Colored resin composition, color filter, and image display device

Abstract

Provided is a colored resin composition having little influence of temperature variation of pre-baking on developing solution solubility and patterning properties. 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, wherein the (A) colorant contains a phthalocyanine compound having a specific chemical structure, and the (E) photopolymerizable monomer contains a photopolymerizable monomer (e1) having a specific partial structure.

Description

Technical Field

[0001] This invention relates to coloring resin compositions, color filters, and image display devices.

[0002] This application claims priority based on Japanese Patent Application No. 2020-139037 and Japanese Patent Application No. 2020-139038, both filed in Japan on August 20, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] Previously, methods for manufacturing color filters used in liquid crystal display devices included pigment dispersion, dyeing, electrodeposition, and printing. Among these, pigment dispersion, which offers excellent balanced properties, is the most widely used method from the perspectives of spectral characteristics, durability, pattern shape, and precision.

[0004] In recent years, color filters have been required to have higher brightness, higher contrast, and wider color gamut. As the coloring material that determines the color of the color filter, pigments are usually used from the perspective of heat resistance and lightfastness. However, pigments, especially in terms of high brightness, are gradually failing to meet market requirements, and research is actively underway to use dyes as a substitute for pigments as coloring materials.

[0005] For example, the use of phthalocyanine dyes in green pixel applications is being investigated (see, for example, Patent Document 1).

[0006] On the other hand, Patent Document 2 describes how, by using a coloring resin composition containing a specific photopolymerizable compound, it is possible to reduce post-development residue in the manufacture of color filters, even when the pigment is contained at a high concentration.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2019-113732

[0010] Patent Document 2: Japanese Patent Application Publication No. 2008-164886 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] The inventors conducted research and found that the solubility of the coloring resin composition described in Patent Document 1 in the developing solution changes significantly depending on the temperature during pre-baking (the drying process of the coating performed before the exposure process), especially in the high-temperature region, where the pattern size changes drastically. Therefore, it is evident that there is a problem in the stable manufacture of high-precision color filters, such as those represented by 4K and 8K, which require precise linewidth adjustment.

[0013] Patent Document 2 only evaluated coloring resin compositions containing pigments as colorants, and it is unclear what characteristics would be exhibited when phthalocyanine dyes are used as colorants.

[0014] Therefore, the object of the present invention is to provide a coloring resin composition in which the temperature change during pre-baking has little effect on the solubility and patterning properties of the developer.

[0015] Solution for solving the problem

[0016] The inventors conducted in-depth research and found that by combining a specific photopolymerizable monomer with a specific colorant, the above-mentioned problems could be solved, thus completing the present invention.

[0017] That is, the present invention has the following [1] to [6] configurations.

[0018] [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 photopolymerizable monomer.

[0019] The colorant (A) described above comprises a phthalocyanine compound having the chemical structure shown in the following general formula (1).

[0020] The aforementioned (E) photopolymerizable monomer comprises a photopolymerizable monomer (e1) having a partial structure as shown in the following general formula (I).

[0021]

[0022] (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 atoms in A represent fluorine atoms. 1 ~A 16 One or more of them represent the groups shown in the general formula (2) below.

[0023]

[0024] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.)

[0025]

[0026] (In formula (I), R) 1 Indicates an alkylene group having 2 or more carbon atoms.

[0027] R2 It represents a hydrogen atom or a methyl group.

[0028] n represents an integer greater than or equal to 1.

[0029] * indicates a connection key.

[0030] [2] According to the coloring resin composition of [1], wherein the above-mentioned photopolymerizable monomer (e1) is a compound represented by the following general formula (II).

[0031]

[0032] (In formula (II), R) 1 R 2 And n has the same meaning as in the above formula (I).

[0033] Z represents a direct bond, an oxygen atom, a sulfur atom, a 2-4 valent aliphatic hydrocarbon group, a 4 valent carbon atom, a 2-4 valent non-aromatic heterocyclic group, a 2-4 valent aromatic cyclic group, or a partial structure shown in the following general formula (III).

[0034] p represents an integer from 2 to 6.

[0035] In addition, the structures represented by the various general formulas (II') contained in a molecule may be either the same or different.

[0036]

[0037] (In equation (III), * represents a connecting key.)

[0038] [3] The coloring resin composition according to [1] or [2], wherein the content of the colorant (A) above is 10% by mass or more in all solid components.

[0039] [4] The coloring resin composition according to any one of [1] to [3], wherein the content of the above photopolymerizable monomer (e1) in all solid components is 1% by mass or more.

[0040] [5] A color filter having pixels made using a coloring resin composition of any one of [1] to [4].

[0041] [6] An image display device having a color filter of [5].

[0042] The effects of the invention

[0043] According to the present invention, a coloring resin composition can be provided that has little effect on the solubility and patterning properties of the developer due to temperature changes during pre-baking. Attached Figure Description

[0044] Figure 1 This is a cross-sectional schematic diagram illustrating an example of an organic EL display element having the color filter of the present invention. Detailed Implementation

[0045] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) of polystyrene obtained using GPC (gel permeation chromatography).

[0046] In this invention, "all solid components" 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 solid components.

[0047] 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.

[0048] In this invention, "CI" refers to the Color Index.

[0049] [1] Components of the coloring resin composition

[0050] The coloring resin composition of the present invention comprises (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 added if necessary.

[0051] [1-1](A) Coloring agent

[0052] The colorant (A) contained in the coloring resin composition of the present invention comprises a phthalocyanine compound having the chemical structure shown in the following general formula (1) (hereinafter sometimes referred to as "phthalocyanine compound (1)").

[0053]

[0054] 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 atoms in A represent fluorine atoms. 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0055]

[0056] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.

[0057] The colorant (A) in the coloring resin composition of the present invention comprises a phthalocyanine compound (1). In the phthalocyanine compound (1), one or more hydrogen atoms constituting the phthalocyanine skeleton are replaced by fluorine atoms with small atomic radii, which is a structure that does not easily hinder the association of phthalocyanine compounds (1) with each other. Therefore, when the intermolecular distance decreases due to heating, etc., associative aggregates are formed, which is believed to suppress the decrease in brightness caused by heating. In addition, it is believed that after association, the particle size becomes smaller than that of the pigment, and the brightness in the pattern after thermosetting is considered to be higher.

[0058] It is believed that in the coating film after pre-baking the coloring resin composition of the present invention, the phthalocyanine compound (1) forms small-particle-size aggregates and exists densely, which is believed to create a state in which the developer can easily inhibit penetration and dissolution into the coating film during the subsequent developing process. It is believed that, therefore, the resulting pattern shape is easily changed depending on the amount of residual solvent, for example, the pre-baking temperature dependence of the pore size is easily worsened.

[0059] (A 1 ~A 16 )

[0060] In the above 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 atoms in A represent fluorine atoms. 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0061]

[0062] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.

[0063] As A 1 ~A 16 Halogen atoms in the solution can be, for example, fluorine, chlorine, or bromine atoms. From the perspective of maximizing brightness, fluorine atoms are preferred.

[0064] In addition, A 1 ~A 16In this composition, preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more fluorine atoms are present, and 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 lower limit or above, the stability of the phthalocyanine compound (1) tends to increase; conversely, by setting the value to the upper limit or below, the affinity for dispersants and solvents in the coloring resin composition tends to increase. The upper and lower limits can be combined arbitrarily. For example, A 1 ~A 16 The number of substituents representing fluorine atoms in the form is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and even more preferably 8 to 10.

[0065] (X)

[0066] 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, or -N(R) atoms. a1 )-base(R a1 This refers to a hydrogen atom or an aliphatic hydrocarbon group having 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.

[0067] (Substituents that may be selectively present on the benzene ring)

[0068] 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...). A alkyl, alkoxy (-OR) A Base (where R) A Indicates alkyl group. )), alkoxycarbonyl group (-COOR) A Base (where R) A Indicates alkyl group; aryl group (-R) B aryl group (-OR) B Base (where R) B (representing aryl group) and aryloxycarbonyl group (-COOR) B Base (where R) B (This indicates an aryl group.) From the viewpoint of developing solubility and brightness, an alkoxycarbonyl group is preferred.

[0069] The alkyl groups contained in these groups can be linear, branched, or cyclic, but from the viewpoint of affinity for organic solvents, linear is preferred.

[0070] The number of carbon atoms in the alkyl group is not particularly limited, but is generally 1 or more, preferably 2 or more, and further preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Setting it to the lower limit or above tends to suppress aggregation and thus suppress foreign matter; conversely, setting it to the upper limit or below tends to improve solvent affinity and stability over time. The 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.

[0071] Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. From the viewpoint of suppressing aggregation, methyl or ethyl is preferred, and ethyl is more preferred.

[0072] The aryl groups contained in these groups can be aromatic hydrocarbon cyclic groups or aromatic heterocyclic groups.

[0073] The number of carbon atoms in the aryl group is not particularly limited, but is generally 4 or more, preferably 6 or more, and even more preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By setting it to the lower limit or above, there is a tendency to suppress aggregation through steric repulsion. Furthermore, by setting it to the upper limit or below, there is a tendency to improve solvent affinity and stability over time. The 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.

[0074] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or a fused ring. Examples of aromatic hydrocarbon cyclic groups include benzene rings, naphthalene rings, pentanene rings, indene rings, azurite rings, and heptene rings, which have one free valence.

[0075] 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.

[0076] When the benzene ring in formula (2) has any substituents, its substitution number is not particularly limited. From the viewpoint that the heat resistance is improved by the π-π stacking of dye molecules and the decrease in brightness caused by the decomposition of dye is suppressed, it is preferable that the substitution number relative to one benzene ring is 1.

[0077] When the benzene ring in formula (2) has any substituent, its substitution position can be ortho, meta or para. From the point of view that the densest packing structure can be achieved, para is preferred.

[0078] A 1 ~A 16 One or more of the atoms in the compound represent fluorine atoms. From the viewpoint that an association is formed between two molecules of phthalocyanine compound (1) to improve brightness, A is preferred. 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.

[0079] A 1 ~A 16 From the viewpoint of solubility in organic solvents and brightness, A is preferred if one or more groups represented by formula (2) are present in the formula. 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 shown in formula (2), A 5 ~A 8 Two or more of them are groups shown in formula (2), A 9 ~A12 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).

[0080] From the perspective of suppressing brightness loss through efficient stacking, option A is preferred. 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 Halogen atoms; A is particularly preferred. 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.

[0081] Specific examples of phthalocyanine compounds (1) include the following compounds.

[0082]

[0083] It should be noted that in the above formula, Et represents ethyl.

[0084]

[0085]

[0086] As a method for manufacturing phthalocyanine compound (1), a known method can be used, for example, the method described in Japanese Patent Application Publication No. 05-345861.

[0087] (A) In addition to phthalocyanine compound (1), the colorant may also contain other colorants. Examples of other colorants include pigments and dyes. When used for green pixels, green pigments, green dyes, yellow pigments, and yellow dyes are preferred.

[0088] Examples of green pigments include CI pigments 7, 36, 58, 59, 62, and 63. From the viewpoint of brightness, CI pigment 58 is preferred.

[0089] 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.

[0090] 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, 7 5, 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, 15 0, 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)").

[0091]

[0092] Other compounds that can be included in the nickel azo complex shown in formula (i) are, for example, compounds shown in formula (ii) below.

[0093]

[0094] From the viewpoint of high brightness and high color gamut, CI pigment yellows 83, 117, 129, 138, 139, 154, 155, 180, 185 and the nickel azo complex shown in formula (i) are preferred, and CI pigment yellows 83, 138, 139, 180, 185 and the nickel azo complex shown in formula (i) are even more preferred.

[0095] Examples of yellow dyes include barbiturate azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinoline ketone dyes, and anthocyanin dyes. Specific examples include compounds described in Japanese Patent Application Publication No. 2010-168531.

[0096] 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, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243, and their derivatives.

[0097] From the perspective of suppressing dye decomposition during thermal firing, the preferred solvent yellows are CI 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163.

[0098] The average primary particle size of the pigment is typically 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. When micronizing the pigment, a method such as solvent salt milling is preferred.

[0099] The content of colorant (A) in the coloring resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, 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, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. By setting it to the lower limit or above, there is a tendency to reproduce a wide range of hues, and by setting it to the upper limit or below, there is a tendency to ensure stability over time. The upper and lower limits can be combined arbitrarily. For example, the content of colorant (A) in the coloring resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, further preferably 20 to 60% by mass, even more preferably 25 to 50% by mass, and particularly preferably 30 to 40% by mass in the total solid components of the coloring resin composition.

[0100] 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. Setting it to the lower limit or above tends to increase brightness, while setting it to the upper limit or below tends to ensure stability over time. The upper and lower limits can be combined arbitrarily. For example, the proportion of phthalocyanine compound (1) in the coloring resin composition is 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 solid components of the coloring resin composition.

[0101] When the coloring resin composition of the present invention contains other colorants, the proportion thereof is not particularly limited. Preferably, it accounts for 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 it to the lower limit or above, there is a tendency to reproduce a wide range of hues; conversely, by setting it to the upper limit or below, there is a tendency to ensure stability over time. The upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition contains other colorants, the proportion thereof 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 29% by mass, in the total solid components of the coloring resin composition.

[0102] [1-2](B) Solvent

[0103] (B) The solvent has the function of dissolving or dispersing colorants, alkali-soluble resins, photopolymerization initiators, photopolymerization monomers, other components and adjusting viscosity in the coloring resin composition and pigment dispersion of the present invention.

[0104] As a solvent (B), any solvent that can dissolve or disperse the components is acceptable.

[0105] Examples of such solvents 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, and other diol monoalkyl ethers;

[0106] 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;

[0107] 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;

[0108] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0109] Alkyl acetates such as cyclohexyl acetate;

[0110] Ethers such as pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0111] 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;

[0112] 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;

[0113] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0114] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0115] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0116] 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;

[0117] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0118] Halogenated hydrocarbons such as chlorobutane and chloropentane;

[0119] Ether ketones such as methoxymethylpentanone;

[0120] Nitriles such as acetonitrile and benzonitrile.

[0121] Commercially available solvents belonging to the aforementioned substances include, for example, mineral oil, Varsol #2, Apco #18 solvent, Apco thinner, Socal solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, 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.

[0122] When forming the pixels of a color filter using photolithography, a solvent with a boiling point in the range of 100–200°C (under a pressure of 1013.25 hPa; the same applies to boiling point below) is preferably selected. A solvent with a boiling point of 120–170°C is more preferred.

[0123] Among the solvents mentioned above, diol alkyl ether acetates are preferred, considering their good balance of coatability and surface tension, as well as the high solubility of the components in the composition.

[0124] Diol alkyl ether acetates can be used alone or in combination with other solvents. Diol monoalkyl ethers are particularly preferred as solvents for combination use. Among these, propylene glycol monomethyl ether is particularly preferred from the viewpoint of the solubility of the constituent components in the composition. It should be noted that diol monoalkyl ethers are highly polar; if added in excessive amounts, the pigment tends to aggregate, resulting in a gradual increase in the viscosity of the resulting colored resin composition and a decrease in storage stability. Therefore, when using diol monoalkyl ethers in combination, the proportion of diol monoalkyl ethers in solvent (B) is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

[0125] 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 helps to prevent 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 solvents with boiling points of 150°C or higher in solvent (B) is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. By setting this to the lower limit or higher, it is easier to avoid defects such as foreign matter caused by the precipitation and curing of coloring material components at the tip of the slit nozzle. Furthermore, by setting this to the 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.

[0126] 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 include a solvent with a boiling point above 150°C.

[0127] 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.

[0128] When forming the pixels of a color filter using inkjet printing, a solvent with a boiling point typically above 130°C and below 300°C, preferably above 150°C and below 280°C, is suitable. By setting the value above the lower limit mentioned above, the uniformity of the resulting coating tends to improve, and by setting the value below the upper limit mentioned above, it tends to be easier to reduce residual solvent during firing.

[0129] From the viewpoint of the uniformity of the resulting coating, solvents with a vapor pressure typically below 10 mmHg, preferably below 5 mmHg, and more preferably below 1 mmHg can be used.

[0130] When manufacturing color filters using inkjet printing, the ink ejected from the nozzle is extremely fine, ranging from a few pL 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, it preferably contains 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, it contains a solvent with a boiling point of 220°C or higher. The proportion of solvent with a boiling point of 180°C or higher in solvent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting this to the lower limit or above, it is easier to fully exert the effect of preventing solvent evaporation from the droplets.

[0131] Solvents with a boiling point of 180°C or higher include, for example, 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.

[0132] 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. As such a solvent, solvents with low viscosity, high solubility, and low surface tension are preferred, such as ethers, esters, and ketones. Among these, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferred, for example.

[0133] On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet process will deteriorate. When alcohols are used in combination, the alcohol content in the solvent (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0134] The proportion of solvent in the coloring resin composition of the present invention is not particularly limited, but its upper limit is generally 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By setting it below the above-mentioned upper limit, it tends to be easier to form a coating film. On the other hand, considering the viscosity and other factors suitable for coating, the lower limit of the solvent content is generally 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more. The above-mentioned 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.

[0135] [1-3](C) Alkali-soluble resin

[0136] 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.

[0137] As the alkali-soluble resin (C), known polymeric compounds disclosed in, for example, Japanese Patent Application Publication Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, and 2003-233179 can be used. Among these, resins of (C-1) to (C-5) listed below are preferred.

[0138] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)").

[0139] (C-2) A linear, alkali-soluble resin containing carboxyl groups in its main chain (hereinafter sometimes referred to as "resin (C-2)").

[0140] (C-3) A resin obtained by adding an epoxy-containing unsaturated compound to the carboxyl group of the above resin (C-2) (hereinafter sometimes referred to as "resin (C-3)").

[0141] (C-4) (meth)acrylic resins (hereinafter sometimes referred to as "resin (C-4)").

[0142] (C-5) Epoxy (meth)acrylate resins containing carboxyl groups (hereinafter sometimes referred to as "resin (C-5)").

[0143] Among them, resin (C-1) is particularly preferred.

[0144] Resins (C-2) to (C-5) need only have solubility sufficient to be dissolved by alkaline developer and to perform the target development process. Resins described as the same item in Japanese Patent Application Publication No. 2009-025813 are preferred.

[0145] (C-1) A resin obtained by adding an unsaturated monobasic 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.

[0146] As one of the preferred methods for resin (C-1), one example is "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups of a copolymer of 5 to 90 mol% of epoxy-containing (meth)acrylate and 10 to 95 mol% of other free radical polymerizable monomers, or by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction."

[0147] 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.

[0148] As other free radical polymerizable monomers for copolymerization with epoxy-containing (meth)acrylates, mono(meth)acrylates having the structure shown in the following general formula (V) are preferred.

[0149]

[0150] In equation (V), R 91 ~R 98 Each can independently represent a hydrogen atom or an alkyl group having 1 to 3 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.

[0151] 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.

[0152] Of these, the structure shown in formula (V) is preferably the structure shown in the following general formulas (Va), (Vb) or (Vc).

[0153] 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.

[0154] Mono(meth)acrylates having the structure shown in formula (V) can be used alone or in combination of two or more.

[0155]

[0156] 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.

[0157]

[0158] In equation (VI), R 89 R represents a hydrogen atom or a methyl group. 90 The structure shown in expression (V).

[0159] When a copolymer of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers contains repeating units of a mono(meth)acrylate as shown in formula (VI), the proportion of the repeating units of the mono(meth)acrylate as shown in formula (VI) in the repeating units from the other free radical polymerizable monomers is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%.

[0160] Other free radical polymerizable monomers besides the mono(meth)acrylates shown in formula (VI) are not particularly limited. Specifically, 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, and isopentyl (meth)acrylate. (Meth)hexyl acrylate, (Meth)2-ethylhexyl acrylate, (Meth)lauryl acrylate, (Meth)dodecyl acrylate, (Meth)cyclopentyl acrylate, (Meth)cyclohexyl acrylate, (Meth)2-methylcyclohexyl acrylate, (Meth)dicyclohexyl acrylate, (Meth)isobornyl acrylate, (Meth)adamantane acrylate, (Meth)propargyl acrylate, (Meth)phenyl acrylate, (Meth)naphthalene acrylate, (Meth)anthracite acrylate, (Meth)anthraylnonyl acrylate, (Meth)piperyl acrylate, (Meth)salicyl acrylate, (Meth)furan acrylate, (Meth)furfuryl acrylate, (Meth)tetrahydrofuran acrylate, (Meth) (Meth)acrylates include pyran acrylate, 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, and 2-hydroxypropyl acrylate; (Meth)acrylamide, N,N-dimethylamide, N,N-diethylamide, and propylene glycol. (Methacrylamides) include N,N-dipropylamide, N,N-diisopropylamide, and anthraquinone (meth)acrylic acid; vinyl compounds such as methacrylanilide, methacrylonitrile, 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 itaconic acid; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

[0161] 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.

[0162] 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%.

[0163] 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.

[0164] Examples of solvents used in solution polymerization include: ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, acetic acid cellosolve, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, and butyl carbitol. 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 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.

[0165] In solution polymerization, the amount of solvent used is typically 30 to 1000 parts by mass relative to 100 parts by mass of the resulting copolymer, preferably 50 to 800 parts by mass. By keeping the amount of solvent used within the above range, it is easier to control the molecular weight of the copolymer.

[0166] 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 and azo compound catalysts can be used. As organic peroxide catalysts, those classified as peroxide ketones, peroxy ketals, hydrogen peroxide, diallyl peroxides, diacid peroxides, peroxide esters, and peroxydicarbonates can be listed as examples.

[0167] 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-isopropylperoxide. Hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, dicumyl peroxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxide dicarbonate, diisopropyl peroxide dicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxide)-3,3,5-trimethylcyclohexane.

[0168] Examples of azo compound catalysts include azobisisobutyronitrile (AIBN) and azobiscarbonamide (ACA).

[0169] Among these, one or more free radical polymerization initiators with suitable half-lives can be used depending on the polymerization temperature.

[0170] The amount of free radical polymerization initiator used is typically 0.5 to 20 parts by mass relative to the total amount of monomers used in the copolymerization reaction (100 parts by mass), preferably 1 to 10 parts by mass.

[0171] 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, a free radical polymerization initiator can be added to the solvent and the monomers can be added dropwise while heating.

[0172] The reaction conditions can be set according to the target molecular weight.

[0173] 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.

[0174] By setting the proportion of repeating units from epoxy-containing (meth)acrylates above the aforementioned lower limit, there is a tendency for the addition amount of unsaturated monocarboxylic acids and polycarboxylic anhydrides, as described later, to become sufficient.

[0175] 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.

[0176] 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 containing epoxy resin and other free radical polymerizable monomers.

[0177] As an unsaturated monocarboxylic acid that adds to an epoxy group, a known unsaturated monocarboxylic acid can be used, for example, an unsaturated carboxylic acid having an olefinic unsaturated double bond.

[0178] 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. (Meth)acrylic acid is preferred. These unsaturated monocarboxylic acids can be used alone or in combination of two or more.

[0179] Polymerization can be imparted to resins (C-1) by adding unsaturated monocarboxylic acids to epoxy groups.

[0180] An unsaturated monobasic acid is added to the epoxy groups of the copolymer, typically 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. By setting the value to the lower limit or above, the coloring resin composition tends to have better stability over time.

[0181] As a method for adding an unsaturated monocarboxylic acid to the epoxy group of a copolymer, a known method can be used.

[0182] Alternatively, a known polyacid anhydride can be used as the polyacid anhydride added to the hydroxyl group formed when an unsaturated monocarboxylic acid is added to the epoxy group of the copolymer.

[0183] 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.

[0184] By adding a polyacid anhydride to the hydroxyl group generated when an unsaturated monoacid is added to the epoxy group of the copolymer, the resin (C-1) can be made alkali-soluble.

[0185] 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 typically 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%. By setting it to the upper limit or below the above, there is a tendency for the residual film rate during development to become better; in addition, by setting it to the lower limit or above the above, there is a tendency for the solubility to become sufficient.

[0186] As a method for adding a polybasic acid anhydride to a hydroxyl group formed by adding an unsaturated monobasic acid to an epoxy group in a copolymer, a known method can be used.

[0187] Furthermore, in order to improve photosensitivity, after the addition of a polyacid anhydride, glycidyl (meth)acrylate or a glycidyl ether compound with a polymerizable unsaturated group can be added to a portion of the generated carboxyl group.

[0188] To improve developability, a glycidyl ether compound without polymerizable unsaturated groups can be added to a portion of the generated carboxyl group.

[0189] Alternatively, both of these can be added.

[0190] Examples of glycidyl ether compounds that do not have polymerizable unsaturated groups include those having phenyl or alkyl groups.

[0191] As commercially available products, examples include those manufactured by Nagase ChemteX Corporation under the names "DENACOLEX-111", "DENACOL EX-121", "DENACOL EX-141", "DENACOL EX-145", "DENACOL EX-146", "DENACOL EX-171", and "DENACOL EX-192".

[0192] 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.

[0193] The weight-average molecular weight of the resin (C-1) converted from polystyrene as measured 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 lower limit or above, there is a tendency for improved heat resistance and film strength; conversely, by setting it to the upper limit or below, there is a tendency for improved solubility relative to the developer.

[0194] 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.

[0195] From the viewpoint of coating curability under ultraviolet exposure, among (C) alkali-soluble resins, (C1) acrylic copolymer resins having olefinic unsaturated groups in their side chains are preferred.

[0196] (c1) The partial structure of the acrylic copolymer resin having olefinic 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.

[0197]

[0198] 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.

[0199] Furthermore, from the viewpoint of sensitivity and alkali developability, the partial structure shown in formula (CI) is preferred among the partial structures shown in general formula (CI').

[0200]

[0201] In formula (CI'), R 1 and R 2 Each can independently represent a hydrogen atom or a methyl group. R X It represents a hydrogen atom or a polyacid residue.

[0202] 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.

[0203] 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.

[0204] These polyacids can be used alone or in combination of two or more.

[0205] (c1) When the acrylic copolymer resin having olefinically unsaturated groups in its side chain has a partial structure as shown in formula (CI), the proportion of the partial structure as shown in formula (CI) in the acrylic copolymer resin having olefinically unsaturated groups in its 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 also 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 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 upper limit or below, there is a tendency to improve the alkali solubility under alkali development. The 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%.

[0206] (c1) When the acrylic copolymer resin having olefinically unsaturated groups in its side chain has a partial structure shown in formula (CI'), the proportion of the partial structure shown in formula (CI') in the acrylic copolymer resin having olefinically unsaturated groups in its 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 also 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 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 upper limit or below, there is a tendency to improve the alkali solubility under alkali development. The upper and lower limits can be combined arbitrarily. For example, (c1) in an acrylic copolymer resin having olefinic unsaturated groups in the side chain, the proportion of the partial structure shown in formula (CI') 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%.

[0207] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chain includes the partial structure shown in formula (CI), the additional partial structure is not particularly limited. From the viewpoint of alkali solubility during alkali development, it is preferred, for example, to have the partial structure shown in the following general formula (CII).

[0208]

[0209] 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.

[0210] (R 4 )

[0211] 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.

[0212] As R 4 The alkyl group in the alkyl group can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and also 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. Setting it to the lower limit or above tends to improve lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to improve hydrophilicity and alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18, further preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.

[0213] 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.

[0214] 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.

[0215] As R 4The 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. Setting the value to the lower limit or above tends to increase lipophilicity and solubility in solvents; conversely, setting the value to the upper limit or below tends to increase hydrophilicity and alkali solubility. The 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.

[0216] The aromatic hydrocarbon ring in an aromatic hydrocarbon ring group can be a monocyclic or fused ring, and examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, and benzo[a]pyrene rings. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0217] 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.

[0218] From the viewpoint of reproducibility, benzene ring group and naphthyl ring group are preferred, and benzene ring group is more preferred.

[0219] 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.

[0220] As R 4The 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. Setting it to the lower limit or above tends to improve lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to improve hydrophilicity and alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0221] 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.

[0222] 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.

[0223] R 4 The 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.

[0224] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in its side chain has a partial structure shown in formula (CII), the content ratio of the partial structure shown in formula (CII) in the acrylic copolymer resin having olefinic 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 also 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 the content to the lower limit or above, there is a tendency to improve alkali solubility; conversely, by setting the content to the upper limit or below, there is a tendency to improve the storage stability of the colored resin composition. The 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 olefinic unsaturated groups in its side chain 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%.

[0225] (c1) In the case of an acrylic copolymer resin containing a partial structure as shown in formula (CI), from the viewpoint of suppressing the decrease in brightness by improving heat resistance, it is preferable to include a partial structure as shown in general formula (CIII) below as an additional partial structure.

[0226]

[0227] 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.

[0228] (R 6 )

[0229] 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.

[0230] As R 6 The alkyl group in the alkyl group can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, 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. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12.

[0231] 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.

[0232] 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.

[0233] As R 6The 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. Setting it to the lower limit or above tends to improve lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to improve hydrophilicity and alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0234] 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.

[0235] 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.

[0236] 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. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility. The 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.

[0237] 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.

[0238] 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.

[0239] As R 6Halogen 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.

[0240] 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. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

[0241] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy.

[0242] 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.

[0243] As R 6 The alkyl sulfide group in the alkyl sulfide 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. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents; conversely, setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the alkyl sulfide group preferably has 1 to 20 carbon atoms, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

[0244] 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 are preferred.

[0245] 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.

[0246] 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.

[0247] In equation (CIII), t represents an integer from 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.

[0248] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in its side chain has the partial structure shown in formula (CIII), the content ratio of the partial structure shown in formula (CIII) in the acrylic copolymer resin having olefinic unsaturated groups in its side chain 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 also 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 lower limit or above, there is a tendency to improve heat resistance and suppress the decrease in brightness. In addition, by setting it to the upper limit or below, there is a tendency to increase the content ratio of other partial structures and improve alkali solubility. The upper and lower limits mentioned above can be combined arbitrarily. For example, the content ratio of the partial structure shown in formula (CIII) in the acrylic copolymer resin having olefinic unsaturated groups in its side chain 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%.

[0249] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chain 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 an additional included partial structure.

[0250]

[0251] In formula (CIV), R 7 It represents a hydrogen atom or a methyl group.

[0252] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in its side chain includes the partial structure shown in formula (CIV), the content ratio of the partial structure shown in formula (CIV) in the acrylic copolymer resin having olefinic unsaturated groups in its side chain is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. By setting the content to the lower limit or above, there is a tendency to improve alkali solubility; conversely, by setting the content to the upper limit or below, there is a tendency to improve the storage stability of the colored resin composition. The upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure shown in formula (CIV) in the acrylic copolymer resin having olefinic unsaturated groups in its side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

[0253] (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, and also preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, further preferably 200 mg KOH / g or less, and even more preferably 150 mg KOH / g or less. Setting the acid value to the lower limit or above tends to increase alkali solubility, while setting it to the upper limit or below tends to increase the storage stability of the colored resin composition. The upper and lower limits can be combined arbitrarily. For example, (C) the acid value of the alkali-soluble resin is preferably 10 to 300 mg KOH / g, more preferably 30 to 300 mg KOH / g, even more preferably 40 to 250 mg KOH / g, even more preferably 50 to 200 mg KOH / g, and particularly preferably 60 to 150 mg KOH / g.

[0254] (C) The weight-average molecular weight of the alkali-soluble resin is not particularly limited, but is generally 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, even more preferably 7000 or more, particularly preferably 8000 or more, and generally 30000 or less, preferably 20000 or less, more preferably 15000 or less, and even more preferably 10000 or less. Setting the value to the lower limit or above tends to improve heat resistance and coating curability; conversely, setting the value to the upper limit or below tends to improve alkali solubility. The upper and lower limits can be combined arbitrarily. For example, the weight-average molecular weight of (C) 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, particularly preferably 7000 to 15000, and especially preferably 8000 to 10000.

[0255] The content of the alkali-soluble resin (C) in the coloring resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and 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 it to the lower limit or above, there is a tendency to improve the curability of the coating film under ultraviolet exposure; and by setting it to the upper limit or below, there is a tendency to improve the solubility of the developer and suppress residue. The upper and lower limits can be combined arbitrarily. For example, the content 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 solid components of the coloring resin composition.

[0256] [1-4](D) Photopolymerization initiator

[0257] The coloring resin composition of the present invention contains a (D) photopolymerization initiator. By containing a (D) photopolymerization initiator, photopolymerization-based film curability can be imparted.

[0258] (D) Photopolymerization initiators can also be used in the form of a mixture with accelerators (chain transfer agents) and additives such as sensitizing pigments as needed (photopolymerization initiation systems). A photopolymerization initiation system is a component that has the function of directly absorbing light or being photosensitized to induce decomposition or hydrogen abstraction reactions, thereby generating polymerization-active free radicals.

[0259] Examples of photopolymerization initiators include, for instance, metallocene compounds containing dititanium compounds as 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 as described in Japanese Patent Application Publication No. 10-39503; α-aminoalkyl phenyl ketone compounds; and oxime ester initiators as described in Japanese Patent Application Publication No. 2000-80068.

[0260] The following are specific examples of photopolymerization initiators that can be used in this invention.

[0261] 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;

[0262] 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;

[0263] 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;

[0264] Benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and other benzoin alkyl ethers;

[0265] Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone;

[0266] Benzophenone, milchone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives;

[0267] 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;

[0268] Thioxanone, 2-ethylthioxanone, 2-isopropylthioxanone, 2-chlorothioxanone, 2,4-dimethylthioxanone, 2,4-diethylthioxanone, 2,4-diisopropylthioxanone and other thioxanone derivatives;

[0269] Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

[0270] Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;

[0271] 9,10-Dimethylbenzophenazine and other phenazine derivatives;

[0272] anthrone derivatives such as benzoanthrone;

[0273] 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.

[0274] 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;

[0275] 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).

[0276] From the perspective of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred.

[0277] 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.

[0278] Examples of oxime ester compounds include those represented by the general formula (I-1) below.

[0279]

[0280] 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.

[0281] R 21b It indicates any substituent containing an aromatic ring or a heteroaromatic ring.

[0282] R 22a This indicates an alkyl acyl group or an aromatic acyl group that may optionally have a substituent.

[0283] 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 generally 1 or more, preferably 2 or more, and generally 20 or less, preferably 15 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, 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.

[0284] Examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, and propyl.

[0285] 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.

[0286] As R 21a The aromatic cyclic group in the composition 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.

[0287] 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.

[0288] 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.

[0289] From the perspective of radioactivity, as R 21a Preferably, the alkyl group has a substituent, more preferably a non-substituted alkyl group, and even more preferably a methyl group.

[0290] 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 sulfide group, or a fluorene group, which are either substituted or connected 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 or connected to a carbonyl group.

[0291] Examples of substituents that may be optionally present in the carbazoyl group include, for example, alkyl groups having 1 to 10 carbon atoms such as methyl and ethyl; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy; halogen atoms such as F, Cl, Br, and I; acyl groups having 1 to 10 carbon atoms; alkyl ester groups having 1 to 10 carbon atoms; alkoxy carbonyl groups having 1 to 10 carbon atoms; haloalkyl groups having 1 to 10 carbon atoms; aromatic cyclic groups having 4 to 10 carbon atoms; amino groups; aminoalkyl groups having 1 to 10 carbon atoms; hydroxyl groups; nitro groups; CN groups; aromatic acyl groups having optional substituents; heteroaromatic acyl groups having optional substituents; and thiophenecarboxyl groups having optional substituents.

[0292] 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 generally 2 or more, preferably 3 or more, and generally 20 or less, preferably 15 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, 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.

[0293] Examples of alkyl acyl groups include acetyl, ethyl, propionyl, and butyryl.

[0294] 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.

[0295] 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 generally 7 or more, preferably 8 or more, and generally 20 or less, preferably 15 or less, and more preferably 10 or less. The above-mentioned 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, further preferably 7 to 10, and particularly preferably 8 to 10.

[0296] Examples of aromatic acyl groups include benzoyl and naphthyl.

[0297] 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.

[0298] 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).

[0299]

[0300] In equations (I-2) and (I-3), R 21a and R 22a It has the same meaning as in equation (I-1).

[0301] R 23a This indicates an alkyl group that may have a substituent.

[0302] 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.

[0303] The benzene ring constituting the carbazole ring may be further condensed through an aromatic ring to form a polycyclic aromatic ring.

[0304] R 23a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in a solvent, it is generally 1 or more, preferably 2 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. The above-mentioned 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.

[0305] Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl.

[0306] 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.

[0307] As R 23a From the viewpoint of solubility in solvents and ease of synthesis, ethyl is preferred.

[0308] 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 generally 1 or more, preferably 2 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. The above-mentioned 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.

[0309] Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl.

[0310] 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.

[0311] 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 generally 7 or more, preferably 8 or more, more preferably 9 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 9 or less. The above-mentioned 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.

[0312] Examples of aromatic acyl groups include benzoyl and naphthyl.

[0313] 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.

[0314] R 24a The number of carbon atoms in the heteroaryl group is not particularly limited, but from the viewpoint of solubility in solvents, it is generally 7 or more, preferably 8 or more, more preferably 9 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 9 or less. The above-mentioned 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.

[0315] Examples of heteroaryl groups include fluorobenzoyl, chlorobenzoyl, bromobenzoyl, fluoronaphthoyl, chloronaphthoyl, and bromonaphthoyl.

[0316] Examples of substituents that can be optionally present in the heteroaryl group include carbonyl, carboxyl, hydroxyl, phenyl, benzyl, cyclohexyl, and nitro. From the viewpoint of ease of synthesis, non-substituted groups are preferred.

[0317] 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.

[0318] The benzene ring constituting the carbazole ring may be further condensed through an aromatic ring to form a polycyclic aromatic ring.

[0319] 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.

[0320] Specifically, the following compounds can be listed as oxime ester compounds.

[0321]

[0322]

[0323]

[0324] These photopolymerization initiators can be used alone or in combination of two or more.

[0325] 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.

[0326] 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 higher 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.

[0327] 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 containing an aromatic ring; 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 include 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. From the viewpoint of surface smoothness, compounds having multiple thiol groups are preferred.

[0328] 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 are preferred.

[0329] 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).

[0330] These chain transfer agents can be used alone or in combination of two or more.

[0331] 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 1.0% by mass or more, particularly preferably 1.2% by mass or more, and also preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less. By setting it to the above-mentioned lower limit value or above, there is a tendency to improve the curability of the coating film; in addition, by setting it to the above-mentioned upper limit value or below, there is a tendency to improve the brightness by reducing visible light absorption. The above-mentioned upper and lower limits can be combined arbitrarily. For example, in the coloring resin composition, the content ratio of (D) photopolymerization initiator is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, further preferably 1.0 to 6% by mass, and particularly preferably 1.2 to 4% by mass in the total solid components of the coloring resin composition.

[0332] 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. Setting the proportion to the lower limit or above tends to improve solvent resistance, while setting it to the upper limit or below tends to improve storage stability. The 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 solid components 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.

[0333] [1-5](E) Photopolymerizable monomers

[0334] The coloring resin composition of the present invention contains (E) a photopolymerizable monomer. 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 a concept relative to so-called high-molecular-weight substances, and includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.

[0335] The photopolymerizable monomer (E) in the coloring resin composition of the present invention comprises a photopolymerizable monomer (e1) having a partial structure shown in the following general formula (I) (hereinafter sometimes referred to as "photopolymerizable monomer (e1)").

[0336]

[0337] (In formula (I), R) 1 Indicates an alkylene group having 2 or more carbon atoms.

[0338] R 2 It represents a hydrogen atom or a methyl group.

[0339] n represents an integer greater than or equal to 1.

[0340] * indicates a connection key.

[0341] It can be considered that the photopolymerizable monomer (e1), by having an oxyalkylene chain, can maintain good developer permeability even in a coating state with low residual solvent, such as 100°C. Thus, even coloring resin compositions containing phthalocyanine compounds (1) can suppress the decrease in pore size dependent on the pre-baking temperature.

[0342] (R 1 )

[0343] In equation (I), R 1 This indicates an alkylene group having two or more carbon atoms. Alkylene groups do not have substituents.

[0344] The alkylene group can be linear, branched, cyclic, or a combination thereof. From the viewpoint of solvent solubility and solvent resistance, linear alkylene groups are preferred.

[0345] There is no particular limitation as long as the number of carbon atoms in the alkylene group is 2 or more, but it is preferably 4 or less, more preferably 3 or less, and even more preferably 2. By setting it to the above-mentioned upper limit value, there is a tendency to improve the coating film sensitivity and solvent resistance. For example, the number of carbon atoms in the alkylene group is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2.

[0346] Examples of alkylene compounds include ethylene, n-propylene, n-butylene, and isopropylene. From the viewpoint of coating curability, n-propylene and ethylene are preferred, and ethylene is more preferred.

[0347] (n)

[0348] In formula (I), n represents an integer greater than or equal to 1, preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. By setting it to the upper limit value mentioned above, there is a tendency to improve the curability of the coating film. For example, n is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.

[0349] From the viewpoint of coating curability, compounds represented by the following general formula (II) are preferred as photopolymerizable monomers (e1).

[0350]

[0351] (In formula (II), R) 1 R 2 And n has the same meaning as in equation (I).

[0352] Z represents a direct bond, an oxygen atom, a sulfur atom, a 2-4 valent aliphatic hydrocarbon group, a 4 valent carbon atom, a 2-4 valent non-aromatic heterocyclic group, a 2-4 valent aromatic cyclic group, or a partial structure shown in the following general formula (III).

[0353] p represents an integer from 2 to 6.

[0354] It should be noted that the structures represented by the various general formulas (II') contained in a molecule may be either the same or different.

[0355]

[0356] (In equation (III), * represents a connecting key.)

[0357] (Z)

[0358] In formula (II), X represents direct bonding, oxygen atom, sulfur atom, 2-4 valent aliphatic hydrocarbon group, 4 valent carbon atom, 2-4 valent non-aromatic heterocyclic group, 2-4 valent aromatic cyclic group, or a partial structure shown in formula (III).

[0359] The divalent to tetravalent aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations thereof. The number of carbon atoms in the divalent to tetravalent aliphatic hydrocarbon groups is not particularly limited, but is preferably 10 or less, more preferably 9 or less, even more preferably 8 or less, and generally 1 or more. By setting the number below the aforementioned upper limits, there is a tendency to improve the curability of the coating film and improve solvent resistance. For example, the number of carbon atoms in the divalent to tetravalent aliphatic hydrocarbon groups is preferably 1 to 10, more preferably 1 to 9, and even more preferably 1 to 8.

[0360] Examples of aliphatic hydrocarbon groups with 2 to 4 free valences include methane, ethane, propane, and butane.

[0361] The non-aromatic heterocycle in a 2–4 ​​valent non-aromatic heterocyclic group can be a monocyclic or fused ring. A non-aromatic heterocycle is a non-aromatic ring containing any one of nitrogen, sulfur, or oxygen atoms as heteroatoms. When a non-aromatic heterocycle contains multiple heteroatoms, these heteroatoms can be the same or different.

[0362] The number of carbon atoms in the divalent to tetravalent non-aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, and preferably 8 or less, more preferably 6 or less. Setting it to the lower limit or above tends to improve heat resistance, while setting it to the upper limit or below tends to improve solvent solubility. The upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the divalent to tetravalent non-aromatic heterocyclic group is preferably 3 to 8, more preferably 3 to 6, and even more preferably 4 to 6.

[0363] Examples of non-aromatic heterocyclic groups with 2 to 4 valences include piperidine rings and pyrrolidine rings with 2 to 4 free valences.

[0364] Examples of aromatic cyclic groups with 2 to 4 valences include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups with 2 to 4 valences.

[0365] The aromatic hydrocarbon ring in the di- to tetravalent aromatic hydrocarbon cyclic group can be a monocyclic or a fused ring. The number of carbon atoms in the aromatic hydrocarbon cyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and preferably 15 or less, more preferably 12 or less, and even more preferably 9 or less. Setting the value to the lower limit or above tends to improve heat resistance, while setting it to the upper limit or below tends to improve brightness. The upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the di- to tetravalent aromatic hydrocarbon cyclic group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9.

[0366] Examples of aromatic hydrocarbon cyclic groups with 2 to 4 free valences include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0367] The aromatic heterocycle in the 2- to 4-valent aromatic heterocyclic group can be a monocyclic or a fused ring. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and preferably 15 or less, more preferably 12 or less, and even more preferably 9 or less. Setting the value to the lower limit or above tends to improve heat resistance, while setting it to the upper limit or below tends to improve brightness. The upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the 2- to 4-valent aromatic heterocyclic group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9.

[0368] Examples of aromatic heterocyclic groups with 2 to 4 free valences 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, cyclophosphine rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazoline ketone rings, and azurite rings.

[0369] From the viewpoint of curability and patterning properties, oxygen atom, sulfur atom, and tetravalent carbon atom are preferred as Z, and tetravalent carbon atom is more preferred.

[0370] (p)

[0371] In formula (II), p represents an integer from 2 to 6. Preferably, it is 3 or more, further preferably 5 or less, and more preferably 4 or less. By setting it to the lower limit or above, there is a tendency to improve electrical reliability; conversely, by setting it to the upper limit or below, there is a tendency to improve coating curability. The upper and lower limits can be combined arbitrarily. For example, p is preferably 3 to 5, and more preferably 3 to 4.

[0372] The following monomers can be listed as photopolymerizable monomers (e1).

[0373]

[0374] The photopolymerizable monomer (E) in the coloring resin composition of the present invention optionally includes photopolymerizable monomers other than photopolymerizable monomer (e1) (hereinafter sometimes referred to as "other photopolymerizable monomers (e2)"). As other photopolymerizable monomers (e2), it is particularly desirable to use polyfunctional olefin monomers having two or more olefin double bonds in one molecule. The number of olefin double bonds in the polyfunctional olefin monomer is not particularly limited, but is generally two or more, preferably four or more, more preferably five or more, and also preferably eight or less, more preferably seven or less. By setting it to the lower limit or above, there is a tendency to achieve high sensitivity, and by setting it to the upper limit or below, there is a tendency to improve solubility in solvents. The 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 4 to 8, and even more preferably 5 to 7.

[0375] Other photopolymerizable monomers (e2) 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 having a carbamate skeleton obtained by reacting polyisocyanate compounds with hydroxy compounds containing (meth)acryloyl groups.

[0376] Examples of acrylates that are aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene 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.

[0377] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and pyrogallol triacrylate.

[0378] 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.

[0379] Examples of alkenyl compounds 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; and aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, which react 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.

[0380] In addition, examples include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate.

[0381] Other photopolymerizable monomers (e2) can be monomers with acid values. Acid-valued monomers are esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Preferably, they are polyfunctional monomers that have acid groups by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl groups of the aliphatic polyhydroxy compound. Particularly preferred are polyfunctional monomers in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

[0382] 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.

[0383] 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 lower limit tends to improve developing and dissolving properties, while setting it below the 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 composition of all polyfunctional monomers to be within the aforementioned range.

[0384] 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.

[0385] 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.

[0386] 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.

[0387] The proportion of (E) photopolymerizable monomer in the coloring resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. Setting the content to the lower limit or above tends to improve the curability of the coating film, and setting it to the upper limit or below tends to improve storage stability. The upper and lower limits can be combined arbitrarily. For example, the proportion of (E) photopolymerizable monomer in the coloring resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, further preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass in the total solids of the coloring resin composition.

[0388] The proportion of photopolymerizable monomer (e1) in the coloring resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. By setting the content to the lower limit or above, there is a tendency for improved developer solubility and better patterned shape when the hot plate temperature rises. Furthermore, by setting the content to the upper limit or below, there is a tendency for improved storage stability and pattern adhesion. The upper and lower limits can be combined arbitrarily. For example, the proportion of photopolymerizable monomer (e1) in the coloring resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, further preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass in the total solid component of the coloring resin composition.

[0389] In the coloring resin composition of the present invention, the content ratio of photopolymerizable monomer (e1) to photopolymerizable monomer (E) is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, particularly preferably 55% by mass or more, and preferably 98% by mass or less, more preferably 96% by mass or less, further preferably 94% by mass or less, and particularly preferably 92% by mass or less. Setting the content to the lower limit or above tends to improve the solubility in the developer, while setting it to the upper limit or below tends to improve the patterning properties. The upper and lower limits can be combined arbitrarily. For example, the content ratio of photopolymerizable monomer (e1) to photopolymerizable monomer (E) is preferably 40 to 98% by mass, more preferably 45 to 96% by mass, further preferably 50 to 94% by mass, and particularly preferably 55 to 92% by mass.

[0390] [1-6] Other solid components

[0391] In the coloring resin composition of the present invention, solid components other than those described above may be further incorporated as needed. Examples of such components include dispersants, dispersing aids, surfactants, and adhesion enhancers.

[0392] [1-6-1] Dispersants, dispersing aids

[0393] When the coloring resin composition of the present invention contains a pigment as a colorant (A), it is preferable to contain a dispersant in order to stably disperse the pigment. When a high molecular weight dispersant is used, excellent dispersion stability over time is achieved, and therefore it is preferred.

[0394] Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants.

[0395] As polymeric dispersants, examples by trade name include EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK), Disparlon (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), and the dispersants described in Japanese Patent Application Publication No. 2013-119568.

[0396] 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.

[0397] As block copolymers having functional groups containing nitrogen atoms, AB block copolymers and BAB block copolymers are preferred, which are composed of A blocks having quaternary ammonium salt groups and / or amino groups in the side chains and B blocks not having quaternary ammonium salt groups and amino groups.

[0398] Functional groups containing nitrogen atoms include primary amines, secondary amines, tertiary amines, and quaternary ammonium groups. From the viewpoint of dispersibility and storage stability, primary amines, secondary amines, and tertiary amines are preferred, and tertiary amines are more preferred.

[0399] 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.

[0400]

[0401] 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 is a hydrogen atom or a methyl group. X is a divalent linking group.

[0402] The number of carbon atoms of the optional alkyl group with substituents in formula (d1) is not particularly limited, but is generally 1 or 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.

[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 any type, either straight-chain or branched. The alkyl group can contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0404] The number of carbon atoms of the optional aryl group with substituents in formula (d1) 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, it is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 8.

[0405] 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.

[0406] The number of carbon atoms in the optional aralkyl group with substituents in formula (d1) is not particularly limited, but is generally 7 or 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.

[0407] 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.

[0408] From the perspectives of dispersibility, storage stability, electrical reliability, and developability, as R 1 and R 2 Each of the alkyl groups is preferably substituted, with methyl or ethyl groups being more preferred.

[0409] 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.

[0410] In equation (d1), R is used as 1 With R 2The cyclic structure formed by mutual bonding can be exemplified by, for example, a nitrogen-containing heterocyclic monocyclic ring with 5 to 7 members, or a fused ring formed by the fusion of two of these. The nitrogen-containing heterocyclic ring preferably does not have aromaticity, and more preferably is a saturated ring. Specifically, examples of cyclic structures are shown in (IV) below.

[0411]

[0412] These ring structures may optionally have substituents.

[0413] In formula (d1), the divalent linking group X can be, for example, an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a -CONH-R group. 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 -COOR. 14 -base.

[0414] The proportion of the repeating unit shown in formula (d1) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20 mol% or more, especially preferably 25 mol% or more, and even more preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, and especially preferably 40 mol% or less. Within the above range, there is a tendency to balance 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) in all repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, especially preferably 20 to 50%, and especially preferably 25 to 40 mol%.

[0415] From the viewpoint of improving the compatibility of dispersants with binder components such as solvents and improving dispersion stability, block copolymers preferably have repeating units as shown in the following general formula (d2).

[0416]

[0417] 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.

[0418] R in equation (d2) 11The number of carbon atoms in the alkyl group with substituents is not particularly limited, but is generally 1 or more, preferably 2 or more, and even more 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 in 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.

[0419] 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 any type, either straight-chain or branched. The alkyl group can contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0420] Substituents that may be optionally present in the alkyl group include, for example, halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0421] 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 further preferably 10 or less, more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, n is preferably 1 to 10, more preferably 2 to 5.

[0422] The proportion of the repeating unit shown in formula (d2) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Within the above range, there is a tendency to balance compatibility with binder components such as solvents and dispersion stability. The above upper and lower limits can be combined arbitrarily. For example, the proportion of the repeating unit shown in formula (d2) in all repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%.

[0423] From the viewpoint of improving the compatibility of the dispersant with the solvent and other binder components and improving the dispersion stability, the block copolymer preferably has repeating units as shown in the following general formula (d3).

[0424]

[0425] 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.

[0426] R in equation (d3) 8The number of carbon atoms in the optional alkyl group with substituents is not particularly limited, but is generally 1 or 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.

[0427] 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 any type, either straight-chain or branched. The alkyl group can contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0428] R in equation (d3) 8 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, and more preferably 12 or less. For example, 6 to 16 is preferred, and 6 to 12 is more preferred.

[0429] 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.

[0430] R in equation (d3) 8 The number of carbon atoms in the optional aralkyl group with substituents is not particularly limited, but is generally 7 or more, preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 is preferred, and 7 to 12 is more preferred.

[0431] 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.

[0432] From the perspective of solvent compatibility and dispersion stability, as R 8 Preferably alkyl or aralkyl, more preferably methyl, ethyl or phenylmethylene.

[0433] As R 8 The alkyl group may optionally have substituents, such as halogen atoms or alkoxy groups.

[0434] Substituents that may be optionally present in an aryl or aralkyl group include, for example, chain-like alkyl groups, halogen atoms, and alkoxy groups.

[0435] As R 8 The chain-like alkyl groups shown include any of the straight-chain and branched forms.

[0436] The proportion of the repeating unit shown in formula (d3) in all repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 80 mol% or less, even more preferably 70 mol% or less. Within the above range, there is a tendency to balance 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 (d3) in all repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 70 mol%.

[0437] Block copolymers may also have repeating units other than those shown in formula (d1), formula (d2), and formula (d3). Examples of such repeating units include 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.

[0438] 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).

[0439] Repeating units other than those shown in formula (d1) may be included in block A. 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%.

[0440] Repeating units other than those shown in formula (d2) and formula (d3) may be included in the B block. 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%.

[0441] From the perspective of dispersibility, the acid value of the block copolymer is preferably low, and particularly preferably 0 mg KOH / g.

[0442] Here, acid value indicates the number of mg of KOH required to neutralize 1g of solid dispersant component.

[0443] 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, particularly preferably 100 mg KOH / g or more, especially 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, especially preferably 100–130 mg KOH / g, and particularly preferably 105–130 mg KOH / g.

[0444] 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.

[0445] The weight-average molecular weight of the block copolymer is preferably between 1,000 and 30,000. Within this range, the dispersion stability becomes good, and there is a tendency to be less prone to the generation of drying foreign matter when applying it using a slit nozzle.

[0446] Block copolymers can be manufactured using known methods. For example, they can be manufactured by living polymerization of the monomers used to introduce the repeating units described above.

[0447] As a living polymerization method, known methods described below can be used: for example, 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); BC Anderson, GD Andrews et al. al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986); Koichi Ue, Koichi Hatada, Polymer Processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985); DY Sogoh, W. Hertler et al, Macromolecules, 20, 1473 (1987).

[0448] When the coloring resin composition of the present invention contains a dispersant, the proportion of the dispersant is not particularly limited. However, 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. Setting the content to the lower limit or above tends to improve dispersibility and storage stability. Furthermore, setting the content to the upper limit or below tends to improve electrical reliability and developability. The 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 solid component 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.

[0449] When the coloring resin composition of the present invention includes a pigment and a dispersant, the proportion of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. By setting it within the above 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 includes a pigment and a dispersant, the proportion of the dispersant relative to 100 parts by mass of the pigment is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, further preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass.

[0450] 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, for example.

[0451] Examples of pigment derivatives include derivatives of azo, phthalocyanine, quinacrine, benzimidazolone, quinophthalone, isoindolineone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, pyrene, diketopyrrolopyrrole, and dioxazine pigments. Examples of substituents in pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups bonded directly or via alkyl, aryl, or heterocyclic groups to the pigment skeleton. Sulfonamide groups and their quaternary salts, and sulfonic acid groups are preferred, with sulfonic acid groups being more preferred. Furthermore, multiple substituents may be substituted onto a single pigment skeleton, or a mixture of compounds with different numbers of substitutions may be used. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinoline pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacrine pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0452] [1-6-2] Surfactants

[0453] As surfactants, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. From the perspective of minimizing the possibility of adverse effects on various properties, nonionic surfactants are preferred. When the coloring resin composition of the present invention contains a surfactant, the proportion of the surfactant is not particularly limited. It is generally used in the range of 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and generally 10% by mass or less, 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 solid components of the coloring resin composition. The above-mentioned upper and lower limits can be combined arbitrarily. For example, the proportion of the surfactant in the total solid components 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.

[0454] [1-6-3] Adhesion enhancer

[0455] To improve adhesion to the substrate, the coloring resin composition of the present invention may contain an adhesion enhancer. Examples of adhesion enhancers include silane coupling agents and titanium coupling agents. Silane coupling agents are preferred.

[0456] Examples of silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicones), Z-6040, Z-6043, and Z-6062 (manufactured by Dow Corning Toray Co., Ltd.). A single silane coupling agent can be used, or two or more can be combined in any ratio.

[0457] The photosensitive resin composition of the present invention may contain a binding enhancer other than a silane coupling agent. Examples include phosphoric acid-based binding enhancers and other binding enhancers.

[0458] As a phosphoric acid-based binding enhancer, phosphate esters containing (meth)acryloyloxy groups are preferred. Phosphoric acid-based binding enhancers represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0459]

[0460] 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.

[0461] Other sealing enhancers include, for example, TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphoric acid-based sealing enhancers and other sealing agents can be used alone or in combination of two or more.

[0462] When the coloring resin composition of the present invention contains an adhesion enhancer, its content ratio is not particularly limited, but 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 also 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 above-mentioned lower limit value or above, there is a tendency to improve patterning characteristics and pattern adhesion under high humidity conditions. In addition, by setting it to the above-mentioned upper limit value or below, there is a tendency to suppress residue generation. The above-mentioned upper and lower limits can be combined arbitrarily. For example, when the coloring resin composition contains an adhesion enhancer, its content ratio 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 in the total solid components.

[0463] [2] Preparation of coloring resin composition

[0464] Next, the method for preparing the coloring resin composition of the present invention (hereinafter sometimes referred to as a photoresist) will be described.

[0465] In preparing a coloring resin composition containing pigment as a colorant, firstly, specified amounts of pigment, solvent, and dispersant are weighed separately. The pigment-containing colorant is then dispersed in a dispersion treatment step to prepare a pigment dispersion. This dispersion treatment step can utilize a paint shaker, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, etc. 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 on the finished color filter substrate.

[0466] When dispersing pigments, as described above, it is preferable to use a suitable combination of dispersing aids or dispersing resins.

[0467] 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 for dispersion is typically above 0°C, preferably above room temperature, and typically below 100°C, preferably below 80°C. It should be noted that the appropriate time varies depending on the composition of the pigment dispersion and the size of the sand mill, etc., so the dispersion time should be adjusted accordingly.

[0468] A homogeneous dispersion solution is prepared by mixing a solvent, an alkali-soluble resin, a photopolymerization initiator, and other components not mentioned above, 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 treatment and mixing processes; therefore, it is preferable to filter the obtained pigment dispersion solution using a filter or similar device.

[0469] When the colorant does not contain pigment, it can be obtained by mixing the colorant, solvent, alkali-soluble resin, photopolymerization initiator, and other components not mentioned above as needed, in the form of a homogeneous solution. It is preferable to filter the obtained solution using a filter or the like.

[0470] [3] Fabrication of color filter substrate

[0471] The color filter of the present invention has pixels made using the coloring resin composition of the present invention.

[0472] [3-1] Transparent substrate (support)

[0473] As for the transparent substrate of the color filter, its 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, thermoplastic resin sheets made of polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resin, unsaturated polyester resin, thermosetting resin sheets made of poly(meth)acrylic acid resin, and various types of glass. From the viewpoint of heat resistance, glass or heat-resistant resins are preferred.

[0474] To improve surface properties such as adhesion, the transparent substrate and the black matrix forming substrate 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 transparent substrate is typically 0.05 mm or more, preferably 0.1 mm or more, and also typically 10 mm or less, preferably 7 mm or less. Furthermore, when performing film formation treatment with various resins, the film thickness is typically 0.01 μm or more, preferably 0.05 μm or more, and also typically 10 μm or less, preferably 5 μm or less. For example, 0.01–10 μm, 0.05–5 μm.

[0475] [3-2] Black Matrix

[0476] The color filter of the present invention can be manufactured by forming a black matrix on a transparent substrate and typically further 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 or blue pixels (resist patterns) among the red, green, and blue pixels. Using the green or blue pixel (resist pattern) forming coating liquid, various processes such as coating, heating and drying, image exposure, development, and thermosetting 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 metallic material such as a chromium compound, thereby forming a pixel image.

[0477] A black matrix is ​​formed on a transparent substrate using a coloring resin composition and a light-shielding metal film or a black matrix. As the light-shielding metal material, chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, as well as nickel and tungsten alloys, can be used, and these materials can be stacked in multiple layers.

[0478] These metal 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 etchant of cerium ammonium nitrate and perchloric acid and / or nitric acid. For other materials, an etchant appropriate to the material is used. Finally, the positive photoresist is stripped with a special stripping agent, thereby forming a black matrix.

[0479] In this case, thin films of these metals or metal / metal oxides are 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. Then, a photomask with repeating patterns such as stripes, mosaics, or triangles is used to expose and develop the coating, forming a resist image. Finally, the coating can be etched to form a black matrix.

[0480] 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 coloring materials such as carbon black, graphite, iron black, aniline black, Cyanine Black, and titanium black, or a black coloring material obtained by mixing appropriately selected red, green, and blue pigments or dyes from inorganic or organic pigments or dyes, can be used to form a black matrix by operating in the same manner as the method for forming red, green, and blue pixel images described later.

[0481] [3-3] Pixel formation

[0482] A coloring resin composition of one of the colors red, green, and blue is coated onto a transparent substrate with a black matrix. After drying, a photomask is superimposed on the coating. The image is then exposed, developed, and thermally or photocured as needed through the photomask to form a pixel image. By performing this operation on the red, green, and blue coloring resin compositions respectively, a color filter image can be formed.

[0483] The coating of color filter resin compositions can be performed using methods such as spin coating, wire rod coating, flow coating, die coating, roller coating, and spray coating. Among these methods, die coating can significantly reduce the amount of coating liquid used, completely avoids the effects of mist and other adhering substances that occur when using spin coating, and can also suppress the generation of foreign matter, making it the preferred method from a comprehensive point of view.

[0484] 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 it is too thin, it is difficult to increase the pigment concentration, and sometimes the desired color cannot be achieved. The coating thickness, measured after drying, is typically 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and typically 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. For example, it is 0.2–20 μm, 0.5–10 μm, or 0.8–5 μm.

[0485] [3-4] Drying of the coating

[0486] The drying (pre-baking) of the coating film after applying the coloring resin composition to the substrate is preferably based on a drying method using a hot plate, IR oven, or convection oven. Typically, after pre-drying, the coating film is dried again by heating. 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 typically 40°C or higher, preferably 50°C or higher, and also typically 80°C or lower, preferably 70°C or lower; the drying time is typically 15 seconds or higher, preferably 30 seconds or higher, and also typically 5 minutes or lower, preferably 3 minutes or lower.

[0487] Regarding the temperature conditions for reheating and drying, a temperature higher than the pre-drying temperature is preferred. Specifically, it is typically 50°C or higher, preferably 70°C or higher, and typically 200°C or lower, preferably 160°C or lower, and particularly preferably 130°C or lower. Furthermore, while the drying time also depends on the heating temperature, it is typically 10 seconds or higher, particularly preferably 15 seconds or higher, and typically 10 minutes or lower, particularly preferably 5 minutes or lower. Higher drying temperatures improve adhesion to the transparent substrate, but excessively high temperatures can sometimes cause the adhesive resin to decompose, leading to thermal polymerization and poor development. It should be noted that, as a drying process for this coating, a vacuum drying method can also be used, where drying is performed in a vacuum chamber without raising the temperature.

[0488] [3-5] Exposure process

[0489] Image exposure is performed by overlaying a negative matrix pattern onto a coating of the coloring resin composition and irradiating it with an ultraviolet or visible light source through the mask pattern. To prevent a decrease in 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, as needed. There are no particular limitations on the light source used in the above image 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, optical filters can also be used.

[0490] [3-6] Developing process

[0491] After exposing the coating film using the coloring resin composition of the present invention to the light source described above, developing it with an aqueous solution containing a surfactant and an alkaline compound, an image can be formed on the substrate to manufacture the color filter of the present invention.

[0492] The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes, or pigments.

[0493] 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.

[0494] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aromatic 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.

[0495] 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.

[0496] There are no particular limitations on the development conditions, but the preferred development temperature is generally above 10°C, especially above 15°C, further above 20°C, and generally below 50°C, especially below 45°C, further below 40°C. The development method can be based on any of the following: immersion development, spray development, brush development, ultrasonic development, etc.

[0497] [3-7] Thermosetting treatment

[0498] The developed color filter is then subjected to a heat-curing process. The heat-curing conditions are as follows: temperature is typically above 100°C, preferably above 150°C, and typically below 280°C, preferably below 250°C; the time is selected to be between 5 and 60 minutes. Through this series of steps, a patterned image of one color is formed. This process is repeated sequentially to pattern black, red, green, and blue, thereby forming the color filter. It should be noted that the order in which these four colors are patterned is not limited to the order described above.

[0499] [3-8] Formation of transparent electrodes

[0500] The color filter of the present invention can directly form transparent electrodes such as ITO on an image in this state, and 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.

[0501] [4] Image display device (panel)

[0502] The image display device of the present invention has the color filter of the present invention.

[0503] The following provides a detailed description of liquid crystal display devices and organic EL display devices as image display devices.

[0504] [4-1] Liquid Crystal Display Device

[0505] 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 the color filter of the present invention, spacers are dispersed 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 obtain a surface state that allows adjustment of the tilt of the liquid crystal.

[0506] The spacers can be spacers of a size corresponding to the gap between the opposing substrates; typically, spacers of 2–8 μm are suitable. Alternatively, photosensitive spacers (PS) formed on the color filter substrate using photolithography can be used instead of spacers. As the opposing substrate, array substrates are commonly used, and TFT (thin-film transistor) substrates are particularly suitable.

[0507] 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 typically selected within the range of 2μm to 8μm. 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, thus sealing the area around the liquid crystal cell.

[0508] After being cut into panel units, the sealed liquid crystal cell is depressurized within a vacuum chamber. The liquid crystal injection port is then immersed in liquid crystal, which leaks into the chamber, thereby injecting the liquid crystal into the liquid crystal cell. The depressurization level within the liquid crystal cell is typically 1 × 10⁻⁶. -2 Pa or higher, preferably 1×10 -3The above, and usually 1×10 -7 Pa or less, preferably 1×10 -6 The temperature range is below Pa. Furthermore, it is preferable to heat the liquid crystal cell during depressurization, with the heating temperature typically above 30°C, preferably above 50°C, and also typically below 100°C, preferably below 90°C.

[0509] The temperature rise during decompression is typically maintained within a range of 10 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).

[0510] 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.

[0511] As thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known, and any of them can be used.

[0512] [4-2] Organic EL display device

[0513] When manufacturing an organic EL display device having the color filter 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.

[0514] Examples of stacking methods for the organic light-emitting element 500 include: 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 sequentially 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 manufactured in this way can be used in both passive-drive and active-drive organic EL display devices.

[0515] Example

[0516] The present invention will now be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples without departing from its spirit.

[0517] <Phalothocyanin compound A>

[0518] Phthalocyanine compound A, having the following chemical structure, was synthesized using Example 30 based on Japanese Patent Application Publication No. 05-345861.

[0519]

[0520] It should be noted that Et in the formula represents ethyl.

[0521] <Dispersant A>

[0522] This is 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.

[0523] The proportions of the repeating units shown in equations (1a), (2a), (3a), (4a) and (5a) in the total number of repeating units are less than 1 mol%, 34.5 mol%, 6.9 mol%, 13.8 mol%, and 6.9 mol%, respectively.

[0524]

[0525] <Alkali-soluble resin A>

[0526] For 145 parts by weight of propylene glycol monomethyl ether acetate, the mixture was stirred while purging with nitrogen and heated to 120°C. Then, 10 parts by weight of styrene, 90 parts by weight of glycidyl methacrylate, and 10 parts by weight of monomethacrylate with a tricyclic decane backbone (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and the mixture was stirred continuously at 120°C for 2 hours. Next, the reaction vessel was changed to air purging, and 0.7 parts by weight of tris(dimethylaminomethyl)phenol and 0.12 parts by weight of hydroquinone were added to 50 parts by weight of acrylic acid, and the reaction was continued at 120°C for 6 hours. Then, 13 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the reaction was continued at 120°C for 3.5 hours. The alkali-soluble resin A obtained in this way has a polystyrene weight-average molecular weight (Mw) of approximately 9000, an acid value of 25 mg KOH / g, and a double bond equivalent of 260 g / mol, as measured by GPC.

[0527] <Alkali-soluble resin B>

[0528] Prepare a separable flask with a condenser to serve as the reaction vessel. Add 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and then heat in an oil bath while stirring to raise the temperature of the reaction vessel to 90°C.

[0529] 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 started dropwise from the monomer tank and the chain transfer agent tank to initiate polymerization. The addition was carried out dropwise for 135 minutes while maintaining the temperature at 90°C. After the addition was completed, the temperature was raised to 110°C after 60 minutes.

[0530] After maintaining the mixture at 110°C for 3 hours, a gas inlet tube was installed on a separable flask, and bubbling of a gas mixture of oxygen / nitrogen = 5 / 95 (v / v) was initiated. 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 continued at 110°C for 9 hours under these conditions.

[0531] After cooling to room temperature, alkali-soluble resin B was obtained, which had a weight-average molecular weight (Mw) of 9000 (calculated from polystyrene using GPC), an acid value of 101 mg KOH / g, and a double bond equivalent of 550 g / mol.

[0532] <Preparation of Green Dye Dispersion A>

[0533] As shown 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.

[0534] <Preparation of Green Pigment Dispersion A>

[0535] As shown in Table 1, 13.9 parts by weight of CI pigment green 58, 1.9 parts by weight of dispersant A (based on solids content), 4.2 parts by weight of alkali-soluble resin B (based on solids content), 80.0 parts by weight of propylene glycol monomethyl ether acetate as solvent (also including solvent from dispersant A and solvent from alkali-soluble resin B), 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 green pigment dispersion A.

[0536] <Preparation of Yellow Pigment Dispersion A>

[0537] 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), 5.7 parts by weight of alkali-soluble resin B (based on solids), 76.0 parts by weight of propylene glycol monomethyl ether acetate (as solvent, also including solvent from dispersant A and solvent from alkali-soluble resin B), 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.

[0538] [Table 1]

[0539]

[0540] <Photopolymerizable monomer A>

[0541] Polyethoxylated tetramethylolmethane tetraacrylate (NK ESTER ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) is ethoxylated pentaerythritol tetraacrylate, wherein each mole contains an average of 4 moles of ethylene oxide. It belongs to the photopolymerizable monomer category (e1).

[0542] <Photopolymerizable monomer B>

[0543] A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). It is not a photopolymerizable monomer (e1).

[0544] <Photopolymerizable monomer C>

[0545] Ethylene oxide modified (12) dipentaerythritol hexaacrylate (KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.). It belongs to the photopolymerizable monomer (e1).

[0546] <Photopolymerization Initiator A>

[0547] Oxime ester compounds having the following chemical structures.

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

[0549]

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

[0551] <Chain transfer agent A>

[0552] Pentaerythritol tetra(3-mercaptopropionate) (manufactured by Starch Chemical Company)

[0553] <Surfactant A>

[0554] MEGAFAC F-554 (manufactured by DIC)

[0555] <Seam-Adhesive Enhancer A>

[0556] Compounds having the following chemical structures.

[0557]

[0558] It should be noted that in the formula, C2H4 represents dimethylene and C3H6 represents trimethylene.

[0559] <Preparation of Coloring Resin Compositions>

[0560] The coloring resin composition was prepared by mixing the components listed in Table 2 according to the stated solid content ratios. It should be noted that propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used to achieve a total solid content of 17.3% by mass in the coloring resin composition. The resulting coloring resin composition had a PGMEA / PGME mixing ratio (by mass) of 90 / 10.

[0561] [Table 2]

[0562]

[0563] <Determination of Color Characteristics>

[0564] The resulting colored resin composition was spin-coated onto a 50 mm square, 0.7 mm thick glass substrate (AN100, manufactured by AGC) using a spin coating method, dried under reduced pressure, and then pre-baked on a hot plate at 90°C for 90 seconds. Next, it was heated using a 2 kW high-pressure mercury lamp at 40 mJ / cm². 2 Exposure, illuminance 30mW / cm 2 Perform full-area exposure. Then, develop using a 0.04% (w / w) potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Next, develop at 1 kg / cm². 2 The substrate is then subjected to a 10-second spray water wash under high water pressure. Next, it undergoes a 20-minute thermosetting process at 230°C in a clean oven to produce the colored substrate.

[0565] For the obtained colored substrate, the transmission spectrum was measured using a Hitachi U-3310 spectrophotometer, and the luminance at a chromaticity of sy = 0.576 under C light source was calculated. The results are shown in Table 2.

[0566] <Evaluation of Pattern Formation>

[0567] A coloring resin composition was spin-coated onto a 50 mm square, 0.7 mm thick glass substrate (AN100, manufactured by AGC) with a chromaticity of sy = 0.576 under C light source after thermosetting. The mixture was then pre-baked at 80°C for 90 seconds. Next, a 2 kW high-pressure mercury lamp was used at 40 mJ / cm². 2 Exposure, illuminance 30mW / cm 2 Exposure was performed through an exposure mask with a circular cover of 30 μm in diameter. Then, development was performed for 60 seconds using a 0.04% (w / w) potassium hydroxide aqueous solution at a developer temperature of 23°C. Following this, development was carried out at 1 kg / cm². 2 The substrate was subjected to a 10-second spray water wash under high water pressure. Then, it underwent a 20-minute thermosetting process at 230°C to produce a patterned substrate. For the resulting patterned substrate A, the diameter (μm) of the holes in the pattern (hole diameter A) was measured using an optical microscope.

[0568] Then, in the above process of pattern substrate A, the pre-baking temperature is changed from 80°C to 100°C, and pattern substrate B is produced under the same conditions. For the obtained pattern substrate B, the diameter (μm) of the hole in the pattern (hole diameter B) is measured using an optical microscope.

[0569] The effect of pre-baking temperature on pore diameter was calculated using pore size A and pore size B, serving as an indicator of temperature dependence. The results of the temperature dependence (=│(pore size A-pore size B)[μm] / (100-80)[℃]│) are shown in Table 2.

[0570] As shown in Table 2, compared with the coloring resin composition containing CI pigment green 58 in Comparative Example 2, the brightness is improved when phthalocyanine compound A is used as in Comparative Example 1. However, due to the use of phthalocyanine compound A, the pre-baking temperature dependence of the pore size is significantly worse.

[0571] Unlike pigments, dyes can achieve high brightness and high tinting strength when they exist as single molecules in the system. However, because the molecules are in an isolated state, they have poor heat resistance and will sublimate and oxidize due to the heat curing process used to obtain the pattern. Therefore, the pattern after heat curing tends to have reduced brightness.

[0572] In contrast, phthalocyanine compound (1) has a structure in which one or more hydrogen atoms constituting the phthalocyanine skeleton are replaced by fluorine atoms with small atomic radii, making it difficult to suppress the association between phthalocyanine compounds (1). Therefore, when the intermolecular distance decreases due to heating, etc., the decrease in brightness caused by heating is suppressed by forming associative aggregates. In addition, after association, its particle size becomes smaller than CI pigment green 58, so it is believed that the brightness of the pattern increases after thermosetting treatment.

[0573] On the other hand, a comparison between Comparative Example 1 and Comparative Example 2 shows that the use of phthalocyanine compound (1) makes the pre-baking temperature dependence of pore size worse.

[0574] In Comparative Example 1, the phthalocyanine compound (1) formed small-particle-size aggregates that densely existed within the coating film, creating a state that easily inhibited the penetration and dissolution of the developer into the coating film. It can be considered that when the pre-baking temperature is 80°C, the residual solvent exists in the coating film in a certain amount, thereby promoting the penetration of the developer into the coating film. On the other hand, at high-temperature regions such as pre-baking temperatures of 100°C, the residual solvent is less, and the penetration of the developer into the interior of the coating film is insufficient. In the unexposed areas, the solubility of the coating film in the developer is also insufficient, resulting in poor patterning formation and smaller pore size, thereby reducing the pre-baking temperature dependence of the pore size.

[0575] In contrast, in Examples 1, 2, and 3, which contained phthalocyanine compound (1), high brightness was maintained and the pre-baking temperature dependence of pore size was good. In Examples 1, 2, and 3, part or all of the photopolymerizable monomer B of Comparative Example 1 was replaced with the photopolymerizable monomer (e1). The photopolymerizable monomer (e1) has an oxyalkylene chain, so even in a coating state with low residual solvent, such as 100°C, the developer penetration is maintained well, thereby forming pores with the same diameter as in a coating state with high residual solvent, such as 80°C. It is believed that this suppressed the deterioration of the pre-baking temperature dependence of pore size.

[0576] In addition, regarding the coloring resin composition containing CI pigment green 58 in Comparative Example 2, the particle size of CI pigment green 58 is larger than that of the phthalocyanine compound (1) associated in Examples 1, 2, 3 and Comparative Example 1. In order to ensure sufficient gaps for the developer to penetrate into the coating, it has sufficient developer penetration regardless of the amount of residual solvent, that is, regardless of the pre-baking temperature. It is considered that the pore size has good pre-baking temperature dependence.

[0577] The present invention has been described in detail using specific methods, but those skilled in the art will of course make various changes and modifications without departing from the intent and scope of the present invention.

[0578] Explanation of reference numerals in the attached figures

[0579] 10 Transparent support substrate

[0580] 20 pixels

[0581] 30 Organic protective layer

[0582] 40 Inorganic oxide film

[0583] 50 transparent anode

[0584] 51 Hole Injection Layer

[0585] 52 Hole Transport Layer

[0586] 53. Emissive Layer

[0587] 54 Electron Injection Layer

[0588] 55 Cathode

[0589] 100 Organic EL Components

[0590] 500 Organic Light-Emitting Organoluminescent Materials

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). The (E) photopolymerizable monomer comprises a photopolymerizable monomer (e1), which is a compound represented by the following general formula (II). 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 but less than ten 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 equipped with any substituents, and * represents a linking bond. In equation (II), R 1 Indicates an alkylene group having 2 or more carbon atoms. R 2 Indicates a hydrogen atom or a methyl group. n represents an integer greater than or equal to 1. Z represents direct bonding, oxygen atom, sulfur atom, aliphatic hydrocarbon group with 2-4 valence, tetravalent carbon atom, non-aromatic heterocyclic group with 2-4 valence, or aromatic cyclic group with 2-4 valence. p represents an integer from 2 to 4. Furthermore, the structures represented by the multiple general formulas (II') contained in a molecule may be either the same or different. 。 2. The coloring resin composition according to claim 1, wherein, The colorant (A) is present in a proportion of 10% by mass or more in all solid components.

3. The coloring resin composition according to claim 1 or 2, wherein, The proportion of the photopolymerizable monomer (e1) in the total solid components is more than 1% by mass.

4. A color filter having pixels made using the coloring resin composition according to any one of claims 1 to 3.

5. An image display device having the color filter of claim 4.

Images