Colored resin composition, color filter, and image display device

Abstract

Provided is a colored resin composition in which the effect of temperature changes during prebaking on developer solubility and patterning characteristics is low. The present invention is a colored resin composition containing (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, wherein the coloring agent (A) includes a phthalocyanine compound having a specific chemical structure, and the photopolymerizable monomer (E) includes a photopolymerizable monomer (e1) having a specific partial structure.

Description

[Technical Field]

[0001] The present invention relates to a colored resin composition, a color filter, and an image display device. 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, and the contents thereof are incorporated herein by reference. [Background technology]

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

[0003] In recent years, there has been a growing demand for higher brightness, higher contrast, and wider color gamut in color filters. While pigments are generally used as the colorants that determine the color of color filters due to their heat resistance, lightfastness, and other factors, pigments are no longer able to meet market demands, especially for high brightness. As a result, there is a growing interest in using dyes as colorants instead of pigments.

[0004] For example, studies have been conducted on using phthalocyanine-based dyes for green pixel applications (see, for example, Patent Document 1).

[0005] On the other hand, Patent Document 2 describes that by using a colored resin composition containing a specific photopolymerizable compound, it is possible to reduce the amount of residue after development in the manufacture of color filters, even when the pigment is present at a high concentration. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2019-113732 [Patent Document 2] Japanese Patent Publication No. 2008-164886 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The inventors' investigations revealed that the colored resin composition described in Patent Document 1 exhibits significant changes in solubility in the developer depending on the temperature during pre-baking (the drying process of the coated film performed before the exposure process), and that the pattern size changes significantly, especially at high temperatures. This revealed a problem in that high-definition color filters, such as 4K and 8K filters, which require precise line width adjustment, cannot be manufactured stably. Patent Document 2 only evaluated colored resin compositions containing pigments as colorants, and it was unclear what properties would be exhibited when phthalocyanine-based dyes were included as colorants.

[0008] Therefore, the present invention aims to provide a colored resin composition in which the influence of pre-baking temperature changes on developer solubility and patterning properties is small. [Means for solving the problem]

[0009] As a result of diligent research by the inventors, we discovered that the above problem can be solved by using a specific photopolymerizable monomer in combination with a specific colorant, leading to the present invention. In other words, the present invention has the following configurations [1] to [6].

[0010] [1] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, The aforementioned (A) coloring agent contains a phthalocyanine compound having a chemical structure represented by the following general formula (1), A colored resin composition characterized in that the (E) photopolymerizable monomer comprises a photopolymerizable monomer (e1) having a substructure represented by the following general formula (I).

[0011] [Chemical formula]

[0012] (In formula (1), A

[0017] , ~A 16 each independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 ~A 16 represents a fluorine atom, and one or more of A 1 ~A 16 represents a group represented by the following general formula (2).)

[0013] [Chemical formula]

[0014] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

[0015] [Chemical formula]

[0016] (In formula (I), R 1 represents an alkylene group having 2 or more carbon atoms. R 2 represents a hydrogen atom or a methyl group. n represents an integer of 1 or more. * represents a bond.)

[0017] [2] The colored resin composition according to [1], wherein the photopolymerizable monomer (e1) is a compound represented by the following general formula (II).

[0018] [Chemical formula]

[0019] (In formula (II), R 1 , R 2And n are equivalent to those in equation (I) above. Z represents a direct bond, an oxygen atom, a sulfur atom, a di- to tetravalent aliphatic hydrocarbon group, a tetravalent carbon atom, a di- to tetravalent non-aromatic heterocyclic group, a di- to tetravalent aromatic ring group, or a substructure represented by the following general formula (III). p represents an integer between 2 and 6. Furthermore, a single molecule contains multiple structures represented by the following general formula (II').

[0020] [ka]

[0021] They may be the same, or they may be different.

[0022] [ka]

[0023] (In equation (III), * represents a bond.)

[0024] [3] The colored resin composition according to [1] or [2], wherein the content of the colorant (A) is 10% by mass or more in the total solid content. [4] A colored resin composition according to any of [1] to [3], wherein the content of the photopolymerizable monomer (e1) is 1% by mass or more in the total solid content. A color filter having pixels created using one of the colored resin compositions [5][1] to [4]. An image display device having the color filters [6][5]. [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a colored resin composition in which the influence of pre-baking temperature changes on developer solubility and patterning properties is small. [Brief explanation of the drawing]

[0026] [Figure 1]Figure 1 is a schematic cross-sectional view showing an example of an organic EL display element having the color filter of the present invention. [Modes for carrying out the invention]

[0027] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) calculated on a polystyrene basis by GPC (gel permeation chromatography). In this invention, "total solids" refers to all components in the colored resin composition other than the solvent. Even if components other than the solvent are liquid at room temperature, they are not included in the solvent and are included in the total solids. In this invention, unless otherwise specified, "amine value" refers to the amine value on an effective solids basis, and is a value expressed by the amount of base and the equivalent amount of KOH per gram of solids of the dispersant. In this invention, "CI" means color index.

[0028] [1] Components of the colored resin composition The colored resin composition according to 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 other than the above components may be included as required.

[0029] [1-1] (A) Colorants The coloring agent (A) contained in the colored resin composition of the present invention includes a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter sometimes referred to as "phthalocyanine compound (1)").

[0030] [ka]

[0031] In formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, A 1 ~A 16One or more of these represent a fluorine atom, and A 1 ~A 16 One or more of these represent a group represented by the following general formula (2).

[0032] [ka]

[0033] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituents. * represents a bond.

[0034] The colorant (A) in the colored resin composition of the present invention contains a phthalocyanine compound (1). The phthalocyanine compound (1) has one or more hydrogen atoms constituting the phthalocyanine skeleton substituted with fluorine atoms with a small atomic radius, and has a structure that does not easily inhibit the association of phthalocyanine compounds (1) with each other. Therefore, it is thought that when the intermolecular distance is reduced by heating, etc., aggregates are formed, thereby suppressing the decrease in brightness due to heating. Furthermore, even after association, the particle size is thought to be smaller than that of the pigment, and it is thought that the brightness will be higher in the pattern after heat curing treatment.

[0035] In the coating film obtained after pre-baking the colored resin composition of the present invention, the phthalocyanine compound (1) is thought to be densely present as aggregates with small particle sizes, and it is thought that the penetration and dissolution of the developer into the coating film in the subsequent development process is easily suppressed. Therefore, the resulting pattern shape is likely to change depending on the amount of residual solvent, and for example, the pre-baking temperature dependence of the hole diameter is likely to worsen.

[0036] (A 1 ~A 16 ) In the above formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, A 1 ~A 16 One or more of these represent a fluorine atom, and A 1~A 16 One or more of these represent a group represented by the following general formula (2).

[0037] [ka]

[0038] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituents. * represents a bond.

[0039] A 1 ~A 16 Examples of halogen atoms in this product include fluorine, chlorine, and bromine atoms. Fluorine atoms are preferred from the viewpoint of increasing brightness. Also, A 1 ~A 16 Preferably, six or more of these are fluorine atoms, more preferably seven or more, even more preferably eight or more, and also preferably 15 or less, preferably 12 or less, and more preferably 10 or less. Setting the value above the lower limit tends to improve the stability of the phthalocyanine compound (1), and setting it below the upper limit tends to improve the affinity with dispersants and solvents in the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, A 1 ~A 16 The number of substituents representing fluorine atoms is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and even more preferably 8 to 10.

[0040] (X) In formula (2), X represents a divalent linking group. The divalent linking group is not particularly limited, but can be an oxygen atom, a sulfur atom, or -N(R a1 )-group(R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples include ). From the viewpoint of stability during calcination, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0041] (Substituents that the benzene ring may have) The benzene ring in formula (2) may have any substituent. The substituent is not particularly limited, but for example, a halogen atom, an alkyl group (-R A (-OR) group, alkoxy group (-OR) A Base (however, R A represents an alkyl group. )), alkoxycarbonyl group (-COOR A Base (however, R A )), aryl group (-R B (-OR) group, aryloxy group (-OR) B Base (however, R B represents an aryl group. )), aryloxycarbonyl group (-COOR B Base (however, R B represents an aryl group. )) are examples. From the viewpoint of developability and brightness, an alkoxycarbonyl group is preferred.

[0042] The alkyl groups contained in these groups may be linear, branched, or cyclic, but they are preferably linear from the viewpoint of affinity with organic solvents. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Setting it above the lower limit tends to suppress aggregation and foreign matter, while setting it below the upper limit tends to improve solvent affinity and long-term stability. The above upper and lower limits can be arbitrarily combined. 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. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. From the viewpoint of suppressing aggregation, methyl or ethyl groups are preferred, and ethyl groups are more preferred.

[0043] The aryl groups contained in these groups may be aromatic hydrocarbon ring groups or aromatic heterocyclic groups. The number of carbon atoms in the aryl group is not particularly limited, but is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting it above the lower limit tends to suppress aggregation due to steric repulsion, and setting it below the upper limit tends to improve solvent affinity and stability over time. The above upper and lower limits can be arbitrarily combined; for example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0044] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monoring or a fused ring. Examples of aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, pentalene rings, indene rings, azulene rings, and heptalene rings, all of which have one free valence atom. The aromatic heterocyclic group may be a monocyclic or fused ring. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thiopyran rings, pyridine rings, 1,3-oxazole rings, isoxazole rings, 1,3-thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazan rings, pyrazine rings, pyrimidine rings, pyridazine rings, 1,3,5-triazine rings, and benzofuran rings, all of which have one free valence atom. Examples include 2-benzofuran rings, benzothiophene rings, 2-benzothiophene rings, 1H-pyrrolidine rings, indole rings, isoindole rings, indidine rings, 2H-1-benzopyran rings, 1H-2-benzopyran rings, quinoline rings, isoquinoline rings, 4H-quinoridine rings, benzimidazole rings, 1H-indazole rings, quinoxaline rings, quinazoline rings, sinnoline rings, phthalazine rings, 1,8-naphthyridine rings, purine rings, and pteridine rings.

[0045] When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited, but from the viewpoint of improving heat resistance through π-π stacking among dye molecules and suppressing the decrease in brightness due to the decomposition of the dye, it is preferable that there is one substitution per benzene ring. If the benzene ring in formula (2) has any substituent, the substitution position may be at the ortho-, meta-, or para-position, but the para-position is preferred from the viewpoint of enabling stacking in a close-packed structure.

[0046] A 1 ~A 16 One or more of these represent fluorine atoms, but from the viewpoint of improving brightness by forming an intermolecular aggregate of phthalocyanine compound (1), A 1 ~A 4 One or more of them are fluorine atoms, 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 Preferably, one or more of them are fluorine atoms; 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 It is more preferable that two or more of them are fluorine atoms.

[0047] A 1 ~A 16 One or more of these represent a group represented by formula (2), but from the viewpoint of solubility in organic solvents and brightness, A 1 ~A 4 One or more of these are bases represented by formula (2), and A 5 ~A 8 One or more of these are bases represented by formula (2), and A 9 ~A 12 One or more of these are bases represented by formula (2), and A 13 ~A 16 Preferably, one or more of them are groups represented by formula (2); A 1 ~A 4 Two or more of these are bases represented by formula (2), and A 5 ~A8 Two or more of them are groups represented by formula (2), and A 9 ~A 12 Two or more of them are groups represented by formula (2), and 13 ~A 16 It is more preferable that two or more of them are groups represented by formula (2). From the viewpoint that luminance reduction is suppressed by efficient stacking, A 2 、A 3 、A 6 、A 7 、A 10 、A 11 、A 14 、and A 15 are groups represented by formula (2), and 1 、A 4 、A 5 、A 8 、A 9 、A 12 、A[[ID=4]] 13 、and A 16 are preferably halogen atoms; 2 、A 3 、A 6 、A 7 、A 10 、A 11 、A 14 、and A 15 are groups represented by formula (2), and 1 、A 4 、A 5 、A 8 、A 9 、A 12 、A 13 、and A 16 are particularly preferably fluorine atoms.

[0048] Specific examples of the phthalocyanine-based dye (1) include, for example, the following compounds.

[0049]

Chemical formula

[0050] In the above formula, Et represents ethyl.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] A known method can be used to produce the phthalocyanine dye (1), for example, the method described in Japanese Patent Publication No. 05-345861 can be used.

[0055] (A) The colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of other colorants include pigments and dyes. When used for green pixel applications, for example, it is preferable to use green pigments, green dyes, yellow pigments, or yellow dyes. Examples of green pigments include CI Pigment Green 7, 36, 58, 59, 62, and 63, with CI Pigment Green 58 being preferred from the viewpoint of brightness. As for green dyes, among those classified as dyes in the color index, examples of CI solvent dyes include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. As for CI acid dyes, examples of CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and CI Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. From the viewpoint of suppressing dye decomposition during heat firing, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred.

[0056] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 8 1, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 15 4, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196 Examples include compounds obtained by inserting other compounds into a 1:1 complex of azobarbituric acid represented by formula (i) below with nickel, or its interchangeable isomer (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

[0057] [ka]

[0058] Other compounds that can be inserted into the nickel azo complex represented by formula (i) include, for example, the compound represented by the following formula (ii).

[0059] [ka]

[0060] Among these, CI Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and the nickel azo complex represented by formula (i) are preferred from the viewpoint of high brightness and wide color gamut, and CI Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by formula (i) are more preferred.

[0061] Examples of yellow dyes include barbiturate azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples include the compounds described in Japanese Patent Publication No. 2010-168531. As for yellow dyes, among those classified as dyes in the Color Index, examples of CI solvent dyes include CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163, etc. 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, Examples include 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and their derivatives. Examples of CI direct dyes include CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, and 141. Examples of CI modant dyes include CI Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65.Preferably, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 1 Examples include 57, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243, and their derivatives. From the viewpoint of suppressing dye decomposition during heat firing, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163 are preferred.

[0062] 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. For micronization of the pigment, methods such as solvent salt milling are preferably used.

[0063] The content of colorant (A) in the colored resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 30% by mass or more, and also preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. Setting it above the lower limit tends to allow for the reproduction of a wide range of hues, and setting it below the upper limit tends to ensure stability over time. The above upper and lower limits can be combined arbitrarily. For example, the content of colorant (A) in the colored resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, even more preferably 20 to 60% by mass, even more preferably 25 to 50% by mass, and particularly preferably 30 to 40% by mass, based on the total solid content of the colored resin composition.

[0064] The content of phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Setting it above the lower limit tends to improve brightness, and setting it below the upper limit tends to ensure stability over time. The above upper and lower limits can be combined arbitrarily. For example, the content of phthalocyanine compound (1) in the colored resin composition is more preferably 3 to 50% by mass, even more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass, based on the total solid content of the colored resin composition.

[0065] When the colored resin composition of the present invention contains other colorants, the proportion of these colorants is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass or more, and also preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Setting the proportion above the lower limit tends to allow for the reproduction of a wide range of hues, and setting it below the upper limit tends to ensure stability over time. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains other colorants, the proportion of these colorants is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, even more preferably 5 to 25% by mass, even more preferably 7 to 25% by mass, and particularly preferably 10 to 29% by mass, all within the total solid content of the colored resin composition.

[0066] [1-2](B) Solvent (B) The solvent has the function of dissolving or dispersing colorants, alkali-soluble resins, photopolymerization initiators, photopolymerizable monomers, and other components in the colored resin composition and pigment dispersion of the present invention, and adjusting the viscosity. (B) Any solvent that can dissolve or disperse each component is acceptable.

[0067] Examples of such solvents include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0068] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0069] Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether; Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, and methoxymethylpentanone; Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

[0070] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Chain-like or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Examples include nitriles such as acetonitrile and benzonitrile.

[0071] Examples of commercially available solvents that fall under the above category include Mineral Spirit, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, and Digrime (all trade names). These solvents may be used individually or in combination of two or more.

[0072] When forming pixels of a color filter using photolithography, it is preferable to select a solvent with a boiling point in the range of 100 to 200°C (under a pressure of 1013.25 [hPa]; the same applies to all boiling point references below). More preferably, the solvent has a boiling point of 120 to 170°C. Among the above solvents, glycol alkyl ether acetates are preferred because they offer a good balance of applicability and surface tension, and the solubility of the constituent components in the composition is relatively high.

[0073] Glycol alkyl ether acetates may be used alone, or in combination with other solvents. Glycol monoalkyl ethers are particularly preferred as the solvent to be used in combination. Among these, propylene glycol monomethyl ether is particularly preferred from the viewpoint of the solubility of the constituent components in the composition. However, glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease, such as the viscosity of the colored resin composition obtained later increasing. Therefore, when using glycol monoalkyl ethers in combination, the proportion of glycol monoalkyl ethers in solvent (B) is preferably 5% to 30% by mass, and more preferably 5% to 20% by mass.

[0074] In another embodiment, a solvent with a boiling point of 150°C or higher can be used in combination. By using a solvent with a boiling point of 150°C or higher, the colored resin composition becomes less likely to dry, but it has the effect of making it less likely for the interrelationships of the constituent components in the pigment dispersion to be destroyed by rapid drying. When using a solvent with a boiling point of 150°C or higher, the content of the solvent with a boiling point of 150°C or higher in (B) solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. Setting it above the lower limit tends to make it easier to avoid, for example, the precipitation and solidification of colorant components at the tip of the slit nozzle, which can cause foreign matter defects, and setting it below the upper limit tends to make it easier to avoid problems such as poor cycle time in the vacuum drying process or pin marks from pre-baking, as the drying speed of the composition slows down. The solvent with a boiling point of 150°C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether; in this case, it is not necessary to include a solvent with a boiling point of 150°C or higher separately. Preferred solvents with a boiling point of 150°C or higher include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin.

[0075] When forming pixels of a color filter using an inkjet method, the solvent should have a boiling point of typically 130°C to 300°C, preferably 150°C to 280°C. Using a boiling point above the lower limit tends to result in better uniformity of the resulting coating film, while using a boiling point below the upper limit tends to reduce residual solvent during firing. From the viewpoint of uniformity of the resulting coating film, the vapor pressure of the solvent should typically be 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

[0076] In the inkjet method for manufacturing color filters, the ink emitted from the nozzle is very fine, ranging from a few to tens of pL. Therefore, the solvent tends to evaporate and concentrate the ink before it lands around the nozzle opening or within the pixel bank. To avoid this, it is preferable that solvent (B) contains a solvent with a high boiling point, specifically, a solvent with a boiling point of 180°C or higher. It is more preferable that it contains a solvent with a boiling point of 200°C or higher, and particularly preferable that it contains a solvent with a boiling point of 220°C or higher. The content ratio 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. Setting it above the lower limit tends to ensure that the effect of preventing solvent evaporation from droplets is sufficiently exhibited.

[0077] Examples of solvents with a boiling point of 180°C or higher include, among the various solvents mentioned above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin. To adjust the viscosity of the colored resin composition and the solubility of the solids, a solvent with a boiling point lower than 180°C may be included. Such solvents are preferably low viscosity, highly soluble, and have low surface tension; for example, ethers, esters, and ketones are preferred. Among these, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are particularly preferred.

[0078] On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. When alcohols are used in combination, (B) the alcohol content in the solvent is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0079] The solvent content in the colored resin composition of the present invention is not particularly limited, but its upper limit is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. Keeping it below the upper limit tends to make it easier to form a coated film. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, taking into consideration viscosity suitable for coating. The above upper and lower limits can be arbitrarily combined. For example, the solvent content in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and even more preferably 80 to 85% by mass.

[0080] [1-3](C) Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curing by photopolymerization and solubility with a developer. (C) As the alkali-soluble resin, for example, known polymer compounds described in Japanese Patent Publication No. 7-207211, Japanese Patent Publication No. 8-259876, Japanese Patent Publication No. 10-300922, Japanese Patent Publication No. 11-140144, Japanese Patent Publication No. 11-174224, Japanese Patent Publication No. 2000-56118, and Japanese Patent Publication No. 2003-233179 can be used. Among these, the resins (C-1) to (C-5) below are preferred. (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, or by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction, and which is an alkali-soluble resin (hereinafter sometimes referred to as "resin (C-1)"). (C-2) A linear alkali-soluble resin containing carboxyl groups in the main chain (hereinafter sometimes referred to as "resin (C-2)"). (C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as "resin (C-3)"). (C-4)(meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)") (C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)"). Of these, resin (C-1) is particularly preferred.

[0081] The resins (C-2) to (C-5) only need to be so soluble in an alkaline developer that the desired developing process can be carried out. Preferably, each resin is one of those described in the same section of Japanese Patent Application Publication No. 2009-025813.

[0082] (C-1) A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, or by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction, thereby obtaining an alkali-soluble resin. One preferred embodiment of resin (C-1) is "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups in a copolymer of 5 to 90 mol% epoxy group-containing (meth)acrylate and 10 to 95 mol% of another radical polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups produced by the addition reaction."

[0083] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Glycidyl (meth)acrylate is preferred among these. These epoxy group-containing (meth)acrylates may be used individually or in combination of two or more.

[0084] As other radical polymerizable monomers copolymerized with epoxy group-containing (meth)acrylates, mono(meth)acrylates having the structure represented by the following general formula (V) are preferred.

[0085] [ka]

[0086] In formula (V), R 91 ~R 98 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 96 and R 98 , or R 95 and R 97 These elements may be connected to each other to form a ring. In equation (V), R 96 and R 98 , or R 95 and R 97 The ring formed by the linkage of these elements is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

[0087] Among these, the structures represented by formula (V) are preferably those represented by the following general formulas (Va), (Vb), or (Vc). By introducing these structures into an alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition is improved, and the intensity of pixels formed using the colored resin composition tends to increase.

[0088] A mono(meth)acrylate having the structure represented by formula (V) may be used alone or in combination of two or more types.

[0089] [ka]

[0090] As a mono(meth)acrylate having the structure represented by formula (V), various known mono(meth)acrylates can be used as long as they have the structure represented by formula (V), but mono(meth)acrylates represented by the following general formula (VI) are particularly preferred.

[0091] [ka]

[0092] In formula (VI), R 89 R represents a hydrogen atom or a methyl group. 90 This represents the structure expressed by equation (V).

[0093] In a copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer, if repeating units derived from mono(meth)acrylate represented by formula (VI) are included, the content of repeating units derived from mono(meth)acrylate represented by formula (VI) is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%, of the repeating units derived from the other radical polymerizable monomer.

[0094] Other radical polymerizable monomers besides mono(meth)acrylates represented by formula (VI) are not particularly limited, but specifically include, for example, vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, and ethyl (meth)acrylate. n-butyl lylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, neopentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, dodecyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclohexyl methacrylate Isobolonyl (meth)acrylate, adamantyl (meth)acrylate, propagyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, piperonyl (meth)acrylate, salicylic (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate (meth)acrylic acid esters such as (meth)acrylate, cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-iso-propyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate;Examples include (meth)acrylamides such as (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-di-iso-propylamide, and (meth)acrylate anthracenylamide; vinyl compounds such as (meth)acrylate anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

[0095] Among these other radically polymerizable monomers, styrene, benzyl (meth)acrylate, and monomaleimide are preferred from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition. In a copolymer of epoxy group-containing (meth)acrylate and another radical polymerizable monomer, if any repeating units derived from styrene, benzyl (meth)acrylate, or monomaleimide are included, the total content of repeating units derived from styrene, benzyl (meth)acrylate, and monomaleimide among the repeating units derived from the other radical polymerizable monomer is preferably 1 to 70 mol%, and more preferably 3 to 50 mol%.

[0096] For copolymerization reactions between epoxy group-containing (meth)acrylates and other radically polymerizable monomers, known solution polymerization methods can be applied. The solvent used is not particularly limited as long as it is inert to radical polymerization; commonly used organic solvents can be used. Solvents used in solution polymerization include, for example, ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetic acid esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, and butyl carbitol. Examples include diethylene glycol dialkyl ethers such as 1,4-dioxane and tetrahydrofuran; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; and dimethylformamide and N-methylpyrrolidone. These solvents may be used individually or in combination of two or more.

[0097] The amount of solvent used in the solution polymerization method is typically 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, per 100 parts by mass of the resulting copolymer. Keeping the amount of solvent within this range tends to facilitate control of the molecular weight of the copolymer. The radical polymerization initiator used in copolymerization reactions is not particularly limited as long as it can initiate radical polymerization; commonly used organic peroxide catalysts and azo compound catalysts can be used. Examples of organic peroxide catalysts include those classified as known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

[0098] Examples of radical polymerization initiators used in copolymerization reactions include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, 1,1-bis(t-butyl peroxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-bis(t-butyl peroxy)hexyl-3,3-isopropyl Examples include hydroperoxides, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.

[0099] Examples of azo compound catalysts include azobisisobutyronitrile and azobiscarbamide. From these, one or more radical polymerization initiators with appropriate half-lives are used depending on the polymerization temperature. The amount of radical polymerization initiator used is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the total monomers used in the copolymerization reaction.

[0100] The copolymerization reaction may be carried out by dissolving the monomers and radical polymerization initiators used in the copolymerization reaction in a solvent and raising the temperature while stirring; or by adding the monomers to which the radical polymerization initiator has been added dropwise to a heated and stirred solvent; or by adding the radical polymerization initiator to a solvent and raising the temperature, then adding the monomers dropwise. The reaction conditions can be set according to the target molecular weight.

[0101] In the present invention, the copolymer of epoxy group-containing (meth)acrylate and other radical polymerizable monomers is preferably composed of 5 to 90 mol% repeating units derived from epoxy group-containing (meth)acrylate and 10 to 95 mol% repeating units derived from the other radical polymerizable monomer; more preferably composed of 20 to 80 mol% repeating units derived from epoxy group-containing (meth)acrylate and 80 to 20 mol% repeating units derived from the other radical polymerizable monomer; and particularly preferably composed of 30 to 70 mol% repeating units derived from epoxy group-containing (meth)acrylate and 70 to 30 mol% repeating units derived from the other radical polymerizable monomer.

[0102] By setting the content of repeating units derived from epoxy group-containing (meth)acrylate to above the aforementioned lower limit, the amount of unsaturated monobasic acid and polybasic acid anhydride added, as described later, tends to be sufficient. By setting the content of repeating units derived from other radical polymerizable monomers to above the aforementioned lower limit, sufficient heat resistance and strength tend to be achieved. Next, the epoxy groups of a copolymer of epoxy resin-containing (meth)acrylate and other radical polymerizable monomers are reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic anhydride (alkali-soluble component).

[0103] As the unsaturated monobasic acid to be added to the epoxy group, known unsaturated monobasic acids can be used, for example, unsaturated carboxylic acids having an ethylenically unsaturated double bond. Examples of unsaturated monobasic acids to be added to the epoxy group include (meth)acrylic acid; crotonic acid; o-, m-, p-vinylbenzoic acid; and monocarboxylic acids such as (meth)acrylic acid in which the α-position is substituted with a haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group. Among these, (meth)acrylic acid is preferred. These unsaturated monobasic acids may be used individually or in combination of two or more.

[0104] By adding an unsaturated monobasic acid to the epoxy group, polymerizability can be imparted to the resin (C-1). The unsaturated monobasic acid is added to the epoxy groups of the copolymer in an amount of typically 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. Setting the amount above the lower limit tends to improve the long-term stability of the colored resin composition. Known methods can be used to add an unsaturated monobasic acid to the epoxy group of a copolymer.

[0105] Furthermore, known polybasic anhydrides can be used as the polybasic anhydrides to be added to the hydroxyl groups formed when an unsaturated monobasic acid is added to the epoxy groups of the copolymer. Examples of polybasic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloridenic anhydride; and anhydrides of three or more base acids such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used individually or in combination of two or more.

[0106] By adding a polybasic acid anhydride to the hydroxyl group formed when an unsaturated monobasic acid is added to the epoxy group of a copolymer, alkali solubility can be imparted to the resin (C-1). The polybasic acid anhydride is added to the hydroxyl groups formed by adding an unsaturated monobasic acid to the epoxy groups of the copolymer, typically in amounts of 10 to 100 mol%, preferably 20 to 90 mol%, and more preferably 30 to 80 mol%, of the hydroxyl groups. Setting the amount below the upper limit tends to result in a good residual film rate during development, while setting it above the lower limit tends to result in sufficient solubility. As a method for adding a polybasic acid anhydride to a hydroxyl group formed by adding an unsaturated monobasic acid to an epoxy group of a copolymer, known methods can be employed.

[0107] Furthermore, in order to improve photosensitivity, after adding a polybasic acid anhydride, a glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to some of the resulting carboxyl groups. To improve developability, a glycidyl ether compound that does not have polymerizable unsaturated groups may be added to some of the generated carboxyl groups.

[0108] Alternatively, both of these may be added. Examples of glycidyl ether compounds that do not have polymerizable unsaturated groups include glycidyl ether compounds having phenyl groups or alkyl groups. Examples of commercially available products include the following products manufactured by Nagase ChemteX: "Denacol EX-111," "Denacol EX-121," "Denacol EX-141," "Denacol EX-145," "Denacol EX-146," "Denacol EX-171," and "Denacol EX-192."

[0109] The structure of resin (C-1) is described, for example, in Japanese Patent Publication No. Hei 8-297366 and Japanese Patent Publication No. 2001-89533. The weight-average molecular weight of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably between 3,000 and 100,000, and especially preferably between 5,000 and 50,000. Setting it above the lower limit tends to result in good heat resistance and film strength, while setting it below the upper limit tends to result in good solubility in the developer. As a guideline for molecular weight distribution, the ratio of the weight-average molecular weight (Mw) of the resin (C-1) to the number-average molecular weight (Mw / Mn) is preferably between 2.0 and 5.0.

[0110] From the viewpoint of coating film curing properties when exposed to ultraviolet light, (C) among alkali-soluble resins, (c1) acrylic copolymer resins having ethylenically unsaturated groups in the side chains are preferred. (c1) The substructure of an acrylic copolymer resin having an ethylenically unsaturated group in its side chain is not particularly limited, but from the viewpoint of achieving both coating curability during UV exposure and alkali solubility during alkaline development, it is preferable to have a substructure represented by the following general formula (CI).

[0111] [ka]

[0112] In formula (CI), R 1 and R 2 Each of the symbols independently represents a hydrogen atom or a methyl group. * represents a bonding bond.

[0113] Furthermore, among the substructures represented by formula (CI), the substructure represented by the following general formula (CI') is preferred from the viewpoint of sensitivity and alkali developability.

[0114] [ka]

[0115] In formula (CI'), R 1 and R 2 Each of these independently represents either a hydrogen atom or a methyl group. X represents a hydrogen atom or a polybasic acid residue.

[0116] A polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, with tetrahydrophthalic acid and biphenyltetracarboxylic acid being more preferred. These polybasic acids may be used individually or in combination of two or more.

[0117] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CI), the content of the substructure represented by formula (CI) in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. Setting the value above the lower limit tends to improve the curability of the coating film during UV exposure, and setting it below the upper limit tends to improve the alkali solubility during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the substructure represented by formula (CI) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0118] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CI'), the content of the substructure represented by formula (CI') in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. Setting the value above the lower limit tends to improve the curability of the coating film during UV exposure, and setting it below the upper limit tends to improve the alkali solubility during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the substructure represented by formula (CI) in the acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0119] (c1) When an acrylic copolymer resin having an ethylenically unsaturated group in its side chain contains a substructure represented by formula (CI), the other substructures included are not particularly limited, but from the viewpoint of alkali solubility during alkali development, it is also preferable to have a substructure represented by the following general formula (CII).

[0120] [ka]

[0121] In equation (CII), R 3 R represents a hydrogen atom or a methyl group. 4 This represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

[0122] (R 4 ) In equation (CII), R 4 This represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. R 4 Examples of alkyl groups in this compound include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 8 or more, and also preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.

[0123] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability, dicyclopentanyl and dodecanyl groups are preferred, and dicyclopentanyl is more preferred. Examples of substituents that the alkyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0124] R 4Examples of aromatic ring groups include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic ring groups. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, even more preferably 6 to 20, and particularly preferably 6 to 18. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monoring or a fused ring, and examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorantene ring, and fluorene ring. The aromatic heterocyclic group may be monocyclic or fused rings, and examples include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienopyrrole rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, quinoxaline rings, phenanthidine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. From the viewpoint of developability, benzene ring groups and naphthalene ring groups are preferred, and benzene ring groups are more preferred. Examples of substituents that the aromatic ring group may have include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0125] R 4 Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkenyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0126] 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 developability, vinyl and allyl groups are preferred, and vinyl groups are more preferred.

[0127] Examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0128] R 4represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. From the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred.

[0129] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CII), the content of the substructure represented by formula (CII) in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and also preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. Setting it above the lower limit tends to improve alkali solubility, and setting it below the upper limit tends to improve the storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, in an acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain, the content of the substructure represented by formula (CII) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, even more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

[0130] (c1) When the acrylic copolymer resin contains a substructure represented by formula (CI), it is preferable that the other substructures included include a substructure represented by the following general formula (CIII) from the viewpoint of suppressing brightness reduction by improving heat resistance.

[0131] [ka]

[0132] In formula (CIII), R 5 R represents a hydrogen atom or a methyl group. 6represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group. t represents an integer from 0 to 5.

[0133] (R 6 ) In equation (CIII), R 6 This represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group. R 6 Examples of alkyl groups in this compound include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12.

[0134] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of heat resistance, dicyclopentanyl and dodecanyl groups are preferred, and dicyclopentanyl is more preferred. Examples of substituents that the alkyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0135] R 6 Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkenyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0136] 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 UV exposure, vinyl and allyl groups are preferred, and vinyl groups are more preferred.

[0137] Examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0138] R 6Examples of alkynyl groups include linear, branched, or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkynyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

[0139] Examples of alkynyl groups include 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butyne-2-yl group, 1,4-pentadiiin-3-yl group, 1,3-pentadiiin-5-yl group, and 1-hexyn-6-yl group.

[0140] Examples of substituents that the alkynyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of developability, hydroxy and oligoethylene glycol groups are preferred.

[0141] R 6 Examples of halogen atoms in this compound include fluorine, chlorine, bromine, and iodine atoms. Fluorine atoms are preferred from the viewpoint of storage stability of the acrylic copolymer resin.

[0142] R 6Examples of alkoxy groups include linear, branched, or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

[0143] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups.

[0144] Examples of substituents that the alkoxy group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0145] R 6 Examples of alkyl sulfide groups include linear, branched, or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the number of carbon atoms above the lower limit tends to improve lipophilicity and solvent solubility, while setting the number of carbon atoms below the upper limit tends to improve hydrophilicity and alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

[0146] Examples of alkyl sulfide groups include methyl sulfide groups, ethyl sulfide groups, propyl sulfide groups, and butyl sulfide groups. From the viewpoint of developability, methyl sulfide groups and ethyl sulfide groups are preferred.

[0147] Examples of substituents that the alkyl group in the alkyl sulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the viewpoint of developability, hydroxyl and oligoethylene glycol groups are preferred.

[0148] R 6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkyl sulfide group. From the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0149] In equation (CIII), t represents an integer between 0 and 5. From the viewpoint of ease of manufacture, it is preferable that t is 0.

[0150] (c1) When an acrylic copolymer resin having ethylenically unsaturated groups in its side chains has a substructure represented by formula (CIII), the content of the substructure represented by formula (CIII) in the acrylic copolymer resin having ethylenically unsaturated groups in its side chains (c1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 5 mol% or more, particularly preferably 8 mol% or more, and also preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. Setting it above the lower limit tends to improve heat resistance and suppress brightness reduction, while setting it below the upper limit tends to increase the content of other substructures and improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the content of the substructure represented by formula (CIII) in an acrylic copolymer resin having an ethylenically unsaturated group in the (c1) side chain is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, even more preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

[0151] (c1) When an acrylic copolymer resin having an ethylenically unsaturated group in its side chain has a substructure represented by formula (CI), it is also preferable that it may have a substructure represented by the following general formula (CIV) as another substructure from the viewpoint of developability.

[0152] [ka]

[0153] In formula (IV), R 7 represents a hydrogen atom or a methyl group.

[0154] (c1) When the acrylic copolymer resin having an ethylenically unsaturated group in its side chain contains a substructure represented by formula (CIV), the content of the substructure represented by formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol or less. Setting it above the lower limit tends to improve alkali solubility, and setting it below the upper limit tends to improve the storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, the content of the substructure represented by formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol.

[0155] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, even more preferably 40 mg KOH / g or more, even more preferably 50 mg KOH / g or more, particularly preferably 60 mg KOH / g or more, and also preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and even more preferably 150 mg KOH / g or less. Setting it above the lower limit tends to improve alkali solubility, and setting it below the upper limit tends to improve the storage stability of the colored resin composition. The above upper and lower limits can be combined arbitrarily. For example, the acid value of (C) alkali-soluble resin is preferably 10 to 300 mg KOH / g, more preferably 30 to 300 mg KOH / g, even more preferably 40 to 250 mg KOH / g, even more preferably 50 to 200 mg KOH / g, and particularly preferably 60 to 150 mg KOH / g.

[0156] (C) The weight-average molecular weight of the alkali-soluble resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, even more preferably 6000 or more, even more preferably 7000 or more, and especially preferably 8000 or more. Also, it is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and even more preferably 10000 or less. Setting it above the lower limit tends to improve heat resistance and coating film curing properties, and setting it below the upper limit tends to improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the weight-average molecular weight of the alkali-soluble resin (C) is preferably 1000 to 30000, more preferably 2000 to 30000, even more preferably 4000 to 20000, even more preferably 6000 to 20000, especially preferably 7000 to 15000, and particularly preferably 8000 to 10000.

[0157] The content of (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and also 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. Setting it above the lower limit tends to improve the curability of the coating film when exposed to ultraviolet light, and setting it below the upper limit tends to improve the solubility in the developer solution and suppress residue. The above upper and lower limits can be arbitrarily combined. For example, the content of (C) alkali-soluble resin in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, even more 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 content of the colored resin composition.

[0158] [1-4](D) Photopolymerization initiator The colored resin composition of the present invention contains a (D) photoinitiator. By containing the (D) photoinitiator, film curability by photopolymerization can be imparted. (D) The photoinitiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and additives such as a sensitizing dye added as necessary. The photopolymerization initiation system is a component that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction and has a function of generating polymerization active radicals.

[0159] Examples of the photoinitiator include, for example, metallocene compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197 of Japan, hexarylbisimidazole derivatives described in JP-A-10-39503 of Japan, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, radical activators such as N-aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone-based compounds, and oxime ester-based initiators described in JP-A-2000-80068 of Japan.

[0160] Specific examples of the photoinitiator that can be used in the present invention are listed below. Halomethylated triazine derivatives such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

[0161] Halomethylated oxadiazole derivatives such as 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; Imidazole derivatives such as 2-(2′-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-chlorophenyl)-4,5-bis(3′-methoxyphenyl)imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4′-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone;

[0162] Benzophenone derivatives such as benzophenone, Michlaz ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; Acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone; Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone;

[0163] Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives such as benzanthrone; Dicyclopentadienyl-Ti-dichloride, dicyclopentadogenyl-Ti-bis-phenyl, dicyclopentadogenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadogenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadogenyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadogenyl-Ti-2,6 Titanocene derivatives such as -diplopheni-1-yl, dicyclopentagenyl-Ti-2,4-difluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluoropheni-1-yl, and dicyclopentagenyl-Ti-2,6-difluoro-3-(pyru-1-yl)-pheni-1-yl;

[0164] α-aminoalkylphenone compounds such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone; Oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime)ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime).

[0165] From the viewpoint of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred. Oxime ester compounds possess structures that absorb ultraviolet light, transmit light energy, and generate radicals, allowing for high sensitivity even in small amounts, and stability against thermal reactions. This enables the design of highly sensitive colored resin compositions using small quantities. In particular, from the viewpoint of light absorption for the i-line (365 nm) of an exposure light source, oxime ester compounds having a carbazole ring, which may have substituents, are preferred.

[0166] Examples of oxime ester compounds include those represented by the following general formula (I-1).

[0167] [ka]

[0168] In formula (I-1), R 21aThis represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group. R 21b represents any substituent containing an aromatic ring or a heteroaromatic ring. R 22a This represents an optionally substituted alkanoyl group or an optionally substituted allyloyl group.

[0169] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 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. Examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, and propyl groups. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl groups, or N-acetyl-N-acetoxyamino groups. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0170] R 21a Examples of aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but it is preferably 5 or more from the viewpoint of solubility in the colored resin composition. Furthermore, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, even more preferably 12 or less, and particularly preferably 8 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, even more preferably 5 to 12, and particularly preferably 5 to 8.

[0171] Examples of aromatic ring groups include phenyl, naphthyl, pyridyl, furyl, and fluorenyl groups. From the viewpoint of developability, phenyl, naphthyl, and fluorenyl groups are preferred, and phenyl and fluorenyl groups are more preferred. Examples of substituents that the aromatic ring group may have include hydroxyl groups, optionally substituted alkyl groups, optionally substituted alkoxy groups, carboxyl groups, halogen atoms, amino groups, amide groups, and alkyl groups. From the viewpoint of developability, hydroxyl groups and carboxyl groups are preferred, and carboxyl groups are more preferred. Examples of substituents in optionally substituted alkyl groups and optionally substituted alkoxy groups include hydroxyl groups, alkoxy groups, halogen atoms, and nitro groups. From the perspective of developability, R 21a Preferably, the alkyl group may have substituents, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.

[0172] R 21b is any substituent containing an aromatic ring or a heteroaromatic ring. From the viewpoint of solubility in solvents and sensitivity to exposure, optionally substituted carbazolyl groups, optionally substituted tioxantonyl groups, optionally substituted diphenyl sulfide groups, optionally substituted fluorenyl groups, or groups linked to these groups and carbonyl groups are preferred. From the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, optionally substituted carbazolyl groups, or groups linked to optionally substituted carbazolyl groups and carbonyl groups are preferred.

[0173] Examples of the substituent that the carbazolyl group may have include an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a halogen atom such as F, Cl, Br, and I; an acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; an aromatic ring group having 4 to 10 carbon atoms; an amino group; an aminoalkyl group having 1 to 10 carbon atoms; a hydroxyl group; a nitro group; a CN group; an aryloyl group which may have a substituent; a heteroaryloyl group which may have a substituent; and a tenoyl group which may have a substituent.

[0174] R 22a The number of carbon atoms of the alkanoyl group in 22a is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 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 arbitrarily combined. For example, the number of carbon atoms of the alkanoyl group is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 3 to 5. Examples of the alkanoyl group include an acetyl group, an ethyroyl group, a propanoyl group, and a butanoyl group. Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

[0175] R 22a The number of carbon atoms of the aryloyl group in 22a is not particularly limited, but from the viewpoints of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms of the aryloyl group is preferably 7 to 20, more preferably 7 to 15, even more preferably 7 to 10, and particularly preferably 8 to 10. Examples of the aryloyl group include a benzoyl group and a naphthoyl group. Examples of substituents that the allyroyl group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and alkyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0176] Examples of compounds represented by formula (I-1) include those represented by the following general formulas (I-2) or (I-3), from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source.

[0177] [ka]

[0178] [ka]

[0179] In equations (I-2) and (I-3), R 21a and R 22a This is equivalent to equation (I-1). R 23a This represents an alkyl group which may have substituents. R 24a This represents an optionally substituted alkyl group, an optionally substituted allyloyl group, an optionally substituted heteroallyloyl group, or a nitro group. The benzene rings constituting the carbazole ring may be further fused with aromatic rings to form a polycyclic aromatic ring.

[0180] R 23a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 1 or more, preferably 2 or more, and usually 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. Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl groups. Examples of substituents that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted. R 23a From the viewpoint of solubility in solvents and ease of synthesis, an ethyl group is more preferable.

[0181] R 24a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 1 or more, preferably 2 or more, and usually 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. Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl groups. Examples of substituents that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0182] R 24a The number of carbon atoms in the allyroyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the allyroyl group is preferably 7 to 20, more preferably 8 to 15, even more preferably 9 to 10, and particularly preferably 9. Examples of allyroyl groups include benzoyl groups and naphthoyl groups. Examples of substituents that the allyroyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, an ethyl group is preferred.

[0183] R 24a The number of carbon atoms in the heteroaryroyl group is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the heteroaryroyl group is preferably 7 to 20, more preferably 8 to 15, even more preferably 9 to 10, and particularly preferably 9. Examples of heteroaryl groups include fluorobenzoyl, chlorobenzoyl, bromobenzoyl, fluoronaphthoyl, chloronaphthoyl, and bromonaphthoyl groups. Examples of substituents that the heteroaryroyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted. R 24a From the viewpoint of sensitivity, an allyroyl group which may have substituents is preferred, and a benzoyl group is more preferred.

[0184] The benzene rings constituting the carbazole ring may be further fused with aromatic rings to form a polycyclic aromatic ring.

[0185] Examples of commercially available oxime ester compounds include OXE-02 and OXE-03 from BASF, TR-PBG-304 and TR-PBG-314 from Changzhou Strong Electronic New Materials Co., Ltd., and N-1919, NCI-930, and NCI-831 from ADEKA.

[0186] Specific examples of oxime ester compounds include the following:

[0187] [ka]

[0188] [ka]

[0189] [ka]

[0190] These photopolymerization initiators may be used individually or in combination of two or more.

[0191] (D) In ​​addition to the photopolymerization initiator, a chain transfer agent may also be used. A chain transfer agent is a compound that has the function of receiving the generated radical and transferring the received radical to another compound. Various chain transfer agents can be used as long as they possess the above-mentioned functions. For example, mercapto group-containing compounds and carbon tetrachloride are examples, and it is more preferable to use mercapto group-containing compounds because they tend to have a high chain transfer effect. This is thought to be because the low SH bond energy makes bond cleavage more likely, leading to hydrogen abstraction reactions and chain transfer reactions. This is effective for improving sensitivity and surface hardening.

[0192] Examples of mercapto group-containing compounds include aromatic ring-containing mercapto group-containing compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropanetris(3-mercaptopropionate), and trimethylolpropanetris Examples of aliphatic mercapto group-containing compounds include sthioglycolates, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, compounds having multiple mercapto groups are preferred.

[0193] Preferred mercapto group-containing compounds having an aromatic ring include 2-mercaptobenzothiazole and 2-mercaptobenzimidazole, while preferred aliphatic mercapto group-containing compounds include trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptopropionate), pentaerythritoltris(3-mercaptopropionate), trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), pentaerythritoltris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0194] From the standpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, with trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione being preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) being more preferred. These chain transfer agents may be used individually or in combination of two or more.

[0195] In the colored resin composition of the present invention, the content of (D) photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, even more preferably 1.0% 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, even more preferably 6% by mass or less, and particularly preferably 4% by mass or less. Setting it above the lower limit tends to improve the curability of the coating film, and setting it below the upper limit tends to improve brightness by reducing visible light absorption. The above upper and lower limits can be arbitrarily combined. For example, in the colored resin composition, the content of (D) photopolymerization initiator is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass, even more preferably 1.0 to 6% by mass, and particularly preferably 1.2 to 4% by mass, in the total solid content of the colored resin composition.

[0196] When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and also preferably 3% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1.5% by mass or less. Setting the content above the lower limit tends to improve solvent resistance, and setting it below the upper limit tends to improve storage stability. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a chain transfer agent, the content ratio is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, even more preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1.5% by mass, based on the total solid content of the colored resin composition.

[0197] [1-5](E) Photopolymerizable monomer The colored resin composition of the present invention contains (E) a photopolymerizable monomer. The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound") is preferred. An ethylenic compound is a compound having an ethylenic double bond that, when the colored resin composition of the present invention is irradiated with active light, undergoes addition polymerization and hardens due to the action of a photopolymerization initiator. In this invention, the monomer refers to a concept opposite to so-called polymer substances, and includes not only monomers in the narrow sense but also dimers, trimers, and oligomers.

[0198] The (E) photopolymerizable monomer in the colored resin composition of the present invention includes a photopolymerizable monomer (e1) having a substructure represented by the following general formula (I) (hereinafter sometimes referred to as "photopolymerizable monomer (e1)").

[0199] [ka]

[0200] (In formula (I), R 1 This represents an alkylene group with 2 or more carbon atoms. R 2 represents a hydrogen atom or a methyl group. n represents an integer greater than or equal to 1. * represents a bond.

[0201] Since the photopolymerizable monomer (e1) has an alkylene oxide chain, it is thought that good developer penetration can be maintained even in a coating state with little residual solvent, such as at 100°C, thereby suppressing the decrease in the pre-bake temperature dependence of hole diameter even in a colored resin composition containing phthalocyanine compound (1).

[0202] (R 1 ) In formula (I), R 1 The symbol represents an alkylene group having two or more carbon atoms. Alkylene groups do not have substituents. The alkylene group may be linear, branched, cyclic, or a combination thereof. From the viewpoint of solvent solubility and solvent resistance, a linear alkylene group is preferred. The number of carbon atoms in the alkylene group is not particularly limited as long as it is 2 or more, but is preferably 4 or less, more preferably 3 or less, and even more preferably 2. Keeping it below the above upper limit tends to improve coating 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.

[0203] Examples of alkylene groups include ethylene, n-propylene, n-butylene, and isopropylene groups. From the viewpoint of coating film curability, n-propylene and ethylene groups are preferred, and ethylene groups are more preferred.

[0204] (n) In formula (I), n represents an integer of 1 or more, preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. Setting n below the above upper limit tends to improve the coating hardening properties. For example, n is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 to 2.

[0205] As the photopolymerizable monomer (e1), a compound represented by the following general formula (II) is preferred from the viewpoint of coating film curability.

[0206] [ka]

[0207] (In formula (II), R 1 , R 2 And n are equivalent to equation (I). Z represents a direct bond, an oxygen atom, a sulfur atom, a di- to tetravalent aliphatic hydrocarbon group, a tetravalent carbon atom, a di- to tetravalent non-aromatic heterocyclic group, a di- to tetravalent aromatic ring group, or a substructure represented by the following general formula (III). p represents an integer between 2 and 6. Note that the multiple structures represented by the following general formula (II') contained within a single molecule may be the same or different.

[0208] [ka]

[0209] [ka]

[0210] (In equation (III), * represents a bond.)

[0211] (Z) In equation (II), Z This represents a direct bond, an oxygen atom, a sulfur atom, a di- to tetravalent aliphatic hydrocarbon group, a tetravalent carbon atom, a di- to tetravalent non-aromatic heterocyclic group, a di- to tetravalent aromatic ring group, or a substructure represented by formula (III).

[0212] The divalent to tetravalent aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the divalent to tetravalent aliphatic hydrocarbon group is not particularly limited, but is preferably 10 or less, more preferably 9 or less, even more preferably 8 or less, and usually 1 or more. Keeping it below the above upper limit tends to improve coating film curability and solvent resistance. For example, the number of carbon atoms in the divalent to tetravalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 9, and even more preferably 1 to 8. Examples of 2-4 valent aliphatic hydrocarbon groups include methane, ethane, propane, and butane, which have 2-4 free valencies.

[0213] The non-aromatic heterocyclic group with 2-4 valent values ​​may be a monocyclic or fused ring. A non-aromatic heterocyclic ring is one that contains one of the following heteroatoms: nitrogen, sulfur, or oxygen. If a non-aromatic heterocyclic ring contains multiple heteroatoms, these may be the same or different. The number of carbon atoms in the 2-4 valent non-aromatic heterocyclic group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, preferably 8 or less, and more preferably 6 or less. Setting it above the lower limit tends to improve heat resistance, and setting it below the upper limit tends to improve solvent solubility. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the 2-4 valent non-aromatic heterocyclic group is preferably 3 to 8, more preferably 3 to 6, and even more preferably 4 to 6. Examples of 2-4 valent non-aromatic heterocyclic groups include piperidine rings and pyrrolidine rings, which have 2-4 free valencies.

[0214] Examples of di-tetravalent aromatic ring groups include di-tetravalent aromatic hydrocarbon ring groups and di-tetravalent aromatic heterocyclic ring groups. The aromatic hydrocarbon ring in the divalent to tetravalent aromatic hydrocarbon ring group may be a monoring or a fused ring. The number of carbon atoms in the aromatic hydrocarbon ring group is not particularly limited, but is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and also preferably 15 or less, more preferably 12 or less, and even more preferably 9 or less. Setting it above the lower limit tends to improve heat resistance, and setting it below the upper limit tends to improve brightness. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the divalent to tetravalent aromatic hydrocarbon ring group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9. Examples of 2-4 valent aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluorantene rings, and fluorene rings, all of which have 2-4 free valencies.

[0215] The aromatic heterocyclic group with two to four valent carbon atoms may be a monocyclic or 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 also preferably 15 or less, more preferably 12 or less, and even more preferably 9 or less. Setting the number above the lower limit tends to improve heat resistance, and setting it below the upper limit tends to improve brightness. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the two to four valent aromatic heterocyclic group is preferably 3 to 15, more preferably 4 to 12, and even more preferably 5 to 9. Examples of 2-4 valent aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazole rings, pyrrolopyrrole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, phlopyrrole rings, phlofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cinoline rings, phenantholidine rings, benzimidazole rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings, all of which have 2-4 free valencies.

[0216] From the viewpoint of curability and patterning properties, Z is preferably an oxygen atom, a sulfur atom, or a tetravalent carbon atom, and more preferably a tetravalent carbon atom.

[0217] (p) In equation (II), p represents an integer between 2 and 6. A value of 3 or greater is preferred, 5 or less is preferred, and 4 or less is more preferred. Setting p above the lower limit tends to improve electrical reliability, while setting it below the upper limit tends to improve coating film curability. The above upper and lower limits can be combined arbitrarily. For example, p is preferably between 3 and 5, and more preferably between 3 and 4.

[0218] Examples of photopolymerizable monomers (e1) include the following:

[0219] [ka]

[0220] The (E) photopolymerizable monomer in the colored resin composition of the present invention may include other photopolymerizable monomers other than the photopolymerizable monomer (e1) (hereinafter sometimes referred to as "other photopolymerizable monomers (e2)"). As the other photopolymerizable monomer (e2), it is particularly desirable to use a polyfunctional ethylene monomer having two or more ethylene double bonds in one molecule. The number of ethylene double bonds in the polyfunctional ethylene monomer is not particularly limited, but is usually two or more, preferably four or more, more preferably five or more, and preferably eight or fewer, and more preferably seven or fewer. Setting it above the lower limit tends to result in high sensitivity, and setting it below the upper limit tends to improve solubility in the solvent. The above upper and lower limits can be arbitrarily combined. For example, the number of ethylene double bonds in the polyfunctional ethylene monomer is preferably 2 to 8, more preferably 4 to 8, and even more preferably 5 to 7.

[0221] 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 reactions of unsaturated carboxylic acids with polyhydroxy compounds and the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc., and ethylenic compounds having a urethane skeleton obtained by reacting polyisocyanate compounds with (meth)acryloyl-containing hydroxy compounds.

[0222] Examples of esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, examples of methacrylic acid esters obtained by replacing the acrylic acid portion of these acrylates with the methacrylic acid portion, itaconic acid esters obtained by replacing the itaconic acid portion, crotonic acid esters obtained by replacing the crotonic acid portion, or maleic acid esters obtained by replacing the maleic acid portion.

[0223] Examples of esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate. Esters obtained by the esterification reaction of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds are not necessarily single substances but may be mixtures. Examples include condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerin.

[0224] Examples of ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include: aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; and reaction products of (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, and 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

[0225] Other examples include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. Other photopolymerizable monomers (e2) may be monomers having an acid value. The monomers having an acid value are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. Polyfunctional monomers are preferred, where an acid group is formed by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. In this ester, polyfunctional monomers in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol are particularly preferred.

[0226] These monomers may be used individually, but since it is difficult to use a single compound in manufacturing, two or more may be used in mixture form. Furthermore, if necessary, polyfunctional monomers without acid groups and polyfunctional monomers with acid groups may be used in combination. The preferred acid value of polyfunctional monomers having acid groups is 0.1 to 40 mg KOH / g, and particularly preferably 5 to 30 mg KOH / g. Setting the value above the lower limit tends to improve the development and dissolution characteristics, while setting it below the upper limit tends to improve manufacturing and handling, and to improve curing properties such as photopolymerization performance and pixel surface smoothness. Therefore, when using two or more polyfunctional monomers with different acid groups in combination, or when using polyfunctional monomers without acid groups in combination, it is preferable to adjust the total amount of acid groups in the polyfunctional monomer to fall within the above range.

[0227] In the present invention, a more preferred polyfunctional monomer having an acidic group is a mixture mainly composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which are commercially available as TO1382 from Toagosei Co., Ltd. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Furthermore, the polyfunctional monomers described in paragraphs

[0056] and

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

[0228] In the present invention, from the viewpoint of improving the chemical resistance of the pixels and the linearity of the pixel edges, it is preferable to use the polymerizable monomer described in Japanese Patent Publication No. 2013-195971. From the viewpoint of achieving both high sensitivity of the coated film and reduced development time, it is preferable to use the polymerizable monomer described in Japanese Patent Publication No. 2013-195974.

[0229] The content of (E) photopolymerizable monomer in the colored 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, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Setting it above the lower limit tends to improve coating film curability, and setting it below the upper limit tends to improve storage stability. The above upper and lower limits can be arbitrarily combined. For example, the content of (E) photopolymerizable monomer in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass, based on the total solid content of the colored resin composition.

[0230] The content of the photopolymerizable monomer (e1) in the colored 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, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less. Setting it above the lower limit tends to improve developer solubility and patterning shape when the hot plate temperature rises, while setting it below the upper limit tends to improve storage stability and pattern adhesion. The above upper and lower limits can be arbitrarily combined. For example, the content of the photopolymerizable monomer (e1) in the colored resin composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass, based on the total solid content of the colored resin composition.

[0231] In the colored resin composition of the present invention, the content ratio of the photopolymerizable monomer (e1) to the photopolymerizable monomer (E) is not particularly limited, but is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, particularly preferably 55% by mass or more, and also preferably 98% by mass or less, more preferably 96% by mass or less, even more preferably 94% by mass or less, and particularly preferably 92% by mass or less. Setting it above the lower limit tends to improve developer solubility, and setting it below the upper limit tends to improve patterning characteristics. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the photopolymerizable monomer (e1) to the photopolymerizable monomer (E) is preferably 40 to 98% by mass, more preferably 45 to 96% by mass, even more preferably 50 to 94% by mass, and particularly preferably 55 to 92% by mass.

[0232] [1-6] Other solids The colored resin composition of the present invention may further contain solid components other than those mentioned above, as needed. Examples of such components include dispersants, dispersion aids, surfactants, and adhesion enhancers.

[0233] [1-6-1] Dispersants, dispersing aids When the colored resin composition of the present invention contains a pigment as a coloring agent (A), it is preferable to include a dispersant for the purpose of stably dispersing the pigment. Among dispersants, polymer dispersants are preferred because they have excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants. Examples of polymer dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Bic Chemie), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the dispersant described in Japanese Patent Publication No. 2013-119568.

[0234] As a polymer dispersant, block copolymers having functional groups containing nitrogen atoms are preferred from the viewpoint of dispersibility and storage stability, and acrylic block copolymers having functional groups containing nitrogen atoms are more preferred. As block copolymers having functional groups containing nitrogen atoms, AB block copolymers and BAB block copolymers are preferred, which consist of an A block having a quaternary ammonium base and / or an amino group in the side chain and a B block not having a quaternary ammonium base and an amino group.

[0235] Examples of functional groups containing nitrogen atoms include primary to tertiary amino groups and quaternary ammonium bases. From the viewpoint of dispersibility and storage stability, primary to tertiary amino groups are preferred, and tertiary amino groups are more preferred. The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, it is preferable that the repeating unit be represented by the following general formula (d1).

[0236] [ka]

[0237] In formula (d1), R 1 and R 2 Each of these is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R 1 and R 2 They may combine with each other to form a ring structure. 3 is a hydrogen atom or a methyl group. X is a divalent linking group.

[0238] The number of carbon atoms in the optionally substituted alkyl group in formula (d1) is not particularly limited, but is usually 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. For example, 1 to 10 is preferred, 1 to 6 is more preferred, and 1 to 4 is even more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. Alkyl groups may be linear or branched. Alkyl groups may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0239] The number of carbon atoms in the optionally substituted aryl group in formula (d1) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, 6 to 16 is preferred, 6 to 12 is more preferred, and 6 to 8 is even more preferred. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups. Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups are preferred, and phenyl, methylphenyl, and ethylphenyl groups are more preferred.

[0240] The number of carbon atoms in the optionally substituted aralkyl group in formula (d1) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. For example, 7 to 16 is preferred, 7 to 12 is more preferred, and 7 to 9 is even more preferred. Examples of aralkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene groups are preferred, and phenylmethylene and phenylethylene groups are more preferred.

[0241] From the standpoint of dispersibility, storage stability, electrical reliability, and developability, R 1 and R 2 Preferably, alkyl groups may each have substituents independently, and methyl groups and ethyl groups are more preferred.

[0242] Examples of substituents that the alkyl group, aralkyl group, or aryl group in formula (d1) may have include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0243] In equation (d1), R 1 and R 2 Examples of cyclic structures formed by the bonding of these elements include 5-7 membered nitrogen-containing heterocyclic monocyclic rings or fused rings formed by the fusion of two such rings. The nitrogen-containing heterocyclic rings are preferably non-aromatic, and saturated rings are even more preferable. Specifically, examples include the cyclic structure shown in (IV) below.

[0244] [ka]

[0245] These cyclic structures may further have substituents.

[0246] In formula (d1), the divalent linking group X can be, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, or -CONH-R 13 -GROUP, -COOR 14 -Base (however, R 13 and R 14Examples include a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, preferably -COO-R 14 - It is the basis.

[0247] The content of the repeating unit represented by formula (d1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20 mol% or more, especially preferably 25 mol% or more, and also preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content of the repeating unit represented by formula (d1) in the total repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, particularly preferably 20 to 50%, and especially preferably 25 to 40 mol%.

[0248] From the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and thus improving dispersion stability, it is preferable that the block copolymer has repeating units represented by the following general formula (d2).

[0249] [ka]

[0250] In formula (d2), R 10 R is an ethylene group or a propylene group, 11 R is an alkyl group which may have substituents, 12 is a hydrogen atom or a methyl group. n is an integer between 1 and 20.

[0251] R in equation (d2) 11The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is usually 1 or more, preferably 2 or 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. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. Alkyl groups may be linear or branched. Alkyl groups may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups. Examples of substituents that the alkyl group may have include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0252] In formula (d2), n is preferably 1 or more, more preferably 2 or more, and more preferably 10 or less, and more preferably 5 or less, from the viewpoint of compatibility and dispersibility with the solvent and other binder components. The above upper and lower limits can be combined arbitrarily. For example, n is preferably 1 to 10, and more preferably 2 to 5.

[0253] The content of the repeating unit represented by formula (d2) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and also preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability. The above upper and lower limits can be arbitrarily combined. For example, the content of the repeating unit represented by formula (d2) in the total repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%.

[0254] From the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and thus improving dispersion stability, it is preferable that the block copolymer has repeating units represented by the following general formula (d3).

[0255] [ka]

[0256] In equation (d3), R 8 R is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. 9 This is either a hydrogen atom or a methyl group.

[0257] R in equation (d3) 8 The number of carbon atoms in the alkyl group, which may have substituents, is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. For example, 1 to 10 is preferred, and 1 to 6 is more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. Alkyl groups may be linear or branched. Alkyl groups may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0258] R in equation (d3) 8 The number of carbon atoms in the aryl group, which may have substituents, is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 is preferred, and 6 to 12 is more preferred. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups. Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups are preferred, and phenyl, methylphenyl, and ethylphenyl groups are more preferred.

[0259] R in equation (d3) 8 The number of carbon atoms in the aralkyl group, which may have substituents, is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 is preferred, and 7 to 12 is more preferred. Examples of aralkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene are preferred, and phenylmethylene and phenylethylene are more preferred.

[0260] From the viewpoint of solvent compatibility and dispersion stability, R 8 Preferably, alkyl groups and aralkyl groups are used, and more preferably, methyl groups, ethyl groups, and phenylmethylene groups. R8 Examples of substituents that the alkyl group may have include halogen atoms and alkoxy groups. Examples of substituents that the aryl group or aralkyl group may have include linear alkyl groups, halogen atoms, and alkoxy groups. R 8 The linear alkyl groups shown include both linear and branched alkyl groups.

[0261] The content of the repeating unit represented by formula (d3) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 80 mol% or less, and even more preferably 70 mol% or less. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content of the repeating unit represented by formula (d3) in the total repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 70 mol%.

[0262] The block copolymer may have repeating units other than those represented by formula (d1), formula (d2), and formula (d3). Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and glycidyl crotonic acid ether; and repeating units derived from N-methacryloylmorpholine.

[0263] From the viewpoint of further improving dispersibility, it is preferable that the block copolymer has an A block having repeating units represented by formula (d1) and a B block not having repeating units represented by formula (d1). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. It is more preferable that the B block has repeating units represented by formula (d2) and / or repeating units represented by formula (d3).

[0264] Repeating units other than those represented by formula (d1) may be contained in block A. Examples of such repeating units include the repeating units derived from the (meth)acrylic acid esters mentioned above. The content of repeating units other than those represented by formula (d1) in block A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 mol%.

[0265] Repeating units other than those represented by formula (d2) and formula (d3) may be contained in block B. Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylate chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and glycidyl crotonic acid ether; and repeating units derived from N-methacryloylmorpholine. The content of repeating units other than those represented by formula (d2) and formula (d3) in block B is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and even more preferably 0 mol%.

[0266] From the viewpoint of dispersibility, a low acid value is preferable for the block copolymer, and 0 mg KOH / g is particularly preferable. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of dispersant solids.

[0267] From the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, even more preferably 70 mg KOH / g or more, even more preferably 90 mg KOH / g or more, especially preferably 100 mg KOH / g or more, particularly preferably 105 mg KOH / g or more, and also preferably 150 mg KOH / g or less, and even more preferably 130 mg KOH / g or less. The above upper and lower limits can be arbitrarily combined. For example, 30 to 150 mg KOH / g is preferred, 50 to 150 mg KOH / g is more preferred, 70 to 150 mg KOH / g is even more preferred, 90 to 130 mg KOH / g is even more preferred, 100 to 130 mg KOH / g is especially preferred, and 105 to 130 mg KOH / g is particularly preferred. Here, the amine value represents the amine value on an effective solids basis, and is expressed as the amount of base and the equivalent amount of KOH per gram of solids of the dispersant.

[0268] The weight-average molecular weight of the block copolymer is preferably between 1,000 and 30,000. When it is within this range, dispersion stability is good, and the generation of dried foreign matter tends to be less when coating using a slit nozzle method.

[0269] Block copolymers can be produced by known methods. For example, they can be produced by living polymerization of monomers into which each of the above repeating units is introduced. Examples of living polymerization methods include Japanese Patent Publication No. 9-62002, Japanese Patent Publication No. 2002-31713, and P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.C. Anderson, G.D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al. The known methods described in al, Polym.J.17,977(1985),18,1037(1986), Koichi Migite, Koichi Hatada, Polymer Processing,36,366(1987), Toshinobu Higashimura, Mitsuo Sawamoto, Journal of Polymer Science,46,189(1989), M. Kuroki, T. Aida, J. Am. Chem. Soc,109,4737(1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry,43,300(1985), and DY Sogoh, WRHertler et al, Macromolecules,20,1473(1987) can be employed.

[0270] When the colored resin composition of the present invention contains a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, and also preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. Setting it above the lower limit tends to improve dispersibility and storage stability, and setting it below the upper limit tends to improve electrical reliability and developability. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a dispersant, the content of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass, even more preferably 0.1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass, in the total solid content of the colored resin composition.

[0271] When the colored resin composition of the present invention contains a pigment and a dispersant, the content 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, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, per 100 parts by mass of pigment, and also preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. By keeping it within the above range, it is possible to obtain a colorable resin composition with excellent dispersion stability and high brightness. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a pigment and a dispersant, the content of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, even more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass, per 100 parts by mass of pigment.

[0272] If the colored resin composition of the present invention contains a pigment, it may also contain, for example, a pigment derivative as a dispersion aid to improve the dispersibility and dispersion stability of the pigment. Examples of pigment derivatives include derivatives of azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigments. Examples of substituents on the pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups that are directly bonded to the pigment skeleton or via alkyl groups, aryl groups, heterocyclic groups, etc. Preferably, sulfonamide groups and their quaternary salts and sulfonic acid groups are used, and more preferably, sulfonic acid groups. Furthermore, multiple substituents may be substituted on a single pigment skeleton, or a mixture of compounds with different numbers of substitutions may be used. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0273] [1-6-2] Surfactants Various surfactants can be used as surfactants, including anionic, cationic, nonionic, and amphoteric surfactants, but nonionic surfactants are preferred because they are less likely to adversely affect the properties. When the colored resin composition of the present invention contains a surfactant, the surfactant content is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, in the total solid content of the colored resin composition. The above upper and lower limits can be arbitrarily combined. For example, the surfactant content is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, even more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass, in the total solid content of the colored resin composition.

[0274] [1-6-3] Adhesion enhancer The colored resin composition of the present invention may contain an adhesion enhancer to improve adhesion to the substrate. Examples of adhesion enhancers include silane coupling agents and titanium coupling agents. Silane coupling agents are preferred. Examples of silane coupling agents include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning Co., Ltd.). A single silane coupling agent may be used alone, or two or more may be used in any combination and ratio. Adhesion enhancers other than silane coupling agents may be included in the photosensitive resin composition of the present invention. Examples include phosphoric acid-based adhesion enhancers and other adhesion enhancers.

[0275] As phosphoric acid-based adhesion enhancers, phosphates containing (meth)acryloyloxy groups are preferred. Phosphoric acid-based adhesion enhancers represented by the following general formulas (g1), (g2), and (g3) are preferred.

[0276] [ka]

[0277] In equations (g1), (g2), and (g3), R 51 Each of the following independently represents a hydrogen atom or a methyl group. l and l' each independently represent an integer from 1 to 10, and m each independently represents 1, 2, or 3. Other adhesion enhancers include, for example, TEGO® Add Bond LTH (manufactured by Evonik). These phosphoric acid-based adhesion enhancers and other adhesion enhancers may be used individually or in combination of two or more.

[0278] When the colored resin composition of the present invention contains an adhesion improver, the content ratio is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and also preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. Setting the content above the lower limit tends to improve patterning characteristics and improve pattern adhesion under high humidity conditions, while setting it below the upper limit tends to suppress residue generation. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains an adhesion improver, the content ratio is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, even more preferably 0.3 to 1.5% by mass, and particularly preferably 0.4 to 1% by mass, based on the total solid content.

[0279] [2] Preparation of colored resin composition Next, a method for preparing the colored resin composition (hereinafter sometimes referred to as "resist") according to the present invention will be described.

[0280] When preparing a coloring agent containing a pigment, first, the pigment, solvent, and dispersant are weighed in predetermined quantities, and then the coloring agent containing the pigment is dispersed in a dispersion process to prepare a pigment dispersion. In this dispersion process, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc., can be used. This dispersion process results in the coloring agent being atomized into fine particles, which improves the coating properties of the colored resin composition and improves the transmittance of pixels on the color filter substrate of the product.

[0281] When dispersing pigments, it is preferable to use a dispersion aid or dispersion resin in combination as appropriate, as described above. When performing dispersion using a sand grinder, it is preferable to use glass beads or zirconia beads with a diameter of 0.1 to several millimeters. The temperature during dispersion should be set to a range of 0°C or higher, preferably room temperature or higher, and usually 100°C or lower, preferably 80°C or lower. The dispersion time should be adjusted as appropriate, as the appropriate time will vary depending on the composition of the pigment dispersion and the size of the sand grinder equipment.

[0282] The pigment dispersion obtained by the above dispersion process is mixed with a solvent, alkali-soluble resin, photopolymerization initiator, and other components as needed to obtain a homogeneous dispersion solution. Since fine dust may be introduced during the dispersion process and mixing process, it is preferable to filter the obtained pigment dispersion using a filter or the like.

[0283] If the coloring agent does not contain pigments, a homogeneous solution can be obtained by mixing the coloring agent, solvent, alkali-soluble resin, photopolymerization initiator, and other components as needed. It is preferable to filter the obtained solution using a filter or the like.

[0284] [3] Manufacturing of color filter substrates The color filter according to the present invention has pixels created using the colored resin composition of the present invention.

[0285] [3-1] Transparent substrate (support) The transparent substrate for a color filter is not particularly limited in material, as long as it is transparent and has adequate strength. Examples of materials include thermoplastic resin sheets such as polyethylene terephthalate (polyester resin), polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, or various types of glass. Among these, glass or heat-resistant resin is preferred from the viewpoint of heat resistance.

[0286] The transparent substrate and the black matrix-forming substrate may be subjected to corona discharge treatment, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents or urethane resins, as necessary, in order to improve surface properties such as adhesion. The thickness of the transparent substrate is usually in the range of 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When thin film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less. For example, 0.01 to 10 μm and 0.05 to 5 μm.

[0287] [3-2] Black Matrix The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and further forming pixel images, usually in red, green, and blue. The colored resin composition of the present invention is preferably used as a coating liquid for forming green or blue pixels (resist patterns) among the red, green, and blue pixels. Using the coating liquid for forming green or blue pixels (resist patterns), pixel images are formed by performing coating, heat drying, image exposure, development, and thermocuring processes on the resin black matrix forming surface formed on the transparent substrate, or on the metal black matrix forming surface formed using a chromium compound or other light-shielding metal material.

[0288] The black matrix is ​​formed on a transparent substrate using a light-shielding metal thin film or a colored resin composition for the black matrix. The light-shielding metal material may include chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, or nickel-tungsten alloys, and may be arranged in multiple layers. These metal light-shielding films are generally formed by sputtering. A desired pattern is formed in film form using a positive-type photoresist, and then, for chromium, an etching solution of cerium ammonium nitrate and perchloric acid and / or nitric acid is used. For other materials, an etching solution appropriate to the material is used, and finally, the positive-type photoresist is removed with a special release agent to form a black matrix.

[0289] In this case, first, a thin film of these metals or metal / metal oxides is formed on a transparent substrate by methods such as vapor deposition or sputtering. Next, a coating film of a colored resin composition is formed on this thin film, and then the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, or triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

[0290] When using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form the black matrix. For example, a colored resin composition containing a black colorant, either alone or in combination with other black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, or titanium black, or a mixture of red, green, blue, etc., appropriately selected from inorganic or organic pigments and dyes, can be used to form the black matrix in the same manner as the method for forming red, green, and blue pixel images described below.

[0291] [3-3] Pixel formation A colored resin composition of one of three colors (red, green, or blue) is applied to a transparent substrate with a black matrix. After drying, a photomask is placed on top of the applied film, and a pixel image is formed by image exposure, development, and, if necessary, heat curing or photocuring through the photomask. By performing this operation for each of the three colored resin compositions (red, green, and blue), a color filter image can be formed.

[0292] The colored resin composition for color filters can be applied by methods such as the spinner method, wire bar method, flow coating method, die coating method, roll coating method, and spray coating method. Among these, the die coating method is preferable from an overall standpoint because it significantly reduces the amount of coating solution used, completely eliminates the effects of mist and other contaminants that adhere when using the spin coating method, and further suppresses the generation of foreign matter.

[0293] If the thickness of the coating film is too large, pattern development becomes difficult, and gap adjustment in the liquid crystal cell formation process may also become difficult. On the other hand, if it is too small, it becomes difficult to increase the pigment concentration, and the desired color may not be achieved. The thickness of the coating film, as the film thickness after drying, is usually in the range of 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. For example, 0.2 to 20 μm, 0.5 to 10 μm, and 0.8 to 5 μm.

[0294] [3-4] Drying of the coating film After applying the colored resin composition to the substrate, the coating film is preferably dried (pre-baked) using a hot plate, IR oven, or convection oven. Typically, after pre-drying, it is heated again to dry. The pre-drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. The drying temperature and drying time are selected depending on the type of solvent component, the performance of the dryer used, etc. Specifically, the drying temperature is usually in the range of 40°C or higher, preferably 50°C or higher, and usually 80°C or lower, preferably 70°C or lower, and the drying time is usually in the range of 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less.

[0295] The temperature conditions for reheat drying are preferably higher than the pre-drying temperature, specifically in the range of 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, and particularly preferably 130°C or lower. The drying time depends on the heating temperature, but is preferably in the range of 10 seconds or more, more preferably 15 seconds or more, and usually 10 minutes or less, more preferably 5 minutes. Higher drying temperatures improve adhesion to the transparent substrate, but if the temperature is too high, the binder resin may decompose, inducing thermal polymerization and resulting in development problems. As for the drying process of this coating film, a vacuum drying method may be used, in which drying is performed in a vacuum chamber without raising the temperature.

[0296] [3-5] Exposure process Image exposure is performed by superimposing a negative matrix pattern onto a coated film of a colored resin composition and irradiating it with ultraviolet or visible light through this mask pattern. If necessary, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen-blocking layer, such as a polyvinyl alcohol layer, may be formed on the photopolymerizable layer before exposure. The light source used for the above image exposure is not particularly limited. Examples of light sources include lamps such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, as well as lasers such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. Optical filters can also be used when irradiating with light of a specific wavelength.

[0297] [3-6]Developing process The color filter according to the present invention can be manufactured by forming an image on a substrate by exposing a coated film using the colored resin composition according to the present invention to an image using the above-mentioned light source, and then developing it using an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes, or pigments.

[0298] Examples of alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, as well as organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono-, or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used individually or in combination of two or more.

[0299] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters; and amphoteric surfactants such as alkyl betaines and amino acids.

[0300] Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. These organic solvents can be used in combination with aqueous solutions. There are no particular restrictions on the development conditions, but the development temperature is usually 10°C or higher, preferably 15°C or higher, and even more preferably 20°C or higher, and usually 50°C or lower, preferably 45°C or lower, and even more preferably 40°C or lower. The development method can be any of the following: immersion development, spray development, brush development, ultrasonic development, etc.

[0301] [3-7] Thermosetting treatment After development, the color filters are subjected to a heat-curing treatment. The heat-curing conditions are typically set to a temperature of 100°C or higher, preferably 150°C or higher, and typically 280°C or lower, preferably 250°C or lower, with a duration of 5 minutes or more and 60 minutes or less. After these steps, the formation of a single-color patterned image is completed. This process is repeated sequentially to pattern black, red, green, and blue, forming the color filters. Note that the order of patterning the four colors is not limited to the order described above.

[0302] [3-8] Formation of transparent electrodes The color filter according to the present invention can be used as is, with transparent electrodes such as ITO formed on the image, as part of components for color displays, liquid crystal displays, etc. However, to improve surface smoothness and durability, a topcoat layer such as polyamide or polyimide can be provided on the image as needed. In some applications, such as planar orientation driving methods (IPS mode), transparent electrodes may not be formed.

[0303] [4] Image display device (panel) The image display device of the present invention has the color filter of the present invention. Below, we will describe liquid crystal display devices and organic light-emitting diode (OLED) display devices in detail as image display devices.

[0304] [4-1]Liquid crystal display device A method for manufacturing a liquid crystal display device according to the present invention will now be described. In a liquid crystal display device according to the present invention, an alignment film is usually formed on a color filter of the present invention, spacers are scattered on the alignment film, and then the film is bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is then injected into the formed liquid crystal cell and connected to a counter electrode to complete the device. A resin film such as polyimide is preferred for the alignment film. Gravure printing and / or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After curing the alignment film by heat firing, the surface is treated by irradiation with ultraviolet light or treatment with a rubbing cloth to process it into a surface state in which the tilt of the liquid crystal can be adjusted.

[0305] The spacer used is sized according to the gap (clearance) with the opposing substrate, and is usually 2 to 8 μm in size. A photospacer (PS) made of a transparent resin film can also be formed on the color filter substrate by photolithography and used as a spacer. An array substrate is usually used as the opposing substrate, and a TFT (thin-film transistor) substrate is particularly preferred.

[0306] The gap between the liquid crystal display and the opposing substrate varies depending on the application of the liquid crystal display device, but is usually selected within the range of 2 μm to 8 μm. After bonding to the opposing substrate, the areas other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, sealing the area around the liquid crystal cell. After sealing the edges of the liquid crystal cell, it is cut into panel units, then the pressure is reduced in a vacuum chamber. The liquid crystal injection port is then immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the chamber. The degree of pressure reduction inside the liquid crystal cell is typically 1 × 10⁻⁶. -2 Pa or higher, preferably 1 × 10 -3 In addition, normally 1 x 10 -7 Pa or less, preferably 1 × 10⁻⁶ -6 The pressure is in the range of Pa or less. Furthermore, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is usually in the range of 30°C or higher, preferably 50°C or higher, and usually 100°C or lower, preferably 90°C or lower.

[0307] The heating and holding period during depressurization is typically between 10 and 60 minutes, after which the cells are immersed in liquid crystal. The liquid crystal cells into which the liquid crystal has been injected are then sealed by curing a UV-curing resin around the liquid crystal injection port, completing the liquid crystal display device (panel). There are no particular restrictions on the type of liquid crystal; any conventionally known liquid crystal, such as aromatic, aliphatic, or polycyclic compounds, is acceptable, including lyotropic and thermotropic liquid crystals. Thermotropic liquid crystals include nematic liquid crystals, smetic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[0308] [4-2] Organic EL display device When creating an organic EL display device having the color filter of the present invention, for example, as shown in Figure 1, a multi-color organic EL element is fabricated by laminating an organic light-emitting element 500 via an organic protective layer 30 and an inorganic oxide film 40 onto a blue color filter on which pixels 20 are formed using the colored resin composition of the present invention, on a transparent support substrate 10.

[0309] Methods for laminating the organic light-emitting element 500 include sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, or laminating an organic light-emitting element 500 formed on a separate substrate onto an inorganic oxide film 40. The organic EL element 100 fabricated in this way can be applied to both passively driven organic EL display devices and actively driven organic EL display devices. [Examples]

[0310] Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

[0311] <Phthalocyanine compound A> We used phthalocyanine compound A, which has the following chemical structure and was synthesized based on Example 30 of Japanese Patent Publication No. 05-345861.

[0312] [ka]

[0313] Note that Et in the formula represents ethyl.

[0314] <Dispersant A> A methacrylic AB block copolymer comprising an A block having nitrogen atom-containing functional groups and a B block having solvent-philic groups. It has repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a). The amine value is 120 mgKOH / g and the acid value is less than 1 mgKOH / g.

[0315] The percentages of repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a) within the total repeating units are less than 1 mol%, 34.5 mol%, 6.9 mol%, 13.8 mol%, and 6.9 mol%, respectively.

[0316] [ka]

[0317] <Alkali-soluble resin A> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen purging and heated to 120°C. 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate, and 10 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M, Hitachi Chemical Co., Ltd.) were added dropwise, and stirring continued at 120°C for 2 hours. Next, the reaction vessel was changed to air purging, and 50 parts by mass of acrylic acid, 0.7 parts by mass of trisdimethylaminomethylphenol, and 0.12 parts by mass of hydroquinone were added, and the reaction was continued at 120°C for 6 hours. Subsequently, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours. The weight-average molecular weight Mw of the resulting alkali-soluble resin A, measured by GPC, was approximately 9000 in polystyrene terms, the acid value was 25 mgKOH / g, and the double bond equivalent was 260 g / mol.

[0318] <Alkali-soluble resin B> A separable flask equipped with a condenser was prepared as the reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate were added, and after purging with nitrogen, the temperature of the reaction vessel was raised to 90°C by heating in an oil bath while stirring.

[0319] Meanwhile, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of t-butyl peroxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were charged into the monomer tank, and 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into the chain transfer agent tank. After the temperature of the reaction vessel stabilized at 90°C, dropwise addition from the monomer tank and chain transfer agent tank was started to initiate polymerization. Dropwise addition was carried out over 135 minutes each while maintaining the temperature at 90°C, and 60 minutes after the dropwise addition was completed, the temperature was raised to 110°C.

[0320] After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel, and the mixture was allowed to react at 110°C for 9 hours. After cooling to room temperature, an alkali-soluble resin B was obtained with a polystyrene-based weight-average molecular weight Mw of 9000, an acid value of 101 mgKOH / g, and a double bond equivalent of 550 g / mol, as measured by GPC.

[0321] <Preparation of Green Dye Dispersion A> As shown in Table 1, 9.9 parts by mass of phthalocyanine compound A, 0.1 parts by mass of dispersant A (on a solid content basis), 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant A), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were packed into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads and dispersion were separated by filtration to prepare green dye dispersion A.

[0322] <Preparation of Green Pigment Dispersion A> As shown in Table 1, 13.9 parts by mass of CI Pigment Green 58, 1.9 parts by mass of Dispersant A (on a solids basis), 4.2 parts by mass of Alkali-Soluble Resin B (on a solids basis), 80.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including solvents derived from Dispersant A and Alkali-Soluble Resin B), and 225 parts by mass 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 and dispersion were separated by filtration to prepare green pigment dispersion A.

[0323] <Preparation of yellow pigment dispersion A> As shown in Table 1, 11.4 parts by mass of CI Pigment Yellow 138, 2.9 parts by mass of dispersant A (on a solids basis), 5.7 parts by mass of alkali-soluble resin B (on a solids basis), 76.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including solvents derived from dispersant A and alkali-soluble resin B), 4.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads and dispersion were separated by filtration to prepare yellow pigment dispersion A.

[0324] [Table 1]

[0325] <Photopolymerizable monomer A> Polyethoxylated tetramethylolmethane tetraacrylate (NK ester ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and ethoxylated pentaerythritol tetraacrylate, to which an average of 4 moles of ethylene oxide are added per mole. It corresponds to a photopolymerizable monomer (e1).

[0326] <Photopolymerizable monomer B> A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). It does not fall under the category of photopolymerizable monomer (e1).

[0327] <Photopolymerizable monomer C> Ethylene oxide-modified (12) dipentaerythritol hexaacrylate (KAYARAD DPEA-12, manufactured by Nippon Kayaku Co., Ltd.). It is classified as a photopolymerizable monomer (e1).

[0328] <Photopolymerization initiator A> Oxime ester compounds having the following chemical structure (4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate methyl)

[0329] [ka]

[0330] Note that Me in the formula represents methyl.

[0331] <Chain transfer agent A> Pentaerythritol tetra(3-mercaptopropionate) (manufactured by Yodo Chemical Co., Ltd.)

[0332] <Surfactant A> Megafuck F-554 (manufactured by DIC Corporation)

[0333] <Adhesion enhancer A> A compound having the following chemical structure.

[0334] [ka]

[0335] In the formula, C2H4 represents dimethylene and C3H6 represents trimethylene.

[0336] <Preparation of colored resin composition> A colored resin composition was prepared by mixing the components listed in Table 2 in the solid content ratios indicated. Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used so that the total solid content of the colored resin composition was 17.3% by mass. The PGMEA / PGME mixing ratio (by mass) in the obtained colored resin composition was 90 / 10.

[0337] [Table 2]

[0338] <Measurement of color characteristics> The obtained colored resin composition was applied to a 50mm square, 0.7mm thick glass substrate (AGC Corporation, AN100) by spin coating, dried under reduced pressure, and then pre-baked on a hot plate at 90°C for 90 seconds. Subsequently, it was subjected to a 40mJ / cm³ treatment using a 2kW high-pressure mercury lamp. 2 Exposure dose, illuminance 30 mW / cm² 2 Full-surface exposure treatment was performed. Then, development was carried out using a 0.04 mass% potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Subsequently, 1 kg / cm³ was applied. 2 The substrate was spray-washed with water pressure for 10 seconds. Then, it underwent a heat-curing treatment in a clean oven at 230°C for 20 minutes to create a colored substrate.

[0339] The transmission spectrum of the obtained colored substrates was measured using a Hitachi U-3310 spectrophotometer, and the luminance was calculated when the chromaticity was sy = 0.576 using a C light source. The results are shown in Table 2.

[0340] <Evaluation of pattern formation ability> A 50mm square, 0.7mm thick glass substrate (AGC, AN100) was coated by spin coating with the obtained colored resin composition so that the chromaticity after heat curing was sy = 0.576 under a C light source, and each was pre-baked at 80°C for 90 seconds. Subsequently, a 2kW high-pressure mercury lamp was used to heat the substrate at 40mJ / cm². 2 Exposure dose, illuminance 30 mW / cm² 2 The exposure treatment was then performed using an exposure mask having a circular covering area with a diameter of 30 μm. Subsequently, development was performed using a 0.04 mass% potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Then, 1 kg / cm³ 2 The substrate was spray-washed with water at a water pressure of 10 seconds. Then, a heat-curing treatment was performed at 230°C for 20 minutes to create a patterned substrate. The diameter (μm) of the holes in the pattern of the resulting patterned substrate A was measured using an optical microscope (hole diameter A).

[0341] Next, pattern substrate B was prepared under the same conditions as pattern substrate A, except that the pre-bake temperature was changed from 80°C to 100°C. The diameter (μm) of the holes in the pattern of the obtained pattern substrate B was measured using an optical microscope (hole diameter B).

[0342] The effect of pre-bake temperature on hole diameter was calculated from hole diameters A and B, and this was used as an index of temperature dependence. The results of the temperature dependence (=│(hole diameter A - hole diameter B)[μm] / (100-80)[℃]│) are shown in Table 2.

[0343] As is clear from Table 2, the brightness is higher when phthalocyanine compound A is used, as in Comparative Example 1, compared to the colored resin composition containing CI pigment green 58 in Comparative Example 2. However, the pre-bake temperature dependence of the hole diameter deteriorates significantly when phthalocyanine compound A is used.

[0344] Generally, unlike pigments, dyes can achieve high brightness and coloring power by existing as single molecules in the system. However, because the molecules are isolated, they have poor heat resistance and are susceptible to sublimation and oxidation during the heat-curing process used to create patterns, resulting in a tendency for the brightness of the pattern to decrease after heat curing. In contrast, phthalocyanine compound (1) has one or more hydrogen atoms constituting the phthalocyanine skeleton substituted with fluorine atoms, which have a smaller atomic radius. This structure does not easily inhibit the association of phthalocyanine compounds (1) with each other. Therefore, it is thought that it suppresses the decrease in brightness due to heating by forming aggregates when the intermolecular distance is reduced due to heating, etc. Furthermore, even after association, its particle size is thought to be smaller compared to CI Pigment Green 58, and overall, the brightness is thought to be higher in the pattern after thermosetting treatment.

[0345] On the other hand, a comparison between Comparative Example 1 and Comparative Example 2 shows that using phthalocyanine compound (1) worsens the pre-bake temperature dependence of the hole diameter. In Comparative Example 1, the phthalocyanine compound (1) is thought to be densely present within the coating film as aggregates with small particle sizes, which is thought to suppress the penetration and dissolution of the developer into the coating film. When the pre-bake temperature is 80°C, it is thought that a certain amount of residual solvent is present in the coating film, which promotes the penetration of the developer into the coating film. On the other hand, in the high-temperature range such as 100°C, there is little residual solvent, so the developer does not penetrate sufficiently into the coating film, and even in the unexposed areas, the solubility of the coating film in the developer is insufficient, leading to poor pattern formation and a decrease in hole diameter, which is thought to worsen the pre-bake temperature dependence of the hole diameter.

[0346] In contrast, Examples 1, 2, and 3, which contain phthalocyanine compound (1), maintain high brightness while exhibiting good pre-bake temperature dependence of hole diameter. Examples 1, 2, and 3 are obtained by replacing some or all of the photopolymerizable monomer B in Comparative Example 1 with photopolymerizable monomer (e1). Since photopolymerizable monomer (e1) has an alkylene oxide chain, it is possible to maintain good developer penetration even in coating film conditions with little residual solvent, such as at 100°C, thereby forming holes with a diameter similar to that of coating film conditions with a lot of residual solvent, such as at 80°C, and thus suppressing the deterioration of the pre-bake temperature dependence of hole diameter.

[0347] Furthermore, regarding the colored 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 aggregate of phthalocyanine compound (1) in Examples 1, 2, 3 and Comparative Example 1. This ensures sufficient gaps for the developer to penetrate the coating film. Therefore, regardless of the amount of residual solvent, i.e., regardless of the pre-bake temperature, sufficient developer penetration was observed, and the pre-bake temperature dependence of the hole diameter was considered to be good.

[0348] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible without departing from the intent and scope of the invention. [Explanation of symbols]

[0349] 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 transparent anode 51 Hole injection layer 52 Hole transport layer 53. Emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL elements 500 Organic Luminescent Materials

Claims

1. A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, The coloring agent (A) comprises a phthalocyanine compound having a chemical structure represented by the following general formula (1), A colored resin composition characterized in that the (E) photopolymerizable monomer comprises a photopolymerizable monomer (e1) which is a compound represented by the following general formula (II). 【Chemistry 1】 (In formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, A 1 ~A 16 One to ten of these represent fluorine atoms, and A 1 ~A 16 One or more of these represent a base expressed by the following general formula (2). 【Chemistry 2】 (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.) 【Transformation 3】 (In formula (II), R 1 This represents an alkylene group with two or more carbon atoms. R 2 represents a hydrogen atom or a methyl group. n represents an integer greater than or equal to 1. Z represents a direct bond, an oxygen atom, a sulfur atom, a di- to tetravalent aliphatic hydrocarbon group, a tetravalent carbon atom, a di- to tetravalent non-aromatic heterocyclic group, or a di- to tetravalent aromatic ring group. p represents an integer between 2 and 4. Note that the multiple structures represented by the following general formula (II') contained within a single molecule may be the same or different. 【Chemistry 4】

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

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

4. A color filter having pixels created using the colored resin composition described in any one of claims 1 to 3.

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

Images