Colored resin composition, color filter, and image display device

Abstract

The present invention provides a colored resin composition that has high brightness and suppresses the generation of residues. The colored resin composition of the present invention is a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, in which the (A) colorant contains a phthalocyanine compound having a chemical structure represented by the following general formula (1), and the (B) solvent contains a high-boiling-point solvent having a boiling point of 160°C or higher at 1013.25 hPa: [C1] (In formula (1), A 1 ~A 16 each independently represents a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2): 1 ~A 16 At least one of A represents a fluorine atom, and 1 ~A 16 At least one of the groups represents a group represented by the following general formula (2): [C2] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

Description

[Technical Field]

[0001] The present invention relates to a colored resin composition, a color filter, and an image display device. The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-030548, filed with the Japan Patent Office on February 22, 2019; the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2019-119240, filed with the Japan Patent Office on June 27, 2019; and some or all of the contents disclosed in the documents cited herein are incorporated herein by reference as disclosures herein. [Background technology]

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

[0003] In recent years, there has been a growing demand for higher brightness, higher contrast, and wider color gamut in color filters. While pigments are generally used as colorants to determine the color of color filters due to their heat resistance, lightfastness, and other factors, pigments are no longer able to meet market demands, particularly for high brightness. Therefore, there is a growing interest in using dyes as colorants instead of pigments. For green pixels, studies are being conducted on using specific phthalocyanine compounds as dyes (see, for example, Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2009-051896 [Patent Document 2] International Publication No. 2014 / 157387 [Patent Document 3] Japanese Patent Publication No. 2014-43556 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The inventors' investigations revealed that the colored resin compositions described in Patent Documents 1 and 2 do not provide sufficient brightness for practical use. Furthermore, the inventors found that the colored resin composition described in Patent Document 3 does not exhibit sufficient alkaline developability during the alkaline development process in the manufacture of color filters, resulting in the generation of residue originating from the colored resin composition on the glass substrate. Therefore, the present invention aims to provide a colored resin composition that exhibits high brightness and suppresses the generation of residue. [Means for solving the problem]

[0006] As a result of diligent research by the inventors, it was discovered that the above problems can be solved by using a specific phthalocyanine compound as a coloring agent and a solvent with a boiling point above a specific level, leading to the present invention. In other words, the present invention has the following configuration.

[0007] [1] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, 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 solvent (B) contains a high-boiling-point solvent having a boiling point of 160°C or higher at 1013.25 hPa.

[0008] [ka]

[0009] (In formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, A1 ~A 16 One or more of these represent a fluorine atom, and A 1 ~A 16 One or more of these represent a base represented by the following general formula (2).

[0010] [ka]

[0011] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)

[0012] [2] The colored resin composition according to [1], wherein the content of solvent (B) in the colored resin composition is 50% by mass or more. [3] The colored resin composition according to [1] or [2], wherein the content of the high-boiling point solvent in the solvent (B) is 0.5% by mass or more. [4] The colored resin composition according to any one of [1] to [3], wherein the content of the phthalocyanine compound is 5% by mass or more in the total solid content. [5] The colored resin composition according to any one of [1] to [4], wherein the (D) photopolymerization initiator comprises an oxime ester-based photopolymerization initiator.

[0013] [6] A color filter having pixels created using any of the colored resin compositions described in [1] to [5]. [7] [6] An image display device having the color filter described above. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a colored resin composition that has high brightness and suppresses the generation of residue. [Brief explanation of the drawing]

[0015] [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]

[0016] The constituent elements of the present invention will be described in detail below, but these are merely examples of embodiments of the present invention and are not limited to these. In this invention, "weight-average molecular weight" means the weight-average molecular weight (Mw) calculated on a polystyrene basis by GPC (gel permeation chromatography). 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 per gram of solids of the dispersant and the mass of the equivalent amount of KOH. In this invention, "CI" means color index. Furthermore, in this invention, "(meth)acrylic," "(meth)acrylate," etc., mean "acrylic and / or methacrylic," "acrylate and / or methacrylate," etc., and for example, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid." In the present invention, "total solids" means all components other than solvent components contained in the pigment dispersion or colored resin composition. Furthermore, in this invention, a numerical range represented using "~" means a range that includes the numerical values ​​written before and after "~".

[0017] [1] Components of the colored resin composition The components of the colored resin composition of the present invention are described below. The colored resin composition of the present invention comprises (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator as essential components, and may also contain other additives as required. The following describes each component.

[0018] [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)").

[0019]

Chem.

[0020] In formula (1), A 1 ~A 16 each independently represents a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, one or more of A 1 ~A 16 represent a fluorine atom, and one or more of A 1 ~A 16 represent a group represented by the following general formula (2).

[0021]

Chem.

[0022] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have an arbitrary substituent. * represents a bond.

[0023] The (A) colorant contained in the colored resin composition of the present invention contains a phthalocyanine compound (1). By having a group represented by the general formula (2), the phthalocyanine compound (1) has high solubility in a solvent and does not require a dispersion treatment step, or the amount of a dispersant or the like required in the dispersion treatment step can be made very small. Therefore, in the colored resin composition, there is no dispersant or alkali-soluble resin around the phthalocyanine compound (1), or only a very small amount exists, and it is considered that the affinity between the phthalocyanine compound (1) and the alkali-soluble resin in the colored resin composition is weak. In particular, the phthalocyanine compound (1) is likely to associate molecules with each other by π-π interaction between phthalocyanine rings and π-π interaction between groups represented by the general formula (2). Further, by having a fluorine atom with a small atomic radius, the packing between molecules becomes denser, the luminance becomes higher, and it is considered that the affinity with the alkali-soluble resin becomes weak.

[0024] While high solubility in the solvent results in high brightness, it is thought that during the alkaline development process, the interaction between the alkaline developer and the phthalocyanine compound (1) is small, and the phthalocyanine compound (1) does not dissolve sufficiently in the alkaline developer, making it more likely to remain on the glass substrate.

[0025] Therefore, the colored resin composition of the present invention contains a high-boiling point solvent with a boiling point of 160°C or higher at 1013.25 hPa, which is thought to suppress drying of the coating film during the alkaline development process, keeping it sufficiently wet, allowing the alkaline developer to penetrate deep into the coating film and promote the neutralization reaction, thus reducing the generation of residue derived from the colored resin composition on the glass substrate.

[0026] (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).

[0027] [ka]

[0028] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituents. * represents a bond.

[0029] (X) In the general formula (2) above, 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 a1represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.) are examples of these. Among these, from the viewpoint of the stability of the phthalocyanine compound (1) during baking, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

[0030] (Substituents that the benzene ring may have) Furthermore, the benzene ring in formula (2) may have any substituent. The substituent is not particularly limited, but may include a halogen atom, an alkyl group (-R A Base (however, R A )), alkoxy group (-OR A Base (however, R A represents an alkyl group. )), alkoxycarbonyl group (-COOR A Base (however, R A )), aryl group (-R B Base (however, R B )), 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, and alkyl groups (-R) contained in these groups A (Axyl group) or aryl group (-R B The group may be further substituted with these substituents. Among these, the alkoxycarbonyl group is preferred from the viewpoint of solubility in solvents and brightness.

[0031] The alkyl groups included in these groups may be linear, branched, or cyclic, but they are preferably linear from the viewpoint of solubility in 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 improve lipophilicity and the solubility of the phthalocyanine compound (1) in solvents, while setting it below the upper limit tends to improve hydrophilicity and the solubility of the colored resin composition containing the phthalocyanine compound (1) in alkaline developers. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. From the viewpoint of achieving both lipophilicity and hydrophilicity, that is, achieving both the solubility of the phthalocyanine compound (1) in the solvent and the solubility of the colored resin composition containing the phthalocyanine compound (1) in the alkaline developer, methyl or ethyl groups are preferred, and ethyl groups are more preferred.

[0032] Furthermore, 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 improve the solubility of the phthalocyanine compound (1) in the solvent, and setting it below the upper limit tends to suppress the color change caused by the aryl group.

[0033] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring 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. Furthermore, the aromatic heterocyclic group may be a monocyclic or a 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, benzofuran rings, 2-benzofuran rings, and benzfuran rings, all of which have one free valence atom. Examples of these groups include zothiophene rings, 2-benzothiophene rings, 1H-pyrrolidine rings, indole rings, isoindole rings, indidine rings, 2H-1-benzopyran rings, 1H-2-benzopyran rings, quinoline rings, isoquinoline rings, 4H-quinoridine rings, benzimidazole rings, 1H-indazole rings, quinoxaline rings, quinazoline rings, sinnoline rings, phthalazine rings, 1,8-naphthyridine rings, purine rings, and pteridine rings.

[0034] When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited, but from the viewpoint of balancing the polarity of the phthalocyanine compound (1), that is, the lipophilicity which affects the solubility of the phthalocyanine compound (1) in solvents, and the hydrophilicity which affects the solubility of the colored resin composition containing the phthalocyanine compound (1) in alkaline developers, it is preferable that there is one substitution per benzene ring. Furthermore, if the benzene ring in formula (2) has any substituent, the substitution position may be ortho-, meta-, or para-. However, from the viewpoint of balancing the polarity of the phthalocyanine compound (1), that is, the lipophilicity which affects the solubility of the phthalocyanine compound (1) in solvents, and the hydrophilicity which affects the solubility of the colored resin composition containing the phthalocyanine compound (1) in alkaline developers, the para-position is preferred.

[0035] A 1 ~A 16One or more of these represent fluorine atoms, but from the viewpoint of balancing lipophilicity, which affects brightness and the solubility of phthalocyanine compound (1) in solvents, and hydrophilicity, which affects the alkali developability of the colored resin composition containing phthalocyanine compound (1), it is preferable that two or more are fluorine atoms, more preferably four or more, even more preferably six or more, and also preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less. For example, A 1 ~A 16 Of these, 1 to 14 fluorine atoms are preferred, 2 to 14 are more preferred, 4 to 12 are even more preferred, and 6 to 10 are particularly preferred.

[0036] A 1 ~A 16 One or more of these represent fluorine atoms, but from the viewpoint of balancing lipophilicity, which affects brightness and the polarity of phthalocyanine compound (1), that is, the solubility of phthalocyanine compound (1) in solvents, and hydrophilicity, which affects the alkali developability of the colored resin composition containing 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.

[0037] A 1 ~A 16One or more of these represent a group represented by the general formula (2), but from the viewpoint of solubility in solvents, two or more are preferred, four or more are more preferred, six or more are even more preferred, and 14 or fewer are preferred, 12 or fewer are more preferred, and 10 or fewer are even more preferred. For example, A 1 ~A 16 Of these, groups represented by the general formula (2) are preferably 1 to 14, more preferably 2 to 14, even more preferably 4 to 12, and particularly preferably 6 to 10.

[0038] Also, A 1 ~A 16 One or more of these represent a group represented by the general formula (2), but from the viewpoint of solubility in solvents, A 1 ~A 4 One or more of these are groups represented by the general formula (2), and A 5 ~A 8 One or more of these are groups represented by the general formula (2), and A 9 ~A 12 One or more of these are groups represented by the general formula (2), and A 13 ~A 16 Preferably, one or more of them are groups represented by the general formula (2), A 1 ~A 4 Two or more of these are groups represented by the general formula (2), and A 5 ~A 8 Two or more of these are groups represented by the general formula (2), and A 9 ~A 12 Two or more of these are groups represented by the general formula (2), and A 13 ~A 16 It is more preferable that two or more of these groups are represented by the general formula (2). In particular, from the standpoint of the color, brightness, and solubility in solvents required for color filters, A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 is a group represented by the general formula (2), and A 1 , A4 、 A 5 、 A 8 、 A 9 、 A 12 、 A 13 、 and A 16 It is particularly preferable that is a fluorine atom.

[0039] Specific examples of the phthalocyanine compound (1) include, for example, the following.

[0040] [Chemical formula]

[0041] Et in the formula represents ethyl.

[0042] [Chemical formula]

[0043] [Chemical formula]

[0044] [Chemical formula]

[0045] As the production method of the phthalocyanine compound (1), a known method can be adopted. For example, the method described in JP-A-5-345861 can be adopted.

[0046] (A) The colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of other colorants include pigments and dyes. Among these, when the colored resin composition of the present invention is used for green pixel applications, it is preferable to use green pigments, green dyes, yellow pigments, yellow dyes, etc. Examples of green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, 63, etc. From the viewpoint of brightness, C.I. Pigment Green 58 is preferable. Among the green dyes classified as dyes in the color index, examples include CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 as CI Solvent dyes, CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109 as CI Acid dyes, and CI Modant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53 as CI Modant dyes. Of these, CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred from the viewpoint of suppressing dye decomposition during heat firing.

[0047] As for yellow pigments, CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 8 3, 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, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 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)").

[0048] [ka]

[0049] Furthermore, other compounds that can be inserted into the 1:1 complex of azobarbituric acid with nickel represented by formula (i) above, or its interchangeable isomers, include the compound represented by formula (ii) below.

[0050] [ka]

[0051] 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.

[0052] 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. Among those classified as dyes in the Color Index, CI Solvent dyes include CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163, etc. Additionally, CI Acid dyes include 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. Examples include 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.Furthermore, examples of CI modant dyes include CI modant yellows 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, and preferably CI solvent yellows 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, and CI acid yellows 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. Examples include 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25, 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243, and their derivatives. Among these, from the viewpoint of suppressing dye decomposition during heat firing, it is preferable to use at least one selected from the group consisting of CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163.

[0053] 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.

[0054] The content of colorant (A) 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 35% by mass or more, and also preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less. Setting it above the lower limit tends to improve color characteristics such as brightness and color gamut, and setting it below the upper limit tends to improve pattern formation properties. For example, the content of colorant (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, even more preferably 20 to 50% by mass, even more preferably 30 to 45% by mass, and particularly preferably 35 to 45% by mass.

[0055] The content of phthalocyanine compound (1) 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 35% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less. Setting it above the lower limit tends to improve color characteristics such as brightness and color gamut, and setting it below the upper limit tends to improve pattern formation properties.

[0056] If other colorants are included, their content is not particularly limited, but preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less. Setting the content above the lower limit tends to improve color characteristics such as brightness and color gamut, while setting it below the upper limit tends to improve pattern formation.

[0057] [1-2](B) Solvent (B) The solvent has the function of dissolving or dispersing the colorant, alkali-soluble resin, photopolymerization initiator, and other components in the colored resin composition of the present invention, and adjusting the viscosity. The solvent in question (B) can be any solvent that can dissolve or disperse each component.

[0058] In the colored resin composition of the present invention, (B) solvent contains a high-boiling-point solvent (hereinafter sometimes referred to as "high-boiling-point solvent") having a boiling point of 160°C or higher at 1013.25 hPa. By including such a high-boiling-point solvent, drying of the coating film during the alkaline development process is suppressed, resulting in a sufficiently wet state, allowing the alkaline developer to penetrate sufficiently into the coating film and promoting the neutralization reaction. It is believed that even if the coating film contains phthalocyanine compound (1), residue is less likely to be generated on the glass substrate.

[0059] The boiling point of the aforementioned high-boiling-point solvent at 1013.25 hPa (hereinafter simply referred to as "boiling point" unless otherwise specified) is usually 160°C or higher, preferably 165°C or higher, more preferably 170°C or higher, even more preferably 180°C or higher, even more preferably 190°C or higher, particularly preferably 200°C or higher, most preferably 220°C or higher, and also preferably 340°C or lower, more preferably 300°C or lower, and even more preferably 280°C or lower. Setting it above the lower limit improves alkali solubility and tends to suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, while setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the boiling point of the high-boiling point solvent is preferably 160 to 340°C, more preferably 165 to 340°C, even more preferably 170 to 300°C, even more preferably 180 to 300°C, particularly preferably 190 to 300°C, especially preferably 200 to 280°C, and most preferably 220 to 280°C. The high-boiling point solvent may be used alone or in combination of two or more types.

[0060] Furthermore, the vapor pressure of the high-boiling point solvent at 20°C is not particularly limited, but is preferably 1 Pa or more, more preferably 5 Pa or more, even more preferably 10 Pa or more, and also preferably 2000 Pa or less, more preferably 1500 Pa or less, even more preferably 1000 Pa or less, and particularly preferably 500 Pa or less. Setting it above the lower limit tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and setting it below the upper limit tends to improve alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) during the color filter manufacturing process. For example, the vapor pressure of the high-boiling point solvent at 20°C is preferably 1 to 2000 Pa, more preferably 1 to 1500 Pa, even more preferably 5 to 1000 Pa, and particularly preferably 10 to 500 Pa.

[0061] Specific examples of the aforementioned high-boiling point solvents include glycol ethers such as ethylene glycol mono-n-butyl ether (boiling point: 171°C), propylene glycol mono-n-butyl ether (boiling point: 170°C), diethylene glycol diethyl ether (boiling point: 188°C), diethylene glycol monoethyl ether (boiling point: 202°C), ethyl 3-ethoxypropionate (boiling point: 170°C), 3-methoxybutyl acetate (boiling point: 171°C), and 3-methoxy-3-methylbutyl acetate (boiling point: 187°C); Glycol ether acetates such as ethylene glycol mono-n-butyl ether acetate (boiling point: 192°C), diethylene glycol monoethyl ether acetate (boiling point: 217°C), and diethylene glycol mono-monobutyl ether acetate (boiling point: 245°C); Glycol diacetates such as ethylene glycol diacetate (boiling point: 191°C) and 1,3-butylene glycol diacetate (boiling point: 232°C); Examples include amides such as N-methylpyrrolidone (boiling point: 202°C), and from the viewpoint of solubility of the phthalocyanine compound (1) in the colored resin composition, glycol ethers and glycol ether acetates are preferred, with glycol ethers being more preferred.

[0062] Among these high-boiling-point solvents, it is preferable to use a high-boiling-point solvent with a boiling point of 160°C or higher and less than 200°C (hereinafter sometimes referred to as "high-boiling-point solvent A") from the viewpoint of appropriately suppressing residue and improving the efficiency of VCD (vacuum drying) during the color filter manufacturing process. The boiling point of high-boiling-point solvent A is not particularly limited as long as it is between 160°C and 200°C, but is preferably 165°C or higher, more preferably 170°C or higher, even more preferably 175°C or higher, and also preferably 195°C or lower, more preferably 190°C or lower, and even more preferably 185°C or lower. Setting it above the lower limit improves alkali solubility and tends to suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, while setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the boiling point of high-boiling-point solvent A is preferably 165°C to 195°C, more preferably 170°C to 190°C, and even more preferably 175°C to 185°C. High-boiling-point solvent A may be used alone or in combination of two or more types.

[0063] Specific examples of high-boiling-point solvent A include glycol ethers such as ethylene glycol mono-n-butyl ether (boiling point: 171°C), propylene glycol mono-n-butyl ether (boiling point: 170°C), diethylene glycol diethyl ether (boiling point: 188°C), ethyl 3-ethoxypropionate (boiling point: 170°C), 3-methoxybutyl acetate (boiling point: 171°C), and 3-methoxy-3-methylbutyl acetate (boiling point: 187°C); Glycol ether acetates such as ethylene glycol mono-n-butyl ether acetate (boiling point: 192°C); Examples include glycol diacetates such as ethylene glycol diacetate (boiling point: 191°C), and from the viewpoint of solubility of the phthalocyanine compound (1) in the colored resin composition, glycol ethers and glycol ether acetates are preferred, with glycol ethers being more preferred.

[0064] Among these high-boiling-point solvents, it is preferable to use a high-boiling-point solvent with a boiling point of 200°C to 340°C (hereinafter sometimes referred to as "high-boiling-point solvent B") from the viewpoint of efficient residue suppression and suppression of bumping during VCD (vacuum drying) in the color filter manufacturing process. The boiling point of high-boiling-point solvent B is not particularly limited as long as it is between 200°C and 340°C, but is preferably 210°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, preferably 320°C or lower, more preferably 300°C or lower, and even more preferably 280°C or lower. Setting it above the lower limit improves alkali solubility and tends to suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, while setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the boiling point of high-boiling-point solvent B is preferably 210°C to 320°C, more preferably 220°C to 300°C, and even more preferably 230°C to 280°C. High-boiling-point solvent B may be used alone or in combination of two or more types.

[0065] Specific examples of high-boiling point solvent B include glycol ethers such as diethylene glycol monoethyl ether (boiling point: 202°C); Glycol ether acetates such as diethylene glycol monoethyl ether acetate (boiling point: 217°C), diethylene glycol monomonobutyl ether acetate (boiling point: 245°C); Glycol diacetates such as 1,3-butylene glycol diacetate (boiling point: 232°C); Examples include amides such as N-methylpyrrolidone (boiling point: 202°C), and from the viewpoint of solubility of the phthalocyanine compound (1) in the colored resin composition, glycol ethers and glycol ether acetates are preferred, with glycol ether acetates being more preferred.

[0066] Among high-boiling-point solvents, it is preferable to use high-boiling-point solvent A alone from the viewpoint of moderately suppressing residue and improving the efficiency of VCD (vacuum drying) during the color filter manufacturing process. Furthermore, it is preferable to use high-boiling-point solvent B alone from the viewpoint of efficient residue suppression and suppression of bumping during VCD (vacuum drying) during the color filter manufacturing process. On the other hand, from the viewpoint of suppressing residue while simultaneously improving the efficiency of VCD (vacuum drying) during the color filter manufacturing process and suppressing bumping during VCD (vacuum drying), it is preferable to use high-boiling-point solvent A and high-boiling-point solvent B in combination.

[0067] Furthermore, in the colored resin composition of the present invention, it is preferable that (B) solvent contains a low-boiling-point solvent having a boiling point of less than 160°C (hereinafter sometimes referred to as "low-boiling-point solvent"). Including a low-boiling-point solvent tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and the coating film dries more easily with VCD or heat drying, resulting in a thinner coating film. This allows ultraviolet light to penetrate deeper into the coating film during UV exposure, improving coating film curability and making pattern formation more advantageous.

[0068] The boiling point of the low-boiling solvent is not particularly limited as long as it is less than 160°C, but is preferably 150°C or lower, more preferably 140°C or lower, even more preferably 130°C or lower, particularly preferably 120°C or lower, and also preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. Setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and setting it above the lower limit tends to improve alkali solubility.

[0069] Specific examples of low-boiling point solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-peptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, methyl-3-methoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, dibutyl ether, ethyl pyruvate, n-butyl acetate, isobutyl Examples of suitable materials include propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate, with propylene glycol monomethyl ether acetate being more preferred from the viewpoint of solubility and storage stability in relation to components of the colored resin composition other than the solvent.

[0070] The content of solvent (B) in the colored resin composition of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and also preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 88% by mass or less. Setting it above the lower limit tends to improve the storage stability and coatability of the colored resin composition, and setting it below the upper limit tends to keep the film thickness during coating below a certain level. For example, the solvent content is preferably 50 to 95% by mass, more preferably 60 to 95% by mass, even more preferably 70 to 90% by mass, and particularly preferably 80 to 88% by mass.

[0071] Furthermore, in the colored resin composition of the present invention, the content of the high-boiling point solvent in solvent (B) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, especially preferably 10% by mass or more, particularly preferably 15% by mass or more, most preferably 20% by mass or more, and also preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less. Setting it above the lower limit improves alkali solubility and tends to suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, and setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the content of the high-boiling point solvent in solvent (B) is preferably 0.5 to 80% by mass, more preferably 1 to 80% by mass, even more preferably 2 to 60% by mass, even more preferably 5 to 60% by mass, particularly preferably 10 to 40% by mass, especially preferably 15 to 40% by mass, and most preferably 20 to 30% by mass.

[0072] When the colored resin composition of the present invention contains the low-boiling point solvent, the content of the low-boiling point solvent in solvent (B) is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, and also preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less. Setting it above the lower limit tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and setting it below the upper limit tends to improve alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) during the color filter manufacturing process. For example, the content of the low-boiling point solvent in solvent (B) is preferably 20 to 99% by mass, more preferably 40 to 98% by mass, even more preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass.

[0073] When solvent (B) in the colored resin composition of the present invention contains the high-boiling point solvent A and the low-boiling point solvent, the content of the high-boiling point solvent A in solvent (B) is not particularly limited, but is preferably 1% by mass or more, 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 alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, and setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the content of the high-boiling point solvent A in solvent (B) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 20% by mass.

[0074] When solvent (B) in the colored resin composition of the present invention contains the high-boiling-point solvent A and the low-boiling-point solvent, the content of the low-boiling-point solvent in solvent (B) is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, and also preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less. Setting it above the lower limit tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and setting it below the upper limit tends to improve alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) during the color filter manufacturing process. For example, the content of the low-boiling-point solvent in solvent (B) is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, even more preferably 70 to 90% by mass, and particularly preferably 80 to 85% by mass.

[0075] When the solvent (B) in the colored resin composition of the present invention contains the high-boiling point solvent B and the low-boiling point solvent, the content of the high-boiling point solvent B in the solvent (B) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, and also preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Setting it above the lower limit efficiently improves alkali solubility and tends to suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, and setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the content of the high-boiling point solvent B in the solvent (B) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.

[0076] When the solvent (B) in the colored resin composition of the present invention contains the high-boiling-point solvent B and the low-boiling-point solvent, the content of the low-boiling-point solvent in solvent (B) is not particularly limited, but is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and also preferably 99.9% by mass or less, more preferably 99.5% by mass or less, even more preferably 99% by mass or less, and particularly preferably 98% by mass or less. Setting it above the lower limit tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and setting it below the upper limit tends to improve alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) during the color filter manufacturing process. For example, the content of the low-boiling-point solvent in solvent (B) is preferably 80 to 99.9% by mass, more preferably 85 to 99.5% by mass, even more preferably 90 to 99% by mass, and particularly preferably 95 to 98% by mass.

[0077] When the solvent (B) in the colored resin composition of the present invention contains the high-boiling point solvent A, the high-boiling point solvent B, and the low-boiling point solvent, the content of the high-boiling point solvent A in the solvent (B) is not particularly limited, but is preferably 1% by mass or more, 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 alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, and setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the content of the high-boiling point solvent A in the solvent (B) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 20% by mass.

[0078] When the solvent (B) in the colored resin composition of the present invention contains the high-boiling point solvent A, the high-boiling point solvent B, and the low-boiling point solvent, the content of the high-boiling point solvent B in the solvent (B) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, particularly preferably 2% by mass or more, and also preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. Setting it above the lower limit tends to efficiently improve alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) in the color filter manufacturing process, and setting it below the upper limit tends to improve the efficiency of VCD (vacuum drying) in the color filter manufacturing process. For example, the content of the high-boiling point solvent B in the solvent (B) is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.

[0079] When the solvent (B) in the colored resin composition of the present invention contains the high-boiling solvent A, the high-boiling solvent B, and the low-boiling solvent, the content of the low-boiling solvent in solvent (B) is not particularly limited, but is preferably 30% by mass or more, more preferably 45% by mass or more, even more preferably 60% by mass or more, particularly preferably 75% by mass or more, and also preferably 98.9% by mass or less, more preferably 94.5% by mass or less, even more preferably 89% by mass or less, and particularly preferably 83% by mass or less. Setting it above the lower limit tends to improve the efficiency of VCD (vacuum drying) during the color filter manufacturing process, and setting it below the upper limit tends to improve alkali solubility and suppress the occurrence of bumping during VCD (vacuum drying) during the color filter manufacturing process. For example, the content of the low-boiling point solvent in solvent (B) is preferably 30 to 98.9% by mass, more preferably 45 to 94.5% by mass, even more preferably 60 to 89% by mass, and particularly preferably 75 to 83% 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 alkali-soluble resins, 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, Japanese Patent Publication No. 2003-233179, etc., can be used, but among them, 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 (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, and will be described in detail below.

[0081] Furthermore, the resins (C-2) to (C-5) are not limited as long as they are solubilized to the extent that they can be dissolved by an alkaline developer and the desired developing process can be carried out. Preferably, each of them can be those described as such in Japanese Patent 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 of 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 the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and the like. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

[0084] As the other radically polymerizable monomer copolymerized with the epoxy group-containing (meth)acrylate, a mono(meth)acrylate having a structure represented by the following general formula (V) is preferred.

[0085] [Chemical formula]

[0086] In formula (V), R 91 ~R 98 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Incidentally, R 96 and R 98 , or R 95 and R 97 may be linked to each other to form a ring. In formula (V), the ring formed by linking R 96 and R 98 , or R 95 and R 97 is preferably an aliphatic ring and may be either saturated or unsaturated. The ring formed by linking R 95 and R 97 preferably has 5 to 6 carbon atoms.

[0087] Among them, as the structure represented by the general formula (V), the structures represented by the following formula (Va), (Vb), or (Vc) are preferred. By introducing these structures into alkali-soluble resins, when the colored resin composition of the present invention is used for forming color filters, 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] Furthermore, mono(meth)acrylates having the structure represented by general formula (V) may be used individually or in combination of two or more types.

[0089] [ka]

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

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

[0094] In addition, other radical polymerizable monomers other than the mono(meth)acrylate represented by the general 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, and isopropyl (meth)acrylate. Pill, (meth)acrylate n-butyl, (meth)acrylate sec-butyl, (meth)acrylate tert-butyl, (meth)acrylate pentyl, (meth)acrylate neopentyl, (meth)acrylate isoamyl, (meth)acrylate hexyl, (meth)acrylate 2-ethylhexyl, (meth)acrylate lauryl, (meth)acrylate dodecyl, (meth)acrylate cyclopentyl, (meth)acrylate cyclohexyl, (meth)acrylate 2-methylcyclohexyl, (meth)acrylate Dicyclohexyl acid, isobolonyl (meth)acrylate, adamantyl (meth)acrylate, propagyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, piperonyl (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, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate;Examples include (meth)acrylamides such as (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-diisopropylamide, and (meth)acrylate anthracenylamide; vinyl compounds such as (meth)acrylate anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

[0095] Among these other radical polymerizable monomers, it is preferable to include one or more selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide, from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition. In particular, it is preferable that the content of repeating units derived from one or more selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide in the repeating units derived from other radical polymerizable monomers be 1 to 70 mol%, and more preferably 3 to 50 mol%.

[0096] Furthermore, known solution polymerization methods are applied to the copolymerization reaction between the epoxy group-containing (meth)acrylate and the other radical polymerizable monomer. The solvent used is not particularly limited as long as it is inert to radical polymerization, and commonly used organic solvents can be used. Examples of solvents include: ethylene glycol monoalkyl ether acetates such as 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 ethyl acetate, isopropyl acetate, and dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; and diethyl carbitol, ethyl carbitol, and butyl carbitol. Examples include ethylene glycol dialkyl ethers; 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-based solvents such as petroleum ethers, 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 these solvents used 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 used within this range tends to facilitate control of the molecular weight of the copolymer. Furthermore, the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. Examples of such organic peroxide catalysts include those classified as known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

[0098] Specific examples 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-butylperoxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide. Examples include t-butyl hydroperoxide, dicumyl peroxide, 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 azobiscarbonamide. 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 the solvent with the radical polymerization initiator added dropwise to a heated and stirred solvent. Alternatively, the monomers may be added dropwise to a solvent with the radical polymerization initiator added and then heated. The reaction conditions can be freely changed according to the target molecular weight.

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

[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. On the other hand, by setting the content of repeating units derived from other radical polymerizable monomers to above the aforementioned lower limit, the heat resistance and strength tend to be sufficient. Next, the epoxy group portion of a copolymer of epoxy resin-containing (meth)acrylate and other radical polymerizable monomers is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).

[0103] Known unsaturated monobasic acids can be used as the unsaturated monobasic acids to be added to the epoxy group, for example, unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples 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. One of these may be used alone, or two or more may be used in combination.

[0104] By adding such components, polymerizability can be imparted to the resin (C-1). These unsaturated monobasic acids are typically added to 10 to 100 mol% of the epoxy groups of the copolymer, preferably to 30 to 100 mol%, and more preferably to 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 the unsaturated monobasic acids to the epoxy groups of the 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 group of the copolymer. Examples 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 basic acids such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among these, tetrahydrophthalic anhydride and / or succinic anhydride are preferred. These polybasic acid anhydrides may be used individually or in combination of two or more.

[0106] By adding such components, alkali solubility can be imparted to the resin (C-1). These polybasic acid anhydrides are typically added to 10 to 100 mol% of the hydroxyl groups formed by adding an unsaturated monobasic acid to the epoxy groups of the copolymer, preferably to 20 to 90 mol%, and more preferably to 30 to 80 mol%. Setting the amount below the upper limit tends to result in a good residual film rate during development, while setting it above the lower limit tends to result in sufficient solubility. Known methods can be used to add the polybasic acid anhydrides to the hydroxyl groups.

[0107] Furthermore, in order to improve photosensitivity, after adding the aforementioned 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. Furthermore, 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. Specific examples of glycidyl ether compounds that do not have polymerizable unsaturated groups include glycidyl ether compounds having phenyl groups or alkyl groups. Commercially available products include, for example, Nagase ChemteX's product names "Denacol EX-111," "Denacol EX-121," "Denacol EX-141," "Denacol EX-145," "Denacol EX-146," "Denacol EX-171," and "Denacol EX-192."

[0109] Furthermore, the structure of such resins is already publicly known, as it is described, for example, in Japanese Patent Publication No. Hei 8-297366 and Japanese Patent Publication No. 2001-89533. The weight-average molecular weight (Mw) 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. Furthermore, as a guideline for molecular weight distribution, the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) is preferably between 2.0 and 5.0.

[0110] On the other hand, 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 (hereinafter sometimes referred to as "(c1) acrylic copolymer resin") are preferred. (c1) The substructure of the acrylic copolymer resin, which includes a side chain having an ethylenically unsaturated group, is not particularly limited, but from the viewpoint of achieving both coating film curability during UV exposure and alkaline solubility during alkaline development, it is preferable to have a substructure represented by the following general formula (I).

[0111] [ka]

[0112] In formula (I), 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 (I), the substructure represented by the following general formula (I') is preferred from the viewpoint of sensitivity and alkali developability.

[0114] [ka]

[0115] In formula (I'), 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 one or more selected from 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. Among these, 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, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred.

[0117] (c1) The content of the substructure represented by the general formula (I) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain 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, 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 it 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. For example, the content of the substructure represented by the general formula (I) 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 50 to 70 mol%.

[0118] (c1) The content of the substructure represented by the general formula (I') in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain 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, 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 it 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. For example, the content of the substructure represented by the general formula (I') 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 50 to 70 mol%.

[0119] (c1) When an acrylic copolymer resin having an ethylenically unsaturated group in its side chain contains a substructure represented by the general formula (I), 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 (II).

[0120] [ka]

[0121] In the above equation (II), 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 the above equation (II), 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, 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 value above the lower limit tends to improve lipophilicity and solvent solubility, while setting the value below the upper limit tends to improve hydrophilicity and alkali solubility.

[0123] Specific examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of developability, dicyclopentanyl or dodecanyl groups are preferred, and dicyclopentanyl groups are more preferred. Furthermore, examples of substituents that alkyl groups may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups, with hydroxyl and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0124] R 4 Examples 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 aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monoring or a fused ring, and examples include groups such as 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. Furthermore, the aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic or fused ring, 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, phenanthridine rings, perimidine rings, quinazoline rings, quinazolinone rings, and azulene rings. Among these, from the viewpoint of developability, benzene ring groups or naphthalene ring groups are preferred, and benzene ring groups are more preferred. Furthermore, 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, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.

[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.

[0126] Specific examples of alkenyl groups include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 2-penten-1-yl group, 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, and cyclohexenyl. Among these, vinyl group or allyl group is preferred from the viewpoint of developability, and vinyl group is more preferred.

[0127] Furthermore, examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0128] Thus, R 4 The group represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. Among these, alkyl groups or alkenyl groups are preferred from the viewpoint of developability and film strength, and alkyl groups are more preferred.

[0129] (c1) The content of the substructure represented by general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain 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 content of the substructure represented by general formula (II) 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 the general formula (I), it is preferable that the other substructures included include a substructure represented by the general formula (III) below, from the viewpoint of improving the alkali solubility of the phthalocyanine compound (1) by enhancing the affinity between the phthalocyanine compound (1) and the (c1) acrylic copolymer resin.

[0131] [ka]

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

[0133] (R 6 ) In the above equation (III), R 6This 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 value above the lower limit tends to improve lipophilicity and solvent solubility, while setting the value below the upper limit tends to improve hydrophilicity and alkali solubility.

[0134] Specific examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of heat resistance, dicyclopentanyl or dodecanyl groups are preferred, and dicyclopentanyl groups are more preferred. Furthermore, examples of substituents that alkyl groups may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups, with hydroxyl and oligoethylene glycol groups being preferred from the viewpoint of developability.

[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.

[0136] Specific examples of alkenyl groups include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 2-penten-1-yl group, 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, and cyclohexenyl. Among these, vinyl group or allyl group is preferred from the viewpoint of exposure sensitivity during ultraviolet exposure, and vinyl group is more preferred.

[0137] Furthermore, examples of substituents that the alkenyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0138] R 6 Examples 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.

[0139] Specific 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, 1-hexyn-6-yl group, and the like.

[0140] Furthermore, examples of substituents that the alkynyl group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0141] R 6 Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms, and among these, fluorine is preferred from the viewpoint of the storage stability of (c1) acrylic copolymer resin.

[0142] R 6 Examples 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.

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

[0144] Furthermore, 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, with hydroxyl and oligoethylene glycol groups being preferred from the viewpoint of developability.

[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.

[0146] Specific examples of alkyl sulfide groups include methyl sulfide groups, ethyl sulfide groups, propyl sulfide groups, and butyl sulfide groups. Among these, methyl sulfide groups or ethyl sulfide groups are preferred from the viewpoint of developability.

[0147] Furthermore, 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, with hydroxyl and oligoethylene glycol groups being preferred from the viewpoint of developability.

[0148] Thus, R 6 The group 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. Among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0149] In equation (III) above, t represents an integer from 0 to 5, but from the viewpoint of ease of manufacture, it is preferable that t is 0.

[0150] (c1) The content of the substructure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain 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 the affinity between the phthalocyanine compound (1) and the (c1) acrylic copolymer resin, and improve alkali solubility, while setting it below the upper limit tends to increase the content of other substructures, and improve alkali solubility. For example, the content of the substructure represented by the general formula (III) 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 ethylenically unsaturated groups in its side chains has a substructure represented by the general formula (I), it is also preferable that it may have a substructure represented by the following general formula (IV) as another substructure, from the viewpoint of developability.

[0152] [ka]

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

[0154] (c1) When an acrylic copolymer resin having an ethylenically unsaturated group in its side chain has a substructure represented by the general formula (IV), the content of such substructure is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and also preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. Setting the content 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. For example, when the substructure represented by the general formula (IV) is present, the content of such substructure is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

[0155] On the other hand, the acid value of (C) 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. 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 (Mw) 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. For example, the weight-average molecular weight (Mw) 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 most 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 usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more, and is usually 80% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. Setting it above the lower limit tends to result in a strong film and excellent adhesion to the substrate. Setting it below the upper limit tends to reduce the penetration of the developer into the exposed area, which tends to suppress deterioration of the surface smoothness and sensitivity of the pixels. For example, the content of (C) alkali-soluble resin is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, even more preferably 10 to 60% by mass, even more preferably 20 to 60% by mass, particularly preferably 25 to 50% by mass, and most preferably 30 to 40% by mass.

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

[0159] Examples of photopolymerization initiators include metallocene compounds containing titanocene compounds as described in Japanese Patent Publication No. 59-152396 and Japanese Patent Publication No. 61-151197, radical activators such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters as described in Japanese Patent Publication No. 10-39503, α-aminoalkylphenone compounds, and oxime ester initiators as described in Japanese Patent Publication No. 2000-80068.

[0160] Specific examples of photopolymerization initiators 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, and 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; Titanocene derivatives such as dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl-Ti-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,4-difluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl, and dicyclopentadienyl-Ti-2,6-difluoro-3-(pyrrole-1-yl)-phenyl;

[0164] α-aminoalkylphenone compounds such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 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] Among these, from the viewpoints of sensitivity and surface properties, an oxime ester compound (an oxime ester-based photoinitiator) is preferred. Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it has high sensitivity in a small amount, is stable against thermal reactions, and enables the design of a highly sensitive colored resin composition in a small amount. In particular, from the viewpoint of light absorption properties with respect to the i-line (365 nm) of the exposure light source, an oxime ester compound having a carbazole ring which may have a substituent is preferred.

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

[0167]

Chemical formula

[0168] In the above formula (I-1), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R 21b represents any substituent containing an aromatic ring or a heteroaromatic ring. R 22a represents an alkanoyl group which may have a substituent, or an aroyl group which may have a substituent.

[0169] R 21a The number of carbon atoms of the alkyl group in is not particularly limited, but from the viewpoints of solubility in a solvent 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. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and the like. 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.

[0171] Specific examples of aromatic ring groups include phenyl groups, naphthyl groups, pyridyl groups, furyl groups, and fluorenyl groups. Among these, from the viewpoint of developability, phenyl groups, naphthyl groups, or fluorenyl groups are preferred, and phenyl groups or 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, alkyl groups, etc. 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. Among these, from the perspective of developability, R 21a It is preferably an alkyl group which may have substituents, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.

[0172] R 21bThe substituent is any substituent containing an aromatic ring or a heteroaromatic ring, but from the viewpoint of solubility in solvents and sensitivity to exposure, preferably a substituted carbazolyl group, a substituted thioxanthonyl group, a substituted diphenyl sulfide group, or a substituted fluorenyl group, or a group formed by linking these groups with a carbonyl group, are mentioned. Among these, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, a substituted carbazolyl group, or a group formed by linking a substituted carbazolyl group with a carbonyl group, is preferred.

[0173] R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is 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. Specific examples of alkanoyl groups include acetyl groups, propanoyl groups, and butanoyl groups. The substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups, and from the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted.

[0174] R 22a The number of carbon atoms in the allyroyl group is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, and more preferably 10 or less. Specific examples of allyroyl groups include benzoyl groups and naphthoyl groups. The substituents that the allyroyl group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, alkyl groups, etc., and from the viewpoint of ease of synthesis, it is preferable that it be unsubstituted.

[0175] Among the compounds represented by the general formula (I-1) mentioned above, compounds represented by the following general formulas (I-2) or (I-3) are particularly noteworthy from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source.

[0176] [ka]

[0177] [ka]

[0178] In the above formula (I-2) or (I-3), R 21a and R 22a This is equivalent to the general formula (I-1) above. 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.

[0179] 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. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc. Examples of substituents that the alkyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group, and from the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted. Among these, R 23a From the viewpoint of solubility in solvents and ease of synthesis, an ethyl group is more preferable.

[0180] R 24aThe 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. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc. Examples of substituents that the alkyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group, and from the viewpoint of ease of synthesis, it is preferable that the alkyl group be unsubstituted.

[0181] 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. Specific examples of allyroyl groups include benzoyl groups and naphthoyl groups. The substituents that the allyroyl group may have include a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group, and from the viewpoint of ease of synthesis, an ethyl group is preferred.

[0182] 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. Specific examples of heteroaryroyl groups include francarbonyl group, thiophencarbonyl group, pyrrolylcarbonyl group, pyridinecarbonyl group, etc. The substituents that the heteroaryroyl group may have include carboxyl groups, hydroxyl groups, phenyl groups, benzyl groups, cyclohexyl groups, or nitro groups, and from the viewpoint of ease of synthesis, it is preferable that the group be unsubstituted. Among these, R 24aFrom the viewpoint of sensitivity, an aryloyl group which may have a substituent is preferable, and a benzoyl group is more preferable.

[0183] The benzene ring constituting the carbazole ring may be further condensed with an aromatic ring to form a polycyclic aromatic ring.

[0184] Examples of commercially available products of such oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., and N-1919, NCI-930, NCI-831, etc. manufactured by ADEKA.

[0185] Examples of the oxime ester compound include, but are not limited to, the compounds specifically exemplified below.

[0186]

Chemical formula

[0187]

Chemical formula

[0188]

Chemical formula

[0189] These photoinitiators may be used individually or in combination of two or more.

[0190] In addition to the (D) photoinitiator, a chain transfer agent may be further used. A chain transfer agent is a compound having a function of receiving a generated radical and transferring the received radical to another compound. Various compounds with the above-mentioned functions can be used as chain transfer agents, but examples include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use compounds containing mercapto groups 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.

[0191] 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, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, and trishydroxy Examples of aliphatic mercapto group-containing compounds include ethyl 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 particularly preferred.

[0192] Of these, among the mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto group-containing compounds, 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 are preferred.

[0193] Furthermore, in terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, specifically 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, with pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) being more preferred. These may be used individually or in combination of two or more types.

[0194] In the colored resin composition of the present invention, the content of (D) photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 4% by mass or more, particularly preferably 5% by mass or more, and also preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 6% by mass or less. Setting it above the lower limit tends to ensure patterning characteristics after development, and setting it below the upper limit tends to suppress the decrease in transmittance due to the addition of an excess of photopolymerization initiator. For example, the content of (D) photopolymerization initiator is preferably 1 to 15% by mass, more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, even more preferably 4 to 8% by mass, and particularly preferably 5 to 6% by mass.

[0195] When the colored resin composition of the present invention contains a chain transfer agent, its content is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, and also preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. Keeping it within the above range tends to ensure storage stability and pattern formation ability during alkaline development. When a chain transfer agent is included, for example, its content is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.2 to 3% by mass, even more preferably 0.5 to 3% by mass, even more preferably 1 to 2% by mass, and particularly preferably 1.5 to 2% by mass.

[0196] [1-5] 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 photopolymerizable monomers, dispersants, dispersing aids, and surfactants.

[0197] [1-5-1] 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 term monomer refers to a concept opposite to so-called polymers, and includes not only monomers in the narrow sense but also dimers, trimers, and oligomers. In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds in the polyfunctional ethylenic 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 the number above the lower limit tends to result in high sensitivity, and setting it below the upper limit tends to improve solubility in solvents.

[0198] Examples of ethylenic compounds include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification reactions of unsaturated carboxylic acids with polyhydroxy compounds such as polycarboxylic acids and aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and ethylenic compounds having a urethane skeleton obtained by reacting polyisocyanate compounds with (meth)acryloyl-containing hydroxy compounds.

[0199] Examples of esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, examples of 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.

[0200] 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. Typical 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.

[0201] 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.

[0202] Other useful ethylenic compounds used in the present invention include, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate. Furthermore, the ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyfunctional monomer is preferred in which an acid group is formed by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. Particularly preferred is that in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

[0203] 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.

[0204] 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. Other polyfunctional monomers can also be used in combination with this polyfunctional monomer. Alternatively, those described in paragraphs

[0056] and

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

[0205] Furthermore, 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 improved sensitivity of the coating film and reduced development time, it is preferable to use the polymerizable monomer described in Japanese Patent Publication No. 2013-195974.

[0206] When the colored resin composition of the present invention contains a photopolymerizable monomer, the content of the photopolymerizable monomer is not particularly limited, but is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more, and is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less. Setting it above the lower limit tends to improve the curability of the coating film, and setting it below the upper limit tends to suppress the decrease in alkali developability. For example, when the colored resin composition of the present invention contains a photopolymerizable monomer, the content of the photopolymerizable monomer is preferably 0 to 70% by mass, more preferably 5 to 60% by mass, even more preferably 10 to 50% by mass, particularly preferably 15 to 40% by mass, and most preferably 20 to 30% by mass.

[0207] [1-5-2] 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. Specific examples of these 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 those described in Japanese Patent Publication No. 2013-119568.

[0208] Among polymer dispersants, block copolymers having functional groups containing nitrogen atoms are preferred from the viewpoint of dispersibility and storage stability, and acrylic block copolymers are more preferred. As a block copolymer having a functional group containing a nitrogen atom, AB block copolymer and / or BAB block copolymer 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 / or an amino group.

[0209] 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, it is preferable to have primary to tertiary amino groups, and more preferable to have tertiary amino groups. 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 it is a repeating unit represented by the following general formula (1).

[0210] [ka]

[0211] In the above equation (1), 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.

[0212] The number of carbon atoms in the alkyl group, which may have substituents, in formula (1) above 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. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Among these, methyl, ethyl, propyl, butyl, pentyl, or hexyl groups are preferred, and methyl, ethyl, propyl, or butyl groups are more preferred. The alkyl group may be linear or branched. It may also include cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0213] The number of carbon atoms in the aryl group in formula (1) above, which may have substituents, 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. Specific examples of aryl groups include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, or diethylphenyl group are preferred, and phenyl group, methylphenyl group, or ethylphenyl group are more preferred.

[0214] The number of carbon atoms in the aralkyl group in formula (1) above, which may have substituents, 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. Specific examples of aralkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Among these, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene are preferred, and phenylmethylene or phenylethylene are more preferred.

[0215] Among these, R 1 and R 2Alkyl groups, each of which may independently have substituents, are preferred, and methyl or ethyl groups are more preferred.

[0216] Examples of substituents that the alkyl group, aralkyl group, or aryl group in formula (1) may have include halogen atoms, alkoxy groups, benzoyl groups, hydroxyl groups, etc., and from the viewpoint of ease of synthesis, it is preferable that they be unsubstituted.

[0217] Furthermore, in equation (1) above, 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 those listed in (IV) below.

[0218] [ka]

[0219] These cyclic structures may further have substituents.

[0220] In formula (1) above, 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, -COO-R 14 -Base [However, R 13 and R 14 Examples include a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, preferably -COO-R 14 - It is the basis.

[0221] Furthermore, the content of the repeating unit represented by formula (1) 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% or more, most 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. When within the above range, it tends to be possible to achieve both dispersion stability and high brightness. For example, the content of the repeating unit represented by formula (1) 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 most preferably 25 to 40 mol%.

[0222] Furthermore, the block copolymer is preferably made of repeating units represented by the following formula (2) from the viewpoint of improving compatibility with binder components such as dispersants and thus improving dispersion stability.

[0223] [ka]

[0224] In equation (2) above, R 10 R is an ethylene group or a propylene group, 11 R is an alkyl group which may have substituents, 12 This is either a hydrogen atom or a methyl group. n is an integer between 1 and 20.

[0225] R in equation (2) above 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. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Among these, methyl, ethyl, propyl, butyl, pentyl, or hexyl groups are preferred, and methyl, ethyl, propyl, or butyl groups are more preferred. The alkyl group may be linear or branched. It may also contain cyclic structures such as cyclohexyl and cyclohexylmethyl groups. Optional substituents 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.

[0226] Furthermore, in formula (2) above, n is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, and more preferably 5 or less, from the viewpoint of compatibility and dispersibility with binder components such as solvents.

[0227] Furthermore, the content of the repeating unit represented by formula (2) 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, preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability. For example, the content of the repeating unit represented by formula (2) 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%.

[0228] Furthermore, the block copolymer is preferably made of repeating units represented by the following formula (3) from the viewpoint of improving compatibility with binder components such as dispersants and thus improving dispersion stability.

[0229] [ka]

[0230] In equation (3) above, 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.

[0231] R in equation (3) above 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 1 or more, preferably 10 or less, and more preferably 6 or less. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Among these, methyl, ethyl, propyl, butyl, pentyl, or hexyl groups are preferred, and methyl, ethyl, propyl, or butyl groups are more preferred. The alkyl group may be linear or branched. It may also contain cyclic structures such as cyclohexyl and cyclohexylmethyl groups.

[0232] R in equation (3) above 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. Specific examples of aryl groups include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, or diethylphenyl group are preferred, and phenyl group, methylphenyl group, or ethylphenyl group are more preferred.

[0233] R in equation (3) above 8The 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. Specific examples of aralkyl groups include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, and phenylisopropylene. Among these, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene are preferred, and phenylmethylene or phenylethylene are more preferred.

[0234] Among these, R 8 The alkyl group or aralkyl group is preferred, and a methyl group, ethyl group, or phenylmethylene group is more preferred. R 8 In this context, possible substituents on the alkyl group include halogen atoms and alkoxy groups. Furthermore, possible substituents on the aryl group or aralkyl group include linear alkyl groups, halogen atoms, and alkoxy groups. Also, R 8 The linear alkyl groups shown include both linear and branched alkyl groups.

[0235] Furthermore, the content of the repeating unit represented by formula (3) 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. When within this range, it tends to be possible to achieve both dispersion stability and high brightness. For example, the content of the repeating unit represented by formula (3) 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%.

[0236] The block copolymer may have repeating units other than the repeating unit represented by general formula (1), the repeating unit represented by general formula (2), and the repeating unit represented by general formula (3). Examples of such repeating units include repeating units derived from 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 N-methacryloylmorpholine.

[0237] From the viewpoint of further improving dispersibility, it is preferable that the block copolymer has an A block having repeating units represented by the general formula (1) and a B block not having repeating units represented by the general formula (1). The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Furthermore, it is more preferable that the B block has repeating units represented by the general formula (2) and repeating units represented by the general formula (3).

[0238] Furthermore, repeating units other than those represented by the general formula (1) may be contained in Block A. Examples of such repeating units include the repeating units derived from the (meth)acrylic acid ester monomers mentioned above. The content of repeating units other than those represented by the general formula (1) in Block A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is most preferable that such repeating units are not contained in Block A.

[0239] Repeating units other than those represented by general formula (2) and general formula (3) 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, glycidyl crotonic acid ether; and repeating units derived from monomers such as N-methacryloylmorpholine. The content of repeating units other than those represented by general formula (2) and general formula (3) in block B is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but it is most preferable that such repeating units are not contained in block B.

[0240] Furthermore, the acid value of the block copolymer is preferably low, and particularly preferably 0 mg KOH / g, from the viewpoint of dispersibility. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of dispersant solids.

[0241] Furthermore, 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, particularly preferably 100 mg KOH / g or more, most preferably 110 mg KOH / g or more, and also preferably 150 mg KOH / g or less, and more preferably 130 mg KOH / g or less. Here, the amine value represents the amine value on an effective solid content basis, and is a value expressed by the amount of base and the equivalent amount of KOH per gram of solid content of the dispersant. For example, the amine value of the block copolymer is preferably 30 to 150 mg KOH / g, more preferably 50 to 150 mg KOH / g, even more preferably 70 to 150 mg KOH / g, even more preferably 90 to 130 mg KOH / g, particularly preferably 100 to 130 mg KOH / g, and most preferably 110 to 130 mg KOH / g.

[0242] Furthermore, the molecular weight of the block copolymer is preferably in the range of 1,000 to 30,000 in terms of polystyrene-equivalent weight-average molecular weight (hereinafter sometimes referred to as "Mw"). When it is within this range, dispersion stability is good, and drying foreign matter tends to be less likely to occur when coating using the slit nozzle method.

[0243] The aforementioned block copolymer can be produced by known methods, but for example, it 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. 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), DY Sogoh, WRHertler et al., Macromolecules, 20,1473(1987), etc. can be employed.

[0244] 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, particularly preferably 1% 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. For example, the content of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, and particularly preferably 1 to 10% by mass, in the total solid content of the colored resin composition.

[0245] 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 colored resin composition with excellent dispersion stability and high brightness. For example, when containing 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.

[0246] Furthermore, if the colored resin composition of the present invention contains a pigment, it may also contain a pigment derivative or the like as a dispersion aid to improve the dispersibility and dispersion stability of the pigment. Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine pigment derivatives. Examples of substituents on the pigment derivative include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., which are directly bonded to the pigment skeleton or via alkyl groups, aryl groups, heterocyclic groups, etc. Preferably, sulfonamide groups and their quaternary salts, and sulfonic acid groups are included, and more preferably, sulfonic acid groups. In addition, multiple substituents may be substituted on a single pigment skeleton, or a mixture of compounds with different numbers of substitutions may be used. Specific 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.

[0247] [1-5-3] Surfactants Various types of surfactants can be used, such as anionic, cationic, nonionic, and amphoteric surfactants, but nonionic surfactants are preferred because they are less likely to adversely affect the properties. 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, relative to the total solid content of the colored resin composition. For example, when a surfactant is included, 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 even more preferably 0.1 to 0.3% by mass, relative to the total solid content of the colored resin composition.

[0248] [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.

[0249] When preparing a coloring agent containing a pigment, first, the pigment, solvent, and dispersant are weighed in predetermined quantities, and then the pigment is dispersed in a dispersion process to prepare a pigment dispersion. In this dispersion process, paint conditioners, sand grinders, ball mills, roll mills, stone mills, jet mills, homogenizers, etc., can be used. This dispersion process results in the pigment 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.

[0250] When dispersing pigments, it is preferable to use a dispersion aid or dispersion resin, as described above, in appropriate combination. 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.

[0251] The pigment dispersion obtained by the above dispersion process is mixed with a solvent, alkali-soluble resin, photopolymerization initiator, and possibly other components 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.

[0252] If the coloring agent does not contain pigments, a homogeneous solution can be obtained by mixing a coloring agent, solvent, alkali-soluble resin, photopolymerization initiator, and possibly other components. It is preferable to filter the obtained solution using a filter or the like.

[0253] [3] Manufacturing of color filter substrates Next, the color filter according to the present invention will be described. The color filter according to the present invention has pixels formed using the colored resin composition of the present invention. Preferably, the colored resin composition of the present invention is a colored resin composition for forming pixels in a color filter.

[0254] [3-1]Transparent substrate (support) The transparent substrate for the 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 polyester resins like polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, thermosetting resin sheets such as poly(meth)acrylic resins, or various types of glass. Among these, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

[0255] The transparent substrate and the black matrix-forming substrate may be subjected to corona discharge treatment, ozone treatment, silane coupling agent treatment, or thin film formation treatment of various resins such as 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.

[0256] [3-2] Black Matrix A color filter according to the present invention can be manufactured by providing a black matrix on the transparent substrate described above and further forming pixel images, usually in red, green, and blue. The above colored resin composition is preferably used as a coating solution for forming green pixels (resist patterns) among the red, green, and blue pixels (hereinafter sometimes abbreviated as "green resist"). Using the green resist, a pixel image is formed by applying, heating and 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.

[0257] 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. As the light-shielding metal material, chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, or nickel-tungsten alloys can be used, and these may be layered 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.

[0258] In this case, first, a thin film of these metals or metal / metal oxides is formed on a transparent substrate by 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.

[0259] 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.

[0260] [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.

[0261] 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.

[0262] 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, and more preferably 5 μm or less.

[0263] [3-4] Drying of the coating film Drying the coating film after applying the colored resin composition to the substrate is preferably done using a drying method with a hot plate, IR oven, or convection oven. Typically, pre-drying is performed, followed by reheating for drying. 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.

[0264] 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 alkali-soluble resin may decompose, inducing thermal polymerization and resulting in poor development. 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.

[0265] [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.

[0266] [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 with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0267] 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 also be mixtures of two or more types.

[0268] 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.

[0269] Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. 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.

[0270] [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.

[0271] [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 a component in color displays, liquid crystal displays, etc. However, to improve surface smoothness and durability, a topcoat layer such as polyamide or polyimide can be provided on the image as needed. In some applications, such as planar orientation drive systems (IPS mode), transparent electrodes may not be formed.

[0272] [4] Image display device (panel) Next, the image display device of the present invention will be described. The image display device of the present invention has the aforementioned color filter. Below, liquid crystal display devices and organic EL display devices will be described in detail as image display devices.

[0273] [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 according to 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 injected into the formed liquid crystal cell, and the device is completed by connecting it to a counter electrode. 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.

[0274] 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.

[0275] 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 × 10⁻⁶ -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.

[0276] 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. Among thermotropic liquid crystals, nematic, smetic, and cholesteric liquid crystals are known, and any of these may be used.

[0277] [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.

[0278] 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]

[0279] 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.

[0280] <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.

[0281] [ka]

[0282] In the formula, Et represents ethyl.

[0283] <Phthalocyanine compound B> 5.00 g (18.8 mmol) of tetrachlorophthalonitrile, 3.32 g (18.8 mmol) of 2-cyclohexyl-5-methylphenol, 3.89 g (28.2 mmol) of potassium carbonate, and 50 mL of acetonitrile were mixed and heated to 70°C, then stirred for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and concentrated. The resulting residue was recrystallized with acetonitrile to obtain a mixture of intermediate A and intermediate B, yielding 4.70 g (yield 59%, purity 77.9%, intermediate A / intermediate B = 73 / 23). The purity is an area percentage calculated from the results of high-performance liquid chromatography analysis.

[0284] [ka]

[0285] A mixture of intermediates A and B (3.00 g, 7.15 mmol), zinc iodide (0.69 g, 2.14 mmol), and benzonitrile (7.2 g) was mixed and reacted at 170°C for 6.5 hours. After the reaction was complete, the reaction mixture was cooled and added to 20 mL of methanol. The resulting solid was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 2.62 g (84% yield) of phthalocyanine compound B.

[0286] [ka]

[0287] When 1 mg of phthalocyanine compound B was dissolved in 100 mL of DMSO (dimethyl sulfoxide), the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) with a 1 cm square quartz cell. The maximum absorption wavelength was 651.0 nm, and the molar extinction coefficient (ε) was 4.08 × 10⁻⁶. 5 That was the case.

[0288] <Phthalocyanine compound C> 4.00 g (20 mmol) of tetrafluorophthalonitrile, 2.90 g (5.0 mmol) of potassium fluoride, and 10 mL of acetone were mixed and cooled on ice. Then, a solution of 6.65 g (40 mmol) of ethyl p-hydroxybenzoate in 30 mL of acetone was added, and the mixture was stirred for 5 hours. After the reaction was complete, the reaction solution was filtered and concentrated, and 60 mL of ethanol was added. The precipitate that formed was filtered off and dried to obtain 6.20 g (yield 63%, purity 97.6%) of intermediate C. This purity is an area percentage value calculated from the results of high-performance liquid chromatography analysis.

[0289] [ka]

[0290] In the formula, Et represents ethyl.

[0291] 3.01 g (6.11 mmol) of intermediate C, 0.246 g (1.83 mmol) of copper(II) chloride, and 7.2 g of benzonitrile were mixed and reacted at 160°C for 7 hours. After the reaction was complete, the reaction mixture was cooled and added to 40 mL of methanol. The resulting solid was filtered, washed with methanol, and dried under reduced pressure at 50°C. The obtained solid was purified by medium-pressure preparative liquid chromatography (using a mixed solvent of chloroform and methanol as the developing solvent, with a gradient of 100:0 to 92:8 (volume ratio)) to obtain 1.13 g (40% yield) of phthalocyanine compound C.

[0292] [ka]

[0293] In the formula, Et represents ethyl.

[0294] When 1 mg of phthalocyanine compound C was dissolved in 100 mL of THF (tetrahydrofuran), the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) with a 1 cm square quartz cell. The maximum absorption wavelength was 695.0 nm, and the molar extinction coefficient (ε) was 1.11 × 10⁻¹⁰. 5 That was the case.

[0295] <Phthalocyanine compound D> 5.00 g (25.0 mmol) of tetrafluorophthalonitrile, 6.90 g (50.0 mmol) of potassium carbonate, and 50 mL of acetonitrile were mixed. At room temperature, a solution of 8.21 g (50.0 mmol) of 4-t-amylphenol in acetonitrile (30 mL) was added, and the mixture was stirred for 5 hours. Then, it was heated to 80°C and stirred for a further 2 hours. After cooling the reaction mixture, it was filtered, and acetonitrile was removed from the filtrate using a rotary evaporator. Ethanol was added, and recrystallization was performed. The resulting solid was filtered, and 7.20 g (yield 59%, purity 91.4%) of intermediate D was obtained by vacuum drying. Note that this purity is an area percentage value calculated from the results of high-performance liquid chromatography analysis.

[0296] [ka]

[0297] 1 H-NMR (CDCl3) δ:0.66(t,6H), 1.25(s,12H), 1.60(q,4H), 6.71(d,4H), 7.20(d,4H)

[0298] 4.95 g (10.5 mmol) of intermediate D, 1.00 g (3.14 mmol) of zinc iodide, and 10 g of benzonitrile were mixed and reacted at 160°C for 6 hours. After the reaction was complete, the reaction mixture was cooled and added to 100 mL of methanol. The resulting solid was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 4.46 g (84% yield) of phthalocyanine compound D.

[0299] [ka]

[0300] When 1 mg of phthalocyanine compound D was dissolved in 100 mL of DMSO, the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) with a 1 cm square quartz cell. The maximum absorption wavelength was 701.0 nm, and the molar extinction coefficient (ε) was 1.248 × 10⁻⁶. 5 That was the case.

[0301] <Phthalocyanine compound E> 5.00 g (25.0 mmol) of tetrafluorophthalonitrile, 6.90 g (50.0 mmol) of potassium carbonate, and 85 mL of acetone were mixed and cooled on ice. At 2-4°C, a solution of 7.60 g (50.0 mmol) of p-methyl hydroxybenzoate in 30 mL of acetone was added, and the mixture was stirred for 6 hours. The reaction mixture was filtered, and acetone was removed from the filtrate using a rotary evaporator. Ethanol was added, and recrystallization was performed. The resulting solid was filtered, and 7.20 g (yield 62%, purity 91.5%) of intermediate E was obtained by vacuum drying. Note that this purity is an area percentage value calculated from the results of high-performance liquid chromatography analysis.

[0302] [ka]

[0303] In the formula, Me represents methyl.

[0304] 1 H-NMR (CDCl3) δ:3.91(s,6H), 6.80(d,4H), 7.97(d,4H)

[0305] 5.00 g (10.8 mmol) of intermediate E, 1.03 g (3.23 mmol) of zinc iodide, and 12 mL of benzonitrile were mixed and reacted at 170°C for 9 hours. After the reaction was complete, the reaction mixture was cooled and added to 20 mL of methanol. The resulting solid was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 4.46 g (85% yield) of phthalocyanine compound E.

[0306] [ka]

[0307] In the formula, Me represents methyl.

[0308] 1 H-NMR (DMSO-d6) δ:3.82(s,24H), 7.25(d,16H), 7.78(d,16H)

[0309] When 1 mg of phthalocyanine compound E was dissolved in 100 mL of DMSO, the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) with a 1 cm square quartz cell. The maximum absorption wavelength was 665.0 nm, and the molar extinction coefficient (ε) was 1.190 × 10⁻⁶. 5 That was the case.

[0310] <Phthalocyanine compound F> 3.02 g (15.0 mmol) of tetrafluorophthalonitrile, 4.14 g (30.0 mmol) of potassium carbonate, and 50 mL of acetone were mixed and cooled on ice. At 2-4°C, a solution of 5.40 g (30.0 mmol) of n-propyl p-hydroxybenzoate in 30 mL of acetone was added, and the mixture was stirred for 5 hours. The reaction mixture was filtered, and acetone was removed from the filtrate using a rotary evaporator. Ethanol was added, and recrystallization was performed. The resulting solid was filtered, and 4.0 g (yield 51%, purity 95.9%) of intermediate F was obtained by vacuum drying. Note that this purity is an area percentage value calculated from the results of high-performance liquid chromatography analysis.

[0311] [ka]

[0312] In the formula, n-Pr represents n-propyl.

[0313] 1 H-NMR (CDCl3) δ:1.03(t,6H), 1.78(m,4H), 4.29(t,4H), 6.82(d,4H), 7.98(d,4H)

[0314] 1.00 g (2.15 mmol) of intermediate F, 0.21 g (0.65 mmol) of zinc iodide, and 2.4 mL of benzonitrile were mixed and reacted at 170°C for 13 hours. After the reaction was complete, the reaction mixture was cooled and added to 20 mL of methanol. The resulting solid was filtered, washed with methanol and water, and dried under reduced pressure at 50°C to obtain 0.33 g (yield 29%) of phthalocyanine compound F.

[0315] [ka]

[0316] In the formula, n-Pr represents n-propyl.

[0317] 1 H-NMR (DMSO-d6) δ:0.94(t,24H), 1.88(m,16H), 4.16(t,16H), 7.25(d,16H), 7.78(d,16H)

[0318] When 1 mg of phthalocyanine compound F was dissolved in 100 mL of DMSO (dimethyl sulfoxide), the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) with a 1 cm square quartz cell. The maximum absorption wavelength was 665.0 nm, and the molar extinction coefficient (ε) was 1.202 × 10⁻¹⁰. 5 That was the case.

[0319] <Phthalocyanine compound G> 2.00 g (10 mmol) of tetrafluorophthalonitrile, 1.45 g (2.5 mmol) of potassium fluoride, and 5 mL of acetone were mixed and cooled on ice. Then, a solution of 3.78 g (21 mmol) of methyl 3-(4-hydroxyphenyl)propanoate in 5 mL of acetone was added, and the mixture was stirred for 5 hours. After the reaction was complete, the reaction mixture was extracted with chloroform-water, the organic layer was extracted with saturated brine, and the concentrated mixture was purified by medium-pressure preparative liquid chromatography (using a mixed solvent of hexane and ethyl acetate as the developing solvent, with a gradient of 94:6 to 73:27 (volume ratio)) to obtain 3.00 g (yield 58%, purity 97.8%) of intermediate G. Note that this purity is an area percentage value calculated from the results of high-performance liquid chromatography analysis.

[0320] [ka]

[0321] 1 H-NMR (CDCl3) δ:2.58(t,2H), 2.90(t,2H), 3.67(s,3H), 6.70(d,2H), 7.09(d,2H)

[0322] 1.04 g (2.00 mmol) of intermediate G, 0.19 g (0.6 mmol) of zinc iodide, and 2 mL of benzonitrile were mixed and reacted at 160°C for 8 hours. After the reaction was complete, the reaction mixture was cooled and purified by medium-pressure preparative liquid chromatography (using a mixed solvent of chloroform and methanol as the developing solvent, with a gradient of 100:0 to 93:7 (volume ratio)) to obtain 0.75 g (70% yield) of phthalocyanine compound G.

[0323] [ka]

[0324] When 1 mg of phthalocyanine compound G was dissolved in 100 mL of DMSO, the visible absorption spectrum was measured using a UV-Vis spectrophotometer (Hitachi High-Technologies Corporation U-4100) with a 1 cm square quartz cell. The maximum absorption wavelength was 700.0 nm, and the molar extinction coefficient (ε) was 2.278 × 10⁻⁶. 5 That was the case.

[0325] <Dispersant A: Dispersant "BYK-LPN6919" ​​manufactured by BIC Chemie Co., Ltd.> A methacrylic acid-based AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. It has repeating units of the following formulas (2a) and (3a), but does not have repeating units of the following formula (1a). The amine value is 120 mgKOH / g and the acid value is 1 mgKOH / g or less.

[0326] The proportions of the following formulas (2a) and (3a) in the total repeating units are 33.3 mol% and 6.7 mol%, respectively.

[0327] [ka]

[0328] <Preparation of Green Pigment Dispersion 1> 11.0 parts by mass of CI Pigment Green 58, 1.6 parts by mass of Dispersant A (on a solids basis), 3.3 parts by mass of Alkali-Soluble Resin A (as described later) (on a solids basis), 84.1 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including solvents derived from Dispersant A and Alkali-Soluble Resin A), and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed in a paint shaker for 6 hours. After dispersion, the beads and dispersion were separated by filter to prepare Green Pigment Dispersion 1.

[0329] <Preparation of Green Pigment Dispersion 2> 11.0 parts by mass of CI Pigment Green 59, 1.6 parts by mass of Dispersant A (on a solids basis), 3.3 parts by mass of Alkali-Soluble Resin A (as described later) (on a solids basis), 84.1 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including solvents derived from Dispersant A and Alkali-Soluble Resin A), and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed in a paint shaker for 6 hours. After dispersion, the beads and dispersion were separated by filtration to prepare Green Pigment Dispersion 2.

[0330] <Alkali-soluble resin A> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen purging and heated to 120°C. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 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 27 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, 52 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. After cooling to room temperature, an alkali-soluble resin A was obtained with a polystyrene-based weight-average molecular weight Mw of 8000 and an acid value of 80 mgKOH / g, as measured by GPC.

[0331] <Photopolymerizable monomer A> A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0332] <Photopolymerizable monomer B> Succinic anhydride modified product of the reaction between dipentaerythritol and acrylic acid

[0333] <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)

[0334] [ka]

[0335] In the formula, Me represents methyl.

[0336] <Surfactant A> Megafuck (registered trademark) F-559 (manufactured by DIC Corporation)

[0337] <Preparation of colored resin composition> Each component was mixed according to the solid content ratio and solvent ratio described in Tables 1 and 2 to prepare colored resin compositions with a total solid content of 15% by mass. "Solid content ratio" refers to the ratio (by mass) of the solid content of each component to the total solid content. "Solvent ratio" refers to the ratio (by mass) of each solvent to the total solvent, and the amount of each solvent includes solvents derived from alkali-soluble resins and pigment dispersions. In Comparative Examples 7 and 8, the content of CI Pigment Green 58 and CI Pigment Green 59 was set to 40.0% by mass of the total solid content.

[0338] [Table 1]

[0339] [Table 2]

[0340] Further details about the various solvents listed in Tables 1 and 2 are provided in Table 3. The boiling points (°C) in the tables are values ​​at 1013.25 hPa.

[0341] [Table 3]

[0342] <Evaluation of alkaline development time and residue on glass substrate> An evaluation substrate was obtained by applying the above-mentioned colored resin composition to a 50mm square, 0.7mm thick glass substrate (AGC Corporation, AN100) using a spin coater so that the film thickness after drying was 2.3μm, and then drying it at 80°C for 3 minutes. The evaluation substrate was developed using a 0.4% by mass potassium hydroxide aqueous solution at 23°C, and the time until the coating film dissolved and the substrate surface was exposed (dissolution time) was measured.

[0343] Next, the evaluation substrate obtained using the same procedure was subjected to a developing treatment using a 0.4 mass% potassium hydroxide aqueous solution at 23°C for twice the dissolution time, and then 1 kg / cm³ was added. 2 Residue evaluation substrate 1 was prepared by spray washing with water pressure for 10 seconds. Residue evaluation substrate 2 was prepared using the same procedure, except that the development time was changed to 60 seconds.

[0344] Visual inspection was performed on the residue evaluation substrate 1. The area of ​​the part where no residue was observed (A) and the area of ​​the part where residue was observed (B) were measured on a 50 mm square glass substrate, and the residue generation area ratio (%) was evaluated as (B) / {(A)+(B)}×100. The results are shown in Table 4.

[0345] [Table 4]

[0346] Next, the residue evaluation substrate 2 was also visually inspected, and the residue generation area ratio (%) was evaluated in the same manner as the residue evaluation substrate 1. The results were as follows: Example 1: 1%, Example 2: 0%, Example 3: 1%, Example 4: 0%, Example 5: 0%, Example 6: 0%, Example 7: 0%, Example 8: 0%, Example 9: 0%, Example 10: 0%, Example 11: 1%, Example 12: 0%, Example 13: 0%, Example 14: 0%, Example 15: 1%, and Example 16: 1%.

[0347] <Color Characteristics Evaluation> The colored resin compositions of Examples 1, 4, 8, 13, 14, 15, 16, Comparative Examples 5, 6, 7, and 8 were applied to a 50mm square, 0.7mm thick glass substrate (AGC, AN100) using a spin coater, and then dried at 80°C for 3 minutes. Subsequently, a 40mJ / cm³ high-pressure mercury lamp was used to heat the substrate. 2 The entire surface was exposed with the specified exposure level. Then, development was performed using a 0.4% potassium hydroxide aqueous solution at 23°C. Next, 3 kg / cm³ was applied. 2A colored resin composition coated substrate was prepared by spray washing with water at a water pressure of 0 for 10 seconds. Subsequently, a heat curing treatment was performed at 230°C for 30 minutes to create a colored substrate with a film thickness of 2.0 μm. The transmission spectrum of the obtained colored substrate was measured using a Hitachi U-3310 spectrophotometer with a C light source, and the chromaticity (sx, sy) and luminance were calculated. In Example 1, the chromaticity was sx=0.220, sy=0.460, and luminance LY was 58.7. In Example 4, the chromaticity was sx=0.220, sy=0.460, and luminance LY was 58.8. In Example 8, the chromaticity was sx=0.220, sy=0.460, and luminance LY was 58.7. Furthermore, in Example 13, the chromaticity was sx=0.249, sy=0.355, and the luminance LY was 65.4; in Example 14, the chromaticity was sx=0.266, sy=0.341, and the luminance LY was 79.9; in Example 15, the chromaticity was sx=0.224, sy=0.459, and the luminance LY was 58.3; and in Example 16, the chromaticity was sx=0.228, sy=0.466, and the luminance LY was 57.3. Comparative Example 5 had a chromaticity of sx=0.219, sy=0.425, and a luminance LY of 50.0. Comparative Example 6 had a chromaticity of sx=0.297, sy=0.428, and a luminance LY of 47.3. Comparative Example 7 had a chromaticity of sx=0.238, sy=0.556, and a luminance LY of 51.6. Comparative Example 8 had a chromaticity of sx=0.172, sy=0.483, and a luminance LY of 38.5.

[0348] Furthermore, when the surfaces of the colored substrates from Examples 1 to 12, which were prepared using the same procedure, were visually inspected, no foreign matter was observed.

[0349] As is clear from Table 4, in the colored resin composition containing phthalocyanine compound (1), when a high-boiling point solvent with a boiling point of 160°C or higher was not included, as in Comparative Examples 1 to 4, a large amount of residue was generated on the glass substrate. Because phthalocyanine compound (1) has high solubility in solvents and does not require a dispersion process, there are almost no dispersants or alkali-soluble resins around phthalocyanine compound (1), and it is thought that the affinity between phthalocyanine compound (1) and alkali-soluble resin is weak in the colored resin composition. In particular, phthalocyanine compound (1) readily associates with other molecules due to π-π interactions between phthalocyanine rings and π-π interactions between the groups represented by formula (2) above. Furthermore, the presence of fluorine atoms with small atomic radii results in denser packing between molecules, leading to a weak affinity with alkali-soluble resin. This makes it difficult for the alkaline developer to penetrate phthalocyanine compound (1) during alkaline development, resulting in reduced alkali solubility and a tendency for residue to remain on the glass substrate.

[0350] In contrast, as shown in Examples 1 to 16, when a colored resin composition containing phthalocyanine compound (1) contains a high-boiling-point solvent with a boiling point of 160°C or higher, almost no residue is generated on the glass substrate. In particular, as shown in Examples 6, 8, 9, and 10, when the boiling point of the solvent is high or when the content of a solvent with a boiling point of 160°C or higher is high, no residue is generated on the glass substrate at all. This is thought to be because the inclusion of a high-boiling-point solvent with a boiling point of 160°C or higher suppresses drying of the coating film during the alkaline development process, resulting in a sufficiently moist state. This allows the alkaline developer to penetrate deeply into the coating film, promoting the neutralization reaction, and ensuring that the phthalocyanine compound (1) is sufficiently dissolved in the alkaline developer, thus reducing the generation of residue derived from the colored resin composition on the glass substrate.

[0351] On the other hand, a comparison of Comparative Examples 1 with Comparative Examples 5 and 6 in Table 4 shows that phthalocyanine compounds B and C, which do not satisfy formula (1), have a larger residue area than phthalocyanine compound (1). This is thought to be because phthalocyanine compound B has chlorine atoms instead of fluorine atoms, which lowers the polarity of the phthalocyanine compound and thus reduces its solubility in highly polar developer (alkaline aqueous solution). Furthermore, phthalocyanine compound C has copper as its central metal, which lowers the ionization tendency of the phthalocyanine compound and thus reduces its solubility in developer (alkaline aqueous solution). Furthermore, as mentioned above, Example 1 exhibits higher brightness compared to Comparative Examples 5 and 6. This is thought to be because the phthalocyanine compound (1) contained in Example 1 has a fluorine atom, which increases the polarity of the phthalocyanine compound, resulting in higher solubility in the solvent in the colored resin composition and suppression of aggregation between phthalocyanine compounds. Additionally, the presence of zinc as the central metal optimizes the crystal structure.

[0352] Furthermore, as in Comparative Examples 7 and 8, in colored resin compositions containing a green pigment instead of phthalocyanine compound (1), a large amount of dispersion resin and dispersant are present near the green pigment in the colored resin composition, resulting in a strong affinity with the alkali-soluble resin. This is thought to result in high alkali solubility of the green pigment, and less residue remaining on the glass substrate despite the absence of high-boiling point solvents with a boiling point of 160°C or higher. [Explanation of Symbols]

[0353] 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, and (D) a photopolymerization initiator, 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 solvent (B) contains a high-boiling point solvent having a boiling point of 175°C or higher at 1013.25 hPa (excluding those containing N-methylpyrrolidone). 【Chemistry 1】 (In formula (1), A 1 ~A 16 Each of these independently represents a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, A 1 ~A 16 One or more of these represent a fluorine atom, and A 1 ~A 16 One or more of these represent a base expressed by the following general formula (2). 【Chemistry 2】 (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent only at the p-position when viewed from the position where X is substituted. * represents a bond.)

2. The colored resin composition according to claim 1, wherein the content of solvent (B) in the colored resin composition is 50% by mass or more.

3. The colored resin composition according to claim 1 or 2, wherein the content of the high-boiling point solvent in the solvent (B) is 0.5% by mass or more.

4. The colored resin composition according to any one of claims 1 to 3, wherein the content of the phthalocyanine compound is 5% by mass or more in the total solid content.

5. The colored resin composition according to any one of claims 1 to 4, wherein the (D) photopolymerization initiator comprises an oxime ester-based photopolymerization initiator.

6. A color filter having pixels created using the colored resin composition described in any one of claims 1 to 5.

7. An image display device having the color filter described in claim 6.

Images