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

Abstract

The present invention relates to a colored resin composition, a cured product, a color filter, and an image display device. A colored resin composition is provided which has a fast developing solution speed even at a low pre-baking temperature. The colored resin composition of the present invention is characterized by containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, the aforementioned (A) colorant containing a phthalocyanine compound having a specific chemical structure and a yellow color material, and the aforementioned phthalocyanine compound in the aforementioned (A) colorant being contained at a specific ratio.

Description

[0001] This application is a divisional application of the application filed on March 15, 2023, with application number 202380026537.2 and entitled "Coloring Resin Composition, Cured Product, Color Filter and Image Display Device". Technical Field

[0002] This invention relates to coloring resin compositions, cured products, color filters, and image display devices.

[0003] This application claims priority under Japanese Patent Application No. 2022-040964, filed on March 16, 2022, the contents of which are incorporated herein by reference. Background Technology

[0004] Previously, methods for manufacturing color filters used in liquid crystal display devices included pigment dispersion, dyeing, electrodeposition, and printing. Among these, pigment dispersion, which possesses excellent balanced properties, is the most widely used method from the perspectives of spectral characteristics, durability, pattern shape, and precision.

[0005] In recent years, color filters have been required to offer higher brightness, higher contrast, and wider color gamut. As the colorant determining the color of a color filter, pigments are typically used from the perspectives of heat resistance and lightfastness. However, pigments, especially in terms of high brightness, are gradually failing to meet market demands, leading to active research into using dyes as a substitute for pigments. For example, research has been conducted on using phthalocyanine dyes in green pixel applications (see, for example, Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2020 / 171060 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] During their research, the inventors discovered that the solubility of the coloring resin composition described in Patent Document 1 in the developing solution varies significantly depending on the content ratio of the aforementioned phthalocyanine dye in the colorant. When the content ratio of the aforementioned phthalocyanine dye is low, the dissolution rate in the developing solution is slower. In particular, this tendency is more pronounced at lower pre-baking temperatures.

[0011] It was also found that the coloring resin composition described in Patent Document 1 may produce residue after development due to the content ratio of the aforementioned phthalocyanine dye in the colorant, and the contrast of the resulting green pixels may be poor.

[0012] Therefore, the object of the present invention is to provide a coloring resin composition that dissolves quickly in the developer even at low pre-baking temperatures and has high production efficiency.

[0013] Furthermore, the object of the present invention is to provide a coloring resin composition in which the generation of residue is suppressed and the resulting green pixels have excellent contrast.

[0014] Solution for solving the problem

[0015] The inventors conducted in-depth research and found that the above-mentioned problems could be solved by setting the content ratio of a specific phthalocyanine compound in the colorant to a specific ratio or higher, thereby realizing the present invention.

[0016] That is, the present invention has the following structure.

[0017] [1] A coloring resin composition, characterized in that it contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerization monomer.

[0018] The aforementioned colorant (A) comprises a phthalocyanine compound having the chemical structure shown in the following general formula (1) and a yellow pigment.

[0019] The aforementioned phthalocyanine compound in the aforementioned colorant (A) is present in an amount of 65% by mass or more and 90% by mass or less.

[0020]

[0021] (In formula (1), A) 1 ~A 16 Each of these can independently represent a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below. Wherein, A 1 ~A 16 One or more of them represent fluorine atoms, and A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0022]

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

[0024] [2] According to the coloring resin composition of [1], wherein the content of the aforementioned phthalocyanine compound in the aforementioned colorant (A) is 70% by mass or more and 90% by mass or less.

[0025] [3] According to the coloring resin composition of [1] or [2], wherein A in the aforementioned formula (1) is...1 ~A 16 The halogen atom in it is a fluorine atom.

[0026] [4] A coloring resin composition according to any one of [1] to [3], wherein, in the aforementioned formula (1), A 1 ~A 4 One or more of them are fluorine atoms, A 5 ~A 8 One or more of them are fluorine atoms, A 9 ~A 12 One or more of them are fluorine atoms, and A 13 ~A 16 One or more of them are fluorine atoms.

[0027] [5] A coloring resin composition according to any one of [1] to [4], wherein the benzene ring in the aforementioned formula (2) has an alkoxy carbonyl group.

[0028] [6] A coloring resin composition according to any one of [1] to [5], wherein X in the aforementioned formula (2) is an oxygen atom.

[0029] [7] A coloring resin composition according to any one of [1] to [6], wherein, in the aforementioned formula (1), A 1 ~A 4 One or more of them are groups represented by the aforementioned formula (2), A 5 ~A 8 One or more of them are groups represented by the aforementioned formula (2), A 9 ~A 12 One or more of them are groups represented by the aforementioned formula (2), and A 13 ~A 16 One or more of them are groups represented by the aforementioned formula (2).

[0030] [8] The coloring resin composition according to any one of [1] to [7], wherein the aforementioned yellow colorant is selected from at least one of the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 185 and the nickel azo complex shown in formula (i) below.

[0031]

[0032] [9] According to the coloring resin composition of [1], wherein the yellow pigment in the aforementioned (A) colorant is present in an amount of 10% by mass or more and 35% by mass or less.

[0033]

[10] The coloring resin composition according to any one of [1] to [9], wherein the content of the aforementioned colorant (A) in the total solids of the coloring resin composition is 10% by mass or more and 80% by mass or less.

[0034]

[11] A cured product formed by curing a coloring resin composition of any one of [1] to

[10] .

[0035]

[12] A color filter having pixels made using a coloring resin composition of any one of [1] to

[10] .

[0036]

[13] An image display device having a color filter of

[12] .

[0037] The effects of the invention

[0038] According to the present invention, a coloring resin composition that dissolves quickly in the developer even at low pre-baking temperatures and has high production efficiency can be provided.

[0039] In addition, according to the present invention, a coloring resin composition can be provided in which the generation of residue is suppressed and the resulting green pixels have excellent contrast. Attached Figure Description

[0040] Figure 1 This is a cross-sectional schematic diagram illustrating an example of an organic EL element having the color filter of the present invention.

[0041] Explanation of reference numerals in the attached figures

[0042] 10 Transparent support substrate

[0043] 20 pixels

[0044] 30 Organic protective layer

[0045] 40 Inorganic oxide film

[0046] 50 transparent anode

[0047] 51 Hole Injection Layer

[0048] 52 Hole Transport Layer

[0049] 53. Emissive Layer

[0050] 54 Electron Injection Layer

[0051] 55 Cathode

[0052] 100 Organic EL Components

[0053] 500 Organic Light-Emitting Organoluminescent Materials Detailed Implementation

[0054] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) of polystyrene obtained using GPC (gel permeation chromatography).

[0055] In this invention, "total solids content" refers to all components in the coloring resin composition except for the solvent. Even if a component other than the solvent is liquid at room temperature, it is not contained in the solvent but is included in the total solids content.

[0056] In this invention, unless otherwise specified, "amine value" refers to the amine value converted from the effective solid component, which is expressed as the mass of KOH equivalent to the amount of alkali per 1g of dispersant solid component.

[0057] In this invention, "CI" refers to the Color Index.

[0058] [1] Coloring resin composition

[0059] The coloring 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-mentioned components may be incorporated if necessary.

[0060] [1-1] (A) Coloring agent

[0061] The colorant (A) contained in the coloring resin composition of the present invention comprises a phthalocyanine compound (hereinafter sometimes referred to as "phthalocyanine compound (1)") having the chemical structure shown in the following general formula (1) and a yellow pigment. The phthalocyanine compound (1) in the colorant (A) is present in an amount of 65% by mass or more and 90% by mass or less.

[0062]

[0063] In equation (1), A 1 ~A 16 Each of these can independently represent a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below. Wherein, A 1 ~A 16 One or more of them represent fluorine atoms, and A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0064]

[0065] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.

[0066] The coloring resin composition of the present invention contains a colorant (A) comprising a phthalocyanine compound (1), wherein the content of the phthalocyanine compound (1) in the colorant (A) is 65% by mass or more and 90% by mass or less.

[0067] In phthalocyanine compound (1), one or more hydrogen atoms constituting the phthalocyanine skeleton are replaced by fluorine atoms with small atomic radii, resulting in a structure that does not easily hinder the association of phthalocyanine compounds (1) with each other. Therefore, it can be considered that when the intermolecular distance is shortened by heating during pre-baking, an associative body will be formed, thereby forming a complex by wrapping the (C) alkali-soluble resin contained in the coloring resin composition of the present invention around it, and the dissolution rate is faster than that of phthalocyanine compound (1) alone. At this time, if the pre-baking temperature is low, the association of phthalocyanine compounds (1) with each other is not likely to occur. On the other hand, it can be considered that by making the content of phthalocyanine compound (1) 65% by mass or more, the association between phthalocyanine compounds (1) is not easily hindered by other colorants. Even at a low pre-baking temperature, regular assemblage of phthalocyanine compound (1) will be formed, and local aggregation is not likely to occur. Therefore, while the transmittance and contrast are increased, the molecular weight based on the assemblage is increased. As a result, alkali-soluble resin is easily wrapped around it, so the dissolution rate is faster and the generation of residue during development is also suppressed.

[0068] (A) 1 ~A 16 )

[0069] In the aforementioned equation (1), A 1 ~A 16 Each of these can independently represent a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below. Wherein, A 1 ~A 16 One or more of them represent fluorine atoms, and A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0070]

[0071] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.

[0072] As A 1 ~A 16 Halogen atoms in the solution can be exemplified by fluorine, chlorine, and bromine atoms. From the viewpoint of maximizing brightness, fluorine atoms are preferred.

[0073] In addition, A 1 ~A 16Preferably, one or more fluorine atoms are present, more preferably six or more, even more preferably seven or more, particularly preferably eight or more. The number of fluorine atoms is 15 or less, preferably 12 or less, and more preferably 10 or less. By setting the value to the aforementioned lower limit or above, there is a tendency for increased stability of the phthalocyanine compound (1). Furthermore, by setting the value to the aforementioned upper limit or below, there is a tendency for increased affinity with dispersants and solvents in the coloring resin composition. The aforementioned 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.

[0074] (X)

[0075] In formula (2), X represents a divalent linking group. There are no particular limitations on the divalent linking group; examples include oxygen atoms, sulfur atoms, and -N(R) atoms. a1 )-base (R a1 (Representing a hydrogen atom or an aliphatic hydrocarbon group with 1 to 6 carbon atoms). From the viewpoint of stability during firing, oxygen atoms or sulfur atoms are preferred, and oxygen atoms are more preferred.

[0076] (The benzene ring may contain any of the substituents)

[0077] The benzene ring in formula (2) may optionally have any substituents. There are no particular limitations on the substituents; examples include halogen atoms, alkyl groups (-R...), etc. A alkyl, alkoxy (-OR) A Base (where R) A (representing alkyl), alkoxycarbonyl (-COOR) A Base (where R) A (representing alkyl), aryl (-R) B aryl group (-OR) B Base (where R) B (representing aryl) and aryloxycarbonyl (-COOR) B Base (where R) B (representing aryl). From the viewpoint of developing solubility and brightness, alkoxycarbonyl is preferred.

[0078] The alkyl groups contained in these groups (R) A It can be linear, branched, or cyclic. From the viewpoint of affinity with organic solvents, linear alkyl groups are preferred.

[0079] Alkyl (R) AThe number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. By setting it to the aforementioned lower limit or above, there is a tendency to suppress aggregation and foreign matter; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to improve solvent affinity and stability over time. The aforementioned 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 even more preferably 2 to 4.

[0080] As alkyl (R) A Examples of such compounds include methyl, ethyl, propyl, butyl, pentyl, and hexyl. From the viewpoint of inhibiting aggregation, methyl or ethyl is preferred, and ethyl is more preferred.

[0081] The aryl group (R) contained in these groups B () can be an aromatic hydrocarbon cyclic group or an aromatic heterocyclic group.

[0082] Aryl (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, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By setting it to the aforementioned lower limit or above, there is a tendency to suppress aggregation due to steric repulsion; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to improve solvent affinity and stability over time. The aforementioned upper and lower limits can be combined arbitrarily. 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.

[0083] Aromatic hydrocarbon rings, as aromatic hydrocarbon cyclic groups, can be monocyclic or fused. Examples of aromatic hydrocarbon cyclic groups include benzene rings, naphthalene rings, pentanene rings, indene rings, azurite rings, and heptane rings, which have one free valence.

[0084] Aromatic heterocycles, as part of aromatic heterocyclic groups, can be either monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thioran rings, pyridine rings, 1,3-oxazole rings, isoxazole rings, 1,3-thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazine rings, pyrazine rings, pyrimidine rings, pyridazine rings, 1,3,5-triazine rings, benzofuran rings, 2-benzofuran rings, benzothiophene rings, 2-benzothiophene rings, 1H-pyrrolidine rings, indole rings, isoindole rings, indoleazine rings, 2H-1-benzopyran rings, 1H-2-benzopyran rings, quinoline rings, isoquinoline rings, 4H-quinazine rings, benzimidazole rings, 1H-indazole rings, quinoxaline rings, quinazoline rings, cyclophosphine rings, phthalazine rings, 1,8-naphthidine rings, purine rings, and pteridine rings.

[0085] When the benzene ring in formula (2) has any substituents, its number of substitutions is not particularly limited. From the viewpoint that dye molecules can stack π-π on each other, heat resistance is improved, and brightness reduction caused by dye decomposition is suppressed, the number of substitutions is preferably 1 relative to 1 benzene ring.

[0086] When the benzene ring in formula (2) has any substituent, its substitution position can be ortho, meta, or para. From the viewpoint that it can be stacked to present a close-packed structure, para is preferred.

[0087] A 1 ~A 16 One or more of them represent fluorine atoms. From the viewpoint of improving brightness through the formation of intermolecular associations of phthalocyanine compound (1), the preferred option is: A 1 ~A 4 One or more of them are fluorine atoms, A 5 ~A 8 One or more of them are fluorine atoms, A 9 ~A 12 One or more of them are fluorine atoms, and A 13 ~A 16 One or more of them are fluorine atoms; more preferably: A 1 ~A 4 Two or more of them are fluorine atoms, A 5 ~A 8 Two or more of them are fluorine atoms, A 9 ~A 12 Two or more of them are fluorine atoms, and A 13 ~A 16 Two or more of them are fluorine atoms.

[0088] In equation (1), A 1 ~A 16 One or more of the groups represented by formula (2). From the viewpoint of solubility in organic solvents and brightness, the preferred group is: A 1 ~A 4 One or more of them are groups represented by formula (2), A 5 ~A 8 One or more of them are groups represented by formula (2), A 9 ~A 12 One or more of them are groups represented by formula (2), and A 13 ~A 16 One or more of them are groups represented by formula (2); more preferably: A 1 ~A 4 Two or more of them are groups represented by formula (2), A 5 ~A8 Two or more of them are groups represented by formula (2), A 9 ~A 12 Two or more of them are groups shown in formula (2), and A 13 ~A 16 Two or more of them are groups represented by formula (2).

[0089] From the perspective of suppressing brightness reduction through efficient stacking, the preferred option is: A 2 A 3 A 6 A 7 A 10 A 11 A 14 and A 15 The group is shown in formula (2), and A 1 A 4 A 5 A 8 A 9 A 12 A 13 and A 16 It is a halogen atom; particularly preferred is: A 2 A 3 A 6 A 7 A 10 A 11 A 14 and A 15 The group is shown in formula (2), and A 1 A 4 A 5 A 8 A 9 A 12 A 13 and A 16 It is a fluorine atom.

[0090] Examples of phthalocyanine compounds (1) include the following compounds.

[0091]

[0092] It should be noted that in the above formula, Et represents ethyl.

[0093]

[0094]

[0095]

[0096] As a method for manufacturing phthalocyanine compound (1), a known method may be used, for example, the method described in Japanese Patent Application Publication No. 05-345861.

[0097] Regarding the content ratio of the phthalocyanine compound (1) in the coloring resin composition of the present invention in the colorant (A), it 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 in the total solids content of the colorant (A). By setting it to the aforementioned lower limit value or above, there is a tendency for the dissolution rate to increase even at low pre-baking temperatures, and a tendency for the adhesion to the substrate to become better. Furthermore, there is a tendency for the contrast to increase, and a tendency for residue to be suppressed.

[0098] Furthermore, by setting it below the aforementioned upper limit, there is a tendency to ensure the chromaticity required by the color filter. The aforementioned upper and lower limits can be combined arbitrarily. For example, regarding the content ratio of phthalocyanine compound (1) in the coloring resin composition in colorant (A), it is 65 to 90% by mass in the total solids content of colorant (A), preferably 70 to 90% by mass, more preferably 70 to 85% by mass, and even more preferably 70 to 80% by mass.

[0099] (A) The colorant contains phthalocyanine compound (1) and also contains yellow pigment.

[0100] By including yellow pigment in addition to phthalocyanine compound (1) in colorant (A), there is a tendency to achieve the color reproduction required for green pixels.

[0101] Examples of yellow pigments include yellow pigments and yellow dyes.

[0102] 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, 81, 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, 1 50, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191 : 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and compounds formed by inserting other compounds into the 1:1 complex of azobarbituric acid and nickel shown in formula (i) below or its tautomers (hereinafter sometimes referred to as "nickel azo complex shown in formula (i)").

[0103]

[0104] Other compounds that can be listed as the nickel azo complexes shown in formula (i) include, for example, compounds shown in formula (ii) below.

[0105]

[0106] From the viewpoint of high brightness and high color gamut, the nickel azo complexes shown in CI pigment yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and formula (i) are preferred, and the nickel azo complexes shown in CI pigment yellow 83, 138, 139, 180, 185, and formula (i) are even more preferred.

[0107] Examples of yellow dyes include barbiturate azo dyes, pyridone azo dyes, pyrazolinone azo dyes, quinoline ketone dyes, and anthocyanin dyes. Specific examples include compounds described in Japanese Patent Application Publication No. 2010-168531.

[0108] As yellow dyes, among the yellow dyes classified as dyes in the dye 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, 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, 128, and 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 direct CI 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 mordant CI dyes include CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65. Preferred examples include CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; 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, 128, 134, 135, 138. , 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, and their derivatives.

[0109] From the perspective of suppressing dye decomposition during firing, the preferred solvent yellows are CI 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163.

[0110] From the viewpoint of color reproducibility required for green pixels, the yellow pigment contained in colorant (A) is preferably CI pigment yellow 138, 185, or the nickel azo complex shown in formula (i), and more preferably CI pigment yellow 138.

[0111] (A) The colorant may contain other colorants besides phthalocyanine compound (1) and yellow pigment. Examples of other colorants include pigments and dyes. When the coloring resin composition of the present invention is used for green pixel applications, green pigments and green dyes are preferred, for example.

[0112] Examples of green pigments include CI pigments 7, 36, 58, 59, 62, and 63, with CI pigment 58 being the preferred choice from a brightness perspective.

[0113] Among the green dyes classified as dyes in the dye index, examples of CI solvent dyes include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. Examples of CI acid dyes include 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 thermal firing, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred.

[0114] 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. Solvent milling, for example, is suitable for micronizing the pigment.

[0115] The content of colorant (A) in the coloring resin composition of the present invention is not particularly limited. It is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 30% by mass or more, and 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. By setting it to the aforementioned lower limit or above, there is a tendency to reproduce a wide range of hues. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to ensure stability over time. The aforementioned upper and lower limits can be combined arbitrarily. For example, regarding the content of colorant (A) in the coloring resin composition, it is preferably 10-80% by mass, more preferably 15-80% by mass, further preferably 20-60% by mass, even more preferably 25-50% by mass, and particularly preferably 30-40% by mass in the total solids of the coloring resin composition.

[0116] The proportion of phthalocyanine compound (1) in the coloring resin composition of the present invention is not particularly limited. It is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and 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. By setting it to the aforementioned lower limit or above, there is a tendency to increase brightness; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to ensure stability over time. The aforementioned upper and lower limits can be combined arbitrarily. For example, regarding the proportion of phthalocyanine compound (1) in the coloring resin composition, it is more preferably 3 to 50% by mass, more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass in the total solids of the coloring resin composition.

[0117] In the total solids composition of the coloring resin composition of the present invention, the yellow pigment 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. By setting it to the aforementioned lower limit or above, there is a tendency to reproduce the color required by the green pixel; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for the dissolution rate to increase, and consequently, a tendency for the contrast to increase. The aforementioned upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition includes a yellow pigment as another colorant, the content of the yellow pigment in the total solids composition of the coloring resin composition is preferably 2 to 25% by mass, more preferably 4 to 20% by mass, and even more preferably 6 to 10% by mass.

[0118] Regarding the proportion of yellow pigment in colorant (A), it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and even more preferably 20% by mass or more. Additionally, it is preferably 35% by mass or less, more preferably 30% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency to reproduce the color required by the green pixel; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for the dissolution rate to increase, and consequently, a tendency for the contrast to increase. The aforementioned upper and lower limits can be combined arbitrarily. For example, when colorant (A) contains yellow pigment, regarding the proportion of yellow pigment in colorant (A), it is preferably 5 to 35% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass.

[0119] The mass ratio of phthalocyanine compound (1) to yellow pigment (phthalocyanine compound (1) / yellow pigment) is preferably 1.8 or more, more preferably 2 or more, and even more preferably 2.3 or more. It is also preferably 9 or less, more preferably 7 or less, and even more preferably 6 or less. By setting it to the aforementioned lower limit or above, there is a tendency for the dissolution rate to increase. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to reproduce the color required for the green pixel. The aforementioned upper and lower limits can be combined arbitrarily. For example, when the colorant (A) contains yellow pigment, the mass ratio of phthalocyanine compound (1) to yellow pigment (phthalocyanine compound (1) / yellow pigment) 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.

[0120] When the coloring resin composition of the present invention contains other colorants, the proportion of these colorants is not particularly limited. Preferably, it is 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. By setting the aforementioned lower limit or above, there is a tendency to reproduce a wide range of hues; conversely, by setting the aforementioned upper limit or below, there is a tendency to ensure stability over time. The aforementioned upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition contains other colorants, the proportion of these other colorants in the total solids of the coloring resin composition is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, further preferably 5 to 25% by mass, even more preferably 7 to 25% by mass, and particularly preferably 10 to 20% by mass.

[0121] [1-2] (B) Solvent

[0122] (B) The solvent has the function of dissolving or dispersing (A) colorant, (C) alkali-soluble resin, (D) photopolymerization initiator, (E) photopolymerizable monomer, other components and adjusting viscosity in the coloring resin composition and pigment dispersion of the present invention.

[0123] As a solvent (B), any solvent that can dissolve or disperse the components is acceptable.

[0124] Examples of diol monoalkyl ethers that can be listed as solvents (B) include: 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 tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, etc.

[0125] Dialkyl ethers of glycols, 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;

[0126] 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, 3-methyl-3-methoxybutyl acetate, and other diol alkyl ether acetates;

[0127] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0128] Alkyl acetates such as cyclohexyl acetate;

[0129] Ethers such as pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0130] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0131] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0132] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0133] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0134] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0135] 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 decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone, and other chain or cyclic esters;

[0136] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0137] Halogenated hydrocarbons such as chlorobutane and chloropentane;

[0138] Ether ketones such as methoxymethylpentanone;

[0139] Nitriles such as acetonitrile and benzonitrile.

[0140] Commercially available solvents include, for example, mineral oil, Varsol #2, Apco #18 solvent, Apcothinner, Socal solvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (diglyme) (all trade names). These solvents can be used individually or in combination of two or more.

[0141] When forming the pixels of the color filter using photolithography, the solvent for (B) is preferably a solvent with a boiling point of 100 to 200°C (under a pressure of 1013.25 hPa. Hereinafter, the same applies to boiling point). A solvent with a boiling point of 120 to 170°C is more preferred.

[0142] From the viewpoint of good balance of coatability, surface tension, etc., and high solubility of the constituent components in the composition, glycol alkyl ether acetates are preferred.

[0143] Diol alkyl ether acetates can be used alone or in combination with other solvents.

[0144] As a solvent for use in combination, glycol monoalkyl ethers are particularly preferred. From the viewpoint of the solubility of the constituent components in the composition, propylene glycol monomethyl ether is preferred.

[0145] Diol monoalkyl ethers are highly polar. If too much is added, the pigments tend to aggregate, and the viscosity of the resulting colored resin composition gradually increases, which reduces its storage stability. Therefore, when using diol monoalkyl ethers in combination, the proportion of diol monoalkyl ethers in the solvent (B) is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.

[0146] Alternatively, solvents with boiling points of 150°C or higher can be used in combination. While using solvents with boiling points of 150°C or higher makes the coloring resin composition less prone to drying, it also prevents the disruption of the interrelationships of the components in the pigment dispersion due to rapid drying. When using solvents with boiling points of 150°C or higher, the content of the solvent with a boiling point of 150°C or higher in solvent (B) is preferably 3-50% by mass, more preferably 5-40% by mass, and particularly preferably 5-30% by mass. By setting this to the aforementioned lower limit or higher, it is easier to avoid defects such as foreign matter caused by the precipitation and curing of colorant components at the tip of the slit nozzle. Furthermore, by setting this to the aforementioned upper limit or lower, it is easier to avoid problems such as slow drying speed of the composition, poor cycle time of the reduced pressure drying process, and pin marks from pre-baking.

[0147] Solvents with a boiling point above 150°C can be glycol alkyl ether acetates, or glycol alkyl ethers, in which case it is not necessary to contain a solvent with a boiling point above 150°C.

[0148] Examples of solvents with a boiling point of 150°C or higher include diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and glyceryl triacetate.

[0149] When forming the pixels of a color filter using inkjet printing, the solvent for (B) is preferably a solvent with a boiling point of 130°C or higher and 300°C or lower, more preferably 150°C or higher and 280°C or lower. By setting the value to the aforementioned lower limit or higher, there is a tendency for the uniformity of the resulting coating film to become better, and by setting the value to the aforementioned upper limit or lower, there is a tendency for residual solvent during firing to be reduced more easily.

[0150] From the viewpoint of the uniformity of the resulting coating, the solvent with a vapor pressure of 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 1 mmHg or less can be used.

[0151] When manufacturing color filters using inkjet printing, the ink ejected from the nozzle is extremely fine, ranging from several to tens of pL. Therefore, there is a tendency for the solvent to evaporate before reaching the nozzle or pixel array, resulting in ink concentration / drying. To avoid this, solvent (B) preferably contains a solvent with a high boiling point, specifically, preferably a solvent with a boiling point of 180°C or higher. More preferably, it contains a solvent with a boiling point of 200°C or higher, and particularly preferably 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 proportion of this solvent in solvent (B) is preferably 50% by mass or higher, more preferably 70% by mass or higher, and most preferably 90% by mass or higher. By setting this to the aforementioned lower limit or higher, there is a tendency to effectively prevent solvent evaporation from the droplets.

[0152] Solvents with boiling points above 180°C include diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glyceryl triacetate.

[0153] To adjust the viscosity of the coloring resin composition and the solubility of the solid components, a solvent with a boiling point below 180°C may be included. Such a solvent is preferably one with low viscosity, high solubility, and low surface tension, such as ethers, esters, or ketones. Examples of preferred solvents include cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate.

[0154] If the solvent contains alcohols, the inkjet printing stability may deteriorate. When alcohols are used in combination, the alcohol content in solvent (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0155] (B) The proportion of solvent in the coloring resin composition of the present invention is not particularly limited, but the 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. By setting it below the aforementioned upper limit, there is a tendency for a coating film to be formed more easily. On the other hand, considering the viscosity suitable for coating, 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. The above upper and lower limits can be combined arbitrarily. For example, the proportion of solvent in the coloring 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.

[0156] [1-3] (C) Alkali-soluble resin

[0157] The coloring 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 based on photopolymerization and solubility based on developer.

[0158] As (C) alkali-soluble resin, known polymeric compounds, such as those described in Japanese Patent Application Publication Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, and 2003-233179, can be used.

[0159] The following resins (C-1) to (C-5) are preferably listed.

[0160] (C-1): A resin obtained by adding an unsaturated monocarboxylic acid to at least a portion of the epoxy groups in a copolymer of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or by adding a polycarboxylic acid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)").

[0161] (C-2): A linear, alkali-soluble resin containing carboxyl groups in its main chain (hereinafter sometimes referred to as "resin (C-2)").

[0162] (C-3): A resin obtained by adding an epoxy-containing unsaturated compound to the carboxyl group of the aforementioned resin (C-2) (hereinafter sometimes referred to as "resin (C-3)").

[0163] (C-4): (Meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)")

[0164] (C-5): Epoxy (meth)acrylate resins containing carboxyl groups (hereinafter sometimes referred to as "resin (C-5)")

[0165] Resin (C-1) is particularly preferred.

[0166] Resins (C-2) to (C-5) need only have solubility to the extent that they can be dissolved by alkaline developer to achieve the target development process, and the resins described as the same item in Japanese Patent Application Publication No. 2009-025813 are preferred respectively.

[0167] (C-1): A resin obtained by adding an unsaturated monocarboxylic acid to at least a portion of the epoxy groups of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or by adding a polyacid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction.

[0168] One of the preferred methods for obtaining resin (C-1) is to obtain a resin by adding 10 to 100 mol% of the epoxy groups of a copolymer containing 5 to 90 mol% of epoxy groups to an unsaturated monocarboxylic acid, or by adding 10 to 100 mol% of the hydroxyl groups generated by the addition reaction to a polyacid anhydride.

[0169] Examples of epoxy-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. These epoxy-containing (meth)acrylates can be used alone or in combination of two or more.

[0170] As another free radical polymerizable monomer for copolymerization with epoxy-containing (meth)acrylates, mono(meth)acrylates having the structure shown in the following general formula (V) are preferred.

[0171]

[0172] In equation (V), R 91 ~R 98 Each can independently represent an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. It should be noted that R... 96 With R 98 Or R 95 With R 97 They can be arbitrarily connected to form a loop.

[0173] In equation (V), R 96 With R 98 Or R 95 With R 97 The ring formed by the connection is preferably an aliphatic ring, which can be either saturated or unsaturated, and the number of carbon atoms is preferably 5 to 6.

[0174] Among them, the structure shown in formula (V) is preferably the structure shown in the following general formulas (Va), (Vb) or (Vc).

[0175] By introducing these structures into an alkali-soluble resin, when the coloring resin composition of the present invention is used for filter forming, there is a tendency for the heat resistance of the coloring resin composition to be improved and the strength of the pixels formed using the coloring resin composition to be increased.

[0176] Mono(meth)acrylates having the structure shown in formula (V) can be used alone or in combination of two or more.

[0177]

[0178] As a mono(meth)acrylate having the structure shown in formula (V), any known mono(meth)acrylate can be used as long as it has the structure shown in formula (V), and the mono(meth)acrylate shown in the following general formula (VI) is particularly preferred.

[0179]

[0180] In equation (VI), R 89 R represents a hydrogen atom or a methyl group. 90 The structure shown in expression (V).

[0181] When the copolymer of epoxy-containing (meth)acrylate and other free radical polymerizable monomers contains repeating units of mono(meth)acrylate as shown in formula (VI), the proportion of the repeating units of mono(meth)acrylate as shown in 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 of other free radical polymerizable monomers.

[0182] Other free radical polymerizable monomers besides the mono(meth)acrylates shown in formula (VI) are not particularly limited, and examples include vinyl aromatics such as styrene, α-, ☐-, ☐-, ☐-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, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, and so on. Hexyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantane (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, anthracene nonyl (meth)acrylate, piperyl (meth)acrylate, salicylates (meth)acrylate, furanyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuran (meth)acrylate, (meth)acrylate Pyran acrylates, benzyl acrylate, styrene acrylate, cresol acrylate, 1,1,1-trifluoroethyl acrylate, perfluoroethyl acrylate, perfluoropropyl acrylate, perfluoroisopropyl acrylate, triphenylmethyl acrylate, cumyl acrylate, 3-(N,N-dimethylamino)propyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. (meth)acrylates; acrylamide, N,N-dimethylamide, N,N-diethylamide, etc. N,N-Dipropylamide, N,N-Diisopropylamide (meth)acrylic acid, anthraquinone (meth)acrylic acid, and other (meth)acrylic acids; vinyl compounds such as (meth)acrylanilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itacrylic acid; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

[0183] Among these other free radical 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.

[0184] When the copolymer of epoxy-containing (meth)acrylates and other free radical polymerizable monomers contains any repeating unit from styrene, benzyl (meth)acrylate or monomaleimide, the total percentage of repeating units from styrene, benzyl (meth)acrylate and monomaleimide is preferably 1 to 70 mol% of the repeating units from the other free radical polymerizable monomers, more preferably 3 to 50 mol%.

[0185] In the copolymerization of epoxy-containing (meth)acrylates with other free radical polymerizable monomers, known solution polymerization methods can be used. There are no particular limitations on the solvent used, as long as it is inactive for free radical polymerization; commonly used organic solvents can be used.

[0186] Solvents used in solution polymerization include, for example: ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellolytic acetate, and butyl cellolytic acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, and butyl carbitol. The following solvents are permitted: diethylene glycol dialkyl ethers; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; 1,4-dioxane, tetrahydrofuran, and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and other ketones; benzene, toluene, xylene, octane, decane, and other hydrocarbons; petroleum ethers, naphtha, hydrogenated naphtha, solvent naphtha, and other petroleum-based solvents; methyl lactate, ethyl lactate, butyl lactate, and other lactate esters; dimethylformamide, N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

[0187] In solution polymerization, the amount of solvent used is preferably 30 to 1000 parts by mass relative to 100 parts by mass of the resulting copolymer, more preferably 50 to 800 parts by mass. By keeping the amount of solvent used within the aforementioned range, there is a tendency to easily control the molecular weight of the copolymer.

[0188] There are no particular limitations on the free radical polymerization initiator used in copolymerization reactions, as long as it can initiate free radical polymerization. Commonly used organic peroxide catalysts or azo compound catalysts can be used. Examples of well-known organic peroxide catalysts include those classified as peroxide ketones, peroxy ketals, hydrogen peroxide, diallyl peroxides, diacid peroxides, peroxide esters, and peroxydicarbonates.

[0189] Examples of free radical polymerization initiators used in copolymerization reactions include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide, tert-hexyl peroxide, tert-butyl peroxide (2-ethylhexanoate), tert-hexyl peroxide (2-ethylhexanoate), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyl-3,3-isopropylperoxy Hydrogen peroxide, tert-butyl hydroperoxide, diisopropylbenzene peroxide, diisopropylbenzene hydroperoxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxide dicarbonate, diisopropyl peroxide dicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane.

[0190] Examples of azo compound catalysts include azobisisobutyronitrile (AIBN) and azobiscarbonamide (ACA).

[0191] Among these, one or more free radical polymerization initiators with suitable half-lives can be used depending on the polymerization temperature.

[0192] The amount of free radical polymerization initiator used relative to the total amount of monomers used in the copolymerization reaction is typically 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass per 100 parts by mass.

[0193] Regarding copolymerization, the monomers and free radical polymerization initiators used in the copolymerization reaction can be dissolved in a solvent and heated while stirring. Alternatively, the monomers with added free radical polymerization initiators can be added dropwise to the solvent while heating and stirring. Or, the free radical polymerization initiator can be added to the solvent and the monomers can be added dropwise while heating.

[0194] The reaction conditions can be set according to the target molecular weight.

[0195] In this invention, the copolymer of epoxy-containing (meth)acrylate and other free radical polymerizable monomers is preferably composed of 5 to 90 mol% repeating units from epoxy-containing (meth)acrylate and 10 to 95 mol% repeating units from other free radical polymerizable monomers; more preferably, it is composed of 20 to 80 mol% repeating units from epoxy-containing (meth)acrylate and 80 to 20 mol% repeating units from other free radical polymerizable monomers; particularly preferably, it is composed of 30 to 70 mol% repeating units from epoxy-containing (meth)acrylate and 70 to 30 mol% repeating units from other free radical polymerizable monomers.

[0196] By setting the proportion of repeating units from epoxy-containing (meth)acrylates above the aforementioned lower limit, there is a tendency for the addition of unsaturated monocarboxylic acids and polycarboxylic anhydrides, as described later, to become sufficient.

[0197] By setting the proportion of repeating units from other free radical polymerizable monomers above the aforementioned lower limit, there is a tendency for the heat resistance and strength to become sufficiently adequate.

[0198] Next, the unsaturated monocarboxylic acid (polymerizable component) and polycarboxylic acid anhydride (alkali-soluble component) are reacted with the epoxy groups of the copolymer of (meth)acrylate and other free radical polymerizable monomers containing epoxy groups.

[0199] As an unsaturated monocarboxylic acid that adds to an epoxy group, a known unsaturated monocarboxylic acid can be used, such as unsaturated carboxylic acids having an olefinic unsaturated double bond.

[0200] Examples of unsaturated monocarboxylic acids that undergo addition to an epoxy group include (meth)acrylic acid; crotonic acid; o-, m-, and p-vinylbenzoic acid; and monocarboxylic acids such as (meth)acrylic acid substituted at the α-position with a haloalkyl group, alkoxy group, halogen atom, nitro group, or cyano group, with (meth)acrylic acid being preferred. One type of unsaturated monocarboxylic acid may be used alone, or two or more may be used in combination.

[0201] By adding an unsaturated monocarboxylic acid to an epoxy group, polymerizability can be imparted to the resin (C-1).

[0202] The unsaturated monocarboxylic acid is added to the epoxy groups of the copolymer at a rate of, for example, 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. By setting this to a value above the aforementioned lower limit, there is a tendency for the coloring resin composition to have good stability over time.

[0203] As a method for adding an unsaturated monobasic acid to the epoxy group of a copolymer, a known method can be used.

[0204] In addition, a known polyacid anhydride can be used as the polyacid anhydride added to the hydroxyl group generated when an unsaturated monocarboxylic acid is added to the epoxy group of the copolymer.

[0205] Examples of polybasic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridged anhydride; and tribasic or higher acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides can be used individually or in combination of two or more.

[0206] By adding a polyacid anhydride to a hydroxyl group generated when an unsaturated monoacid is added to the epoxy group of the copolymer, alkali solubility can be imparted to the resin (C-1).

[0207] The amount of polyacid anhydride added to the hydroxyl group formed by adding an unsaturated monocarboxylic acid to the epoxy group of the copolymer is, for example, 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. By setting it to the upper limit mentioned above, there is a tendency for the residual film rate during development to become good; in addition, by setting it to the lower limit mentioned above, there is a tendency for the solubility to become sufficient.

[0208] As a method for adding a polyacid anhydride to a hydroxyl group generated by adding an unsaturated monocarboxylic acid to an epoxy group of a copolymer, a known method can be used.

[0209] Furthermore, in order to improve photosensitivity, after the addition of polyacid anhydrides, glycidyl (meth)acrylate or glycidyl ether compounds with polymerizable unsaturated groups can be added to a portion of the generated carboxyl group.

[0210] To improve developability, a glycidyl ether compound without polymerizable unsaturated groups can be added to a portion of the generated carboxyl group.

[0211] In addition, it can be added to both glycidyl ether compounds having polymerizable unsaturated groups and glycidyl ether compounds not having polymerizable unsaturated groups.

[0212] Examples of glycidyl ether compounds that do not have polymerizable unsaturated groups include those having phenyl or alkyl groups.

[0213] Commercially available glycidyl ether compounds that do not have polymerizable unsaturated groups include, for example, those manufactured by Nagase ChemteX under the trade names “DENACOL EX-111”, “DENACOL EX-121”, “DENACOL EX-141”, “DENACOL EX-145”, “DENACOL EX-146”, “DENACOL EX-171”, and “DENACOL EX-192”.

[0214] The structure of the resin (C-1) is described, for example, in Japanese Patent Application Publication No. 8-297366 and Japanese Patent Application Publication No. 2001-89533.

[0215] The weight-average molecular weight of the resin (C-1) converted from polystyrene by GPC is not particularly limited, but is preferably 3,000 to 100,000, and particularly preferably 5,000 to 50,000. By setting it to the aforementioned lower limit or above, there is a tendency for the heat resistance and film strength to become better; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for the solubility relative to the developer to become better.

[0216] As a standard for molecular weight distribution, the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mw / Mn) of the resin (C-1) is preferably 2.0 to 5.0.

[0217] From the viewpoint of coating curability under ultraviolet exposure, among (C) alkali-soluble resins, (C1) acrylic copolymer resins having olefinic unsaturated groups in the side chains are preferred.

[0218] (c1) The partial structure of the acrylic copolymer resin having olefin unsaturated groups in the side chain is not particularly limited. From the viewpoint of balancing the curing of the coating under ultraviolet exposure and the alkali solubility under alkali development, for example, the partial structure shown in the following general formula (CI) is preferred.

[0219]

[0220] In formula (CI), R 1 and R 2 Each atom can be represented independently as a hydrogen atom or a methyl group. * indicates a connecting bond.

[0221] From the viewpoint of sensitivity and alkali developability, the partial structure shown in formula (CI) is preferred.

[0222]

[0223] In formula (CI'), R 1 and R2 Each can independently represent a hydrogen atom or a methyl group. R X It represents a hydrogen atom or a polyacid residue.

[0224] A polybasic acid residue is a monovalent group formed 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, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, nethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0225] From the perspective of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0226] These polyacids can be used alone or in combination of two or more.

[0227] (c1) When the acrylic copolymer resin having a partial structure shown in formula (CI) has a side chain with olefinically unsaturated groups, the content ratio of the partial structure shown in formula (CI) in the acrylic copolymer resin having a side chain with olefinically unsaturated groups is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further 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 preferably 95 mol% or less, more preferably 90 mol% or less, further 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. By setting the value to the aforementioned lower limit or above, there is a tendency for improved coating curability under ultraviolet exposure; conversely, by setting the value to the aforementioned upper limit or below, there is a tendency for improved alkali solubility under alkali development. The aforementioned upper and lower limits can be combined arbitrarily. For example, (c1) the proportion of the partial structure shown in formula (CI) in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further 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.

[0228] (c1) When the acrylic copolymer resin with olefinic unsaturated groups on the side chain has a partial structure shown in formula (CI'), the content ratio of the partial structure shown in formula (CI') in the acrylic copolymer resin with olefinic unsaturated groups on the side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further 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 preferably 95 mol% or less, more preferably 90 mol% or less, further 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. By setting the value to the aforementioned lower limit or above, there is a tendency to improve the curability of the coating film under ultraviolet exposure; conversely, by setting the value to the aforementioned upper limit or below, there is a tendency to improve the alkali solubility under alkali development. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the partial structure shown in formula (CI') in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further 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.

[0229] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chain contains a partial structure as shown in formula (CI), other partial structures are not particularly limited. From the viewpoint of alkali solubility during alkali development, it is also preferable to have a partial structure as shown in the following general formula (CII).

[0230]

[0231] In formula (CII), R 3 R represents a hydrogen atom or a methyl group. 4 It indicates an alkyl group that may have a substituent, an aromatic cycloal group that may have a substituent, or an alkenyl group that may have a substituent.

[0232] (R) 4 )

[0233] In formula (CII), R 4 It indicates an alkyl group that may have a substituent, an aromatic cycloal group that may have a substituent, or an alkenyl group that may have a substituent.

[0234] As R 4The alkyl group in the alkyl group can be linear, branched, or cyclic. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. By setting the value to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting the value to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned 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, further preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.

[0235] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of reproducibility, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred.

[0236] Examples of substituents that may be optionally present in the alkyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0237] As R 4 The aromatic cyclic group in the aromatic cyclic group can include monovalent aromatic hydrocarbon cyclic groups and monovalent aromatic heterocyclic groups. The number of carbon atoms is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. By setting it to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic cyclic group is preferably 6 to 24, more preferably 6 to 22, even more preferably 6 to 20, and particularly preferably 6 to 18.

[0238] Aromatic hydrocarbon rings, which are the cyclic groups of aromatic hydrocarbons, can be monocyclic or fused rings. Examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, benzo[a]pyrene rings, cyclopentadiene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0239] Aromatic heterocycles, as members of aromatic heterocyclic groups, can be monocyclic or fused rings. Examples include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazine rings, quinoxaline rings, phenanthridine rings, primidine rings, quinazoline rings, quinazoline ketone rings, and azurite rings.

[0240] From the viewpoint of reproducibility, benzene ring group and naphthyl ring group are preferred, and benzene ring group is more preferred.

[0241] Examples of substituents that can be optionally present in the aromatic cyclic group include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluorine, hydroxyl, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0242] As R 4 The alkenyl group in the form can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, 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. By setting it to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned 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.

[0243] 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. From the viewpoint of reproducibility, vinyl and allyl are preferred, and vinyl is more preferred.

[0244] Examples of substituents that can be optionally present in the alkenyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0245] R 4The term indicates an alkyl group, an aromatic cycloal group, or an alkenyl group that may be substituted, with alkyl or alkenyl groups preferred from the viewpoint of developability and film strength, and alkyl groups being more preferred.

[0246] (c1) When the acrylic copolymer resin having a partial structure shown in formula (CII) in its side chain has olefinically unsaturated groups, the content ratio of the partial structure shown in formula (CII) in the acrylic copolymer resin having olefinically unsaturated groups in its side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. By setting it to the aforementioned lower limit or above, there is a tendency for increased alkali solubility; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for increased storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure shown in formula (CII) in the acrylic copolymer resin having olefinically unsaturated groups in its side chain in (c1) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, further preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

[0247] (c1) When an acrylic copolymer resin includes the partial structure shown in formula (CI), from the viewpoint of suppressing the decrease in brightness caused by the improvement in heat resistance, it is preferable to include the partial structure shown in the following general formula (CIII) as other included partial structures.

[0248]

[0249] In equation (CIII), R 5 R represents a hydrogen atom or a methyl group. 6 The denotes are alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, halogen, alkoxy, thiol, or alkyl thioether groups, which may be substituted with a substituted group. t represents an integer from 0 to 5.

[0250] (R) 6 )

[0251] In equation (CIII), R 6 The group may be alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, halogen atom, alkoxy, thiol, or alkyl thioether group with optional substituents.

[0252] As R 6The alkyl group in the alkyl group can be linear, branched, or cyclic. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and 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. By setting the value to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting the value to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned 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.

[0253] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of heat resistance, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred.

[0254] Examples of substituents that may be optionally present in the alkyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0255] As R 6 The alkenyl group in the form can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, 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. By setting it to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned 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.

[0256] 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. From the viewpoint of exposure sensitivity during ultraviolet exposure, vinyl and allyl groups are preferred, and vinyl is more preferred.

[0257] Examples of substituents that can be optionally present in the alkenyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0258] As R 6 The alkynyl group in the alkynyl group can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, 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. By setting it to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned 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.

[0259] Examples of alkynyl groups include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, and 1-hexyn-6-yl.

[0260] Examples of substituents that can be optionally present in the alkynyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0261] As R 6 Halogen atoms in the resin can be, for example, fluorine, chlorine, bromine, and iodine atoms. From the viewpoint of the storage stability of acrylic copolymer resins, fluorine atoms are preferred.

[0262] As R 6 The alkoxy group in the alkoxy group can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, 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. By setting it to the aforementioned lower limit or above, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting it to the aforementioned upper limit or below, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in 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.

[0263] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy.

[0264] Examples of substituents that can be optionally present on the alkoxy group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0265] As R 6 The alkyl sulfide group in the form can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 20 or fewer, more preferably 18 or fewer, even more preferably 16 or fewer, even more preferably 14 or fewer, and particularly preferably 12 or fewer. By setting it to the aforementioned lower limit or higher, there is a tendency for increased lipophilicity and increased solubility in solvents; conversely, by setting it to the aforementioned upper limit or lower, there is a tendency for increased hydrophilicity and increased alkali solubility. The aforementioned upper and lower limits can be combined arbitrarily.

[0266] 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.

[0267] Examples of alkyl thioether groups include methyl thioether, ethyl thioether, propyl thioether, and butyl thioether. From the viewpoint of reproducibility, methyl thioether and ethyl thioether groups are preferred.

[0268] Examples of substituents that may be optionally present in the alkyl group of the alkyl sulfide group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0269] R 6 The term indicates an alkyl group, an alkenyl group, an alkynyl group, a halogen group, an alkoxy group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkyl thioether group, which may be substituted with a substituent. From the viewpoint of reproducibility, a hydroxyl or carboxyl group is preferred, and a carboxyl group is more preferred.

[0270] In equation (CIII), t represents an integer from 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.

[0271] (c1) When the acrylic copolymer resin having a partial structure shown in formula (CIII) has a side chain with olefinic unsaturated groups, the content ratio of the partial structure shown in formula (CIII) in the acrylic copolymer resin having a side chain with olefinic unsaturated groups is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, particularly preferably 8 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve heat resistance and suppress the reduction of brightness. In addition, by setting it to the aforementioned upper limit or below, there is a tendency to increase the content ratio of other partial structures and improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure shown in formula (CIII) in the acrylic copolymer resin having a side chain with olefinic unsaturated groups is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, further preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

[0272] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chains has a partial structure as shown in formula (CI), from the viewpoint of reproducibility, it is also preferable to have a partial structure as shown in the following general formula (CIV) as another included partial structure.

[0273]

[0274] In formula (CIV), R 7 It represents a hydrogen atom or a methyl group.

[0275] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in the side chain contains a portion of the structure shown in formula (CIV), the content ratio of the portion of the structure shown in formula (CIV) in the acrylic copolymer resin having olefinic unsaturated groups in the 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 preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. By setting it to the aforementioned lower limit or above, there is a tendency to increase alkali solubility; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to increase the storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the portion of the structure shown in formula (CIV) in the acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

[0276] (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, further preferably 40 mg KOH / g or more, even more preferably 50 mg KOH / g or more, particularly preferably 60 mg KOH / g or more. It is also preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, further 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. By setting the value to the aforementioned lower limit or above, there is a tendency for increased alkali solubility. Furthermore, by setting the value to the aforementioned upper limit or below, there is a tendency for improved storage stability and substrate adhesion of the coloring resin composition. The aforementioned upper and lower limits can be combined arbitrarily. For example, (C) the acid value of the alkali-soluble resin is preferably 10~300 mgKOH / g, more preferably 30~300 mgKOH / g, even more preferably 40~250 mgKOH / g, even more preferably 50~200 mgKOH / g, and particularly preferably 60~150 mgKOH / g.

[0277] (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, further preferably 4000 or more, even more preferably 6000 or more, even more preferably 7000 or more, particularly preferably 8000 or more, and preferably 30000 or less, more preferably 20000 or less, even more preferably 15000 or less, and particularly preferably 10000 or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve heat resistance and coating curability; conversely, by setting it to the aforementioned upper limit or below, there is a tendency to improve alkali solubility. The aforementioned upper and lower limits can be combined arbitrarily. For example, (C) the weight-average molecular weight of the alkali-soluble resin is preferably 1000 to 30000, more preferably 2000 to 30000, further preferably 4000 to 20000, even more preferably 6000 to 20000, even more preferably 7000 to 15000, and particularly preferably 8000 to 10000.

[0278] The proportion of the alkali-soluble resin (C) in the coloring resin composition of the present invention is not particularly limited. However, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more in the total solids content of the coloring resin composition. Additionally, it is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting the aforementioned lower limit or above, there is a tendency to improve the curability of the coating film under ultraviolet exposure. Furthermore, by setting the aforementioned upper limit or below, there is a tendency to improve the solubility of the developer and suppress residue. The aforementioned upper and lower limits can be combined arbitrarily. For example, the proportion of the alkali-soluble resin (C) in the coloring resin composition is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, further preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass in the total solids content of the coloring resin composition.

[0279] [1-4] (D) Photopolymerization initiator

[0280] The coloring resin composition of the present invention contains a (D) photopolymerization initiator. By containing a (D) photopolymerization initiator, it is possible to impart curable properties to the film using photopolymerization.

[0281] (D) Photopolymerization initiators can also be used in the form of a mixture with accelerators (chain transfer agents) and additives such as sensitizing pigments, which can be added as needed (photopolymerization initiation system). The photopolymerization initiation system is a component that has the function of directly absorbing light or being photosensitized to cause decomposition or hydrogen abstraction reactions, thereby generating polymerization-active free radicals.

[0282] Examples of photopolymerization initiators include, for instance, metallocene compounds including ditectonic compounds described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; hexaaryl diimidazole derivatives, halomethyl triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and other free radical activators described in Japanese Patent Application Publication No. 10-39503; α-aminoalkyl phenyl ketone compounds; and oxime ester initiators described in Japanese Patent Application Publication No. 2000-80068.

[0283] The following lists the photopolymerization initiators that can be used in this invention.

[0284] 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)triazine and other halomethylated triazine derivatives;

[0285] 2-Trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole and other halomethylated oxadiazole derivatives;

[0286] Imidazole derivatives such as 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer;

[0287] Benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and other benzoin alkyl ethers;

[0288] Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone;

[0289] Benzophenone, milchone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives;

[0290] 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-morpholinopropane-1-one, 1,1,1-trichloromethyl-(p-butylphenyl) ketone and other acetophenone derivatives;

[0291] Thioxanone, 2-ethylthioxanone, 2-isopropylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 2,4-diethylthioxanone, 2,4-diisopropylthioxanone and other thioxanone derivatives;

[0292] Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

[0293] Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;

[0294] 9,10-Dimethylbenzophenazine and other phenazine derivatives;

[0295] anthrone derivatives such as benzoanthrone;

[0296] Diocene derivatives include bis(cyclopentadienyl)dichloride, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-tetrafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorophenyl)titanium, bis(cyclopentadienyl)-2,6-difluorophenyltitanium, bis(cyclopentadienyl)-2,4-difluorophenyltitanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and bis(cyclopentadienyl)-2,6-difluoro-3-(pyrrolo-1-yl)phenyltitanium.

[0297] α-aminoalkyl phenyl ketone compounds such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminoacetophenone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone;

[0298] Oxime esters such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime) ethyl ketone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0299] From the viewpoint of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred.

[0300] Oxime ester compounds possess structures that simultaneously absorb ultraviolet light, transfer light energy, and generate free radicals. Therefore, they exhibit high sensitivity even in small quantities and are thermally stable, enabling the design of coloring resin compositions that achieve high sensitivity even in small amounts. Particularly from the viewpoint of light absorption by i-rays (365 nm) from the exposure light source, oxime ester compounds having a carbazole ring with optional substituents are preferred.

[0301] Examples of oxime ester compounds include those represented by the general formula (I-1) below.

[0302]

[0303] In equation (I-1), R 21a Represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic cyclogroup optionally having a substituent.

[0304] R 21b It represents any substituent containing an aromatic ring or a heteroaromatic ring.

[0305] R 22a This indicates an alkyl acyl group or an aromatic acyl group that may optionally have a substituent.

[0306] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvent and sensitivity to exposure, it is preferably 1 or more, more preferably 2 or more, and 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.

[0307] Examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, and propyl.

[0308] Examples of substituents that may be optionally present in the alkyl group include aromatic cyclic 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, non-substituted groups are preferred.

[0309] As R 21a The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is not particularly limited, but from the viewpoint of solubility in the coloring resin composition, it is preferably 5 or more. Furthermore, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further 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 cyclic group is preferably 5 to 30, more preferably 5 to 20, further preferably 5 to 12, and particularly preferably 5 to 8.

[0310] Examples of aromatic cyclic groups include phenyl, naphthyl, pyridyl, furanyl, and fluorenyl. From the viewpoint of reproducibility, phenyl, naphthyl, and fluorenyl are preferred, and phenyl and fluorenyl are more preferred.

[0311] Examples of substituents that may be optionally present in the aromatic cyclic group include hydroxyl, alkyl, alkoxy, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of reproducibility, hydroxyl and carboxyl groups are preferred, and carboxyl groups are more preferred. Examples of substituents in alkyl and alkoxy groups that may be optionally present include hydroxyl, alkoxy, halogen, and nitro groups.

[0312] From the perspective of radioactivity, as R 21a Preferably, it is an alkyl group having a substituent, more preferably an unsubstituted alkyl group, and even more preferably methyl.

[0313] R 21b The substituent may be any group containing an aromatic ring or a heteroaromatic ring. From the viewpoint of solubility in solvents and sensitivity to exposure, it is preferable to have a carbazole group, a thioxanone group, a diphenyl thioether group, or a fluorene group, which are either substituted with a substituent, or a group formed by linking these groups to a carbonyl group. From the viewpoint of light absorption by the exposure source at i-rays (365 nm), it is preferable to have a carbazole group, which is either substituted with a substituent, or a group formed by linking a carbazole group, which is either substituted with a carbonyl group.

[0314] Examples of substituents that may be optionally present in the carbazoyl group include, for example, alkyl groups with 1 to 10 carbon atoms such as methyl and ethyl; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; halogen atoms such as F, Cl, Br, and I; acyl groups with 1 to 10 carbon atoms; alkyl ester groups with 1 to 10 carbon atoms; alkoxy carbonyl groups with 1 to 10 carbon atoms; haloalkyl groups with 1 to 10 carbon atoms; aromatic cyclic groups with 4 to 10 carbon atoms; amino groups; aminoalkyl groups with 1 to 10 carbon atoms; hydroxyl groups; nitro groups; CN groups; aromatic acyl groups with optional substituents; heteroaromatic acyl groups with optional substituents; and thiophenecarboxyl groups with optional substituents.

[0315] R 22a The number of carbon atoms in the alkyl acyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in the solvent, it is preferably 2 or more, more preferably 3 or more, and 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 acyl 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.

[0316] Examples of alkyl acyl groups include acetyl, ethyl, propionyl, and butyryl.

[0317] Examples of substituents that can be optionally present on the alkyl acyl group include aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, non-substituted groups are preferred.

[0318] R 22a The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is preferably 7 or more, more preferably 8 or more, and 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 aryl group is preferably 7 to 20, more preferably 7 to 15, even more preferably 7 to 10, and particularly preferably 8 to 10.

[0319] Examples of aromatic acyl groups include benzoyl and naphthyl.

[0320] Examples of substituents that can be optionally present in the aryl group include hydroxyl, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of ease of synthesis, non-substituted groups are preferred.

[0321] From the viewpoint of light absorption of i-rays (365 nm) from the exposure light source, compounds represented by the following general formulas (I-2) or (I-3) can be listed as compounds represented by formula (I-1).

[0322]

[0323]

[0324] In equations (I-2) and (I-3), R 21a and R 22a It has the same meaning as in equation (I-1).

[0325] R 23a This indicates an alkyl group that may have a substituent.

[0326] R 24a The denoting group represents an alkyl group, an aromatic acyl group, a heteroaromatic acyl group, or a nitro group that may have a substituted group.

[0327] The benzene ring constituting the carbazole ring may be further condensed through an aromatic ring to form a polycyclic aromatic ring.

[0328] R 23aThe number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 1 or more, more preferably 2 or more, and 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.

[0329] Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl.

[0330] Examples of substituents that can be optionally present in an alkyl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro. From the viewpoint of ease of synthesis, non-substituted groups are preferred.

[0331] As R 23a From the viewpoint of solubility in solvents and ease of synthesis, ethyl is preferred.

[0332] R 24a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 1 or more, more preferably 2 or more, and 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.

[0333] Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl.

[0334] Examples of substituents that can be optionally present in an alkyl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro. From the viewpoint of ease of synthesis, non-substituted groups are preferred.

[0335] R 24a The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. Furthermore, it is 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 aryl group is preferably 7 to 20, more preferably 8 to 15, even more preferably 9 to 10, and particularly preferably 9.

[0336] Examples of aromatic acyl groups include benzoyl and naphthyl.

[0337] Examples of substituents that can be optionally present on the aromatic acyl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro. From the viewpoint of ease of synthesis, ethyl is preferred.

[0338] R 24a The number of carbon atoms in the heteroaryl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. Furthermore, it is 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 heteroaryl group is preferably 7 to 20, more preferably 8 to 15, even more preferably 9 to 10, and particularly preferably 9.

[0339] Examples of heteroaryl groups include benzoyl, fluorobenzoyl, chlorobenzoyl, bromobenzoyl, fluoronaphthoyl, chloronaphthoyl, and bromonaphthoyl.

[0340] Examples of substituents that can be optionally present in the heteroaryl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro groups. From the viewpoint of ease of synthesis, non-substituted groups are preferred.

[0341] As R 24a From the viewpoint of sensitivity, it is preferable to choose an aromatic acyl group with a substituent, and more preferably a benzoyl group.

[0342] The benzene ring constituting the carbazole ring may be further condensed through an aromatic ring to form a polycyclic aromatic ring.

[0343] Commercially available oxime ester compounds include, for example, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., and N-1919, NCI-930, and NCI-831 manufactured by ADEKA.

[0344] Specifically, the following compounds can be listed as oxime ester compounds.

[0345]

[0346]

[0347]

[0348] These photopolymerization initiators can be used alone or in combination of two or more.

[0349] In addition to (D) photopolymerization initiators, chain transfer agents can also be used. Chain transfer agents are compounds that have the function of accepting the generated free radicals and transferring the accepted free radicals to other compounds.

[0350] As a chain transfer agent, any compound possessing the aforementioned functions is acceptable. Various chain transfer agents can be used, such as thiol-containing compounds and carbon tetrachloride. However, considering the tendency towards high chain transfer efficiency, thiol-containing compounds are preferred. This is believed to be because the low SH bond energy facilitates bond breaking, hydrogen abstraction reactions, and chain transfer reactions. This is effective in improving sensitivity and surface curing properties.

[0351] Examples of thiol-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazolin, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene, which are compounds with aromatic rings; and hexanedithiol, decandithiol, butanediol bis(3-mercaptopropionate), butanediol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tri(3-mercaptopropionate), and trimethylolpropane tri(3-mercaptopropionate). Compounds containing thiol groups in the aliphatic system, such as alkyltrimercaptoacetate, trihydroxyethyl trimercaptopropionate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tri(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tri(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, are preferred from the viewpoint of surface smoothness.

[0352] As a thiol-containing compound with an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred. As an aliphatic thiol-containing compound, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetras(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

[0353] From the perspective of sensitivity, aliphatic compounds containing thiol groups are preferred, especially trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and more preferably pentaerythritol tetra(3-mercaptopropionate) and pentaerythritol tetra(3-mercaptobutyrate).

[0354] These chain transfer agents can be used alone or in combination of two or more.

[0355] In the coloring resin composition of the present invention, the content ratio 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, further preferably 1% by mass or more, particularly preferably 1.2% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve the curability of the coating film; and by setting it to the aforementioned upper limit or below, visible light absorption is reduced, and therefore, there is a tendency to improve brightness. The above upper and lower limits can be combined arbitrarily. For example, in the coloring resin composition, the content ratio of (D) photopolymerization initiator in the total solids content of the coloring resin composition is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, further preferably 1 to 6% by mass, and particularly preferably 1.2 to 4% by mass.

[0356] When the coloring resin composition of the present invention contains a chain transfer agent, the proportion of the chain transfer agent is not particularly limited. However, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and preferably 3% by mass or less, more preferably 2.5% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. By setting the value to the aforementioned lower limit or above, there is a tendency to improve solvent resistance; conversely, by setting the value to the aforementioned upper limit or below, there is a tendency to improve storage stability. The aforementioned upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition contains a chain transfer agent, its proportion in the total solids of the coloring resin composition is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, further preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1.5% by mass.

[0357] [1-5] (E) Photopolymerizable monomers

[0358] The coloring resin composition of the present invention contains (E) photopolymerizable monomers.

[0359] (E) There are no particular limitations on the photopolymerizable monomer, as long as it is a low-molecular-weight compound capable of polymerization. Preferably, it is a compound capable of addition polymerization having at least one olefinic double bond (hereinafter referred to as "olefinic compound"). The olefinic compound is a compound having an olefinic double bond that is added polymerized and cured by the action of a photopolymerization initiator when the coloring resin composition of the present invention is irradiated by active light. It should be noted that the monomer in the present invention refers to the concept relative to so-called high-molecular-weight substances, and includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.

[0360] As a (E) photopolymerizable monomer, a polyfunctional olefin monomer having two or more olefin double bonds per molecule is particularly desirable. The number of olefin double bonds in the polyfunctional olefin monomer is not particularly limited, but is preferably two or more, more preferably four or more, even more preferably five or more, and preferably eight or less, even more preferably seven or less. By setting the value to the aforementioned lower limit or above, there is a tendency to achieve high sensitivity; by setting the value to the aforementioned upper limit or below, there is a tendency to improve solubility in solvents. The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of olefin double bonds in the polyfunctional olefin monomer is preferably 2 to 8, more preferably 2 to 7, even more preferably 4 to 7, and particularly preferably 5 to 7.

[0361] Examples of olefinic compounds include, for example, 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 of unsaturated carboxylic acids with polycarboxylic acids and the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc., and olefinic compounds with a carbamate skeleton obtained by reacting polyisocyanate compounds with hydroxy compounds containing (meth)acryloyl groups.

[0362] Examples of acrylates that are aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glyceryl acrylate. Additionally, examples include methacrylates formed by replacing the acrylic portion with a methacrylic acid portion, itaconic acid esters formed by replacing the acrylic acid portion, crotonic acid esters formed by replacing the crotonic acid portion, and maleic acid esters formed by replacing the maleic acid portion.

[0363] Examples of esters that are aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0364] Esters obtained by the esterification reaction of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds do not necessarily have to be a single substance; they can also 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 glycerol.

[0365] Examples of alkenes with a carbamate skeleton obtained by reacting polyisocyanate compounds with hydroxyl compounds containing (meth)acryloyl groups include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate, aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and reactants with hydroxyl compounds containing (meth)acryloyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, and 3-hydroxy(1,1,1-trimethylacryloyloxymethyl)propane.

[0366] In addition, examples of olefinic compounds used in this invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate.

[0367] The alkene compound can be a monomer with an acid value. The monomer with an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. Preferably, it is a polyfunctional monomer that has an acid group obtained by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of the aliphatic polyhydroxy compound. Particularly preferred is a polyfunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

[0368] These monomers can be used individually, but since it is difficult to use a single compound in manufacturing, two or more can be mixed. Additionally, polyfunctional monomers without acid groups can be combined with polyfunctional monomers with acid groups as needed.

[0369] The preferred acid value for polyfunctional monomers with acid groups is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. Setting the acid value above the aforementioned lower limit tends to improve developing and dissolving properties, while setting it below the aforementioned upper limit tends to improve manufacturing and handling, and enhance 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 acid group count, based on all polyfunctional monomers, to be within the aforementioned range.

[0370] In this invention, a more preferred polyfunctional monomer having an acid group is a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinates manufactured by Toa Synthetic Co., Ltd. and sold under the name TO1382. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Additionally, the polyfunctional monomer described in paragraphs

[0056] and

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

[0371] In this invention, from the viewpoint of improving the chemical resistance of pixels and the straightness of pixel edges, the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195971 is preferred.

[0372] From the perspective of balancing coating sensitivity and shortening development time, the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195974 is preferred.

[0373] In the coloring resin composition of the present invention, the content ratio of (E) photopolymerizable monomer is not particularly limited. In the total solids content of the coloring resin composition, it is preferably more than 0% by mass, more preferably 5% by mass or more, further 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, further preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency for the curability of the coating film to increase. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency for the reduction of alkali developability to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of (E) photopolymerizable monomer in the coloring resin composition is preferably more than 0% by mass and less than 70% by mass in the total solids content of the coloring resin composition, more preferably 5 to 60% by mass, further preferably 10 to 50% by mass, even more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass.

[0374] [1-6] Other solid components

[0375] The coloring resin composition of the present invention can be further formulated with solid components other than those described above, as needed. Examples of such components include dispersants, dispersing aids, surfactants, and adhesion improvers.

[0376] [1-6-1] Dispersants, dispersing aids

[0377] When the coloring resin composition of the present invention contains a pigment as a colorant (A), it preferably contains a dispersant for the purpose of stabilizing the dispersion of the pigment. Among the dispersants, a polymeric dispersant is preferred because it exhibits excellent dispersion stability over time.

[0378] Examples of polymeric dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0379] Examples of polymeric dispersants include, for instance, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and dispersants described in Japanese Patent Application Publication No. 2013-119568.

[0380] From the viewpoint of dispersibility and storage stability, block copolymers having functional groups containing nitrogen atoms are preferred as polymeric dispersants, and acrylic block copolymers having functional groups containing nitrogen atoms are more preferred.

[0381] As a block copolymer having a functional group containing a nitrogen atom, it is preferably an AB block copolymer or a BAB block copolymer composed of an A block having a quaternary ammonium salt group and / or an amino group in the side chain and a B block not having a quaternary ammonium salt group and an amino group.

[0382] Functional groups containing nitrogen atoms include primary to tertiary amines and quaternary ammonium groups. From the viewpoint of dispersibility and storage stability, primary to tertiary amines are preferred, and tertiary amines are more preferred.

[0383] The structure of the repeating unit with tertiary amino groups in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, the repeating unit shown in the following general formula (d1) is preferred.

[0384]

[0385] In equation (d1), R 1 and R 2 Each is independently a hydrogen atom, optionally an alkyl group with substituents, optionally an aryl group with substituents, or optionally an aralkyl group with substituents, R 1 and R 2 They can be arbitrarily bonded together to form a ring structure. R 3 X represents a hydrogen atom or a methyl group. X is a divalent linker.

[0386] R in equation (d1) 1 R 2 The number of carbon atoms of the optional alkyl group with 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, it is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0387] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Methyl, ethyl, propyl, butyl, pentyl, and hexyl are preferred, and methyl, ethyl, propyl, and butyl are more preferred. The alkyl group can be either straight-chain or branched. The alkyl group can contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0388] R in equation (d1) 1 R 2 The number of carbon atoms in the optional aryl group with substituents is not particularly limited, but is generally 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, more preferably 6 to 12, and even more preferably 6 to 8.

[0389] Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being more preferred.

[0390] R in equation (d1) 1 R 2 The number of carbon atoms in the optional aralkyl group with substituents is not particularly limited, but is preferably 7 or more, and more preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. For example, it is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 9.

[0391] Examples of aryl alkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Phenylenemethylene, phenylethylene, phenylpropylene, and phenylbutylene are preferred, and phenylmethylene and phenylethylene are more preferred.

[0392] From the perspectives of dispersibility, storage stability, electrical reliability, and developability, as R 1 and R 2 Each of them is preferably an alkyl group with a substituent, more preferably methyl or ethyl.

[0393] Substituents that may be optionally present in formula (d1) include alkyl, aralkyl, and aryl groups, such as halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0394] In equation (d1), R is used as 1 and R 2 The cyclic structures formed by mutual bonding can be exemplified by, for example, five- to seven-membered nitrogen-containing heterocyclic monocyclic rings, or fused rings formed by the condensation of two such rings. The nitrogen-containing heterocyclic rings are preferably non-aromatic, and saturated rings are even more preferred. Specifically, examples of cyclic structures are shown in (IV) below.

[0395]

[0396] These ring structures may optionally have substituents.

[0397] In formula (d1), X, as a divalent linking group, can be, for example, an alkylene group with 1 to 10 carbon atoms, an aryl group with 6 to 12 carbon atoms, or -CONH-R. 13 -base, -COOR 14 -base (where R) 13 and R 14 It is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms, preferably -COO-R. 14 -base.

[0398] The proportion of the repeating unit shown in formula (d1) of the block copolymer in all repeating units is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, particularly preferably 25 mol% or more, and 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 aforementioned ranges, there is a tendency to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the repeating unit shown in formula (d1) of the block copolymer in all repeating units is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, further preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, even more preferably 20 to 50 mol%, and particularly preferably 25 to 40 mol%.

[0399] From the viewpoint of improving the compatibility of the dispersant with the binder components such as solvents and improving dispersion stability, block copolymers preferably have repeating units as shown in the following general formula (d2).

[0400]

[0401] In equation (d2), R 10 It is ethylene or propylene, R 11 R is an alkyl group that is optionally substituted. 12 It can be a hydrogen atom or a methyl group. n is an integer from 1 to 20.

[0402] R in equation (d2) 11 The number of carbon atoms of the alkyl group with substituents is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 2 to 4.

[0403] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Methyl, ethyl, propyl, butyl, pentyl, and hexyl are preferred, and methyl, ethyl, propyl, and butyl are more preferred. The alkyl group can be either straight-chain or branched. The alkyl group can contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0404] Examples of substituents that may be optionally present in an alkyl group include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0405] From the viewpoint of compatibility and dispersibility with binder components such as solvents, n in formula (d2) is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, n is preferably 1 to 10, more preferably 2 to 5.

[0406] The proportion of the repeating unit represented by formula (d2) of the block copolymer in all repeating units is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Within the aforementioned ranges, there is a tendency to achieve both compatibility and dispersion stability relative to binder components such as solvents. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the repeating unit represented by formula (d2) of the block copolymer in all repeating units is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%.

[0407] From the viewpoint of improving the compatibility of the dispersant with the binder components such as the solvent and improving the dispersion stability, the block copolymer preferably has repeating units as shown in the following general formula (d3).

[0408]

[0409] In formula (d3), R 8 R can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent. 9 It can be a hydrogen atom or a methyl group.

[0410] R in equation (d3) 8 The number of carbon atoms of the optional alkyl group with substituents is not particularly limited, but is preferably 1 or more, and more preferably 10 or less, and more preferably 6 or less. For example, it is preferably 1 to 10, and more preferably 1 to 6.

[0411] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Methyl, ethyl, propyl, butyl, pentyl, and hexyl are preferred, and methyl, ethyl, propyl, and butyl are more preferred. The alkyl group can be either straight-chain or branched. The alkyl group can contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0412] R in equation (d3) 8 The number of carbon atoms in the optional aryl group with substituents is not particularly limited, but is preferably 6 or more, and more preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 is preferred, and more preferably 6 to 12.

[0413] Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthraceneyl. Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl are preferred, and phenyl, methylphenyl, and ethylphenyl are more preferred.

[0414] R in equation (d3) 8The number of carbon atoms in the optional aralkyl group with substituents is not particularly limited, but is preferably 7 or more, and more preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 is preferred, and more preferably 7 to 12.

[0415] Examples of aryl alkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Phenylenemethylene, phenylethylene, phenylpropylene, and phenylbutylene are preferred, and phenylmethylene and phenylethylene are more preferred.

[0416] From the perspective of solvent compatibility and dispersion stability, as R 8 Preferably, it is an alkyl or aralkyl group, and more preferably methyl, ethyl, or phenylmethylene.

[0417] As R 8 The alkyl group may optionally have substituents, such as halogen atoms and alkoxy groups.

[0418] Substituents that may be optionally present in an aryl or aralkyl group include, for example, chain-like alkyl groups, halogen atoms, and alkoxy groups.

[0419] R 8 The chain-like alkyl groups shown include both straight-chain and branched-chain forms.

[0420] The proportion of the repeating unit represented by formula (d3) of the block copolymer in all repeating units 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, even more preferably 70 mol% or less. Within the aforementioned ranges, there is a tendency to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the repeating unit represented by formula (d3) of the block copolymer in all repeating units is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, even more preferably 50 to 70 mol%.

[0421] Block copolymers may have repeating units other than those shown in formula (d1), formula (d2), and formula (d3). Examples of such repeating units include, for instance, repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonic glycidyl ether; and N-methacryloylmorpholine.

[0422] From the viewpoint of further improving dispersibility, a block copolymer comprising an A block having a repeating unit as shown in formula (d1) and a B block not having a repeating unit as shown in formula (d1) is preferred. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. The B block is more preferably having a repeating unit as shown in formula (d2) and / or a repeating unit as shown in formula (d3).

[0423] Block A may contain repeating units other than those shown in formula (d1). Examples of such repeating units include repeating units derived from the aforementioned (meth)acrylates. The content of repeating units other than those shown in formula (d1) in block A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 mol%.

[0424] The B block may contain repeating units other than those shown in formula (d2) and formula (d3). Examples of such repeating units include, for instance, repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonic glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than those shown in formula (d2) and formula (d3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 mol%.

[0425] From a dispersibility point of view, block copolymers preferably have a low acid value, and are particularly preferably 0 mg KOH / g.

[0426] Here, the acid value indicates the number of mg of KOH required to neutralize 1g of the dispersant solid component.

[0427] 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, further preferably 70 mg KOH / g or more, even more preferably 90 mg KOH / g or more, even more preferably 100 mg KOH / g or more, particularly preferably 105 mg KOH / g or more, and preferably 150 mg KOH / g or less, more preferably 130 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, 30-150 mg KOH / g is preferred, more preferably 50-150 mg KOH / g, further preferably 70-150 mg KOH / g, even more preferably 90-130 mg KOH / g, even more preferably 100-130 mg KOH / g, and particularly preferably 105-130 mg KOH / g.

[0428] Here, the amine value represents the amine value converted from the effective solid component, expressed as the mass of KOH equivalent to the amount of alkali per 1g of dispersant solid component.

[0429] The weight-average molecular weight of the block copolymer is preferably 1,000 to 30,000. Within the aforementioned range, there is a tendency for the dispersion stability to become better, and for the formation of drying foreign matter when coating using a slit nozzle.

[0430] Block copolymers can be manufactured by known methods. For example, they can be manufactured by living polymerization of monomers into which the repeating units described above can be introduced.

[0431] As a living polymerization method, methods such as Japanese Patent Application Publication No. 9-62002, Japanese Patent Application Publication No. 2002-31713, P. Lutz, P. Masson et al, Polym. Bull, 12, 79 (1984), B.C. Anderson, G.D. Andrewset et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J, 17, 977 (1985), K. Hatada, K. Ute, et al. al, Polym.J, 18, 1037 (1986), Koichi Uezu, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collected Papers on Polymers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, WRHertler et al, Macromolecules, 20, 1473 (1987) are known methods.

[0432] When the coloring resin composition of the present invention contains a dispersant, the proportion of the dispersant is not particularly limited. In the total solids content of the coloring resin composition, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, and 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. By setting it to the aforementioned lower limit or above, there is a tendency to improve dispersibility and storage stability. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to improve electrical reliability and developability. The above upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition contains a dispersant, the proportion of the dispersant in the total solids content of the coloring resin composition is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass, further preferably 0.1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass.

[0433] When the coloring resin composition of the present invention comprises a pigment and a dispersant, the proportion of the dispersant relative to the pigment is not particularly limited. However, relative to 100 parts by weight of the pigment, it is preferably 0.5 parts by weight or more, more preferably 5 parts by weight or more, further preferably 10 parts by weight or more, even more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. Additionally, it is preferably 70 parts by weight or less, more preferably 50 parts by weight or less, further preferably 40 parts by weight or less, and particularly preferably 30 parts by weight or less. By setting it within the aforementioned range, there is a tendency to obtain a coloring resin composition with excellent dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition comprises a pigment and a dispersant, the proportion of the dispersant relative to 100 parts by weight of the pigment is preferably 0.5 to 70 parts by weight, more preferably 5 to 70 parts by weight, further preferably 10 to 50 parts by weight, even more preferably 15 to 40 parts by weight, and particularly preferably 20 to 30 parts by weight.

[0434] When the coloring resin composition of the present invention contains pigments, in order to improve the dispersibility and dispersion stability of the pigments, pigment derivatives may be included as dispersing aids.

[0435] Specifically, examples of pigment derivatives include derivatives of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindoleone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, pyrene, diketopyrrolopyrrole, and dioxazine pigments. Examples of substituents for pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups directly bonded to the pigment skeleton or bonded via alkyl, aryl, or heterocyclic groups. Sulfonamide groups and their quaternary salts, and sulfonic acid groups are preferred, and sulfonic acid groups are more preferred. Furthermore, multiple substituents may be present on a single pigment skeleton, or a mixture of compounds with different numbers of substitutions may be present. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinoline 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.

[0436] [1-6-2] Surfactants

[0437] The coloring resin composition of the present invention may contain a surfactant. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants. From the viewpoint of minimizing the possibility of adverse effects on various properties, nonionic surfactants are preferred.

[0438] When the coloring resin composition of the present invention contains a surfactant, the proportion of the surfactant is not particularly limited, but it is preferably used in the range of 0.001% by mass or more, more preferably 0.01% by mass or more, further 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, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less in the total solids content of the coloring resin composition. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the surfactant in the total solids content of the coloring resin composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, further preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0439] [1-6-3] Adhesion Improver

[0440] To improve adhesion to the substrate, the coloring resin composition of the present invention may contain an adhesion improver. Examples of adhesion improvers include silane coupling agents and titanium coupling agents. Silane coupling agents are preferred.

[0441] Examples of silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (manufactured by Shin-Etsu Silicones); and Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning). A single silane coupling agent can be used, or two or more can be used in any combination and ratio.

[0442] The coloring resin composition of the present invention may contain a binding modifier other than a silane coupling agent. Examples include, for instance, phosphoric acid-based binding modifiers and other binding modifiers.

[0443] As a phosphoric acid-based binding modifier, a phosphoric acid ester containing (meth)acryloyloxy group is preferred. Phosphoric acid-based binding modifiers represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0444]

[0445] In equations (g1), (g2), and (g3), R 51 Each of them 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.

[0446] Other sealing modifiers include, for example, TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphoric acid sealing modifiers and other sealing modifiers can be used alone or in combination of two or more.

[0447] When the coloring resin composition of the present invention contains an adhesion improver, its content ratio is not particularly limited. Preferably, it is 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. By setting it to the aforementioned lower limit or above, there is a tendency to improve patterning characteristics and pattern adhesion under high humidity conditions. Furthermore, by setting it to the aforementioned upper limit or below, there is a tendency to suppress residue formation. The aforementioned upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition contains an adhesion improver, its content ratio in the total solids composition is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, further preferably 0.3 to 1.5% by mass, and particularly preferably 0.4 to 1% by mass.

[0448] [2] Preparation of coloring resin composition

[0449] Next, the method for preparing the coloring resin composition of the present invention will be described.

[0450] In preparing a coloring resin composition containing a pigment as a colorant (A), firstly, predetermined amounts of pigment, solvent, and dispersant are weighed separately. In a dispersion treatment step, the colorant containing the pigment is dispersed to prepare a pigment dispersion. In this dispersion treatment step, a paint shaker, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, etc., can be used. By performing this dispersion treatment, the colorant is micronized, thereby improving the coating properties of the coloring resin composition and increasing the transmittance of the pixels in the color filter substrate of the product.

[0451] When dispersing pigments, it is preferable to use dispersing aids in appropriate combinations, as described above.

[0452] When using a sand mill for dispersion, glass beads or zirconia beads with a diameter of 0.1 to several mm are preferred. The temperature during dispersion is preferably set to 0°C or higher, more preferably room temperature or higher, and preferably 100°C or lower, more preferably 80°C or lower. It should be noted that the appropriate dispersion time varies depending on the composition of the pigment dispersion and the size of the sand mill, etc., and can be adjusted appropriately.

[0453] A homogeneous dispersion solution is prepared by mixing a solvent, an alkali-soluble resin, a photopolymerization initiator, a photopolymerization monomer, and other components as needed into the pigment dispersion obtained through the above dispersion treatment. It should be noted that fine dust particles may sometimes be introduced during the dispersion and mixing processes; therefore, it is preferable to filter the obtained pigment dispersion solution using a filter or similar device.

[0454] In the case where the colorant (A) does not contain pigment, the colorant, solvent, alkali-soluble resin, photopolymerization initiator, photopolymerization monomer, and other components as needed, other than those mentioned above, can be mixed to obtain a homogeneous solution. It is preferable to filter the resulting solution using a filter or the like.

[0455] [3] Manufacturing of cured products and color filters

[0456] The cured product of the present invention is formed by curing the coloring resin composition of the present invention.

[0457] Furthermore, the color filter of the present invention includes pixels made using the coloring resin composition of the present invention.

[0458] The following is an example of a method for manufacturing a color filter.

[0459] [3-1] Substrate (Support)

[0460] As the substrate for coating the coloring resin composition of the present invention, a transparent substrate is preferred. The material is not particularly limited as long as it is transparent and has suitable strength. Examples of suitable materials include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, sheets of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, sheets of thermosetting resins such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin, or various types of glass. From the viewpoint of heat resistance, glass or heat-resistant resins are preferred.

[0461] To improve surface properties such as adhesion, the substrate to be coated with the colored resin composition, or the substrate with the black matrix described later, can be subjected to corona discharge treatment, ozone treatment, or film formation treatment with various resins such as silane coupling agents or urethane resins, as needed. The thickness of the substrate is preferably 0.05 mm or more, more preferably 0.1 mm or more, and preferably 10 mm or less, more preferably 7 mm or less. For example, it is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm. Furthermore, when performing film formation treatment with various resins, the film thickness is preferably 0.01 μm or more, more preferably 0.05 μm or more, and preferably 10 μm or less, more preferably 5 μm or less. For example, it is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[0462] [3-2] Black matrix formation process

[0463] The color filter of the present invention can be manufactured by forming a black matrix on a transparent substrate, thereby typically forming red, green, and blue pixel images. The coloring resin composition of the present invention is preferably used as a coating liquid for forming green pixels (resist patterns) among the red, green, and blue pixels. Using the green pixel (resist pattern) forming coating liquid, various processes such as coating, heating and drying, image exposure, development, and firing are performed on the resin black matrix forming surface formed on the transparent substrate or on the metallic black matrix forming surface formed using a light-shielding metal material such as a chromium compound, thereby forming a pixel image.

[0464] A black matrix is ​​formed on a substrate using a coloring resin composition and a light-shielding metal film or a black matrix. Examples of light-shielding metal materials include metallic chromium, chromium oxide, chromium nitride and other chromium compounds, nickel and tungsten alloys, and these materials can be stacked in multiple layers.

[0465] Metallic light-shielding films are typically formed using sputtering. After forming the desired pattern in film form with a positive photoresist, chromium is etched using a mixed etching solution of cerium ammonium nitrate and perchloric acid and / or nitric acid. For other materials, an etching solution appropriate to the material is used. Finally, the positive photoresist is stripped with a special stripping agent, thereby forming a black matrix.

[0466] When using a light-shielding metal thin film, the metal or metal / metal oxide film is first formed on a transparent substrate using methods such as vapor deposition or sputtering. Next, a coating of a colored resin composition is formed on this film, and then the coating is exposed and developed using a photomask with repeating patterns such as stripes, mosaics, or triangles to form a resist image. Finally, the coating can be etched to form a black matrix.

[0467] When using a photosensitive coloring resin composition for a black matrix, a coloring resin composition containing a black colorant is used to form the black matrix. For example, a coloring resin composition containing one or more black colorants such as carbon black, graphite, iron black, aniline black, Cyanine Black, and titanium black, or a black colorant obtained by mixing appropriately selected red, green, and blue pigments or dyes from inorganic or organic sources, can be used to form a black matrix by operating in the same manner as the method for forming red, green, and blue pixels described later.

[0468] [3-3] Pixel Formation Process

[0469] The pixel forming process includes a coating process of coating the aforementioned coloring resin composition onto a substrate and a pre-baking process of pre-baking the coating film obtained in the aforementioned coating process.

[0470] In the pixel formation process, the process may involve, for example, coating a coloring resin composition of one of the colors red, green, and blue onto a substrate having a black matrix; a pre-baking process to dry (pre-baked) the resulting coating; an exposure process to overlay a photomask on the coating and expose the image through the photomask; and a development process. Pixels are then formed by thermal curing or photocuring as needed. By performing these processes separately on the coloring resin compositions of the three colors—red, green, and blue—a color filter image can be formed.

[0471] The coloring resin composition of the present invention is preferably used in the form of a composition for forming green or blue pixels (resist patterns) among red, green, and blue pixels, and more preferably in the form of a composition for forming green pixels. For example, using the composition for forming green or blue pixels (resist patterns), pixels are formed by coating, drying (pre-baking), image exposure, development, and thermal or photocuring processes on a resin black matrix forming surface formed on a substrate or a metallic black matrix forming surface formed using a light-shielding metal material such as a chromium compound.

[0472] [3-4] Coating process

[0473] The coloring resin composition can be coated onto the substrate by methods such as spin coating, wire rod coating, flow coating, mold coating, roller coating, and spray coating. Among these methods, mold coating can significantly reduce the amount of coloring resin composition used, and it completely eliminates the effects of mist or other contaminants that occur with spin coating. Furthermore, the generation of foreign matter is suppressed, making it the preferred method from a comprehensive viewpoint.

[0474] When the coating thickness is too thick, pattern development becomes difficult, and gap adjustment is sometimes difficult during the liquid crystal cell forming process. On the other hand, when the coating thickness is too thin, it is difficult to increase the pigment concentration, and sometimes the desired color cannot be achieved. The coating thickness, measured as the dried film thickness, is preferably 0.2 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. It is 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, more preferably 0.5 to 10 μm, and even more preferably 0.8 to 5 μm.

[0475] [3-5] Pre-baking process

[0476] The drying (pre-baking) of the coating film obtained in the coating process is preferably based on a drying method using a hot plate, an IR oven, or a convection oven. Preferably, after pre-drying, the film is reheated for pre-baking. The pre-drying conditions can be appropriately selected based on the type of solvent component and the performance of the dryer used. The drying temperature and drying time are selected based on the type of solvent component and the performance of the dryer used. Specifically, the drying temperature is preferably 40°C or higher, more preferably 50°C or higher, and preferably 80°C or lower, more preferably 70°C or lower; the drying time is preferably 15 seconds or higher, more preferably 30 seconds or higher, and preferably 5 minutes or lower, more preferably 3 minutes or lower.

[0477] The pre-baking temperature is preferably higher than the pre-drying temperature. Specifically, this is 80°C or higher, more preferably 90°C or higher, particularly preferably 100°C or higher, and further preferably 200°C or lower, more preferably 160°C or lower, and particularly preferably 130°C or lower. Setting the temperature above the aforementioned lower limit tends to increase the dissolution rate, while setting it below the aforementioned upper limit tends to cause the binder resin to decompose, induce thermal polymerization, and result in poor development. The aforementioned upper and lower limits can be combined arbitrarily; for example, the pre-baking temperature is preferably 80~200°C, more preferably 90~130°C, and particularly preferably 100~130°C.

[0478] The drying time for pre-baking also depends on the heating temperature, preferably 10 seconds or more, more preferably 15 seconds or more, and preferably 10 minutes or less, more preferably 5 minutes or less.

[0479] [3-6] Exposure process

[0480] In the pixel formation process, it is preferable to have an exposure process after the pre-baking process.

[0481] The exposure process involves overlaying a negative matrix pattern onto a coating obtained through a pre-baking process, and then irradiating it with an ultraviolet or visible light source through the mask pattern. To prevent a decrease in the sensitivity of the photopolymerizable layer caused by oxygen, an oxygen-blocking layer, such as a polyvinyl alcohol layer, can be formed on the photopolymerizable layer before exposure, if necessary. There are no particular limitations on the light source used in the above exposure. Examples of light sources include: 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 arc lamps, fluorescent lamps, etc.; and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, etc. When using light of a specific wavelength for irradiation, a filter can also be used.

[0482] [3-7] Developing process

[0483] In the pixel formation process, it is preferable to have a development process after the exposure process.

[0484] After the coating obtained using the coloring resin composition of the present invention is exposed through the above exposure process, an image can be formed on the substrate by a development process using an aqueous solution containing a surfactant and an alkaline compound, thereby manufacturing the coating.

[0485] The aqueous solution may also contain organic solvents, buffers, complexing agents, dyes, or pigments.

[0486] Examples of basic compounds include inorganic basic 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; and organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds can be used alone or in combination of two or more.

[0487] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitol alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0488] Examples of organic solvents include isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents can be used in combination with aqueous solutions.

[0489] The developing conditions are not particularly limited, but the developing temperature is preferably 10°C or higher, more preferably 15°C or higher, and even more preferably 20°C or higher. Furthermore, it is 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 developing method can be based on any of the following: immersion developing, spray developing, brush developing, ultrasonic developing, etc.

[0490] [3-7] Thermosetting process

[0491] In the pixel formation process, it is also preferable to have a thermal curing process after the developing process. Regarding the thermal curing conditions in the thermal curing process, the temperature is preferably 100°C or higher, more preferably 150°C or higher, and preferably 280°C or lower, more preferably 250°C or lower; the time is preferably 5 minutes or higher, and preferably 60 minutes or lower.

[0492] After the pixel formation process described above, the patterning of one color's pixels is complete. This process is repeated sequentially to pattern black, red, green, and blue, enabling the creation of a color filter. It should be noted that the patterning order of the four colors is not limited to the order described above.

[0493] [3-8] Formation of transparent electrodes

[0494] The color filter of this invention can form transparent electrodes such as ITO on the image in such a state that it can be used as part of a color display, liquid crystal display device, etc. However, in order to improve surface smoothness and durability, a surface coating such as polyamide or polyimide can also be provided on the image as needed. In addition, in some applications such as planar orientation type driving mode (IPS mode), transparent electrodes are sometimes not formed.

[0495] [4] Image display device (panel)

[0496] The image display device of the present invention has a color filter manufactured by the method of the present invention.

[0497] The following is a detailed description of liquid crystal display devices and organic EL display devices as image display devices.

[0498] [4-1] Liquid Crystal Display Device

[0499] The manufacturing method of the liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention is generally manufactured as follows: an alignment film is formed on a color filter manufactured by the method of the present invention, spacers are arranged on the alignment film, and it is then bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell and connected to a counter electrode. The alignment film is preferably a resin film such as polyimide. When forming the alignment film, gravure printing and / or flexographic printing are typically used, and the thickness of the alignment film is set to several tens of nm. After curing the alignment film by thermal firing, surface treatment is performed by ultraviolet irradiation or by using a rubbing cloth to process it into a surface state that allows adjustment of the tilt of the liquid crystal.

[0500] The spacers can be spacers whose size corresponds to the gap between the opposing substrates, typically 2~8μm. Alternatively, photosensitive spacers (PS) made of transparent resin film can be formed on the color filter substrate using photolithography and used instead of spacers. As the opposing substrate, array substrates are commonly used, and TFT (thin-film transistor) substrates are particularly suitable.

[0501] The gap between the liquid crystal display cell and the opposing substrate varies depending on the application of the liquid crystal display device, and is preferably selected in the range of 2 μm or more and 8 μm or less. After bonding with the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the area around the liquid crystal cell is sealed.

[0502] The sealed liquid crystal cell is cut into panel units and then depressurized within a vacuum chamber. The liquid crystal injection port is immersed in liquid crystal, which then leaks into the chamber, thereby injecting the liquid crystal into the liquid crystal cell. The depressurization rate within the liquid crystal cell is preferably 1×10⁻⁶. -2 Pa or less, more preferably 1×10 Pa -3 Below Pa, and preferably 1×10 -7 Pa or higher, more preferably 1×10 Pa -6 The range is above Pa. For example, 1×10 Pa is preferred. -7 ~1×10 -2 Pa, more preferably 1×10 -6 ~1×10 -3 Pa.

[0503] Furthermore, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is preferably 30°C or higher, more preferably 50°C or higher, and preferably 100°C or lower, more preferably 90°C or lower. For example, 30~100°C is preferred, and 50~90°C is more preferred.

[0504] The temperature rise and hold during decompression is preferably set within a range of 10 minutes to 60 minutes, followed by immersion in liquid crystal. The liquid crystal cell filled with liquid crystal is then sealed by curing a UV-curable resin, thereby completing the liquid crystal display device (panel).

[0505] There are no particular limitations on the type of liquid crystal. It can be any of the known liquid crystals such as aromatic liquid crystals, aliphatic liquid crystals, and polycyclic compounds, or any of the lyotropic liquid crystals and thermotropic liquid crystals.

[0506] As thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known, and any of them can be used.

[0507] [4-2] Organic EL display device

[0508] When manufacturing an organic EL display device having a color filter produced by the method of the present invention, for example, as... Figure 1 As shown, a pixel 20 is formed on a transparent support substrate 10 using the coloring resin composition of the present invention, and an organic light emitter 500 is stacked on the blue color filter on which the pixel 20 is formed, with an organic protective layer 30 and an inorganic oxide film 40 in between, thereby producing a multi-colored organic EL element.

[0509] Examples of stacking methods for 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; and attaching the organic light-emitting element 500 formed on another substrate to an inorganic oxide film 40. The organic EL element 100 fabricated in this way can be used in both passive-drive and active-drive organic EL display devices.

[0510] Example

[0511] The invention will now be described in more detail by way of examples and comparative examples, but the invention is not limited to the following examples without departing from its spirit.

[0512] <Phalocyanine compound A>

[0513] Phthalocyanine compound A having the following chemical structure was synthesized using Example 30 based on Japanese Patent Application Publication No. 05-345861.

[0514]

[0515] It should be noted that Et in the formula represents ethyl.

[0516] <Phalocyanine compound B>

[0517]

[0518] <Dispersant A>

[0519] A methacrylic acid-based AB block copolymer composed of A blocks with nitrogen-containing functional groups and B blocks with solubilizing groups. It has repeating units shown in formula (1a), formula (2a), formula (3a), formula (4a), and formula (5a). The amine value is 120 mg KOH / g, and the acid value is less than 1 mg KOH / g.

[0520] The proportions of the repeating units shown in the following formulas (1a), (2a), (3a), (4a) and (5a) in all repeating units are less than 1 mol%, 34.5 mol%, 6.9 mol%, 13.8 mol% and 6.9 mol%, respectively.

[0521]

[0522] <Alkali-soluble resin A>

[0523] While purging 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, the mixture was stirred and heated to 120°C. Then, 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate, and 66 parts by mass of monomethyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) with a tricyclic decane backbone were added dropwise, and the mixture was stirred continuously at 120°C for 2 hours. Next, the reaction vessel was purged with air, and 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 43 parts by mass of acrylic acid. 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 continued at 120°C for 3.5 hours. The alkali-soluble resin A obtained by this operation has a polystyrene equivalent weight-average molecular weight (Mw) of approximately 8000, an acid value of 30 mg KOH / g, and a double bond equivalent of 410 g / mol, as measured by GPC.

[0524] <Alkali-soluble resin B>

[0525] While purging 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, the mixture was stirred and heated to 120°C. Then, 5 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, and 4 parts by mass of monomethyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) with a tricyclic decane backbone were added dropwise, and the mixture was stirred continuously at 120°C for 2 hours. Next, the reaction vessel was purged with air, and 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 67 parts by mass of acrylic acid. 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 continued at 120°C for 3.5 hours. The alkali-soluble resin B obtained by this operation has a polystyrene equivalent weight-average molecular weight (Mw) of approximately 9000, an acid value of 24 mg KOH / g, and a double bond equivalent of 260 g / mol, as measured by GPC.

[0526] <Alkali-soluble resin C>

[0527] While purging 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen, the mixture was stirred and heated to 120°C. Then, 7 parts by mass of styrene, 92 parts by mass of glycidyl methacrylate, and 62 parts by mass of monomethyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) with a tricyclic decane backbone were added dropwise, and the mixture was stirred continuously at 120°C for 2 hours. Next, the reaction vessel was purged with air, and 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 47 parts by mass of acrylic acid. 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 continued at 120°C for 3.5 hours. The alkali-soluble resin C obtained in this manner had a polystyrene-converted weight-average molecular weight (Mw) of approximately 5700, an acid value of 89 mg KOH / g, and a double bond equivalent of 430 g / mol, as determined by GPC.

[0528] Among the alkali-soluble resins A through C, resin C, with an acid value of 89 mg KOH / g, has the highest solubility. Regarding alkali-soluble resins A and B, which have similarly low acid values, resin B, containing more highly hydrophilic glycidyl methacrylate, has higher solubility.

[0529] <Alkali-soluble resin D>

[0530] As the reaction vessel, a separable flask equipped with a condenser is prepared. 400 parts by mass of propylene glycol monomethyl ether acetate are added, and after nitrogen purging, the temperature of the reaction vessel is raised to 90°C by stirring and heating with an oil bath.

[0531] On the other hand, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of tert-butyl peroxide-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were added to the monomer tank, while 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. After the temperature of the reaction tank stabilized at 90°C, the additives were added dropwise from both the monomer tank and the chain transfer agent tank to initiate polymerization. The temperature was maintained at 90°C while the additives were added dropwise over 135 minutes each. After 60 minutes of dropping, the temperature was raised to 110°C.

[0532] After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was installed on the separable flask, and bubbling of an oxygen / nitrogen mixture of 5 / 95 (v / v) was started. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were added to the reaction vessel, and the reaction was carried out directly at 110°C for 9 hours.

[0533] After cooling to room temperature, an alkali-soluble resin D was obtained, which had a polystyrene-converted weight-average molecular weight (Mw) of 9000, an acid value of 101 mg KOH / g, and a double bond equivalent of 550 g / mol as measured by GPC.

[0534] <Preparation of Green Dye Dispersion A>

[0535] As described in Table 1, 9.9 parts by mass of phthalocyanine compound A, 0.1 parts by mass of dispersant A (converted to solids), 72.0 parts by mass of propylene glycol monomethyl ether acetate (containing solvent 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 were separated from the dispersion using a filter, thereby preparing green dye dispersion A.

[0536] <Preparation of Green Dye Dispersion B>

[0537] Phthalocyanine compound A was replaced with phthalocyanine compound B, and the raw materials were mixed as described in Table 1. Otherwise, green dye dispersion B was prepared using the same method as green dye dispersion A.

[0538] <Preparation of Yellow Pigment Dispersion A>

[0539] As shown in Table 1, 11.4 parts by weight of CI Pigment Yellow 138, 2.9 parts by weight of dispersant A (based on solids content), 5.7 parts by weight of alkali-soluble resin D (based on solids content), 76.0 parts by weight of propylene glycol monomethyl ether acetate as solvent (also containing solvent from dispersant A and solvent from alkali-soluble resin D), 4.0 parts by weight of propylene glycol monomethyl ether, and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing yellow pigment dispersion A.

[0540] [Table 1]

[0541]

[0542] <Photopolymerizable monomer A>

[0543] Pentaerythritol tetraacrylate (Light Acrylate PE-4A, manufactured by Kyoei Chemical Co., Ltd.)

[0544] <Photopolymerizable monomer B>

[0545] Polyethoxylated tetramethylolmethane tetraacrylate (NK ESTER ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0546] <Photopolymerization initiator A>

[0547] Oxime ester compounds having the following chemical structures

[0548] (Methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-5-oxovalerate)

[0549]

[0550] It should be noted that Me in the formula represents a methyl group.

[0551] <Surfactant A>

[0552] Megafac F-554 (manufactured by DIC)

[0553] <Preparation of Coloring Resin Compositions>

[0554] The components listed in Table 2 are mixed in the ratio of the solid components to prepare coloring resin compositions 1 to 8.

[0555] It should be noted that in coloring resin compositions 1 to 8, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are used as solvents, with the total solid content of the coloring resin composition being 15% by mass, and the mixing ratio (mass ratio) of PGMEA / PGME in the resulting coloring resin composition is 90 / 10.

[0556] [Table 2]

[0557]

[0558] Evaluation of Spectral Variation

[0559] The obtained coloring resin composition was coated onto a 50 mm square, 0.7 mm thick glass substrate (manufactured by AGC, AN100) using a spin coating method, with a film thickness of 2.0 μm after thermosetting (firing). After depressurization and drying, the substrate was pre-baked on a hot plate at the temperature described in Table 3 for 90 seconds to produce a colored substrate. Alternatively, the same method was used to perform depressurization drying followed by thermosetting at 230°C for 20 minutes in a clean oven to produce a fired colored substrate.

[0560] For both the obtained colored substrate and the sintered colored substrate, a Hitachi U-3310 spectrophotometer was used to measure the spectrophotometer at 1 nm intervals from 380 nm to 780 nm, and the results were converted into absorption spectra. The absorbance value at wavelength n in the absorption spectrum of the colored substrate was designated as A. n The same value for the colored substrate after firing is set as A0. n At this point, the spectral variation is defined by the following mathematical formula as an indicator of the difference in the absorption spectrum of the colored substrate compared with the sintered substrate. The calculated spectral variation is shown in Table 3. The smaller the spectral variation in the following mathematical formula, the more the phthalocyanine compound (1) forms an association during pre-baking, and the closer it is to the state after sintering and complete formation of the association.

[0561]

[0562] <Evaluation of dissolution rate>

[0563] The above-mentioned colored substrate was developed using a 0.04% by mass potassium hydroxide aqueous solution at a developer temperature of 23°C. The time until complete dissolution was measured and is shown in Table 3.

[0564] <Evaluation of Fit>

[0565] The obtained colored resin composition was spin-coated onto a 50 mm square, 0.7 mm thick glass substrate (AN100, manufactured by AGC) to a thickness of 2.0 μm after thermosetting (firing), and pre-baked at 100°C for 90 seconds. Then, it was heated using a 2 kW high-pressure mercury lamp at 40 mJ / cm². 2 Exposure, 30mW / cm 2 Exposure was performed using an exposure mask with multiple straight openings ranging from 1 to 50 μm in width, under appropriate illuminance. Subsequently, development was carried out for 60 seconds using a 0.04% (w / w) potassium hydroxide aqueous solution at a developer temperature of 23°C. Following this, development was performed at 1 kg / cm². 2 The substrate was subjected to a 10-second spray water wash under high water pressure. Subsequently, it was heat-cured at 230°C for 20 minutes to create a patterned substrate. Using an optical microscope, the patterns corresponding to multiple straight openings with widths ranging from 1 to 50 μm were observed. Among the patterns that remained after development, those with opening widths of 7 μm or less were designated as A, those exceeding 7 μm but less than 15 μm were designated as B, and those exceeding 15 μm were designated as C. The evaluation results are shown in Tables 3 and 4.

[0566] The narrower the opening, the better the adhesion between the cured coloring resin composition and the substrate.

[0567] <Evaluation of Contrast Ratio>

[0568] The obtained colored resin composition was spin-coated onto a 50 mm square, 0.7 mm thick glass substrate (AN100, manufactured by AGC) to a thickness of 2.0 μm after thermosetting (firing), and pre-baked at 100°C for 90 seconds. Then, it was heated using a 2 kW high-pressure mercury lamp at 40 mJ / cm². 2 Exposure, 30mW / cm 2 The substrate for contrast evaluation is prepared by exposing it to the illuminance and then performing a heat curing process at 230°C for 20 minutes.

[0569] Using a CT-1 contrast ratio meter (manufactured by Tsubosaka Electric Co., Ltd.), orthogonal parallelism was measured on the obtained substrate, and the contrast ratio (1:12000) was calculated in the form of parallel / orthogonal. A contrast ratio of 6000 or higher was designated as A, 4000 or higher but less than 6000 as B, and less than 4000 as C. The evaluation results are shown in Table 4.

[0570] <Residue Review>

[0571] Patterned substrates were fabricated in the same manner as those used for the fit evaluation, and the patterns corresponding to the straight openings with a width of 50 μm were observed using an optical microscope.

[0572] Case A is defined as no residue observed in the opening; case B is defined as slight residue observed in the opening but not a practical problem; and case C is defined as residue observed in the opening. The evaluation results are shown in Table 4.

[0573] [Table 3]

[0574]

[0575] [Table 4]

[0576]

[0577] Table 3 clearly shows that as the proportion of phthalocyanine compound (1) in colorant (A) increases, the spectral change at lower pre-baking temperatures decreases. In other words, the higher the proportion of phthalocyanine compound (1) in colorant (A), the lower the pre-baking temperature required for phthalocyanine compound (1) to form an associative compound. In particular, it can be seen that in Comparative Example 2, the spectral change value was also slightly larger at a pre-baking temperature of 105°C, indicating that phthalocyanine compound (1) did not completely form an associative compound. This can be attributed to the fact that colorant (A) contains colorants other than phthalocyanine compound (1), which hinder the association of phthalocyanine compound (1) with each other through π-π stacking of aromatic rings contained in its structure. In addition, the dissolution rate also shows the same tendency; as the proportion of phthalocyanine compound (1) in colorant (A) increases, the pre-baking temperature at which the dissolution rate reaches a constant decreases when the pre-baking temperature is gradually increased from 80°C. This can be attributed to the fact that, since the phthalocyanine compound (1) forms an associative complex, the complex is formed by wrapping around the alkali-soluble resin (C) contained in the coloring resin composition, and the dissolution rate is faster compared to the case of the phthalocyanine compound (1) alone.

[0578] Because the coloring resin composition dissolves faster, a shorter development time is sufficient. Furthermore, the ability to accelerate the dissolution rate at a lower pre-baking temperature helps improve the production efficiency of color filters, etc. It can also be argued that because of the rapid dissolution rate, the solubility of (C) alkali-soluble resin is relatively reduced, thus making the pattern less prone to peeling during development and improving adhesion.

[0579] According to the comparison between Examples 1-3 and Comparative Examples 1-3 in Table 4, it is clear that: (A) When the content of phthalocyanine compound (1) in the colorant is 65% by mass or more, the residue and contrast are significantly improved. This can be attributed to the fact that: as the content of phthalocyanine compound (1) increases, the association between phthalocyanine compounds (1) is less likely to be hindered by other colorants, and the formation of regular associative aggregates of phthalocyanine compounds (1) occurs, thereby increasing the contrast. In addition, the dissolution rate is faster due to the formation of regular associative aggregates of phthalocyanine compounds (1).

[0580] Furthermore, as clearly shown in Comparative Examples 4 and 5 of Table 4, when using phthalocyanine compound B, which is not a phthalocyanine compound (1), the residue and contrast are poor regardless of the proportion of phthalocyanine compound B in the colorant (A). It can be assumed that the chlorine atom occupies a larger volume than the fluorine atom, hindering the formation of regularized associative aggregates of phthalocyanine compounds, thus failing to improve contrast and dissolution rate.

[0581] The present invention has been described in detail using specific methods, but various changes and modifications can be made without departing from the intent and scope of the invention, which is self-evident to those skilled in the art.

Claims

1. A coloring resin composition, characterized in that, It contains (A) colorant, (B) solvent, (C) alkali-soluble resin, (D) photopolymerization initiator and (E) photopolymerizable monomer. The colorant (A) comprises a phthalocyanine compound having the chemical structure shown in the following general formula (1) and a yellow pigment. The phthalocyanine compound in the colorant (A) is present in a proportion of 65% by mass or more and 90% by mass or less. In equation (1), A 1 ~A 16 Each of these groups independently represents a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below, wherein A 1 ~A 16 One or more of them represent fluorine atoms, and A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2), In formula (2), X represents a divalent linking group, the benzene ring in formula (2) can be optionally substituented, and * represents a linking bond.

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

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

4. The coloring resin composition according to claim 1, wherein, In the above formula (1), A 1 ~A 4 One or more of them are fluorine atoms, A 5 ~A 8 One or more of them are fluorine atoms, A 9 ~A 12 One or more of them are fluorine atoms, and A 13 ~A 16 One or more of them are fluorine atoms.

5. The coloring resin composition according to claim 1, wherein, The benzene ring in formula (2) has an alkoxy carbonyl group.

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

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

8. The coloring resin composition according to claim 1, wherein, The yellow pigment is selected from at least one of the following groups: CI Pigment Yellow 138, CI Pigment Yellow 185, and a nickel azo complex as shown in formula (i) below. 。 9. The coloring resin composition according to claim 1, wherein, The yellow pigment in the colorant (A) is present in a proportion of 10% by mass or more and 35% by mass or less.

10. The coloring resin composition according to claim 1, wherein, The colorant (A) in the total solids composition of the coloring resin composition contains 10% by mass or more and 80% by mass or less.

11. The coloring resin composition according to claim 1, wherein, It also contains a dispersant, the amine value of which is above 90 mg KOH / g.

12. A cured product formed by curing the coloring resin composition according to any one of claims 1 to 11.

13. A color filter comprising pixels made using the coloring resin composition according to any one of claims 1 to 11.

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

Images