be set according to the target molecular weight.

[0096] In the present invention, the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers is preferably composed of 5 to 90 mol% repeating units derived from epoxy group-containing (meth)acrylate and 10 to 95 mol% repeating units derived from the other radical polymerizable monomer; more preferably composed of 20 to 80 mol% repeating units derived from epoxy group-containing (meth)acrylate and 80 to 20 mol% repeating units derived from the other radical polymerizable monomer; and particularly preferably composed of 30 to 70 mol% repeating units derived from epoxy group-containing (meth)acrylate and 70 to 30 mol% repeating units derived from the other radical polymerizable monomer.

[0097] By setting the content of repeating units derived from epoxy group-containing (meth)acrylate to above the aforementioned lower limit, the amount of unsaturated monobasic acid and polybasic acid anhydride added, as described later, tends to be sufficient. By setting the content of repeating units derived from other radical polymerizable monomers to above the aforementioned lower limit, sufficient heat resistance and strength tend to be achieved. Next, the epoxy group of the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).

[0098] As the unsaturated monobasic acid to be added to the epoxy group, known unsaturated monobasic acids can be used, for example, unsaturated carboxylic acids having an ethylenically unsaturated double bond. Examples of unsaturated monobasic acids to be added to the epoxy group include (meth)acrylic acid; crotonic acid; o-, m-, p-vinylbenzoic acid; and monocarboxylic acids such as (meth)acrylic acid in which the α-position is substituted with a haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group; with (meth)acrylic acid being preferred. One unsaturated monobasic acid may be used alone, or two or more may be used in combination.

[0099] By adding an unsaturated monobasic acid to the epoxy group, polymerizability can be imparted to the resin (C-1). The unsaturated monobasic acid is added to the epoxy groups of the copolymer in an amount of, for example, 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. Setting the amount above the lower limit tends to improve the long-term stability of the colored resin composition. Known methods can be used to add an unsaturated monobasic acid to the epoxy group of a copolymer.

[0100] Furthermore, known polybasic anhydrides can be used as the polybasic anhydrides to be added to the hydroxyl groups formed when an unsaturated monobasic acid is added to the epoxy groups of the copolymer. Examples of polybasic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloridenic anhydride; and anhydrides of three or more base acids such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used individually or in combination of two or more.

[0101] By adding a polybasic acid anhydride to the hydroxyl group formed when an unsaturated monobasic acid is added to the epoxy group of a copolymer, alkali solubility can be imparted to the resin (C-1). The polybasic acid anhydride is added to the hydroxyl groups formed by adding an unsaturated monobasic acid to the epoxy groups of the copolymer, for example, in an amount of 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. Setting the amount below the upper limit tends to result in a good residual film rate during development, while setting it above the lower limit tends to result in sufficient solubility. As a method for adding a polybasic acid anhydride to a hydroxyl group formed by adding an unsaturated monobasic acid to an epoxy group of a copolymer, known methods can be employed.

[0102] Furthermore, to improve photosensitivity, after adding a polybasic acid anhydride, a glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to some of the resulting carboxyl groups. To improve developability, a glycidyl ether compound that does not have polymerizable unsaturated groups may be added to some of the generated carboxyl groups.

[0103] Furthermore, both glycidyl ether compounds having polymerizable unsaturated groups and glycidyl ether compounds not having polymerizable unsaturated groups may be added. Examples of glycidyl ether compounds that do not have polymerizable unsaturated groups include glycidyl ether compounds having phenyl groups or alkyl groups. Examples of commercially available glycidyl ether compounds that do not have polymerizable unsaturated groups include the following products manufactured by Nagase ChemteX Corporation: "Denacol EX-111," "Denacol EX-121," "Denacol EX-141," "Denacol EX-145," "Denacol EX-146," "Denacol EX-171," and "Denacol EX-192."

[0104] The structure of resin (C-1) is described, for example, in Japanese Patent Publication No. Hei 8-297366 and Japanese Patent Publication No. 2001-89533. The weight-average molecular weight of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably between 3,000 and 100,000, and especially preferably between 5,000 and 50,000. Setting it above the lower limit tends to result in good heat resistance and film strength, while setting it below the upper limit tends to result in good solubility in the developer. As a guideline for molecular weight distribution, the ratio of the weight-average molecular weight (Mw) of the resin (C-1) to the number-average molecular weight (Mw / Mn) is preferably between 2.0 and 5.0.

[0105] From the viewpoint of coating film curing properties when exposed to ultraviolet light, (C) among alkali-soluble resins, (c1) acrylic copolymer resins having ethylenically unsaturated groups in the side chains are preferred. (c1) The substructure of an acrylic copolymer resin having an ethylenically unsaturated group in its side chain is not particularly limited, but from the viewpoint of achieving both coating curability during UV exposure and alkali solubility during alkaline development, it is preferable to have a substructure represented by the following general formula (CI).

[0106] [ka]

[0107] In formula (CI), R 1 and R 2 Each of the symbols independently represents a hydrogen atom or a methyl group. * represents a bonding bond.

[0108] Among the substructures represented by formula (CI), the substructure represented by the following general formula (CI') is preferred from the viewpoint of sensitivity and alkali developability.

[0109] [ka]

[0110] In formula (CI'), R 1 and R 2 Each of these independently represents either a hydrogen atom or a methyl group. X represents a hydrogen atom or a polybasic acid residue.

[0111] A polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, with tetrahydrophthalic acid and biphenyltetracarboxylic acid being more preferred. These polybasic acids may be used individually or in combination of two or more.

[0112] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CI), the content of the substructure represented by formula (CI) in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. Setting the value above the lower limit tends to improve the curability of the coating film during UV exposure, and setting it below the upper limit tends to improve the alkali solubility during alkali development. The above upper and lower limits can be combined arbitrarily. For example, in an acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain, the content of the substructure represented by formula (CI) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0113] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CI'), the content of the substructure represented by formula (CI') in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. Setting the value above the lower limit tends to improve the curability of the coating film during UV exposure, and setting it below the upper limit tends to improve the alkali solubility during alkali development. The above upper and lower limits can be combined arbitrarily. For example, in an acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain, the content of the substructure represented by formula (CI) is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0114] (c1) When an acrylic copolymer resin having an ethylenically unsaturated group in its side chain contains a substructure represented by formula (CI), the other substructures included are not particularly limited, but from the viewpoint of alkali solubility during alkali development, it is also preferable to have a substructure represented by the following general formula (CII).

[0115] [ka]

[0116] In equation (CII), R 3 R represents a hydrogen atom or a methyl group. 4 This represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

[0117] (R 4 ) In equation (CII), R 4 This represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. R 4 Examples of alkyl groups in this compound include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 8 or more, and also preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.

[0118] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability, dicyclopentanyl and dodecanyl groups are preferred, and dicyclopentanyl is more preferred. Examples of substituents that the alkyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0119] R 4Examples of aromatic ring groups include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic ring groups. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, even more preferably 6 to 20, and particularly preferably 6 to 18. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monoring or a fused ring, and examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorantene ring, and fluorene ring. The aromatic heterocyclic group may be monocyclic or fused rings, and examples include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, quinoxaline rings, phenanthidine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. From the viewpoint of developability, benzene ring groups and naphthalene ring groups are preferred, and benzene ring groups are more preferred. Examples of substituents that the aromatic ring group may have include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0120] R 4 Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkenyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0121] Examples of alkenyl groups include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups. From the viewpoint of developability, vinyl and allyl groups are preferred, and vinyl groups are more preferred.

[0122] Examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0123] R 4represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. From the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred.

[0124] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CII), the content of the substructure represented by formula (CII) in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and also preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. Setting it above the lower limit tends to improve alkali solubility, and setting it below the upper limit tends to improve the storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, in an acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain, the content of the substructure represented by formula (CII) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, even more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

[0125] (c1) When the acrylic copolymer resin contains a substructure represented by formula (CI), it is preferable that the other substructures included include a substructure represented by the following general formula (CIII) from the viewpoint of suppressing brightness reduction by improving heat resistance.

[0126] [ka]

[0127] In formula (CIII), R 5 R represents a hydrogen atom or a methyl group. 6represents an optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, hydroxyl group, carboxyl group, halogen atom, optionally substituted alkoxy group, thiol group, or optionally substituted alkyl sulfide group. t represents an integer from 0 to 5.

[0128] (R 6 ) In equation (CIII), R 6 This represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group. R 6 Examples of alkyl groups in this compound include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12.

[0129] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of heat resistance, dicyclopentanyl and dodecanyl groups are preferred, and dicyclopentanyl is more preferred. Examples of substituents that the alkyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0130] R 6 Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkenyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0131] Examples of alkenyl groups include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups. From the viewpoint of exposure sensitivity during UV exposure, vinyl and allyl groups are preferred, and vinyl groups are more preferred.

[0132] Examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0133] R 6Examples of alkynyl groups include linear, branched, or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkynyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0134] Examples of alkynyl groups include 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butyne-2-yl group, 1,4-pentadiiin-3-yl group, 1,3-pentadiiin-5-yl group, and 1-hexyn-6-yl group.

[0135] Examples of substituents that the alkynyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0136] R 6 Examples of halogen atoms in this compound include fluorine, chlorine, bromine, and iodine atoms. Fluorine atoms are preferred from the viewpoint of storage stability of the acrylic copolymer resin.

[0137] R 6Examples of alkoxy groups include linear, branched, or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

[0138] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups.

[0139] Examples of substituents that the alkoxy group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0140] R 6 Examples of alkyl sulfide groups include linear, branched, or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined in any way. For example, the number of carbon atoms in the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

[0141] Examples of alkyl sulfide groups include methyl sulfide groups, ethyl sulfide groups, propyl sulfide groups, and butyl sulfide groups. From the viewpoint of developability, methyl sulfide groups and ethyl sulfide groups are preferred.

[0142] Examples of substituents that the alkyl group in the alkyl sulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0143] R 6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkyl sulfide group. From the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0144] In equation (CIII), t represents an integer between 0 and 5. From the viewpoint of ease of manufacture, it is preferable that t is 0.

[0145] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CIII), the content of the substructure represented by formula (CIII) in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 5 mol% or more, particularly preferably 8 mol% or more, and also preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. Setting it above the lower limit tends to improve heat resistance and suppress brightness reduction, while setting it below the upper limit tends to increase the content of other substructures and improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the content of the substructure represented by formula (CIII) in an acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, even more preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

[0146] (c1) When an acrylic copolymer resin having an ethylenically unsaturated group in its side chain has a substructure represented by formula (CI), it is also preferable that it may have a substructure represented by the following general formula (CIV) as another substructure from the viewpoint of developability.

[0147] [ka]

[0148] In formula (CIV), R 7 represents a hydrogen atom or a methyl group.

[0149] (c1) When the acrylic copolymer resin having an ethylenically unsaturated group in its side chain contains a substructure represented by formula (CIV), the content of the substructure represented by formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and also preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol or less. Setting it above the lower limit tends to improve alkali solubility, and setting it below the upper limit tends to improve the storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, the content of the substructure represented by formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol.

[0150] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 40 mg KOH / g or more, even more preferably 50 mg KOH / g or more, particularly preferably 60 mg KOH / g or more, and also preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, even more preferably 150 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less. Setting it above the lower limit tends to improve alkali solubility, and setting it below the upper limit tends to improve the storage stability and substrate adhesion of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, the acid value of (C) alkali-soluble resin is preferably 10 to 300 mg KOH / g, more preferably 30 to 300 mg KOH / g, even more preferably 40 to 250 mg KOH / g, even more preferably 50 to 200 mg KOH / g, and particularly preferably 60 to 150 mg KOH / g.

[0151] (C) The weight average molecular weight of the alkali-soluble resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 4000 or more, even more preferably 6000 or more, even more preferably 7000 or more, particularly preferably 8000 or more, and is preferably 30000 or less, more preferably 20000 or less, still more preferably 15000 or less, particularly preferably 10000 or less. By setting it to be not less than the lower limit value, the heat resistance and the coating film curability tend to be improved, and by setting it to be not more than the upper limit value, the alkali solubility tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, the weight average molecular weight of the (C) alkali-soluble resin is preferably from 1000 to 30000, more preferably from 2000 to 30000, still more preferably from 4000 to 20000, even more preferably from 6000 to 20000, even more preferably from 7000 to 15000, and particularly preferably from 8000 to 10000.

[0152] The content ratio of the (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more in the total solid content of the colored resin composition, and is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably 50% by mass or less. By setting it to be not less than the lower limit value, the coating film curability during ultraviolet exposure tends to be improved, and by setting it to be not more than the upper limit value, the developer solubility is improved and the residue tends to be suppressed. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the (C) alkali-soluble resin in the colored resin composition is preferably from 5 to 80% by mass, more preferably from 10 to 80% by mass, still more preferably from 20 to 70% by mass, even more preferably from 30 to 60% by mass, and particularly preferably from 40 to 50% by mass in the total solid content of the colored resin composition.

[0153] [1-4] (D) Photoinitiator The colored resin composition of the present invention contains (D) a photoinitiator. By containing (D) a photoinitiator, film curability by photopolymerization can be imparted. (D) The photoinitiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and additives such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction and has a function of generating polymerization active radicals.

[0154] Examples of the photoinitiator include metallocene compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 of Japan, hexarylbisimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, radical activators such as N-aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone-based compounds, and oxime ester-based initiators described in JP-A-2000-80068 of Japan.

[0155] The photoinitiators that can be used in the present invention are listed below. Halomethylated triazine derivatives such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

[0156] Halomethylated oxadiazole derivatives such as 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; Imidazole derivatives such as 2-(2′-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-chlorophenyl)-4,5-bis(3′-methoxyphenyl)imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4′-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone;

[0157] Benzophenone derivatives such as benzophenone, Michlaz ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; Acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone;

[0158] Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives such as benzanthrone; Dicyclopentadienyl-Ti-dichloride, dicyclopentadogenyl-Ti-bis-phenyl, dicyclopentadogenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadogenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadogenyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadogenyl-Ti-2,6 Titanocene derivatives such as -diplopheni-1-yl, dicyclopentagenyl-Ti-2,4-difluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluoropheni-1-yl, and dicyclopentagenyl-Ti-2,6-difluoro-3-(pyru-1-yl)-pheni-1-yl;

[0159] α-aminoalkylphenone compounds such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone; Oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime)ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0160] From the viewpoint of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred. Oxime ester compounds possess structures that absorb ultraviolet light, transmit light energy, and generate radicals, allowing for high sensitivity even in small amounts, and stability against thermal reactions. This enables the design of highly sensitive colored resin compositions using small quantities. In particular, from the viewpoint of light absorption for the i-line (365 nm) of an exposure light source, oxime ester compounds having a carbazole ring, which may have substituents, are preferred.

[0161] Examples of oxime ester compounds include those represented by the following general formula (I-1).

[0162] [ka]

[0163] In formula (I-1), R 21aThis represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group. R 21b represents any substituent containing an aromatic ring or a heteroaromatic ring. R 22a This represents an optionally substituted alkanoyl group or an optionally substituted allyloyl group.

[0164] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity to exposure, it is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 2 to 5. Examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, and propyl groups. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl groups, or N-acetyl-N-acetoxyamino groups. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0165] R 21a Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but it is preferably 5 or more from the viewpoint of solubility in the colored resin composition. Furthermore, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, even more preferably 12 or less, and particularly preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 12, and particularly preferably 5 to 8.

[0166] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and a fluorenyl group. From the viewpoint of developability, a phenyl group, a naphthyl group, and a fluorenyl group are preferable, and a phenyl group and a fluorenyl group are more preferable. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of developability, a hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable. Examples of the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group. From the viewpoint of developability, R 21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.

[0167] R 21b is an arbitrary substituent including an aromatic ring or a heteroaromatic ring. From the viewpoints of solubility in a solvent and sensitivity to exposure, a carbazolyl group which may have a substituent, a thioxanthonyl group which may have a substituent, a diphenyl sulfide group which may have a substituent, or a fluorenyl group which may have a substituent, or a group formed by linking these groups with a carbonyl group is preferable. From the viewpoint of light absorption property with respect to i-line (365 nm) of an exposure light source, a carbazolyl group which may have a substituent, or a group formed by linking a carbazolyl group which may have a substituent with a carbonyl group is preferable.

[0168] Examples of substituents that the carbazolyl group may have include C1-C10 alkyl groups such as methyl and ethyl groups; C1-C10 alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as F, Cl, Br, and I; C1-C10 acyl groups; C1-C10 alkyl ester groups; C1-C10 alkoxycarbonyl groups; C1-C10 halogenated alkyl groups; C4-C10 aromatic ring groups; amino groups; C1-C10 aminoalkyl groups; hydroxyl groups; nitro groups; CN groups; optionally substituted allyloyl groups; optionally substituted heteroallyloyl groups; and optionally substituted tenoyl groups.

[0169] R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkanoyl group is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 3 to 5. Examples of alkanoyl groups include acetyl, ethiloyl, propanoyl, and butanoyl groups. Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0170] R 22a The number of carbon atoms in the allyroyl group is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, more preferably 8 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the allyroyl group is preferably 7 to 20, more preferably 7 to 15, even more preferably 7 to 10, and particularly preferably 8 to 10. Examples of allyroyl groups include benzoyl groups and naphthoyl groups. Examples of substituents that the allyroyl group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and alkyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0171] Examples of compounds represented by formula (I-1) include those represented by the following general formulas (I-2) or (I-3), from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source.

[0172] [ka]

[0173] [ka]

[0174] In equations (I-2) and (I-3), R 21a and R 22a This is equivalent to equation (I-1). R 23a This represents an alkyl group which may have substituents. R 24a This represents an optionally substituted alkyl group, an optionally substituted allyloyl group, an optionally substituted heteroallyloyl group, or a nitro group. The benzene rings constituting the carbazole ring may be further fused with aromatic rings to form a polycyclic aromatic ring.

[0175] R 23aThe number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 2 to 5. Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl groups. Examples of substituents that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted. R 23a From the viewpoint of solubility in solvents and ease of synthesis, an ethyl group is more preferable.

[0176] R 24a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 1 or more, more preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 2 to 5. Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl groups. Examples of substituents that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0177] R 24aThe number of carbon atoms in the allyroyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 7 or more, more preferably 8 or more, even more preferably 9 or more, and also preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the allyroyl group is preferably 7 to 20, more preferably 8 to 15, even more preferably 9 to 10, and particularly preferably 9. Examples of allyroyl groups include benzoyl groups and naphthoyl groups. Examples of substituents that the allyroyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, an ethyl group is preferred.

[0178] R 24a The number of carbon atoms in the heteroaryroyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 7 or more, more preferably 8 or more, even more preferably 9 or more, and also preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the heteroaryroyl group is preferably 7 to 20, more preferably 8 to 15, even more preferably 9 to 10, and particularly preferably 9. Examples of heteroaryl groups include benzoyl, fluorobenzoyl, chlorobenzoyl, bromobenzoyl, fluoronaphthoyl, chloronaphthoyl, and bromonaphthoyl groups. Examples of substituents that the heteroaryroyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted. R 24a From the viewpoint of sensitivity, an allyroyl group which may have substituents is preferred, and a benzoyl group is more preferred.

[0179] The benzene rings constituting the carbazole ring may be further fused with aromatic rings to form a polycyclic aromatic ring.

[0180] Examples of commercially available oxime ester compounds include OXE-02 and OXE-03 from BASF, TR-PBG-304 and TR-PBG-314 from Changzhou Strong Electronic New Materials Co., Ltd., and N-1919, NCI-930, and NCI-831 from ADEKA.

[0181] Specific examples of oxime ester compounds include the following:

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] These photopolymerization initiators may be used individually or in combination of two or more.

[0186] (D) In ​​addition to the photopolymerization initiator, a chain transfer agent may also be used. A chain transfer agent is a compound that has the function of receiving the generated radical and transferring the received radical to another compound. Various chain transfer agents can be used as long as they possess the above-mentioned functions. For example, mercapto group-containing compounds and carbon tetrachloride are examples, and it is more preferable to use mercapto group-containing compounds because they tend to have a high chain transfer effect. This is thought to be because the low SH bond energy makes bond cleavage more likely, leading to hydrogen abstraction reactions and chain transfer reactions. This is effective for improving sensitivity and surface hardening.

[0187] Examples of mercapto group-containing compounds include aromatic ring-containing mercapto group-containing compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropanetris(3-mercaptopropionate), and trimethylolpropanetris Examples of aliphatic mercapto group-containing compounds include sthioglycolates, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, compounds having multiple mercapto groups are preferred.

[0188] Preferred mercapto group-containing compounds having an aromatic ring include 2-mercaptobenzothiazole and 2-mercaptobenzimidazole, while preferred aliphatic mercapto group-containing compounds include trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), pentaerythritoltris(3-mercaptopropionate), trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), pentaerythritoltris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0189] From the standpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, with trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione being preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) being more preferred. These chain transfer agents may be used individually or in combination of two or more.

[0190] In the colored resin composition of the present invention, the content of (D) photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, even more preferably 1% by mass or more, particularly preferably 1.2% by mass or more, and also preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, and particularly preferably 4% by mass or less. Setting it above the lower limit tends to improve the curability of the coating film, and setting it below the upper limit tends to improve brightness by reducing visible light absorption. The above upper and lower limits can be arbitrarily combined. For example, in the colored resin composition, the content of (D) photopolymerization initiator is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, even more preferably 1 to 6% by mass, and particularly preferably 1.2 to 4% by mass, in the total solid content of the colored resin composition.

[0191] When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and also preferably 3% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. Setting the content above the lower limit tends to improve solvent resistance, and setting it below the upper limit tends to improve storage stability. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a chain transfer agent, the content ratio is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, even more preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1.5% by mass, based on the total solid content of the colored resin composition.

[0192] [1-5](E) Photopolymerizable monomer The colored resin composition of the present invention contains (E) a photopolymerizable monomer. (E) The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular-weight compound, but an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound") is preferred. An ethylenic compound is a compound having an ethylenic double bond that, when the colored resin composition of the present invention is irradiated with active light, undergoes addition polymerization and hardens due to the action of a photopolymerization initiator. In this invention, the monomer refers to a concept opposite to so-called polymer substances, and includes not only monomers in the narrow sense but also dimers, trimers, and oligomers. (E) As the photopolymerizable monomer, it is particularly desirable to use a polyfunctional ethylene monomer having two or more ethylene double bonds in one molecule. The number of ethylene double bonds in the polyfunctional ethylene monomer is not particularly limited, but is preferably two or more, more preferably four or more, even more preferably five or more, and also preferably eight or fewer, and even more preferably seven or fewer. Setting it above the lower limit tends to result in high sensitivity, and setting it below the upper limit tends to improve solubility in solvents. The above upper and lower limits can be arbitrarily combined. For example, the number of ethylene double bonds in the polyfunctional ethylene monomer is preferably 2 to 8, more preferably 2 to 7, even more preferably 4 to 7, and particularly preferably 5 to 7.

[0193] Examples of ethylenic compounds include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyhydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and ethylenic compounds having a urethane skeleton obtained by reacting polyisocyanate compounds with (meth)acryloyl-containing hydroxy compounds.

[0194] Examples of esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, examples of esters obtained by replacing the acrylic acid portion of these acrylates with the methacrylic acid portion include methacrylic acid esters, itaconic acid esters obtained by replacing the itaconic acid portion, crotonic acid esters obtained by replacing the crotonic acid portion, or maleic acid esters obtained by replacing the maleic acid portion.

[0195] Examples of esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. Esters obtained by the esterification reaction of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds are not necessarily single substances but may be mixtures. Examples include condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0196] Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; and reaction products of (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

[0197] Other ethylenic compounds used in the present invention include, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A polyfunctional monomer is preferred, obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acid group. In this ester, a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol is particularly preferred.

[0198] These monomers may be used individually, but since it is difficult to use a single compound in manufacturing, two or more may be used in mixture form. Furthermore, if necessary, polyfunctional monomers without acid groups and polyfunctional monomers with acid groups may be used in combination. The preferred acid value of polyfunctional monomers having acid groups is 0.1 to 40 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g. Setting the value above the lower limit tends to improve the development and dissolution characteristics, while setting it below the upper limit tends to improve manufacturing and handling, and to improve curing properties such as photopolymerization performance and pixel surface smoothness. Therefore, when using two or more polyfunctional monomers with different acid groups in combination, or when using polyfunctional monomers without acid groups in combination, it is preferable to adjust the total amount of acid groups in the polyfunctional monomer to fall within the above range.

[0199] In the present invention, a more preferred polyfunctional monomer having an acidic group is a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which are commercially available as TO1382 from Toagosei Co., Ltd. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Furthermore, the polyfunctional monomers described in paragraphs

[0056] and

[0057] of Japanese Patent Publication No. 2013-140346 can also be used.

[0200] In the present invention, from the viewpoint of improving the chemical resistance of the pixels and the linearity of the pixel edges, it is preferable to use the polymerizable monomer described in Japanese Patent Publication No. 2013-195971. From the viewpoint of achieving both high sensitivity of the coated film and reduced development time, it is preferable to use the polymerizable monomer described in Japanese Patent Publication No. 2013-195974.

[0201] In the colored resin composition of the present invention, the content of (E) photopolymerizable monomer is not particularly limited, but is preferably more than 0% by mass, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less. Setting it above the lower limit tends to improve the curability of the coating film, and setting it below the upper limit tends to suppress the decrease in alkali developability. The above upper and lower limits can be arbitrarily combined. For example, the content of (E) photopolymerizable monomer in the colored resin composition is preferably more than 0% by mass and 70% by mass or less, more preferably 5 to 60% by mass, even more preferably 10 to 50% by mass, even more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass, in the total solid content of the colored resin composition.

[0202] [1-6] Other solids The colored resin composition of the present invention may further contain solid components other than those mentioned above, as needed. Examples of such components include dispersants, dispersion aids, surfactants, and adhesion enhancers.

[0203] [1-6-1] Dispersants, dispersing aids When the colored resin composition of the present invention contains a pigment as a coloring agent (A), it is preferable to include a dispersant for the purpose of stably dispersing the pigment. Among dispersants, polymer dispersants are preferred because they have excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants. Examples of polymer dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Bic Chemie), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the dispersant described in Japanese Patent Publication No. 2013-119568.

[0204] As a polymer dispersant, a block copolymer having a functional group containing a nitrogen atom is preferred from the viewpoint of dispersibility and storage stability, and an acrylic block copolymer having a functional group containing a nitrogen atom is more preferred. As block copolymers having functional groups containing nitrogen atoms, AB block copolymers and BAB block copolymers are preferred, which consist of an A block having a quaternary ammonium base and / or an amino group in the side chain and a B block not having a quaternary ammonium base and an amino group.

[0205] Examples of functional groups containing nitrogen atoms include primary to tertiary amino groups and quaternary ammonium bases. From the viewpoint of dispersibility and storage stability, primary to tertiary amino groups are preferred, and tertiary amino groups are more preferred. The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, it is preferable that the repeating unit be represented by the following general formula (d1).

[0206] [ka]

[0207] In formula (d1), R 1 and R 2 Each of these is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R 1 and R 2 They may combine with each other to form a ring structure. 3 is a hydrogen atom or a methyl group. X is a divalent linking group.

[0208] R in equation (d1) 1 , R 2 The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is preferably 1 or more, more preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. For example, 1 to 10 is preferred, 1 to 6 is more preferred, and 1 to 4 is even more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. Alkyl groups may be linear or branched. Alkyl groups may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0209] R in equation (d1) 1 , R 2 The number of carbon atoms in the optionally substituted aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, 6 to 16 is preferred, 6 to 12 is more preferred, and 6 to 8 is even more preferred. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups being preferred, and phenyl, methylphenyl, and ethylphenyl groups being more preferred.

[0210] R in equation (d1) 1 , R 2The number of carbon atoms in the aralkyl group, which may have substituents, is not particularly limited, but is preferably 7 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. For example, 7 to 16 is preferred, 7 to 12 is more preferred, and 7 to 9 is even more preferred. Examples of aralkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene groups are preferred, and phenylmethylene and phenylethylene groups are more preferred.

[0211] From the standpoint of dispersibility, storage stability, electrical reliability, and developability, R 1 and R 2 Preferably, alkyl groups may each have substituents independently, and methyl groups and ethyl groups are more preferred.

[0212] Examples of substituents that the alkyl group, aralkyl group, or aryl group in formula (d1) may have include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0213] In equation (d1), R 1 and R 2 Examples of cyclic structures formed by the bonding of these elements include 5-7 membered nitrogen-containing heterocyclic monocyclic rings or fused rings formed by the fusion of two such rings. The nitrogen-containing heterocyclic rings are preferably non-aromatic, and saturated rings are even more preferable. Specifically, examples include the cyclic structure shown in (IV) below.

[0214] [ka]

[0215] These cyclic structures may further have substituents.

[0216] In formula (d1), the divalent linking group X can be, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, or -CONH-R 13 -group, -COOR 14 -Base (however, R 13 and R 14 Examples include a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, preferably -COO-R 14 - It is the basis.

[0217] The content of the repeating unit represented by formula (d1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20 mol% or more, especially preferably 25 mol% or more, and also preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content of the repeating unit represented by formula (d1) in the total repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, particularly preferably 20 to 50 mol%, and especially preferably 25 to 40 mol%.

[0218] From the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and thus improving dispersion stability, it is preferable that the block copolymer has repeating units represented by the following general formula (d2).

[0219] [ka]

[0220] In formula (d2), R 10 R is an ethylene group or a propylene group, 11 R is an alkyl group which may have substituents,12 is a hydrogen atom or a methyl group. n is an integer between 1 and 20.

[0221] R in equation (d2) 11 The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 6 or less, and still preferably 4 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, still preferably 1 to 4, and particularly preferably 2 to 4. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. Alkyl groups may be linear or branched. Alkyl groups may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups. Examples of substituents that the alkyl group may have include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0222] In formula (d2), n is preferably 1 or more, more preferably 2 or more, more preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less, from the viewpoint of compatibility and dispersibility with the solvent and other binder components. The above upper and lower limits can be combined arbitrarily. For example, n is preferably 1 to 10, and more preferably 2 to 5.

[0223] The content of the repeating unit represented by formula (d2) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and also preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability. The above upper and lower limits can be arbitrarily combined. For example, the content of the repeating unit represented by formula (d2) in the total repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%.

[0224] From the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and thus improving dispersion stability, it is preferable that the block copolymer has repeating units represented by the following general formula (d3).

[0225] [ka]

[0226] In equation (d3), R 8 R is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. 9 This is either a hydrogen atom or a methyl group.

[0227] R in equation (d3) 8 The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is preferably 1 or more, preferably 10 or less, and more preferably 6 or less. For example, 1 to 10 is preferred, and 1 to 6 is more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. Alkyl groups may be linear or branched. Alkyl groups may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0228] R in equation (d3) 8 The number of carbon atoms in the aryl group, which may have substituents, is not particularly limited, but is preferably 6 or more, preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 is preferred, and 6 to 12 is more preferred. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups. Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups are preferred, and phenyl, methylphenyl, and ethylphenyl groups are more preferred.

[0229] R in equation (d3) 8 The number of carbon atoms in the aralkyl group, which may have substituents, is not particularly limited, but is preferably 7 or more, preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 is preferred, and 7 to 12 is more preferred. Examples of aralkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene groups are preferred, and phenylmethylene and phenylethylene groups are more preferred.

[0230] From the viewpoint of solvent compatibility and dispersion stability, R 8 Preferably, alkyl groups and aralkyl groups are used, and more preferably, methyl groups, ethyl groups, and phenylmethylene groups. R 8Examples of substituents that the alkyl group may have include halogen atoms and alkoxy groups. Examples of substituents that the aryl group or aralkyl group may have include linear alkyl groups, halogen atoms, and alkoxy groups. R 8 The linear alkyl groups shown include both linear and branched alkyl groups.

[0231] The content of the repeating unit represented by formula (d3) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 80 mol% or less, and even more preferably 70 mol% or less. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content of the repeating unit represented by formula (d3) in the total repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 70 mol%.

[0232] The block copolymer may have repeating units other than those represented by formula (d1), formula (d2), and formula (d3). Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and glycidyl crotonic acid ether; and repeating units derived from N-methacryloylmorpholine.

[0233] From the viewpoint of further improving dispersibility, it is preferable that the block copolymer has an A block having repeating units represented by formula (d1) and a B block not having repeating units represented by formula (d1). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. It is more preferable that the B block has repeating units represented by formula (d2) and / or repeating units represented by formula (d3).

[0234] Repeating units other than those represented by formula (d1) may be contained in block A. Examples of such repeating units include the repeating units derived from the (meth)acrylic acid esters mentioned above. The content of repeating units other than those represented by formula (d1) in block A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 mol%.

[0235] Repeating units other than those represented by formula (d2) and formula (d3) may be contained in block B. Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and glycidyl crotonic acid ether; and repeating units derived from N-methacryloylmorpholine. The content of repeating units other than those represented by formula (d2) and formula (d3) in block B is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 mol%.

[0236] From the viewpoint of dispersibility, a low acid value is preferable for the block copolymer, and 0 mg KOH / g is particularly preferable. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of dispersant solids.

[0237] From the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, even more preferably 70 mg KOH / g or more, even more preferably 90 mg KOH / g or more, especially preferably 100 mg KOH / g or more, particularly preferably 105 mg KOH / g or more, and also preferably 150 mg KOH / g or less, and even more preferably 130 mg KOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 30 to 150 mg KOH / g is preferred, 50 to 150 mg KOH / g is more preferred, 70 to 150 mg KOH / g is even more preferred, 90 to 130 mg KOH / g is even more preferred, 100 to 130 mg KOH / g is especially preferred, and 105 to 130 mg KOH / g is particularly preferred. Here, the amine value represents the amine value on an effective solids basis, and is expressed as the amount of base and the equivalent amount of KOH per gram of solids of the dispersant.

[0238] The weight-average molecular weight of the block copolymer is preferably between 1,000 and 30,000. When the molecular weight is within this range, dispersion stability is good, and the generation of dried foreign matter tends to be less when coating using a slit nozzle method.

[0239] Block copolymers can be produced by known methods. For example, they can be produced by living polymerization of monomers into which each of the above repeating units is introduced. Examples of the living polymerization method include Japanese Patent Publication No. 9-62002, Japanese Patent Application Publication No. 2002-31713, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GDAndrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. al,Polym.J.17,977(1985),K.Hatada,K.Ute,et The known methods described in al, Polym.J.18,1037(1986), Koichi Migite, Koichi Hatada, Polymer Processing, 36,366(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Journal of Polymer Science, 46,189(1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109,4737(1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43,300(1985), and DY Sogoh, WRHertler et al, Macromolecules, 20,1473(1987) can be employed.

[0240] When the colored resin composition of the present invention contains a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, and also preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. Setting it above the lower limit tends to improve dispersibility and storage stability, and setting it below the upper limit tends to improve electrical reliability and developability. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a dispersant, the content of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass, even more preferably 0.1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass, in the total solid content of the colored resin composition.

[0241] When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant to the pigment is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, per 100 parts by mass of pigment, and also preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. By keeping it within the above range, it is possible to obtain a colorable resin composition with excellent dispersion stability and high brightness. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a pigment and a dispersant, the content ratio of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, even more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass, per 100 parts by mass of pigment.

[0242] If the colored resin composition of the present invention contains a pigment, it may also contain, for example, a pigment derivative as a dispersion aid to improve the dispersibility and dispersion stability of the pigment. Examples of pigment derivatives include derivatives of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments. Examples of substituents on the pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups that are directly bonded to the pigment skeleton or via alkyl groups, aryl groups, heterocyclic groups, etc. Preferably, sulfonamide groups and their quaternary salts and sulfonic acid groups are included, and more preferably, sulfonic acid groups. Furthermore, multiple substituents may be substituted on a single pigment skeleton, or a mixture of compounds with different numbers of substitutions may be used. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0243] [1-6-2] Surfactants The colored resin composition of the present invention may contain a surfactant, and various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as the surfactant. However, nonionic surfactants are preferred because they are less likely to adversely affect the various properties. When the colored resin composition of the present invention contains a surfactant, the surfactant content is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, relative to the total solid content of the colored resin composition. The above upper and lower limits can be arbitrarily combined. For example, the surfactant content is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, even more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass, relative to the total solid content of the colored resin composition.

[0244] [1-6-3] Adhesion enhancer The colored resin composition of the present invention may contain an adhesion enhancer to improve adhesion to the substrate. Examples of adhesion enhancers include silane coupling agents and titanium coupling agents. Silane coupling agents are preferred. Examples of silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning Co., Ltd.). A single silane coupling agent may be used alone, or two or more may be used in any combination and ratio. Adhesion enhancers other than silane coupling agents may be included in the colored resin composition of the present invention. Examples include phosphate-based adhesion enhancers and other adhesion enhancers.

[0245] As a phosphoric acid-based adhesion enhancer, phosphates containing (meth)acryloyloxy groups are preferred. Phosphoric acid-based adhesion enhancers represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0246] [ka]

[0247] In equations (g1), (g2), and (g3), R 51 Each of the following independently represents a hydrogen atom or a methyl group. l and l' each independently represent an integer from 1 to 10, and m each independently represents 1, 2, or 3. Other adhesion enhancers include, for example, TEGO® Add Bond LTH (manufactured by Evonik). These phosphoric acid-based adhesion enhancers and other adhesion enhancers may be used individually or in combination of two or more.

[0248] When the colored resin composition of the present invention contains an adhesion enhancer, the content ratio is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and also preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. Setting the content above the lower limit tends to improve patterning characteristics and improve pattern adhesion under high humidity conditions, while setting it below the upper limit tends to suppress residue generation. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains an adhesion enhancer, the content ratio is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, even more preferably 0.3 to 1.5% by mass, and particularly preferably 0.4 to 1% by mass, based on the total solid content.

[0249] [2] Preparation of colored resin composition Next, a method for preparing the colored resin composition of the present invention will be described.

[0250] (A) When preparing a coloring agent containing a pigment, first, the pigment, solvent, and dispersant are weighed in predetermined quantities, and in the dispersion process, the coloring agent containing the pigment is dispersed to prepare a pigment dispersion. In this dispersion process, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc., can be used. By performing this dispersion process, the coloring agent is made into fine particles, which improves the coating properties of the colored resin composition and improves the transmittance of pixels on the color filter substrate of the product.

[0251] As mentioned above, when dispersing pigments, it is preferable to use dispersion aids and the like as appropriate. When performing dispersion using a sand grinder, it is preferable to use glass beads or zirconia beads with a diameter of 0.1 to several millimeters. The temperature during dispersion should preferably be set to 0°C or higher, more preferably to room temperature or higher, and preferably to 100°C or lower, more preferably to 80°C or lower. The dispersion time should be adjusted as appropriate, as the appropriate time will vary depending on the composition of the pigment dispersion and the size of the sand grinder equipment.

[0252] The pigment dispersion obtained by the above dispersion process is mixed with a solvent, alkali-soluble resin, photopolymerization initiator, photopolymerizable monomer, and other components as needed to obtain a homogeneous dispersion solution. Since fine dust may be introduced during the dispersion process and mixing process, it is preferable to filter the obtained pigment dispersion using a filter or the like.

[0253] (A) If the coloring agent does not contain a pigment, a homogeneous solution can be obtained by mixing the coloring agent, solvent, alkali-soluble resin, photopolymerization initiator, photopolymerizable monomer, and other components as needed. It is preferable to filter the obtained solution using a filter or the like.

[0254] [3] Manufacturing of cured products and color filters The cured product of the present invention is obtained by curing the colored resin composition of the present invention. Furthermore, the color filter of the present invention comprises pixels created using the colored resin composition of the present invention. The following describes an example of a color filter manufacturing method.

[0255] [3-1] Substrate (support) A transparent substrate is preferred as the substrate to which the colored resin composition of the present invention is applied, and the material is not particularly limited as long as it is transparent and has appropriate strength. Examples of materials include thermoplastic resin sheets such as polyester resins like polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, poly(meth)acrylic resins, and various types of glass. Among these, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

[0256] The substrate to which the colored resin composition is applied, and the substrate with the black matrix described later, may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents or urethane resins, as necessary, in order to improve surface properties such as adhesion. The thickness of the substrate is preferably in the range of 0.05 mm or more, more preferably 0.1 mm or more, preferably 10 mm or less, and more preferably 7 mm or less. For example, preferably 0.05 to 10 mm, and more preferably 0.1 to 7 mm. When thin film formation treatment of various resins is performed, the film thickness is preferably in the range of 0.01 μm or more, more preferably 0.05 μm or more, preferably 10 μm or less, and more preferably 5 μm or less. For example, preferably 0.01 to 10 μm, and more preferably 0.05 to 5 μm.

[0257] [3-2] Black Matrix Formation Process The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and further forming pixel images, usually in red, green, and blue. The colored resin composition of the present invention is preferably used as a coating solution for forming green pixels (resist patterns) among the red, green, and blue pixels. Using the coating solution for forming green pixels (resist patterns), pixel images are formed by applying, heating and drying, image exposure, development, and firing processes on the resin black matrix forming surface formed on the transparent substrate, or on the metal black matrix forming surface formed using a chromium compound or other light-shielding metal material.

[0258] The black matrix is ​​formed on the substrate using a light-shielding metal thin film or a colored resin composition for the black matrix. As the light-shielding metal material, for example, chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, or nickel-tungsten alloys may be used, and these may be laminated in multiple layers. Metal light-shielding films are generally formed by sputtering. A desired pattern is formed in film form using a positive-type photoresist. For chromium, an etching solution mixed with cerium ammonium nitrate and perchloric acid and / or nitric acid is used, and for other materials, an etching solution appropriate to the material is used. Finally, the positive-type photoresist is removed with a special release agent to form a black matrix.

[0259] When using light-shielding metal thin films, first, a thin film of these metals or metal / metal oxides is formed on a transparent substrate by methods such as vapor deposition or sputtering. Next, a coating film of a colored resin composition is formed on this thin film, and then the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, or triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

[0260] When using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form the black matrix. For example, a colored resin composition containing a black colorant, either alone or in combination with other black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, or titanium black, or a mixture of red, green, blue, etc., appropriately selected from inorganic or organic pigments and dyes, can be used to form the black matrix in the same manner as the method for forming red, green, and blue pixels described below.

[0261] [3-3] Pixel formation process The pixel formation step includes a coating step of applying the colored resin composition onto a substrate and a pre-baking step of pre-baking the coating film obtained in the coating step. In the pixel formation process, for example, pixels can be formed by a coating step of applying a colored resin composition of one of three colors (red, green, or blue) onto a substrate with a black matrix; a pre-baking step of drying (pre-baking) the obtained coating film; an exposure step of placing a photomask on the coating film and exposing an image through the photomask; and a development step, followed by thermal curing or photocuring as needed. By performing these steps for each of the three colored resin compositions (red, green, and blue), a color filter image can be formed. The colored resin composition of the present invention is preferably used as a composition for forming green or blue pixels (resist patterns) among red, green, and blue pixels, and more preferably as a composition for forming green pixels. For example, pixels are formed by applying the green or blue pixel (resist pattern) composition to a resin black matrix forming surface formed on a substrate, or to a metal black matrix forming surface formed using a chromium compound or other light-shielding metal material, followed by coating, drying (pre-baking), image exposure, development, and heat curing or photocuring.

[0262] [3-4] Coating process The colored resin composition can be applied to the substrate by, for example, the spinner method, wire bar method, flow coating method, die coating method, roll coating method, or spray coating method. Among these, the die coating method is preferable from an overall standpoint because it significantly reduces the amount of colored resin composition used, completely eliminates the influence of mist and other contaminants that adhere when using the spin coating method, and further suppresses the generation of foreign matter.

[0263] If the thickness of the coating film is too large, pattern development becomes difficult, and gap adjustment in the liquid crystal cell formation process may become difficult. On the other hand, if it is too small, it becomes difficult to increase the pigment concentration, and the desired color may not be achieved. The thickness of the coating film, as the film thickness after drying, is preferably 0.2 μm or more, more preferably 0.5 μm or more, even more preferably 0.8 μm or more, and also preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. For example, 0.2 to 20 μm is preferred, 0.5 to 10 μm is more preferred, and 0.8 to 5 μm is even more preferred.

[0264] [3-5] Pre-bake process The drying (pre-baking) of the coating film obtained in the coating process is preferably carried out by a drying method using a hot plate, an IR oven, or a convection oven. It is preferable to perform pre-baking by heating again after pre-drying. The conditions for pre-drying can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. The drying temperature and drying time are selected depending on the type of solvent component, the performance of the dryer used, etc. Specifically, the drying temperature is preferably 40°C or higher, more preferably 50°C or higher, and preferably 80°C or lower, and more preferably 70°C or lower, and the drying time is preferably 15 seconds or more, more preferably 30 seconds or more, and preferably 5 minutes or less, and more preferably 3 minutes or less.

[0265] The pre-bake temperature is preferably higher than the pre-drying temperature. Specifically in this invention, it is 80°C or higher, preferably 90°C or higher, particularly preferably 100°C or higher, and also preferably 200°C or lower, more preferably 160°C or lower, and particularly preferably 130°C or lower. Setting the temperature above the lower limit tends to increase the dissolution rate, while setting it below the upper limit tends to decompose the binder resin, inducing thermal polymerization and resulting in poor development. The above upper and lower limits can be combined arbitrarily; for example, the pre-bake temperature is preferably 80-200°C, more preferably 90-130°C, and particularly preferably 100-130°C.

[0266] The pre-baking drying time depends on the heating temperature, but is preferably 10 seconds or more, more preferably 15 seconds or more, and preferably 10 minutes or less, more preferably 5 minutes or less.

[0267] [3-6] Exposure process In the pixel formation process, it is preferable to have an exposure process after the pre-baking process. The exposure process involves superimposing a negative matrix pattern onto the coated film obtained through the pre-baking process, and irradiating it with ultraviolet or visible light through this mask pattern. If necessary, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen-blocking layer, such as a polyvinyl alcohol layer, may be formed on the photopolymerizable layer before exposure. The light source used for the exposure is not particularly limited. Examples of light sources include lamps such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, as well as lasers such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. Optical filters can also be used when irradiating with light of a specific wavelength.

[0268] [3-7]Developing process In the pixel formation process, it is preferable to have a development process after the exposure process. The colored resin composition of the present invention can be used to create a coating film, which is then exposed in the exposure step described above. After exposure, the coating film is developed using an aqueous solution containing a surfactant and an alkaline compound. This process allows for the formation of an image on a substrate. This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes, or pigments.

[0269] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, as well as organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono-, or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used individually or in combination of two or more.

[0270] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters; and amphoteric surfactants such as alkyl betaines and amino acids.

[0271] Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. These organic solvents can be used in combination with aqueous solutions. There are no particular restrictions on the development conditions, but the development temperature is preferably 10°C or higher, more preferably 15°C or higher, even more preferably 20°C or higher, and also preferably 50°C or lower, more preferably 45°C or lower, and even more preferably 40°C or lower. For example, it is preferably 10-50°C, more preferably 15-45°C, and even more preferably 20-40°C. The development method can be any of the following methods: immersion development, spray development, brush development, ultrasonic development, etc.

[0272] [3-7] Thermosetting process In the pixel formation process, it is also preferable to have a thermosetting treatment step after the development step. The thermosetting treatment conditions in the thermosetting treatment step are preferably a temperature of 100°C or higher, more preferably 150°C or higher, and preferably 280°C or lower, and more preferably 250°C or lower, and a duration of preferably 5 minutes or more, and preferably 60 minutes or less.

[0273] After the pixel formation process described above, the formation of a single-color patterned pixel is complete. By repeating this process sequentially, black, red, green, and blue patterns can be created to manufacture a color filter. Note that the order in which the four colors are patterned is not limited to the order described above.

[0274] [3-8] Formation of transparent electrodes The color filter in this invention is used as is, with transparent electrodes such as ITO formed on the image, as part of a component in color displays, liquid crystal displays, etc. However, to improve surface smoothness and durability, a topcoat layer such as polyamide or polyimide can be applied to the image as needed. In some applications, such as planar orientation driving methods (IPS mode), transparent electrodes may not be formed.

[0275] [4] Image display device (panel) The image display device according to the present invention has a color filter manufactured by the manufacturing method of the present invention. Below, we will describe liquid crystal display devices and organic light-emitting diode (OLED) display devices in detail as image display devices.

[0276] [4-1]Liquid crystal display device The method for manufacturing a liquid crystal display device according to the present invention will now be described. In the liquid crystal display device according to the present invention, an alignment film is usually formed on a color filter manufactured by the method of the present invention, spacers are scattered on the alignment film, and then it is bonded to a counter substrate to form a liquid crystal cell, liquid crystal is injected into the formed liquid crystal cell, and it is connected to a counter electrode to complete the device. A resin film such as polyimide is preferred for the alignment film. Gravure printing and / or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After curing the alignment film by heat firing, the surface is treated by irradiation with ultraviolet light or treatment with a rubbing cloth to process it into a surface state in which the tilt of the liquid crystal can be adjusted.

[0277] The spacer used is sized according to the gap (clearance) with the opposing substrate, and is usually 2 to 8 μm in size. A photospacer (PS) made of a transparent resin film can also be formed on the color filter substrate by photolithography and used as a spacer. An array substrate is usually used as the opposing substrate, and a TFT (thin-film transistor) substrate is particularly preferred.

[0278] The gap between the liquid crystal display and the opposing substrate varies depending on the application of the liquid crystal display device, but is preferably selected within the range of 2 μm to 8 μm. After bonding to the opposing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, sealing the area around the liquid crystal cell. After sealing the edges of the liquid crystal cell, it is cut into panel units, then the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. The degree of pressure reduction inside the liquid crystal cell is preferably 1 × 10⁻⁶. -2Pa or less, more preferably 1 × 10 -3 The following, and preferably 1 × 10 -7 Pa or higher, comfort level 1 x 10 -6 The range is Pa or higher. For example, preferably 1 × 10 -7 ~1 × 10 -2 Pa, fer1 × 10 -6 ~1 × 10 -3 It is Pa. Furthermore, it is preferable to heat the liquid crystal cell during depressurization, and the heating temperature is preferably in the range of 30°C or higher, more preferably 50°C or higher, and more preferably 100°C or lower, and more preferably 90°C or lower. For example, 30 to 100°C is preferred, and 50 to 90°C is more preferred.

[0279] The heating and holding during reduced pressure is preferably for a period of 10 to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is then sealed by curing a UV-curing resin at the liquid crystal injection port, thereby completing the liquid crystal display device (panel). There are no particular restrictions on the type of liquid crystal; any conventionally known liquid crystal, such as aromatic, aliphatic, or polycyclic compounds, is acceptable, including lyotropic and thermotropic liquid crystals. Thermotropic liquid crystals include nematic liquid crystals, smetic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[0280] [4-2] Organic EL display device When creating an organic EL display device having a color filter manufactured by the manufacturing method of the present invention, for example, as shown in Figure 1, a multi-color organic EL element is manufactured by laminating an organic light-emitting element 500 via an organic protective layer 30 and an inorganic oxide film 40 onto a blue color filter on which pixels 20 formed with the colored resin composition of the present invention are formed on a transparent support substrate 10.

[0281] Methods for laminating the organic light-emitting element 500 include sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, or laminating an organic light-emitting element 500 formed on a separate substrate onto an inorganic oxide film 40. The organic EL element 100 fabricated in this way can be applied to both passively driven organic EL display devices and actively driven organic EL display devices. [Examples]

[0282] Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0283] <Phthalocyanine compound A> We used phthalocyanine compound A, which has the following chemical structure and was synthesized based on Example 30 of Japanese Patent Publication No. 05-345861.

[0284] [ka]

[0285] Note that Et in the formula represents ethyl.

[0286] <Phthalocyanine compound B>

[0287] [ka]

[0288] <Dispersant A> A methacrylic AB block copolymer comprising an A block having nitrogen atom-containing functional groups and a B block having solvent-philic groups. It has repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a). The amine value is 120 mgKOH / g and the acid value is less than 1 mgKOH / g.

[0289] The percentages of repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a) within the total repeating units are less than 1 mol%, 34.5 mol%, 6.9 mol%, 13.8 mol%, and 6.9 mol%, respectively.

[0290] [ka]

[0291] <Alkali-soluble resin A> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen purging and heated to 120°C. 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, Hitachi Chemical Co., Ltd.) were added dropwise, and the mixture was stirred at 120°C for 2 hours. Next, the reaction vessel was purged with air, and 43 parts by mass of acrylic acid were added along with 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone, and the reaction was continued at 120°C for 6 hours. Subsequently, 20 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours. The weight-average molecular weight (Mw) of the resulting alkali-soluble resin A, measured by GPC, was approximately 8000 in polystyrene terms, the acid value was 30 mgKOH / g, and the double bond equivalent was 410 g / mol.

[0292] <Alkali-soluble resin B> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen purging and heated to 120°C. 5 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, and 4 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, Hitachi Chemical Co., Ltd.) were added dropwise, and stirring continued at 120°C for 2 hours. Next, the reaction vessel was changed to air purging, and 67 parts by mass of acrylic acid were added along with 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone, and the reaction was continued at 120°C for 6 hours. Subsequently, 15 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours. The weight-average molecular weight Mw of the resulting alkali-soluble resin B, measured by GPC in terms of polystyrene, was approximately 9000, the acid value was 24 mgKOH / g, and the double bond equivalent was 260 g / mol.

[0293] <Alkali-soluble resin C> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen purging and heated to 120°C. 7 parts by mass of styrene, 92 parts by mass of glycidyl methacrylate, and 62 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, Hitachi Chemical Co., Ltd.) were added dropwise, and the mixture was stirred at 120°C for 2 hours. Next, the reaction vessel was purged with air, and 47 parts by mass of acrylic acid were added along with 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone, and the reaction was continued at 120°C for 6 hours. Subsequently, 39 parts by mass of succinic anhydride and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours. The weight-average molecular weight Mw of the resulting alkali-soluble resin C, measured by GPC in terms of polystyrene, was approximately 5700, the acid value was 89 mgKOH / g, and the double bond equivalent was 430 g / mol.

[0294] Of the alkali-soluble resins A to C, alkali-soluble resin C, with an acid value of 89 mg KOH / g, exhibits the highest solubility. Among alkali-soluble resins A and B, which have similar and low acid values, alkali-soluble resin B, which contains a higher amount of highly hydrophilic glycidyl methacrylate, exhibits higher solubility.

[0295] <Alkali-soluble resin D> A separable flask equipped with a condenser was prepared as the reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate were added, and after purging with nitrogen, the temperature of the reaction vessel was raised to 90°C by heating in an oil bath while stirring.

[0296] Meanwhile, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of t-butyl peroxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were charged into the monomer tank, and 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into the chain transfer agent tank. After the temperature of the reaction vessel stabilized at 90°C, dropwise addition from the monomer tank and chain transfer agent tank was started to initiate polymerization. Dropwise addition was carried out over 135 minutes each while maintaining the temperature at 90°C, and 60 minutes after the dropwise addition was completed, the temperature was raised to 110°C.

[0297] After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel, and the mixture was allowed to react at 110°C for 9 hours. After cooling to room temperature, an alkali-soluble resin D was obtained with a polystyrene-based weight-average molecular weight Mw of 9000, an acid value of 101 mgKOH / g, and a double bond equivalent of 550 g / mol, as measured by GPC.

[0298] <Preparation of Green Dye Dispersion A> As shown in Table 1, 9.9 parts by mass of phthalocyanine compound A, 0.1 parts by mass of dispersant A (on a solid content basis), 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant A), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were packed into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads and dispersion were separated by filtration to prepare green dye dispersion A.

[0299] <Preparation of Green Dye Dispersion B> Green dye dispersion B was prepared in the same manner as green dye dispersion A, except that phthalocyanine compound A was replaced with phthalocyanine compound B and the raw materials were blended as shown in Table 1.

[0300] <Preparation of yellow pigment dispersion A> As shown in Table 1, 11.4 parts by mass of CI Pigment Yellow 138, 2.9 parts by mass of Dispersant A (on a solids basis), 5.7 parts by mass of Alkali-Soluble Resin D (on a solids basis), 76.0 parts by mass of Propylene Glycol Monomethyl Ether Acetate as a solvent (including solvents derived from Dispersant A and Alkali-Soluble Resin D), 4.0 parts by mass of Propylene Glycol Monomethyl Ether, and 225 parts by mass of 0.5 mm diameter zirconia beads were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads and dispersion were separated by filtration to prepare yellow pigment dispersion A.

[0301] [Table 1]

[0302] <Photopolymerizable monomer A> Pentaerythritol tetraacrylate (Light Acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.)

[0303] <Photopolymerizable monomer B> Polyethoxylated tetramethylolmethane tetraacrylate (NK ester ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0304] <Photopolymerization initiator A> Oxime ester compounds having the following chemical structure (4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate methyl)

[0305] [ka]

[0306] Note that Me in the formula represents methyl.

[0307] <Surfactant A> Megafuck F-554 (manufactured by DIC Corporation)

[0308] <Preparation of colored resin composition> Colored resin compositions 1 to 8 were prepared by mixing each component listed in Table 2 in the solid content ratios described. In addition, for colored resin compositions 1 to 8, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used as solvents so that the total solid content of the colored resin composition was 15% by mass, and the mixing ratio (mass ratio) of PGMEA / PGME in the obtained colored resin compositions was 90 / 10.

[0309] [Table 2]

[0310] <Evaluation of spectral change> A colored resin composition was applied by spin coating onto a 50mm square, 0.7mm thick glass substrate (AGC, AN100) to a film thickness of 2.0μm after heat curing (baking) using the spin coating method. After vacuum drying, the substrate was pre-baked on a hot plate at the temperature listed in Table 3 for 90 seconds to create a colored substrate. Alternatively, after performing the same procedure up to vacuum drying, instead of pre-baking, a heat curing treatment was performed in a clean oven at 230°C for 20 minutes to create a colored substrate after baking.

[0311] The obtained colored substrates and the colored substrates after firing were measured using a Hitachi U-3310 spectrophotometer to obtain spectral transmission spectra at 1 nm intervals from 380 nm to 780 nm, and converted to absorption spectra. Among the absorption spectra of the colored substrates, the absorbance value at wavelength n was defined as A. n Assuming that the same value for the colored substrate after firing is A0 n This is the case. At this time, the degree of spectral change was defined by the following formula as an indicator of how much the absorption spectrum of the colored substrate differs from that of the colored substrate after firing. The calculated degree of spectral change is shown in Table 3. The smaller the degree of spectral change in the following formula, the closer the phthalocyanine compound (1) is to the state after it has formed aggregates during pre-baking and after firing, when the aggregates have completely formed.

[0312]

number

[0313] <Evaluation of dissolution rate> The above colored substrates were developed using a 0.04% by mass potassium hydroxide aqueous solution at a developer temperature of 23°C, and the time required for complete dissolution was measured and is shown in Table 3.

[0314] <Evaluation of adhesion> The obtained colored resin composition was applied by spin coating onto a 50 mm square, 0.7 mm thick glass substrate (AGC, AN100) to a film thickness of 2.0 μm after heat curing (baking), and pre-baked at 100°C for 90 seconds. Subsequently, a 2 kW high-pressure mercury lamp was used to heat the sample at a rate of 40 mJ / cm².2 Exposure dose, illuminance 30 mW / cm² 2 The exposure process was then carried out using an exposure mask having multiple linear apertures with widths of 1 to 50 μm. Subsequently, development was performed using a 0.04 mass% potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Then, 1 kg / cm³ was applied. 2 The substrates were spray-washed with water at a specific water pressure for 10 seconds. Then, a heat-curing treatment was performed at 230°C for 20 minutes to create the patterned substrates. Using an optical microscope, patterns corresponding to multiple linear apertures with widths ranging from 1 to 50 μm were observed. If the narrowest aperture remaining in the pattern that did not disappear during development was 7 μm or less, it was classified as A; if it was between 7 μm and 15 μm, it was classified as B; and if it was greater than 15 μm, it was classified as C. The evaluation results are shown in Tables 3 and 4. The narrower the opening, the better the adhesion between the cured colored resin composition and the substrate.

[0315] <Contrast Evaluation> The obtained colored resin composition was applied by spin coating onto a 50 mm square, 0.7 mm thick glass substrate (AGC, AN100) to a film thickness of 2.0 μm after heat curing (baking), and pre-baked at 100°C for 90 seconds. Subsequently, a 2 kW high-pressure mercury lamp was used to heat the sample at a rate of 40 mJ / cm². 2 Exposure dose, illuminance 30 mW / cm² 2 A substrate for contrast evaluation was prepared by exposure treatment and heat curing treatment at 230°C for 20 minutes. The obtained substrates were measured for orthogonality using a contrast tester CT-1 (manufactured by Tsubosaka Electric Co., Ltd.), and the contrast ratio (1:12000) was determined based on parallelism / orthogonality. A contrast ratio of 6000 or higher was rated A, 4000 or higher and less than 6000 was rated B, and less than 4000 was rated C. The evaluation results are shown in Table 4.

[0316] <Evaluation of residue> Similar to the adhesion evaluation, a patterned substrate was fabricated, and the pattern corresponding to a 50 μm wide linear aperture was observed using an optical microscope. If no residue was observed in the opening, it was classified as A; if some residue was observed in the opening but it did not pose a practical problem, it was classified as B; and if residue was observed in the opening, it was classified as C. The evaluation results are shown in Table 4.

[0317] [Table 3]

[0318] [Table 4]

[0319] As is clear from Table 3, the spectral change at lower pre-bake temperatures decreases as the proportion of phthalocyanine compound (1) in the (A) colorant increases. In other words, the higher the proportion of phthalocyanine compound (1) in the (A) colorant, the lower the pre-bake temperature required for phthalocyanine compound (1) to form aggregates. In particular, in Comparative Example 2, the spectral change value was somewhat large even at a pre-bake temperature of 105°C, indicating that phthalocyanine compound (1) was not able to form aggregates. This is thought to be because the presence of colorants other than phthalocyanine compound (1) in the (A) colorant inhibits the association of phthalocyanine compound (1) with each other through π-π stacking with the aromatic ring contained in its structure. The dissolution rate also showed a similar trend; as the proportion of phthalocyanine compound (1) in the (A) colorant increased, the pre-bake temperature at which the dissolution rate became constant when the pre-bake temperature was gradually increased from 80°C became lower. This is thought to be because the phthalocyanine compound (1) formed an aggregate, and the alkali-soluble resin (C) contained in the colored resin composition wrapped around it to form a complex, resulting in a faster dissolution rate compared to when the phthalocyanine compound (1) was alone. The faster dissolution rate of the colored resin composition reduces development time. Furthermore, the ability to accelerate dissolution at lower pre-bake temperatures contributes to improved production efficiency for color filters and other products. Additionally, the faster dissolution rate allows for a relatively lower solubility of (C) alkali-soluble resins, resulting in less pattern peeling during development and improved adhesion.

[0320] As is clear from the comparison between Examples 1-3 and Comparative Examples 1-3 in Table 4, it can be seen that when the content of phthalocyanine compound (1) in the colorant is 65% by mass or more, the residue and contrast are greatly improved. This is thought to be because, as the content of phthalocyanine compound (1) increases, the association of phthalocyanine compound (1) molecules is less inhibited by other colorants, leading to the formation of regular aggregates of phthalocyanine compound (1), which increases the contrast, and also increases the dissolution rate due to the formation of regular aggregates of phthalocyanine compound (1). Furthermore, as is clear from Comparative Examples 4 and 5 in Table 4, when phthalocyanine compound B, which does not correspond to phthalocyanine compound (1), is used, the residue and contrast are inferior regardless of the proportion of phthalocyanine compound B in the colorant (A). It is thought that the larger volume occupied by chlorine atoms compared to fluorine atoms inhibited the regular aggregation of phthalocyanine compounds, resulting in a lack of improvement in contrast and dissolution rate.

[0321] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible without departing from the intent and scope of the invention. [Explanation of symbols]

[0322] 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 transparent anode 51 Hole injection layer 52 Hole transport layer 53. Emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL elements 500 Organic Luminescent Materials

Claims

1. A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, The aforementioned (A) coloring agent comprises a phthalocyanine compound having a chemical structure represented by the following general formula (1) and a yellow coloring agent, A colored resin composition characterized in that the content of the phthalocyanine compound in the colorant (A) is 65% by mass or more and 90% by mass or less. 【Chemistry 1】 (In formula (1), A １ ~A １６ Each of these independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, A １ ~A １６ One or more of these represent a fluorine atom, and A １ ~A １６ One or more of these represent a base expressed by the following general formula (2). 【Chemistry 2】 (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

2. The colored resin composition according to claim 1, wherein the content of the phthalocyanine compound in the colorant (A) is 70% by mass or more and 90% by mass or less.

3. A in formula (1) １ ~A １６ The colored resin composition according to claim 1, wherein the halogen atom is a fluorine atom.

4. In the formula (1), A １ to A ４ where at least one of them is a fluorine atom, and A ５ to A ８ where at least one of them is a fluorine atom, and A ９ to A １２ where at least one of them is a fluorine atom, and A １３ to A １６ where at least one of them is a fluorine atom. The colored resin composition according to claim 1.

5. The colored resin composition according to claim 1, wherein the benzene ring in formula (2) has an alkoxycarbonyl group.

6. The colored resin composition according to claim 1, wherein X in formula (2) is an oxygen atom.

7. In the above formula (1), A １ ~A ４ One or more of these are groups represented by formula (2), and A ５ ~A ８ One or more of these are groups represented by formula (2), and A ９ ~A １２ One or more of these are groups represented by formula (2), and A １３ ~A １６ The colored resin composition according to claim 1, wherein one or more of the groups are represented by formula (2).

8. The colored resin composition according to claim 1, wherein the yellow colorant is at least one selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 185, and a nickel azo complex represented by the following formula (i). 【Transformation 3】

9. The colored resin composition according to claim 1, wherein the content of the yellow colorant in the colorant (A) is 10% by mass or more and 35% by mass or less.

10. The colored resin composition according to claim 1, wherein the content of the coloring agent (A) in the total solid content of the colored resin composition is 10% by mass or more and 80% by mass or less.

11. The colored resin composition according to claim 1, further comprising a dispersant, wherein the amine value of the dispersant is 90 mg KOH / g or more.

12. A cured product obtained by curing a colored resin composition according to any one of claims 1 to 11.

13. A color filter comprising pixels created using the colored resin composition described in any one of claims 1 to 11.

14. An image display device having the color filter described in claim 13.

Images