Colored resin composition, color filter, and image display device

Abstract

A colored resin composition having a small influence of temperature variation of pre-baking on sensitivity is provided. The colored resin composition of the present invention contains a colorant including a phthalocyanine-based dye having a chemical structure represented by formula (1), a solvent, an alkali-soluble resin, and a photopolymerization initiator including a photopolymerization initiator (d1) represented by formula (I). (In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom or the like, and one or more groups represented by formula (2). In formula (2), X represents a divalent linking group, a benzene ring optionally has a substituent, and * represents a bonding site. In formula (I), R d1 represents an alkyl group optionally having a substituent or the like, R d2 represents an alkyl group optionally having a substituent or the like, p represents 0 or 1, and R d3 represents an aromatic ring group optionally having a substituent.)

Description

Technical Field

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

[0002] This application claims priority based on Japanese Special Petition No. 2020-139037 filed with Japan on August 20, 2020, the contents of which are incorporated herein by reference. Background Technology

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

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

[0005] For example, the use of phthalocyanine dyes for green pixel applications is being investigated (e.g., see Patent Document 1), and the use of xatonite dyes for blue pixel applications is also being investigated (e.g., see Patent Document 2).

[0006] On the other hand, Patent Document 3 describes a curable composition containing a specific photopolymerization initiator that can balance sensitivity, transparency, and brightness.

[0007] Existing technical documents

[0008] Patent documents

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

[0010] Patent Document 2: International Publication No. 2018 / 052022

[0011] Patent Document 3: Japanese Patent Application Publication No. 2017-179211 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] The inventors conducted research and found that the sensitivity of the dye-containing coloring resin compositions described in Patent Documents 1 and 2 changes significantly depending on the temperature during pre-baking (the drying process of the coating before the exposure process), especially in the low-temperature region, where the pattern size changes drastically. Therefore, it is evident that there is a problem in the stable manufacture of high-precision color filters, such as those represented by 4K and 8K, which require precise linewidth adjustment.

[0014] Furthermore, Patent Document 3 does not evaluate the composition containing the dye, and it is unclear what characteristics the composition containing the dye will exhibit.

[0015] Therefore, the object of the present invention is to provide a coloring resin composition in which the temperature change during pre-baking has little effect on sensitivity.

[0016] Solution for solving the problem

[0017] The inventors conducted in-depth research and discovered that the above-mentioned problems could be solved by using a specific photopolymerization initiator in a coloring resin composition containing a specific dye, thus completing the present invention.

[0018] That is, the present invention has the following [1] to [8] configuration.

[0019] [1] A coloring resin composition, characterized in that it contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin and (D) a photopolymerization initiator.

[0020] The colorant (A) described above comprises phthalocyanine dyes having the chemical structure shown in the following general formula (1).

[0021] The above-mentioned (D) photopolymerization initiator includes the photopolymerization initiator (d1) shown in the following general formula (I).

[0022]

[0023] (In formula (1), A) 1 ~A 16 Each of these can independently represent a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below. Wherein, A 1 ~A 16 One or more of them represent the groups shown in the general formula (2) below.

[0024]

[0025] (In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.)

[0026]

[0027] (In formula (I), R) d1 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0028] R d2 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0029] p represents 0 or 1.

[0030] R d3 (This indicates an aromatic cyclic group with optional substituents.)

[0031] [2] According to the coloring resin composition of [1], wherein, in the above formula (1), A 1 ~A 16 Six or more in the character represent fluorine atoms.

[0032] [3] A coloring resin composition, characterized in that it contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin and (D) a photopolymerization initiator.

[0033] The colorant (A) described above comprises a xatonne dye having the chemical structure shown in the following general formula (10).

[0034] The above-mentioned (D) photopolymerization initiator includes the photopolymerization initiator (d1) shown in the following general formula (I).

[0035]

[0036] (In equation (10), R) a1 ~R a4 Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0037] R a5 Indicates -SO 3- or -COO - .

[0038] n represents an integer from 1 to 5.

[0039]

[0040] (In formula (I), R) d1 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0041] R d2 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0042] p represents 0 or 1.

[0043] R d3 (This indicates an aromatic cyclic group with optional substituents.)

[0044] [4] A coloring resin composition according to any one of [1] to [3], wherein, in the above-mentioned photopolymerization initiator (d1), R d3 It is a benzene ring with one free valence and optionally substituents.

[0045] [5] A coloring resin composition according to any one of [1] to [4], wherein the content of the colorant (A) is 15% by mass or more in the total solids.

[0046] [6] The coloring resin composition according to any one of [1] to [5], wherein the content of the above-mentioned photopolymerization initiator (d1) is 1.0% by mass or more in the total solids content.

[0047] [7] A color filter having pixels made using a coloring resin composition of any one of [1] to [6].

[0048] [8] An image display device having a color filter of [7].

[0049] The effects of the invention

[0050] According to the present invention, a coloring resin composition in which the temperature change during pre-baking has little effect on sensitivity can be provided. Attached Figure Description

[0051] Figure 1 This is a cross-sectional schematic diagram illustrating an example of an organic EL display element having the color filter of the present invention. Detailed Implementation

[0052] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) of polystyrene obtained using GPC (gel permeation chromatography).

[0053] In this invention, "total solids content" refers to all components in the coloring resin composition except for the solvent. Even if a component other than the solvent is liquid at room temperature, it is not contained in the solvent but is included in the total solids content.

[0054] In this invention, unless otherwise specified, "amine value" refers to the amine value converted from the effective solid component, which is expressed as the mass of KOH equivalent to the amount of alkali per 1g of dispersant solid component.

[0055] In this invention, "CI" refers to the Color Index.

[0056] [1] Coloring resin composition

[0057] The components of the coloring resin composition of the present invention will be described below.

[0058] The coloring resin composition of the first embodiment of the present invention comprises (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator. The (A) colorant comprises a phthalocyanine dye having the chemical structure shown in general formula (1) described later, and the (D) photopolymerization initiator comprises the photopolymerization initiator (d1) described later. The coloring resin composition of this embodiment may also be further formulated with other additives besides the above-mentioned components as needed.

[0059] The second embodiment of the coloring resin composition of the present invention comprises (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator. The (A) colorant comprises a xanthan dye having the chemical structure shown in general formula (10) described later, and the (D) photopolymerization initiator comprises the photopolymerization initiator (d1) described later. The coloring resin composition of this embodiment may also be further formulated with other additives besides the above-mentioned components as needed.

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

[0061] The coloring resin composition of the present invention comprises (A) a colorant. The colorant is a component that colors the coloring resin composition. By comprising (A) the colorant, desired light absorption properties can be obtained.

[0062] The colorant (A) in the coloring resin composition of the present invention comprises a dye. By including the dye, the transmittance is increased, resulting in a high-brightness coloring resin composition.

[0063] The dyes in this invention refer to pigment compounds that are soluble in specific organic solvents. Specific organic solvents may include, for example, those exemplified in the solvent column described below, with propylene glycol monomethyl ether acetate being particularly preferred.

[0064] In the coloring resin composition of the first aspect of the present invention, (A) the colorant comprises a phthalocyanine dye having the chemical structure shown in the following general formula (1) (hereinafter sometimes referred to as "phthalocyanine dye (1)").

[0065]

[0066] In equation (1), A 1 ~A 16 Each of these can independently represent a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below. Wherein, A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0067]

[0068] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.

[0069] (A 1 ~A 16 )

[0070] In the above formula (1), A 1 ~A 16 Each of these can independently represent a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below. Wherein, A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2).

[0071]

[0072] In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may optionally have any substituents. * indicates a linking bond.

[0073] As A 1 ~A 16 Halogen atoms in the solution can be, for example, fluorine, chlorine, or bromine atoms. From the perspective of maximizing brightness, fluorine atoms are preferred.

[0074] A 1 ~A 16 In this composition, 6 or more, more preferably 7 or more, and even more preferably 8 or more are fluorine atoms; and 15 or fewer, more preferably 12 or fewer, and even more preferably 10 or fewer are fluorine atoms. By setting the value to the lower limit or above, the stability of the phthalocyanine dye (1) tends to be improved. By setting the value to the upper limit or below, the affinity with the dispersant and solvent in the coloring resin composition tends to be improved.

[0075] The aforementioned upper and lower limits can be combined arbitrarily. For example, preferred option A is preferred. 1 ~A 16 Of these, 6 to 15, more preferably 7 to 12, and even more preferably 8 to 10 are fluorine atoms.

[0076] (X)

[0077] In the above general formula (2), X represents a divalent linking group. There are no particular limitations on the divalent linking group; examples include oxygen atoms, sulfur atoms, or -N(R) atoms. a1 )-group (R a1 (This refers to a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.) Among these, from the viewpoint of stability during firing, oxygen atoms or sulfur atoms are preferred, and oxygen atoms are more preferred.

[0078] (The benzene ring may contain any substituents)

[0079] The benzene ring in formula (2) may optionally have any substituents. Acceptable substituents are not particularly limited, but may include, for example, halogen atoms, alkyl groups, alkoxy groups (-OR groups). A base (R) A Indicates alkyl group. )), alkoxycarbonyl group (-COOR) A base (R) A Indicates alkyl, aryl, aryloxy (-OR) B base (R) B (representing aryl group) and aryloxycarbonyl group (-COOR) B base (R) B (This indicates an aryl group.) Among these, from the viewpoint of developing solubility and brightness, alkoxycarbonyl groups are preferred.

[0080] The alkyl groups contained in these groups can be linear, branched, or cyclic. From the viewpoint of affinity for organic solvents, linear groups are preferred.

[0081] The number of carbon atoms in the alkyl group is not particularly limited, but is generally 1 or more, preferably 2 or more, and more preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. By setting it to the lower limit or above, there is a tendency to suppress aggregation, thereby suppressing foreign matter. By setting it to the upper limit or below, there is a tendency to improve solvent affinity and improve stability over time.

[0082] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, even more preferably 1 to 4, and particularly preferably 2 to 4.

[0083] Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. From the viewpoint of suppressing aggregation, methyl or ethyl is preferred, and ethyl is more preferred.

[0084] The aryl groups contained in these groups can be aromatic hydrocarbon cyclic groups or aromatic heterocyclic groups.

[0085] The number of carbon atoms in the aryl group is not particularly limited, but is generally 4 or more, preferably 6 or more, further preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By setting it to the lower limit or above, there is a tendency to suppress aggregation through steric repulsion. By setting it to the upper limit or below, there is a tendency to improve solvent affinity and stability over time.

[0086] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aryl group is preferably 4 to 12, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 6 to 8.

[0087] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or a fused ring. Examples of aromatic hydrocarbon cyclic groups include benzene rings, naphthalene rings, pentanene rings, indene rings, azurite rings, and heptene rings, which have one free valence.

[0088] Aromatic heterocycles, as part of aromatic heterocyclic groups, can be either monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thioran rings, pyridine rings, 1,3-oxazole rings, isoxazole rings, 1,3-thiazole rings, isothiazole rings, imidazole rings, pyrazole rings, furazine rings, pyrazine rings, pyrimidine rings, pyridazine rings, 1,3,5-triazine rings, benzofuran rings, 2-benzofuran rings, benzothiophene rings, 2-benzothiophene rings, 1H-pyrrolidine rings, indole rings, isoindole rings, indoleazine rings, 2H-1-benzopyran rings, 1H-2-benzopyran rings, quinoline rings, isoquinoline rings, 4H-quinazine rings, benzimidazole rings, 1H-indazole rings, quinoxaline rings, quinazoline rings, cyclophosphine rings, phthalazine rings, 1,8-naphthidine rings, purine rings, and pteridine rings.

[0089] When the benzene ring in formula (2) has any substituents, the number of substitutions is not particularly limited. From the viewpoint that the heat resistance is improved by the π-π stacking of dye molecules and the decrease in brightness caused by the decomposition of dye is suppressed, it is preferable that the number of substitutions relative to one benzene ring is 1.

[0090] When the benzene ring in formula (2) has any substituent, the substitution position can be ortho, meta, or para. From the point of view that the densest packing structure can be achieved, the para position is preferred.

[0091] A 1 ~A 16 One or more of the groups in the formula (2) above represent the groups shown in the formula. From the viewpoint of solubility in organic solvents and brightness, A is preferred. 1 ~A 4 One or more of them are groups represented by the general formula (2) above, A 5 ~A 8 One or more of them are groups represented by the general formula (2) above, A 9 ~A 12 One or more of them are groups represented by the general formula (2) above, and A 13 ~A 16 One or more of them are groups represented by the general formula (2) above, more preferably A. 1 ~A 4 Two or more of them are groups represented by the general formula (2) above, A 5 ~A 8 Two or more of them are groups represented by the general formula (2) above, A9 ~A 12 Two or more of them are groups represented by the general formula (2) above, and A 13 ~A 16 Two or more of them are groups represented by the general formula (2) above.

[0092] In particular, from the viewpoint of suppressing brightness loss through efficient stacking, A is especially preferred. 2 A 3 A 6 A 7 A 10 A 11 A 14 and A 15 The group is represented by the general formula (2) above, and A 1 A 4 A 5 A 8 A 9 A 12 A 13 and A 16 It is a halogen atom.

[0093] Specific examples of phthalocyanine dyes (1) include the following compounds.

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] As a method for manufacturing phthalocyanine dyes (1), known methods can be used, for example, the method described in Japanese Patent Application Publication No. 05-345861.

[0100] In the second aspect of the coloring resin composition of the present invention, (A) the colorant comprises a xatonne dye having the chemical structure shown in the following general formula (10) (hereinafter sometimes referred to as "xatonne dye (10)").

[0101]

[0102] In equation (10), R a1 ~R a4 Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0103] Ra5 Indicates -SO 3- or -COO - .

[0104] n represents an integer greater than 1 and less than 5.

[0105] (R a1 ~R a4 )

[0106] In the above formula (10), R a1 ~R a4 Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0107] As R a1 ~R a4 The alkyl group in the formula can be linear, branched, or cyclic. It typically has 1 or more carbon atoms, preferably 2 or more, and more preferably 12 or less, and more preferably 6 or less. Setting it to the lower limit or above tends to improve heat resistance and suppress brightness loss. Setting it to the upper limit or below tends to improve developability and solubility.

[0108] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 2 to 6.

[0109] Examples of alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and 3-methylbutyl. From the viewpoint of ease of synthesis, ethyl, n-propyl, and n-butyl are preferred, and n-butyl is more preferred.

[0110] Substituents optionally present in the alkyl group can be, for example, those described in the substituent group W1 below. Examples of alkyl groups with substituents include phenethyl, 2-ethoxyethyl, 4,4,4-trifluorobutyl, aniline, vanillyl, and N-acetamide phenylbutyl.

[0111] As R a1 ~R a4 The aromatic cyclic group in the formula can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. It typically has 4 or more carbon atoms, preferably 6 or more, and more preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting it to the lower limit or above tends to improve heat resistance and suppress brightness loss. Setting it to the upper limit or below tends to improve developability and solubility.

[0112] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 6 to 8.

[0113] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0114] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cyclophosphine rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings.

[0115] From the viewpoint of heat resistance and ease of synthesis, a benzene ring or naphthalene ring with one free valence is preferred, and a benzene ring with one free valence is more preferred.

[0116] Substituents that can be optionally present in an aromatic cyclic group include, for example, groups described in substituent group W2 as described later.

[0117] From the perspective of heat resistance, R a1 and R a2 Each is preferably an aromatic cycloalloy with substituents, more preferably a phenyl group substituted with an alkyl group, and even more preferably a phenyl group with two ortho-positions substituted with alkyl groups.

[0118] From the viewpoint of solubility in developer, R a3 and R a4 Each is preferably an alkyl group with substituents, independently and preferably.

[0119] (R a5 )

[0120] In the above formula (10), R a5 Indicates -SO 3- or -COO - From a brightness perspective, -SO is preferred. 3- R a5 When there are multiple Rs, each R a5 They can be the same or different.

[0121] In the above formula (10), n represents an integer of 1 or more and 5 or less. By setting it to the lower limit or above, there is a tendency to improve solvent affinity and development solubility. By setting it to the upper limit or below, there is a tendency to suppress the aggregation between dyes and improve the long-term stability of the coloring resin composition. For example, n is preferably an integer of 1 or more and 3 or less.

[0122] When n in the above formula (10) is an integer of 2 or more, the xanthan dye (10) preferably forms a salt. As a cation, alkali metals and alkaline earth metals are preferred, alkaline earth metals are more preferred, and calcium is particularly preferred.

[0123] Among the succinate dyes shown in the above formula (10), from the viewpoint of brightness and contrast, the succinate dyes shown in the following general formula (11) are preferred.

[0124]

[0125] In equation (11), R 1 and R 2 Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0126] R 3 and R 4 Each can be independently represented as a divalent hydrocarbon group with a substituent.

[0127] R 5 and R 6 Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0128] R 7 Indicates -SO 3- or -COO - .

[0129] The -CH2- group in the alkyl group, aromatic cyclo group, and hydrocarbon group is optionally selected from -O-, -CO-, -COO-, -CONH-, and -CONR. 8 -、-NH-、-NR 8 -, -SO2-, -SO2NH-, -SO2NR 8 At least one of the groups consisting of - and -S- is substituted. R 8 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0130] (R 1 R 2 )

[0131] In equation (11) above, R 1 and R 2Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0132] As R 1 and R 2 The alkyl group in the formula can be linear, branched, or cyclic. It typically has 1 or more carbon atoms, preferably 2 or more, and more preferably 12 or less, more preferably 6 or less. Setting the formula to the lower limit or above tends to improve heat resistance and suppress brightness loss. Setting the formula to the upper limit or below tends to improve solubility in the developer and suppress residue.

[0133] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 2 to 6.

[0134] Examples of alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and 3-methylbutyl. From the viewpoint of ease of synthesis, ethyl is preferred.

[0135] Substituents optionally present in the alkyl group can be, for example, those described in the substituent group W1 below. Examples of alkyl groups with substituents include phenethyl, 2-ethoxyethyl, and 4,4,4-trifluorobutyl.

[0136] As R 1 and R 2 The aromatic cyclic group in the solvent can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. It typically has 4 or more carbon atoms, preferably 6 or more, and more preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting it to the lower limit or above tends to improve heat resistance. Setting it to the upper limit or below tends to improve solubility in the developer and suppress residue.

[0137] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 6 to 8.

[0138] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0139] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cyclophosphine rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings.

[0140] From the viewpoint of heat resistance, a benzene ring or naphthalene ring with one free valence is preferred, and a benzene ring with one free valence is more preferred.

[0141] Substituents that can be optionally present in an aromatic cyclic group include, for example, groups described in substituent group W2 as described later.

[0142] From the perspective of heat resistance, R 1 and R 2 Each is preferably an aromatic ring having one free valence and optionally having substituents, more preferably a benzene ring having one free valence and being alkyl-substituted, and even more preferably a benzene ring having one free valence and having two ortho-substituted alkyl groups.

[0143] (R 3 R 4 )

[0144] In equation (11) above, R 3 and R 4 Each can be independently represented as a divalent hydrocarbon group with a substituent.

[0145] As divalent hydrocarbon groups, examples include straight-chain, branched, cyclic, or combined hydrocarbon groups. Examples include alkylene, aryl, and groups formed by the linkage of alkylene and aryl groups.

[0146] The divalent hydrocarbon group typically has 1 or more carbon atoms, preferably 3 or more, more preferably 6 or more, even more preferably 8 or more, and preferably 20 or less, more preferably 16 or less, even more preferably 14 or less, even more preferably 12 or less, and particularly preferably 11 or less. Setting the value to the lower limit or above tends to improve heat resistance. Setting the value to the upper limit or below tends to improve solubility in the developer and suppress residue.

[0147] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 20, more preferably 1 to 16, even more preferably 1 to 14, even more preferably 3 to 12, particularly preferably 6 to 11, and especially preferably 8 to 11.

[0148] Examples of alkylene compounds include methylene, ethylene, n-propylene, n-butylene, n-pentylene, cyclopentylene, n-hexylene, cyclohexylene, and n-heptylene. From the viewpoint of heat resistance and solubility, n-butylene is preferred.

[0149] Examples of arylene groups include ortho-, meta-, or para-phenylene, naphthylene, fluorenyl, indoleylene, anthraceneyl, furanyl, and thiopheneyl. From the viewpoint of ease of synthesis, phenylene is preferred.

[0150] Examples of groups formed by the linkage of alkylene and aryl groups include those composed of the aforementioned alkylene and phenylene groups. From the viewpoint of heat resistance and brightness, groups composed of butylene and p-phenylene groups are preferred.

[0151] Substituents that can be optionally present as divalent hydrocarbon groups include, for example, those described in the substituent group W3 described later.

[0152] From the perspective of heat resistance and brightness, R 3 and R 4 Each group is preferably formed by linking an alkylene group with a substituent to an aryl group with a substituent, and more preferably by combining a butylene group with a p-phenylene group.

[0153] (R 5 R 6 )

[0154] In equation (11) above, R 5 and R 6 Each can be independently represented as an alkyl group with optional substituents or an aromatic cycloal group with optional substituents.

[0155] As R 5 and R 6 The alkyl group in the solution can be linear, branched, or cyclic. It typically has 1 or more carbon atoms, preferably 12 or less, more preferably 6 or less, and even more preferably 2 or less. For example, 1 to 12 carbon atoms are preferred, more preferably 1 to 6, and even more preferably 1 to 2. By setting it to the above-mentioned upper limit or below, there is a tendency to improve solubility in the developer and suppress residue.

[0156] Examples of alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and 3-methylbutyl. From the viewpoint of ease of synthesis, methyl is preferred.

[0157] Substituents optionally present in the alkyl group can be, for example, those described in the substituent group W1 below. Examples of alkyl groups with substituents include phenethyl, 2-ethoxyethyl, and 4,4,4-trifluorobutyl.

[0158] As R 5 and R 6 The aromatic cyclic group in the formula can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. It typically has 4 or more carbon atoms, preferably 6 or more, and more preferably 12 or less. For example, 4 to 12 carbon atoms are preferred, and 6 to 12 carbon atoms are more preferred. By setting it to the lower limit or above, it tends to have high heat resistance. By setting it to the upper limit or below, it tends to have improved solubility in the developer and suppress residue.

[0159] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0160] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolin rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings, all having one free valence. From the viewpoint of heat resistance and ease of synthesis, a benzene ring or naphthalene ring with one free valence is preferred, and a benzene ring with one free valence is more preferred.

[0161] Substituents that can be optionally present in an aromatic cyclic group include, for example, groups described in substituent group W2 as described later.

[0162] From the viewpoint of solubility in developer, R 5 and R 6 Each of the components is preferably an alkyl group with substituents, and more preferably a methyl group.

[0163] (R7 )

[0164] In equation (11) above, R 7 Indicates -SO 3- or -COO - From a brightness perspective, -SO is preferred. 3- .

[0165] (Substitution of -CH2-)

[0166] R in equation (II) above 1 ~R 6 In this context, the -CH2- group contained in the alkyl group, the aromatic cyclo group, and the hydrocarbon group is optionally selected from -O-, -CO-, -COO-, -CONH-, and -CONR. 8 -、-NH-、-NR 8 -, -SO2-, -SO2NH-, -SO2NR 8 At least one substitution is made from the group consisting of - and -S. Among these, -O- and -COO- are preferred from the viewpoint of improved solvent affinity and stability over time.

[0167] Examples of divalent groups that can be substituted by these groups include -CH2CH2CH2CH2O- and -CH2CH2CH2CH2OCO-.

[0168] As R 8 Examples include alkyl groups optionally having substituents and aromatic cyclic groups optionally having substituents. From the viewpoint of solvent affinity, alkyl groups optionally having substituents are preferred.

[0169] As R 8 The alkyl group in the formula can be linear, branched, or cyclic. It typically has 1 or more carbon atoms, preferably 2 or more, and more preferably 12 or less, more preferably 6 or less, and even more preferably 3 or less. Setting it to the lower limit or above tends to improve heat resistance. Setting it to the upper limit or below tends to improve solvent affinity and stability over time.

[0170] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 2 to 3.

[0171] Examples of alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and 3-methylbutyl. From the viewpoint of ease of synthesis, ethyl is preferred.

[0172] The alkyl group may be optionally substituted with a group described in the substituent group W1 below.

[0173] As R 8 The aromatic cyclic group in the group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. It typically has 4 or more carbon atoms, preferably 6 or more, and more preferably 12 or less. For example, 2 to 12 carbon atoms are preferred, and 6 to 12 carbon atoms are more preferred. Setting it to the lower limit or above tends to improve heat resistance. Setting it to the upper limit or below tends to improve solvent affinity and stability over time.

[0174] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0175] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolin rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings, all having one free valence. From the viewpoint of brightness, a benzene ring or naphthalene ring with one free valence is preferred, and a benzene ring with one free valence is more preferred.

[0176] Substituents that can be optionally present in an aromatic cyclic group include, for example, groups described in substituent group W2 as described later.

[0177] (Replacement basis set W1)

[0178] Halogen atoms such as fluorine, chlorine, bromine, and iodine; alkenyl groups with 2 to 8 carbon atoms; alkoxy groups with 1 to 8 carbon atoms; aromatic hydrocarbon cyclic groups such as phenyl, mesitylene, tolyl, and naphthyl; cyano; carboxyl; acetoxy; alkyl carbonyloxy groups with 2 to 9 carbon atoms; aminosulfonyl; alkyl aminosulfonyl; alkyl carbonyl groups with 2 to 9 carbon atoms; phenethyl; hydroxyethyl; acetylamido group; dialkylaminoethyl groups bonded with alkyl groups with 1 to 4 carbon atoms; trifluoromethyl; trialkylsilyl with 1 to 8 carbon atoms; nitro; alkylthio groups with 1 to 8 carbon atoms.

[0179] Preferably, it consists of an alkoxy group, a cyano group, an acetoxy group, an alkyl carboxyl group, an aminosulfonyl group, an alkyl aminosulfonyl group, and a fluorine atom, which have 1 to 8 carbon atoms.

[0180] (Substituted basis set W2)

[0181] Halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups with 1 to 8 carbon atoms; alkenyl groups with 2 to 8 carbon atoms; hydroxyl groups; alkoxy groups with 1 to 8 carbon atoms: phenyl, mesitylene, tolyl, naphthyl, and other aromatic hydrocarbon cyclic groups; cyano; carboxyl; acetoxy; alkyl carbonyloxy groups with 2 to 9 carbon atoms; sulfonic acid groups; aminosulfonyl groups; alkyl aminosulfonyl groups with 2 to 9 carbon atoms; carbonyl groups; alkyl carbonyl groups with 2 to 9 carbon atoms; hydroxyethyl; acetamido; dialkylaminoethyl groups bonded with alkyl groups with 1 to 4 carbon atoms; trifluoromethyl; trialkylsilyl, nitro, and alkylthio groups with 1 to 8 carbon atoms.

[0182] Preferably, it is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, an acetoxy group having 2 to 8 carbon atoms, an alkyl carboxyl group having 2 to 8 carbon atoms, an aminosulfonyl group having 2 to 9 carbon atoms, and a fluorine atom.

[0183] (Replacement of basis set W3)

[0184] Halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups with 1 to 8 carbon atoms; alkenyl groups with 2 to 8 carbon atoms; alkoxy groups with 1 to 8 carbon atoms; aromatic hydrocarbon cyclic groups such as phenyl, mesitylene, tolyl, and naphthyl; cyano; carboxyl; acetoxy; alkyl carbonyloxy groups with 2 to 9 carbon atoms; aminosulfonyl; alkyl aminosulfonyl; alkyl carbonyl groups with 2 to 9 carbon atoms; phenethyl; hydroxyethyl; acetamido; dialkylaminoethyl bonded with alkyl groups with 1 to 4 carbon atoms; trifluoromethyl; trialkylsilyl with 1 to 8 carbon atoms; nitro; alkylthio with 1 to 8 carbon atoms.

[0185] Preferably, it consists of an alkoxy group, a cyano group, an acetoxy group, an alkyl carboxyl group, an aminosulfonyl group, an alkyl aminosulfonyl group, and a fluorine atom, which have 1 to 8 carbon atoms.

[0186] From the viewpoint of heat resistance and brightness, the xaton-based dyes shown in the above general formula (11) are preferably those shown in the following general formula (12).

[0187]

[0188] In equation (12), R 1 R 2 R 5 R 6 and R 7 R in equation (11) above 1 R 2 R5 R 6 and R 7 They have the same meaning.

[0189] R 9 and R 10 Each can be used independently to represent an alkylene group.

[0190] The -CH2- group in the aforementioned alkylene group may be optionally selected from -O-, -CO-, -COO-, -CONH-, or -CONR. 8 -、-NH-、-NR 8 -, -SO2-, -SO2NH-, -SO2NR 8 At least one of the groups consisting of - and -S- is substituted. R 8 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0191] (R 9 and R 10 )

[0192] In the above formula (12), R 9 and R 10 Each alkylene group is independently represented. The number of carbon atoms in the alkylene group is typically 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less. Setting the value to the lower limit or above tends to improve heat resistance. Setting the value to the upper limit or below tends to improve solvent affinity and stability over time.

[0193] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, even more preferably 2 to 6, and particularly preferably 3 to 4.

[0194] Examples of alkylene compounds include methylene, ethylene, n-propylene, n-butylene, n-pentylene, cyclopentylene, n-hexylene, cyclohexylene, and n-heptylene. From the viewpoint of solubility and heat resistance, n-butylene is preferred.

[0195] The -CH2- group in the alkylene group may be optionally selected from -O-, -CO-, -COO-, -CONH-, -CONR. 8 -、-NH-、-NR 8 -, -SO2-, -SO2NH-, -SO2NR 8 At least one of the groups consisting of - and -S- is substituted. R 8This indicates an alkyl group optionally having substituents, or an aromatic cyclic group optionally having substituents. Examples of alkylene groups substituted with at least one of these groups in -CH2- include -CH2CH2CH2CH2O-, -CH2CH2CH2CH2OCO-, etc. It should be noted that, as R... 8 The optional alkyl group having a substituent or the optional aromatic cyclic group having a substituent may be used as R in the above formula (11). 8 The listed groups.

[0196] As specific examples of succinyl dyes (10), the following succinyl dyes can be listed.

[0197]

[0198] Xanthan dyes (10) can be commercially available or synthesized using Xanthan dyes (such as “DCSF” manufactured by Chugai Chemical Co., Ltd.) as starting materials, with reference to Japanese Patent Application Publication No. 2013-253168.

[0199] (A) In addition to dyes, colorants may also contain other colorants. Examples of other colorants include pigments. Among these, green pigments, yellow pigments, etc., are preferred when used for green pixels. Furthermore, blue pigments, purple pigments, etc., are preferred when used for blue pixels.

[0200] As green pigments, CI pigments green 7, 36, 58, 59, 62, and 63 can be listed. From the perspective of brightness, CI pigment green 58 is preferred.

[0201] Examples of yellow pigments include CI pigment yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 7 5, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 15 0, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191 : 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and compounds formed by inserting other compounds into the 1:1 complex of azobarbituric acid and nickel shown in formula (i) below or its tautomers (hereinafter sometimes referred to as "nickel azo complex shown in formula (i)").

[0202]

[0203] Other compounds mentioned above include, for example, those represented by formula (ii) below.

[0204]

[0205] From the viewpoint of high brightness and high color gamut, CI pigment yellows 83, 117, 129, 138, 139, 154, 155, 180, 185 and the nickel azo complex shown in formula (i) are preferred, and CI pigment yellows 83, 138, 139, 180, 185 and the nickel azo complex shown in formula (i) are more preferred.

[0206] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0207] From the viewpoint of heat resistance and structural stability, phthalocyanine pigments having a central metal are preferred, and blue copper phthalocyanine pigments are more preferred. Examples of copper phthalocyanine pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, with CI Pigment Blue 15:6 being more preferred.

[0208] Examples of purple pigments include CI pigments 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0209] From the viewpoint of heat resistance, purple dioxazine pigments are preferred. Examples of dioxazine pigments include CI pigments purple 19 and 23, with CI pigment purple 23 being particularly preferred.

[0210] The average primary particle size of the pigment is typically 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. When micronizing the pigment, a method such as milling with solvent salts is suitable.

[0211] The proportion of colorant (A) in the coloring resin composition of the present invention is not particularly limited, but it is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, even more preferably 13% by mass or more, particularly preferably 15% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. By setting it to the lower limit or above, there is a tendency to reproduce a wide range of hues. By setting it to the upper limit or below, there is a tendency to ensure stability over time.

[0212] The above-mentioned upper and lower limits can be combined arbitrarily. For example, although not particularly limited, the content of colorant (A) in the total solids of the coloring resin composition 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 13 to 50% by mass, and particularly preferably 15 to 40% by mass.

[0213] The proportion of dye in the coloring resin composition of the present invention is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more in the total solids content of the coloring resin composition. Furthermore, it is 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 the content to the lower limit or above tends to increase brightness. Setting the content to the upper limit or below tends to ensure stability over time.

[0214] The aforementioned upper and lower limits can be combined arbitrarily. For example, the proportion of dye in the total solids of the coloring resin composition is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 1.5 to 20% by mass.

[0215] When the coloring resin composition of the present invention contains phthalocyanine dyes, the proportion thereof is not particularly limited. Preferably, it accounts for 1% or more by mass of the total solids content of the coloring resin composition; more preferably, 3% or more by mass; further preferably, 5% or more by mass; even more preferably, 10% or more by mass; particularly preferably, 15% or more by mass; and preferably 50% or less by mass; more preferably, 40% or less by mass; further preferably, 30% or less by mass; and particularly preferably 20% or less by mass. Setting the value to the lower limit or above tends to increase brightness. Setting the value to the upper limit or below tends to ensure stability over time.

[0216] The aforementioned upper and lower limits can be combined arbitrarily. For example, the proportion of phthalocyanine dye in the total solids of the coloring resin composition is preferably 1-50% by mass, more preferably 3-50% by mass, even more preferably 5-40% by mass, even more preferably 10-30% by mass, and particularly preferably 15-20% by mass.

[0217] When the coloring resin composition of the present invention contains phthalocyanine dye (1), its content ratio is not particularly limited. Preferably, it accounts for 1% or more by mass of the total solids content of the coloring resin composition, more preferably 3% or more by mass, further preferably 5% or more by mass, even more preferably 10% or more by mass, particularly preferably 15% or more by mass, and preferably 50% or less by mass, more preferably 40% or less by mass, further preferably 30% or less by mass, and particularly preferably 20% or less by mass. Setting it to the lower limit or above tends to increase brightness. Setting it to the upper limit or below tends to ensure stability over time.

[0218] The above-mentioned upper and lower limits can be combined arbitrarily. For example, the content of phthalocyanine dye (1) in the total solids of the coloring resin composition is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, even more preferably 5 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 20% by mass.

[0219] When the coloring resin composition of the present invention contains xatonide dyes, the proportion thereof is not particularly limited. Preferably, it is 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, even more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. Setting it to the lower limit or above tends to increase brightness. Setting it to the upper limit or below tends to ensure stability over time.

[0220] The aforementioned upper and lower limits can be combined arbitrarily. For example, the content of xanthan dye in the total solids of the coloring resin composition is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 1.5 to 10% by mass, and particularly preferably 2 to 5% by mass.

[0221] When the coloring resin composition of the present invention contains a zeolite dye (10), its content is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, even more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. By setting it to the lower limit or above, there is a tendency to increase brightness. By setting it to the upper limit or below, there is a tendency to ensure stability over time.

[0222] The aforementioned upper and lower limits can be combined arbitrarily. For example, the content of xanthan dye (10) in the total solids of the coloring resin composition is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 1.5 to 10% by mass, and particularly preferably 2 to 5% by mass.

[0223] When the coloring resin composition of the present invention contains other colorants, the proportion of those colorants is not particularly limited. Preferably, it accounts for 1% or more by mass of the total solids content of the coloring resin composition; more preferably, 3% or more by mass; further preferably, 5% or more by mass; even more preferably, 7% or more by mass; particularly preferably, 10% or more by mass; and preferably 30% or less by mass; more preferably, 25% or less by mass; further preferably, 20% or less by mass; and particularly preferably 15% or less by mass. By setting the value to the lower limit or above, there is a tendency to reproduce a wide range of hues. By setting the value to the upper limit or below, there is a tendency to ensure stability over time.

[0224] The above-mentioned upper and lower limits can be combined arbitrarily. For example, the content of other colorants in the total solids of the coloring resin composition is preferably 1 to 30% by mass, more preferably 3 to 30% by mass, even more preferably 5 to 25% by mass, even more preferably 7 to 20% by mass, and particularly preferably 10 to 15% by mass.

[0225] [1-2](B) Solvent

[0226] (B) The solvent has the function of dissolving or dispersing colorants, alkali-soluble resins, photopolymerization initiators, and other components, and adjusting viscosity in the coloring resin composition and pigment dispersion of the present invention.

[0227] As the solvent for (B), any solvent capable of dissolving or dispersing the components is acceptable.

[0228] Examples of such solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and other diol monoalkyl ethers;

[0229] Dialkyl ethers of glycols, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0230] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and other diol alkyl ether acetates;

[0231] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0232] Alkyl acetates such as cyclohexyl acetate;

[0233] Ethers such as pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0234] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0235] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0236] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0237] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0238] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0239] Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone, and other chain or cyclic esters;

[0240] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0241] Halogenated hydrocarbons such as chlorobutane and chloropentane;

[0242] Ether ketones such as methoxymethylpentanone;

[0243] Nitriles such as acetonitrile and benzonitrile.

[0244] Commercially available solvents include, for example, mineral oil, Varsol #2, Apco #18 solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (all trade names). These solvents can be used individually or in combination of two or more.

[0245] When forming the pixels of the color filter using photolithography, the solvent for (B) is preferably a solvent with a boiling point of 100 to 200°C (under a pressure of 1013.25 hPa. Hereinafter, the same applies to boiling point). A solvent with a boiling point of 120 to 170°C is more preferred.

[0246] Considering the good balance of coatability and surface tension, as well as the high solubility of the constituent components in the composition, glycol alkyl ether acetates are preferred.

[0247] Diol alkyl ether acetates can be used alone or in combination with other solvents. Diol monoalkyl ethers are particularly preferred as solvents for use in combination with diol alkyl ether acetates. From the viewpoint of solubility of the components in the composition, propylene glycol monomethyl ether is preferred. Diol monoalkyl ethers are highly polar; if added in excessive amounts, pigments tend to aggregate, leading to a gradual increase in the viscosity of the resulting colored resin composition and a decrease in storage stability. When using diol monoalkyl ethers in combination, from the viewpoint of storage stability, the proportion of diol monoalkyl ethers in the solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass, in the (B) solvent contained in the colored resin composition.

[0248] As a solvent used in combination with glycol alkyl ether acetates, a solvent with a boiling point of 150°C or higher is preferred. While using a solvent with a boiling point of 150°C or higher makes the coloring resin composition less prone to drying, it also helps to prevent the disruption of the pigment dispersion's interrelationships due to rapid drying. When using a solvent with a boiling point of 150°C or higher, the proportion of this solvent in the (B) solvent contained in the coloring resin composition is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. By setting this to the lower limit or higher, it is easier to avoid defects such as foreign matter caused by the precipitation and curing of coloring material components at the tip of the slit nozzle. By setting this to the upper limit or lower, it is easier to avoid problems such as slow drying speed of the composition, poor cycle time of the vacuum drying process, and pin marks from pre-baking.

[0249] Solvents with a boiling point above 150°C can be glycol alkyl ether acetates, or glycol alkyl ethers, in which case it is not necessary to include a solvent with a boiling point above 150°C.

[0250] Examples of solvents with a boiling point of 150°C or higher include diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and glyceryl triacetate.

[0251] When forming the pixels of a color filter using inkjet printing, a solvent with a boiling point typically above 130°C and below 300°C, preferably above 150°C and below 280°C, is suitable. Setting the value above the lower limit tends to improve the uniformity of the resulting coating. Setting the value below the upper limit tends to reduce residual solvent during firing.

[0252] From the viewpoint of the uniformity of the obtained coating, the vapor pressure of the solvent used is generally 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

[0253] When manufacturing color filters using inkjet printing, the ink ejected from the nozzle is extremely fine, ranging from a few pL to tens of pL. Therefore, there is a tendency for the solvent to evaporate before reaching the nozzle or pixel array, leading to ink concentration and drying. To avoid this, it is preferable to use a solvent with a high boiling point. Specifically, it is preferable to contain a solvent with a boiling point of 180°C or higher, more preferably 200°C or higher, and particularly preferably 220°C or higher. Furthermore, the solvent with a boiling point of 180°C or higher, more preferably 200°C or higher, and particularly preferably 220°C or higher, is preferably 50% by mass or higher, more preferably 70% by mass or higher, and most preferably 90% by mass or higher in the (B) solvent contained in the coloring resin composition. By setting these values ​​to the lower limit or higher, it is easier to fully exert the effect of preventing solvent evaporation from the droplets.

[0254] Examples of solvents with a boiling point of 180°C or higher, more preferably 200°C or higher, and particularly preferably 220°C or higher, include diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, and glyceryl triacetate.

[0255] For adjusting the viscosity of the coloring resin composition and the solubility of the solid components, containing a solvent with a boiling point below 180°C is also effective. As a solvent with a boiling point below 180°C, solvents with low viscosity, high solubility, and low surface tension are preferred, such as ethers, esters, and ketones. Among these, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are particularly preferred.

[0256] If the solvent contains alcohols, the ejection stability in inkjet printing will deteriorate. From the viewpoint of ejection stability in inkjet printing, the alcohol content in the solvent (B) of the coloring resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0257] The proportion of solvent in the coloring resin composition of the present invention is not particularly limited, but is generally 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By setting it to the above-mentioned upper limit or less, there is a tendency to make it easier to form a coating film. On the other hand, considering the viscosity and other factors suitable for coating, it is generally 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more.

[0258] The aforementioned upper and lower limits can be combined arbitrarily. For example, the solvent content in the coloring resin composition of the present invention is 70-99% by mass, preferably 75-90% by mass, and more preferably 78-85% by mass.

[0259] [1-3](C) Alkali-soluble resin

[0260] The coloring resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curing based on photopolymerization and solubility based on developer.

[0261] As (C) the alkali-soluble resin, known polymeric compounds disclosed in, for example, Japanese Patent Application Publication Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224, 2000-56118, and 2003-233179 can be used, among which resins of (C-1) to (C-5) listed below are preferred.

[0262] (C-1): A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of a copolymer of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "resin (C-1)").

[0263] (C-2) A linear, alkali-soluble resin containing carboxyl groups in its main chain (hereinafter sometimes referred to as "resin (C-2)").

[0264] (C-3) A resin obtained by adding an epoxy-containing unsaturated compound to the carboxyl group of the above resin (C-2) (hereinafter sometimes referred to as "resin (C-3)").

[0265] (C-4) (meth)acrylic resins (hereinafter sometimes referred to as "resin (C-4)").

[0266] (C-5) Epoxy (meth)acrylate resins containing carboxyl groups (hereinafter sometimes referred to as "resin (C-5)").

[0267] Among them, resin (C-1) is particularly preferred.

[0268] Resins (C-2) to (C-5) need only have solubility sufficient to be dissolved by alkaline developer and to perform the target development process. Resins described as the same item in Japanese Patent Application Publication No. 2009-025813 are preferred.

[0269] (C-1) A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of an epoxy-containing (meth)acrylate and other free radical polymerizable monomers, or by adding a polyacid anhydride to at least a portion of the hydroxyl groups generated by the addition reaction.

[0270] As one of the preferred methods for resin (C-1), one example is "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups of a copolymer of 5 to 90 mol% of epoxy-containing (meth)acrylate and 10 to 95 mol% of other free radical polymerizable monomers, or by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction."

[0271] Examples of epoxy-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Glycidyl (meth)acrylate is preferred. Epoxy-containing (meth)acrylates can be used alone or in combination of two or more.

[0272] As other free radical polymerizable monomers for copolymerization with epoxy-containing (meth)acrylates, mono(meth)acrylates having the structure shown in the following general formula (V) are preferred.

[0273]

[0274] In equation (V), R 91 ~R 98 Each can independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It should be noted that R... 96 With R 98 Or R 95 With R 97 They can be arbitrarily connected to form a loop.

[0275] In equation (V), R 96 With R 98 Or R 95 With R 97 When a ring is formed by connecting the links, the formed ring is preferably an aliphatic ring, which can be either saturated or unsaturated, and the number of carbon atoms is preferably 5 to 6.

[0276] As the structure shown in general formula (V), the structure shown in formulas (Va), (Vb), or (Vc) below is preferred.

[0277] By introducing these structures into an alkali-soluble resin, when the coloring resin composition of the present invention is used for filter forming, there is a tendency for the heat resistance of the coloring resin composition to be improved and the strength of the pixels formed using the coloring resin composition to be increased.

[0278] Mono(meth)acrylates having the structure shown in general formula (V) can be used alone or in combination of two or more.

[0279]

[0280] As a mono(meth)acrylate having the structure shown in the general formula (V), any known mono(meth)acrylate can be used as long as it has the structure shown in the general formula (V), and the mono(meth)acrylate shown in the following general formula (VI) is particularly preferred.

[0281]

[0282] In equation (VI), R 89 R represents a hydrogen atom or a methyl group. 90 This represents the structure shown in the following general formula (V).

[0283] In the case of repeating units from mono(meth)acrylate represented by general formula (VI), in copolymers of epoxy-containing (meth)acrylates and other free radical polymerizable monomers, the proportion of repeating units from mono(meth)acrylate represented by general formula (VI) in the repeating units from other free radical polymerizable monomers is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and even more preferably 15 to 50 mol%.

[0284] Other free radical polymerizable monomers besides the mono(meth)acrylates shown in general formula (VI) are not particularly limited. Examples include styrene, vinyl aromatics with alkyl, nitro, cyano, amide, or ester substitutions at the α-, ortho, meta, or para positions of styrene; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, and other dienes; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate Ester, Dodecyl (meth)acrylate, Cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, 2-Methylcyclohexyl (meth)acrylate, Dicyclohexyl (meth)acrylate, Isoboronyl (meth)acrylate, Adamantane (meth)acrylate, Propyl (meth)acrylate, Phenyl (meth)acrylate, Naphthalene (meth)acrylate, Anthracene (meth)acrylate, Anthracite (meth)acrylate, Piperyl (meth)acrylate, Salicylate (meth)acrylate, Furanyl (meth)acrylate, Furfuryl (meth)acrylate, Tetrahydrofuranyl (meth)acrylate, Pyranyl (meth)acrylate, Benzyl (meth)acrylate, (Methyl)acrylate Phthalate, cresol methacrylate, 1,1,1-trifluoroethyl methacrylate, perfluoroethyl methacrylate, perfluoropropyl methacrylate, perfluoroisopropyl methacrylate, triphenylmethyl methacrylate, cumyl methacrylate, 3-(N,N-dimethylamino)propyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. (meth)acrylates; methacrylamide, N,N-dimethylamide, N,N-diethylamide, N,N-dipropylamide, etc. (Meth)acrylamides such as N,N-diisopropylamide and anthraquinone of (meth)acrylic acid; vinyl compounds such as (meth)acrylanilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

[0285] From the viewpoint of imparting excellent heat resistance and strength to the colored resin composition, it is preferable to contain one or more monomers selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimides. In particular, the proportion of repeating units selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimides is preferably 1 to 70 mol% of the repeating units from other free radical polymerizable monomers, more preferably 3 to 50 mol%.

[0286] In the copolymerization of epoxy-containing (meth)acrylates with other free radical polymerizable monomers, known solution polymerization methods can be used. There are no particular limitations on the solvent used, as long as it is inactive for free radical polymerization; commonly used organic solvents can be used.

[0287] Examples include: ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, acetic acid cellosolve, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; and diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, and butyl carbitol. Ethers; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; 1,4-dioxane, tetrahydrofuran, and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and other ketones; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; lactic esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

[0288] The amount of solvent used is typically 30 to 1000 parts by mass relative to 100 parts by mass of the obtained copolymer, preferably 50 to 800 parts by mass. By keeping the amount of solvent used within the above range, it is easier to control the molecular weight of the copolymer.

[0289] There are no particular limitations on the free radical polymerization initiator used in copolymerization reactions, as long as it can initiate free radical polymerization. Commonly used organic peroxide catalysts and azo compound catalysts can be used. Examples include well-known catalysts classified as peroxide ketones, peroxy ketals, hydrogen peroxide, diallyl peroxides, diacid peroxides, peroxide esters, and peroxydicarbonates.

[0290] Examples of organic peroxide catalysts include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide, tert-hexyl peroxide, tert-butyl peroxide (2-ethylhexanoate), tert-hexyl peroxide (2-ethylhexanoate), 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyl-3,3-isopropylhydrogen peroxide. Tert-butyl hydroperoxide, dicumyl peroxide, dicumyl peroxide, acetyl peroxide, bis(4-tert-butylcyclohexyl) peroxide dicarbonate, diisopropyl peroxide dicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxide)-3,3,5-trimethylcyclohexane.

[0291] Examples of azo compound catalysts include azobisisobutyronitrile (AIBN) and azodicarbonamide (ADCA).

[0292] One or more free radical polymerization initiators with suitable half-lives can be used depending on the polymerization temperature. The amount of free radical polymerization initiator used relative to 100 parts by mass of the total amount of monomers used in the copolymerization reaction is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass.

[0293] For copolymerization reactions, the monomers and free radical polymerization initiators used in the copolymerization reaction can be dissolved in a solvent and heated while stirring. Alternatively, the monomers with added free radical polymerization initiators can be added dropwise to the solvent while heating and stirring. Another option is to add the free radical polymerization initiator to the solvent and add the monomer dropwise while heating. The reaction conditions can be adjusted according to the target molecular weight.

[0294] As a copolymer of epoxy-containing (meth)acrylate and other free radical polymerizable monomers, a copolymer consisting of 5 to 90 mol% repeating units from epoxy-containing (meth)acrylate and 95 to 10 mol% repeating units from other free radical polymerizable monomers is preferred; a copolymer consisting of 20 to 80 mol% repeating units from epoxy-containing (meth)acrylate and 80 to 20 mol% repeating units from other free radical polymerizable monomers is more preferred; and a copolymer consisting of 30 to 70 mol% repeating units from epoxy-containing (meth)acrylate and 70 to 30 mol% repeating units from other free radical polymerizable monomers is even more preferred.

[0295] By setting the proportion of repeating units from epoxy-containing (meth)acrylates to the aforementioned lower limit or above, there is a tendency to achieve sufficient addition of unsaturated monocarboxylic acids and polycarboxylic anhydrides, as described later. By setting the proportion of repeating units from other free radical polymerizable monomers to the aforementioned lower limit or above, there is a tendency to achieve sufficient heat resistance and strength.

[0296] Next, the unsaturated monocarboxylic acid (polymerizable component) and polycarboxylic acid anhydride (alkali-soluble component) are reacted with the epoxy group portion of a copolymer of (meth)acrylate containing epoxy resin and other free radical polymerizable monomers.

[0297] As an unsaturated monocarboxylic acid that adds to an epoxy group, a known unsaturated monocarboxylic acid can be used, for example, an unsaturated carboxylic acid having an olefinic unsaturated double bond.

[0298] Examples of monocarboxylic acids include (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and (meth)acrylic acid substituted at the α-position with a haloalkyl group, alkoxy group, halogen atom, nitro group, or cyano group. (Meth)acrylic acid is preferred. One unsaturated monocarboxylic acid may be used alone, or two or more may be used in combination.

[0299] Polymerization can be imparted to resins (C-1) by adding unsaturated monocarboxylic acids.

[0300] An unsaturated monobasic acid is added to the epoxy groups of the copolymer, typically 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. By setting the value to the lower limit or above, the coloring resin composition tends to exhibit improved stability over time. Known methods can be used as a method for adding the unsaturated monobasic acid to the epoxy groups of the copolymer.

[0301] As a polyacid anhydride added to the hydroxyl group formed when an unsaturated monocarboxylic acid is added to the epoxy group of a copolymer, a known polyacid anhydride can be used.

[0302] Examples of dibasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridged anhydride; and tribasic or higher acid anhydrides include trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Tetrahydrophthalic anhydride and succinic anhydride are preferred. A single polybasic acid anhydride can be used alone, or two or more can be used in combination.

[0303] By adding polyacid anhydrides, the resin (C-1) can be endowed with alkali solubility.

[0304] The addition of a polyacid anhydride to a hydroxyl group formed by adding an unsaturated monocarboxylic acid to the epoxy group of the copolymer typically amounts to 10–100 mol%, preferably 20–90 mol%, and more preferably 30–80 mol%. By setting this value below the upper limit, there is a tendency for improved film residue during development. By setting this value above the lower limit, there is a tendency for sufficient solubility. Known methods can be used as a method for adding the polyacid anhydride to the hydroxyl group.

[0305] To improve photosensitivity, after addition of a polyacid anhydride, a glycidyl (meth)acrylate or a glycidyl ether compound with a polymerizable unsaturated group can be added to a portion of the resulting carboxyl group. To improve developability, after addition of a polyacid anhydride, a glycidyl ether compound without a polymerizable unsaturated group can be added to a portion of the resulting carboxyl group. Each of these can also be added.

[0306] Examples of glycidyl ether compounds that are not polymerizable unsaturated groups include those containing phenyl or alkyl groups. Commercially available examples include those manufactured by Nagase ChemteX Corporation under the trade names “DENACOL EX-111”, “DENACOL EX-121”, “DENACOL EX-141”, “DENACOL EX-145”, “DENACOL EX-146”, “DENACOL EX-171”, and “DENACOL EX-192”.

[0307] The structure of the resin (C-1) is described, for example, in Japanese Patent Application Publication No. 8-297366 and Japanese Patent Application Publication No. 2001-89533.

[0308] The weight-average molecular weight (Mw) of the resin (C-1), converted from polystyrene as measured by GPC, is not particularly limited, but is preferably 3,000 to 100,000, and particularly preferably 5,000 to 50,000. Setting it above the lower limit tends to improve heat resistance and film strength. Setting it below the upper limit tends to improve solubility relative to the developer. As a standard for molecular weight distribution, the weight-average molecular weight (Mw) / number-average molecular weight (Mn) is preferably 2.0 to 5.0.

[0309] From the viewpoint of coating curability under ultraviolet exposure, among (C) alkali-soluble resins, (c1) acrylic copolymer resins having olefinic unsaturated groups in the side chains are preferred.

[0310] (c1) The partial structure of an acrylic copolymer resin having olefinically unsaturated groups in its side chains is not particularly limited. From the viewpoint of balancing coating curing under ultraviolet exposure and alkali solubility under alkali development, for example, a partial structure shown in the following general formula (I) is preferred.

[0311]

[0312] In equation (I), R 1 and R 2 Each atom can be represented independently as a hydrogen atom or a methyl group. * indicates a connecting bond.

[0313] Of the partial structures shown in the above formula (I), from the viewpoint of sensitivity and alkali developability, the partial structure shown in the following general formula (I') is preferred.

[0314]

[0315] In formula (I'), R 1 and R 2 Each can independently represent a hydrogen atom or a methyl group. R X It represents a hydrogen atom or a polyacid residue.

[0316] A polybasic acid residue refers to a monovalent group formed by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, nethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. A polybasic acid can be used alone or in combination of two or more.

[0317] From the perspective of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0318] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in its side chain contains a portion of the structure shown in the above general formula (I), the content ratio of the portion of the structure shown in the above general formula (I) in the acrylic copolymer resin having olefinic unsaturated groups in its side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting the value to the lower limit or above, there is a tendency to improve the curability of the coating film under ultraviolet exposure. By setting the value to the upper limit or below, there is a tendency to improve the alkali solubility under alkali development.

[0319] The upper and lower limits mentioned above can be combined arbitrarily. For example, (c1) the content of the partial structure shown in the above general formula (I) in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0320] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in its side chain contains a portion of the structure shown in the above general formula (I'), the content ratio of the portion of the structure shown in the above general formula (I') in the acrylic copolymer resin having olefinic unsaturated groups in its side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also preferably 95 mol% or less, more preferably 90 mol% or less, further preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting the value to the lower limit or above, there is a tendency to improve the curability of the coating film under ultraviolet exposure. By setting the value to the upper limit or below, there is a tendency to improve the alkali solubility under alkali development.

[0321] The upper and lower limits mentioned above can be combined arbitrarily. For example, (c1) the proportion of the partial structure shown in the above general formula (I') in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, further preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

[0322] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chain contains a portion of the structure shown in general formula (I) above, there are no particular limitations on the additional portion of the structure. From the viewpoint of alkali solubility during alkali development, it is preferred, for example, to have a portion of the structure shown in general formula (II) below.

[0323]

[0324] In equation (II) above, R 3 R represents a hydrogen atom or a methyl group. 4 It indicates an alkyl group that may have a substituent, an aromatic cycloal group that may have a substituent, or an alkenyl group that may have a substituent.

[0325] (R 4 )

[0326] In equation (II) above, R 4 It indicates an alkyl group that may have a substituent, an aromatic cycloal group that may have a substituent, or an alkenyl group that may have a substituent.

[0327] As R 4 The alkyl group in the formula can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and also preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the formula to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting the formula to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0328] The upper and lower limits mentioned above can be combined arbitrarily. For example, R 4 The alkyl group in the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.

[0329] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of reproducibility, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred.

[0330] Examples of substituents that may be optionally present in the alkyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0331] As R 4 The aromatic cyclic group in the form can be exemplified by monovalent aromatic hydrocarbon cyclic groups and monovalent aromatic heterocyclic groups. The number of carbon atoms is preferably 6 or more, further preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. Setting the value to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting the value to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0332] The aromatic hydrocarbon ring in an aromatic hydrocarbon ring group can be a monocyclic or fused ring, and examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, and benzo[a]pyrene rings. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0333] Aromatic heterocycles, as members of aromatic heterocyclic groups, can be either monocyclic or fused rings. Examples include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, cyclophosphine rings, quinoxaline rings, phenanthridine rings, primidine rings, quinazoline rings, quinazoline ketone rings, and azurite rings.

[0334] From the viewpoint of radioactivity, benzene rings or naphthalene rings are preferred, with benzene rings being more preferred.

[0335] Examples of substituents that can be optionally present in the aromatic cyclic group include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluorine, hydroxyl, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0336] As R 4 The alkenyl group in the form can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, more preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0337] Examples of alkenyl groups include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. From the viewpoint of reproducibility, vinyl and allyl are preferred, and vinyl is more preferred.

[0338] Examples of substituents that can be optionally present in the alkenyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0339] As R 4 From the viewpoint of developability and film strength, alkyl and alkenyl groups are preferred, with alkyl groups being more preferred.

[0340] (c1) When the acrylic copolymer resin having olefinic unsaturated groups in its side chain contains a portion of the structure shown in general formula (II) above, the content of the portion of the structure shown in general formula (II) in the acrylic copolymer resin having olefinic unsaturated groups in its side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. By setting the content to the lower limit or above, there is a tendency to improve alkali solubility. By setting the content to the upper limit or below, there is a tendency to improve the storage stability of the colored resin composition.

[0341] The upper and lower limits mentioned above can be combined arbitrarily. For example, (c1) the proportion of the partial structure shown in general formula (II) in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, further preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

[0342] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chain contains a partial structure as shown in the above general formula (I), from the viewpoint of suppressing the decrease in brightness by improving heat resistance, it is also preferable to have a partial structure as shown in, for example, the following general formula (III) as an additional partial structure.

[0343]

[0344] In equation (III) above, R 5 R represents a hydrogen atom or a methyl group. 6The denotes are alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, halogen, alkoxy, thiol, or alkyl thioether groups, which may be substituted with a substituted group. t represents an integer from 0 to 5.

[0345] (R 6 )

[0346] In equation (III) above, R 6 The group may be alkyl, alkenyl, alkynyl, hydroxyl, carboxyl, halogen atom, alkoxy, thiol or alkyl thioether group with optional substituents.

[0347] As R 6 The alkyl group in the form can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, even more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less, particularly preferably 12 or less. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0348] The upper and lower limits mentioned above can be combined arbitrarily. For example, R 6 The alkyl group in the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12.

[0349] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of heat resistance, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred.

[0350] Examples of substituents that may be optionally present in the alkyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0351] As R 6 The alkenyl group in the form can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, more preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0352] Examples of alkenyl groups include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. From the viewpoint of exposure sensitivity during ultraviolet exposure, vinyl and allyl groups are preferred, and vinyl is more preferred.

[0353] Examples of substituents that can be optionally present in the alkenyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0354] As R 6 The alkynyl group in the compound can be linear, branched, or cyclic. It preferably has 2 or more carbon atoms, more preferably 22 or fewer, more preferably 20 or fewer, even more preferably 18 or fewer, even more preferably 16 or fewer, and particularly preferably 14 or fewer. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0355] Examples of alkynyl groups include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, and 1-hexyn-6-yl.

[0356] Examples of substituents that can be optionally present in the alkynyl group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl groups. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0357] As R 6 Halogen atoms in the resin can be, for example, fluorine, chlorine, bromine, and iodine atoms. From the viewpoint of the storage stability of acrylic copolymer resins, fluorine atoms are preferred.

[0358] As R 6 The alkoxy group in the sample can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 20 or fewer, more preferably 18 or fewer, even more preferably 16 or fewer, even more preferably 14 or fewer, and particularly preferably 12 or fewer. Setting the value to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting the value to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0359] Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy.

[0360] Examples of substituents that can be optionally present on the alkoxy group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0361] As R 6 The alkyl sulfide group in the form can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 20 or fewer, more preferably 18 or fewer, even more preferably 16 or fewer, even more preferably 14 or fewer, and particularly preferably 12 or fewer. Setting it to the lower limit or above tends to increase lipophilicity and solubility in solvents. Setting it to the upper limit or below tends to increase hydrophilicity and alkali solubility.

[0362] Examples of alkyl thioether groups include methyl thioether, ethyl thioether, propyl thioether, and butyl thioether. From the viewpoint of reproducibility, methyl thioether and ethyl thioether are preferred.

[0363] Examples of substituents that may be optionally present in the alkyl group of the alkyl sulfide group include methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred.

[0364] As R 6 From the viewpoint of reproducibility, hydroxyl or carboxyl groups are preferred, and carboxyl groups are more preferred.

[0365] From the perspective of ease of manufacture, in the above formula (III), t is preferably 0.

[0366] (c1) When the acrylic copolymer resin having olefinically unsaturated groups in its side chain contains a portion of the structure shown in formula (III) above, the content ratio of the portion of the structure shown in formula (III) above in the acrylic copolymer resin having olefinically unsaturated groups in its side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, particularly preferably 8 mol% or more, and also preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less. By setting it to the lower limit or above, there is a tendency to improve heat resistance and suppress the decrease in brightness. By setting it to the upper limit or below, there is a tendency to increase the content ratio of other partial structures and improve alkali solubility.

[0367] The upper and lower limits mentioned above can be combined arbitrarily. For example, (c1) the content of the partial structure shown in formula (III) above in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, even more preferably 5 to 30 mol%, particularly preferably 8 to 20 mol%.

[0368] (c1) When an acrylic copolymer resin having olefinic unsaturated groups in its side chain has a partial structure as shown in the above general formula (I), from the viewpoint of reproducibility, it is also preferable to have a partial structure as shown in, for example, the following general formula (IV).

[0369]

[0370] In equation (IV) above, R 7 It represents a hydrogen atom or a methyl group.

[0371] (c1) When the acrylic copolymer resin having olefinically unsaturated groups in its side chain contains a portion of the structure shown in formula (IV) above, the content of the portion of the structure shown in formula (IV) in the acrylic copolymer resin having olefinically unsaturated groups in its side chain is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. By setting it to the lower limit or above, there is a tendency to improve alkali solubility. By setting it to the upper limit or below, there is a tendency to improve the storage stability of the colored resin composition.

[0372] The upper and lower limits mentioned above can be combined arbitrarily. For example, (c1) the content of the partial structure shown in formula (IV) above in an acrylic copolymer resin having olefinic unsaturated groups in the side chain is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

[0373] (C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 40 mg KOH / g or more, even more preferably 50 mg KOH / g or more, particularly preferably 60 mg KOH / g or more, and also preferably 300 mg KOH / g or less, more preferably 250 mg KOH / g or less, even more preferably 200 mg KOH / g or less, and even more preferably 150 mg KOH / g or less. Setting the acid value to the lower limit or above tends to increase alkali solubility. Setting the acid value to the upper limit or below tends to increase the storage stability of the coloring resin composition.

[0374] The above-mentioned upper and lower limits can be combined arbitrarily. For example, (C) the acid value of the alkali-soluble resin is preferably 10-300 mgKOH / g, more preferably 30-300 mgKOH / g, even more preferably 40-250 mgKOH / g, even more preferably 50-200 mgKOH / g, and particularly preferably 60-150 mgKOH / g.

[0375] Acid value indicates the number of mg of KOH required to neutralize 1g of solid component.

[0376] (C) The weight-average molecular weight (Mw) of the alkali-soluble resin is not particularly limited, but is generally 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, even more preferably 7000 or more, particularly preferably 8000 or more, and generally 30000 or less, preferably 20000 or less, more preferably 15000 or less, and even more preferably 10000 or less. Setting the value to the lower limit or above tends to improve heat resistance and coating curability. Setting the value to the upper limit or below tends to improve alkali solubility.

[0377] The aforementioned upper and lower limits can be combined arbitrarily. For example, the weight-average molecular weight (Mw) of the alkali-soluble resin (C) is preferably 1,000 to 30,000, more preferably 2,000 to 30,000, further preferably 4,000 to 20,000, even more preferably 6,000 to 20,000, particularly preferably 7,000 to 15,000, and most preferably 8,000 to 10,000.

[0378] The proportion of the alkali-soluble resin (C) in the coloring resin composition of the present invention is not particularly limited, but it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less. By setting the content to the lower limit or above, there is a tendency to improve the curability of the coating film under ultraviolet exposure. By setting the content to the upper limit or below, there is a tendency to improve the solubility of the developer and suppress residue.

[0379] The above-mentioned upper and lower limits can be combined arbitrarily. For example, the content of (C) alkali-soluble resin in the total solids of the coloring resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.

[0380] [1-4](D) Photopolymerization initiator

[0381] The coloring resin composition of the present invention contains a (D) photopolymerization initiator. By containing a (D) photopolymerization initiator, photopolymerization-based film curability can be obtained.

[0382] (D) Photopolymerization initiators can also be used in the form of a mixture with accelerators (chain transfer agents) and additives such as sensitizing pigments as needed (photopolymerization initiation systems). A photopolymerization initiation system is a component that has the function of directly absorbing light or being photosensitized to induce decomposition or hydrogen abstraction reactions, thereby generating polymerization-active free radicals.

[0383] The photopolymerization initiator (D) in the coloring resin composition of the present invention comprises a photopolymerization initiator (d1) represented by the following general formula (I) (hereinafter sometimes referred to as "photopolymerization initiator (d1)"). In the photopolymerization initiator (d1), the group bonded to the (keto)oxime ester group is a low-reactivity indole ring, thereby decomposing and reacting slowly, and continuously and intermittently generating free radicals. This suppresses the deactivation of free radicals caused by the dye, and maintains a high level of curability. Therefore, it is believed that even when the pre-baking temperature is in the low-temperature range, resulting in more residual solvent and lower sensitivity, the penetration of the developer into the coating film can be suppressed, and the effect of pre-baking temperature changes on sensitivity can be reduced.

[0384]

[0385] (In formula (I), R) d1 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0386] R d2 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0387] p represents 0 or 1.

[0388] R d3 (This indicates an aromatic cyclic group with optional substituents.)

[0389] (R d1 )

[0390] In the above formula (I), R d1 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0391] R d1The alkyl group can be a straight-chain, branched, or cyclic alkyl group, or an alkyl group formed by their bonding. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, particularly preferably 3 or less, and most preferably 2 or less, and is generally 1 or more. By setting the number of carbon atoms in the alkyl group to the above-mentioned upper limit, there is a tendency to ensure solubility in solvents and ease of synthesis.

[0392] Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, and cyclohexyl. From the viewpoint of ease of synthesis, methyl, ethyl, propyl, and butyl are preferred, methyl and ethyl are more preferred, and methyl is even more preferred.

[0393] Examples of substituents that may be optionally present in the alkyl group include aromatic cyclic groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, and hydroxyl groups. From the viewpoint of solvent solubility, alkoxy groups having 1 to 3 carbon atoms are preferred. From the viewpoint of sensitivity, unsubstituted groups are preferred.

[0394] As R d1 The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. It typically has 4 or more carbon atoms, preferably 6 or more, and more preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting the number of carbon atoms in the aromatic cyclic group to the lower limit or above tends to make the molecule more stable. Setting it to the upper limit or below tends to improve solvent solubility.

[0395] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0396] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0397] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolin rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings, all having one free valence.

[0398] From the viewpoint of solvent solubility, benzene rings and naphthalene rings with one free valence are preferred, and benzene rings with one free valence are more preferred.

[0399] Examples of substituents that can be optionally present in an aromatic cyclic group include alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, and nitro groups. From the viewpoint of solvent solubility, alkoxy groups with 1 to 3 carbon atoms and hydroxyl groups are preferred.

[0400] From the viewpoint of solubility in solvents and ease of synthesis, as R d1 Preferably, the alkyl group has a substituent, more preferably an unsubstituted alkyl group, further preferably methyl or ethyl, and particularly preferably methyl.

[0401] (R d2 )

[0402] In the above formula (I), R d2 This indicates an alkyl group that may have a substituent, or an aromatic cycloal group that may have a substituent.

[0403] R d2 The alkyl group can be a straight-chain, branched, or cyclic alkyl group, or an alkyl group formed by their bonding. From the viewpoint of solvent solubility, straight-chain or branched alkyl groups are preferred, and straight-chain alkyl groups are more preferred. From the viewpoint of sensitivity, unsubstituted straight-chain alkyl groups are preferred.

[0404] The number of carbon atoms in the alkyl group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, further preferably 4 or more, even more preferably 5 or more, and particularly preferably 6 or more. It is also preferably 12 or less, more preferably 10 or less, further preferably 9 or less, and particularly preferably 8 or less. Setting the number of carbon atoms in the alkyl group to the lower limit or above tends to increase sensitivity. Setting it to the upper limit or below tends to increase solvent affinity.

[0405] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 2 to 12, further preferably 3 to 10, even more preferably 4 to 10, particularly preferably 5 to 9, and most preferably 6 to 8.

[0406] Examples of substituents that may be optionally present in the alkyl group include aromatic cyclic groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkathio groups having 1 to 10 carbon atoms, alkoxy carbonyl groups having 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, and hydroxyl groups. From the viewpoint of solvent solubility, alkoxy groups having 1 to 3 carbon atoms are preferred. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0407] Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. From the viewpoint of sensitivity and solvent affinity, propyl, butyl, pentyl, and hexyl are preferred, pentyl and hexyl are more preferred, and hexyl is even more preferred.

[0408] As R d2 The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. It typically has 4 or more carbon atoms, preferably 6 or more, and more preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting the number of carbon atoms in the aromatic cyclic group to the lower limit or above tends to make the molecule more stable. Setting it to the upper limit or below tends to improve solvent solubility.

[0409] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0410] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0411] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolin rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings, all having one free valence.

[0412] From the viewpoint of solvent solubility, benzene rings and naphthalene rings with one free valence are preferred, and benzene rings with one free valence are more preferred.

[0413] Examples of substituents that can be optionally present in an aromatic cyclic group include alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, and nitro groups. The alkyl chain portion of the substituent can be straight-chain or branched, and can optionally include alkoxy groups with 1 to 3 carbon atoms, alkylthio groups with 1 to 3 carbon atoms, halogen atoms, hydroxyl groups, nitro groups, etc. From the viewpoint of solvent solubility, alkoxy groups with 1 to 5 carbon atoms and hydroxyl groups are preferred.

[0414] From the perspective of solvent affinity and sensitivity, as R d2 Preferably, the alkyl group has a substituent, more preferably an unsubstituted alkyl group, further preferably butyl, pentyl, or hexyl, and particularly preferably hexyl.

[0415] (R d3 )

[0416] In the above formula (I), R d3 This indicates an aromatic cyclic group with optional substituents.

[0417] As R d3 The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Its carbon number is typically 4 or more, preferably 6 or more, and more preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting the carbon number of the aromatic cyclic group to the lower limit or above tends to increase the sensitivity during exposure. Setting it to the upper limit or below tends to increase solvent affinity.

[0418] The aforementioned upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

[0419] The aromatic hydrocarbon ring in an aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having one free valence. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0420] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include, for instance, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolin rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings, all having one free valence.

[0421] From the viewpoint of solvent affinity, benzene rings and naphthalene rings with one free valence are preferred, and benzene rings with one free valence are more preferred.

[0422] Examples of substituents that can be optionally present in the aromatic cyclic group include alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, and nitro groups. From the viewpoint of sensitivity during exposure, aryl groups with 6 to 10 carbon atoms and aryl groups with 6 to 10 carbon atoms are preferred.

[0423] From the perspective of solvent affinity and sensitivity during exposure, as R d3 Preferably, it is an aromatic hydrocarbon group with one free valence and optionally a substituent, more preferably a benzene ring group with one free valence and optionally a substituent.

[0424] (p)

[0425] In the above formula (I), from the viewpoint of sensitivity, p is preferably 0. In the above formula (I), from the viewpoint of suppressing residues by increasing solvent affinity, p is preferably 1.

[0426] From the viewpoint of solvent affinity and sensitivity during exposure, the photopolymerization initiator shown in the following general formula (II) is preferred among photopolymerization initiators (d1).

[0427]

[0428] (In formula (II), R) d1R d2 And p has the same meaning as in the above formula (I).

[0429] R d4 (This represents any monovalent substituent. q represents an integer from 0 to 3.)

[0430] (R d4 )

[0431] In equation (II) above, R d4 This represents any monovalent substituent.

[0432] Examples of any monovalent substituent include: alkyl groups with 1 to 10 carbon atoms such as methyl and ethyl; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; halogen atoms such as F, Cl, Br, and I; acyl groups with 1 to 10 carbon atoms; alkyl ester groups with 1 to 10 carbon atoms; alkoxy carbonyl groups with 1 to 10 carbon atoms; haloalkyl groups with 1 to 10 carbon atoms; aromatic cyclic groups with 4 to 10 carbon atoms; amino groups; aminoalkyl groups with 1 to 10 carbon atoms; hydroxyl groups; nitro groups; cyano groups; benzoyl groups optionally having substituents; and thenoyl groups optionally having substituents. Examples of substituents optionally present on benzoyl and thenoyl groups include alkyl groups with 1 to 3 carbon atoms and alkoxy groups with 1 to 3 carbon atoms, which may be present in the range of 0 to 3. From the viewpoint of sensitivity, nitro, cyano, benzoyl groups optionally having substituents, and thenoyl groups optionally having substituents are preferred, and benzoyl groups are more preferred.

[0433] R d4 When q is 2 or higher, multiple R d4 They can bond together to form a ring. The ring can be an aliphatic ring or an aromatic ring.

[0434] R d4 The substitution position is not particularly limited and can be any of the ortho, meta, or para positions. From the point of view of solvent affinity and sensitivity, the para position is preferred.

[0435] (q)

[0436] In the above formula (I), from the viewpoint of suppressing residues by improving solubility in the solvent and improving sensitivity during exposure, q is preferably 0 or 1, and more preferably 1.

[0437] There are no particular limitations on the manufacturing method of the photopolymerization initiator (d1), for example, it can be manufactured by the method described in Japanese Patent Application Publication No. 2017-179211.

[0438] Specific examples of photopolymerization initiators (d1) include the following photopolymerization initiators.

[0439]

[0440] (D) In ​​addition to the photopolymerization initiator (d1), the photopolymerization initiator may also contain other photopolymerization initiators (d2).

[0441] Other photopolymerization initiators (d2) include, for example, the diacetic derivatives containing diacetic compounds described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; the hexaaryl biimidazole derivatives described in Japanese Patent Application Publication No. 2000-56118; the halomethylated oxadiazole derivatives, halomethyltriazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters and other free radical activators, and α-aminoalkylphenyl ketone derivatives described in Japanese Patent Application Publication No. 10-39503; and, for example, the oxime ester derivatives described in Japanese Patent Application Publication Nos. 2000-80068 and 2006-36750.

[0442] Examples of titanium diacene derivatives include bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-tetrafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorophenyl)titanium, bis(cyclopentadienyl)bis(2,6-difluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4-difluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and bis(cyclopentadienyl)-[2,6-difluoro-3-(pyrrolo-1-yl)phenyl]titanium.

[0443] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0444] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6”-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0445] Examples of halomethyltriazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)triazine.

[0446] Examples of α-aminoalkylphenyl ketone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0447] Examples of oxime ester derivatives include those described in Japanese Patent Application Publication Nos. 2004-534797, 2000-80068, 2006-36750, 2008-179611, 2012-526185, and 2012-519191. From a sensitivity point of view, methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-5-oxovalerate can be cited. Examples of preferred product names include OXE-01, OXE-02, OXE-03, OXE-04 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG314 (manufactured by Changzhou Qiangli Company), NCI-831, and NCI-930 (manufactured by ADEKA Company).

[0448] Other photopolymerization initiators (d2) can be used alone or in combination of two or more.

[0449] (D) Photopolymerization initiators can be used alone or in combination of two or more.

[0450] Chain transfer agents can be further used on top of (D) photopolymerization initiators. Chain transfer agents are compounds that have the function of accepting the generated free radicals and transferring them to other compounds.

[0451] As a chain transfer agent, any compound possessing the aforementioned functions can be used, and various chain transfer agents can be employed. Examples of chain transfer agents include thiol-containing compounds and carbon tetrachloride. From the perspective of high chain transfer efficiency, compounds containing thiol groups are preferred. This is believed to be because the SH bond energy is low, making bond breaking, hydrogen abstraction reactions, and chain transfer reactions more likely. This is effective in improving sensitivity and surface curing properties.

[0452] Examples of thiol-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazolin, β-mercaptonaphthalene, and 1,4-dimethylmercaptobenzene, which are compounds containing an aromatic ring; and hexanedithiol, decandithiol, butanediol bis(3-mercaptopropionate), butanediol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tri(3-mercaptopropionate), and trimethylolpropane tri(3-mercaptopropionate). Compounds containing thiol groups in the aliphatic system include alkyltrimercaptoacetate, trihydroxyethyl trimercaptopropionate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tri(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tri(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, compounds having multiple thiol groups are preferred.

[0453] Among thiol-containing compounds with an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred. Among aliphatic thiol-containing compounds, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetras(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0454] From the perspective of sensitivity, aliphatic compounds containing thiol groups are preferred, such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and more preferably pentaerythritol tetra(3-mercaptopropionate) and pentaerythritol tetra(3-mercaptobutyrate).

[0455] These substances can be used individually or in combination.

[0456] In the coloring resin composition of the present invention, the proportion of (D) photopolymerization initiator is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, and preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, and particularly preferably 7% by mass or less. By setting it to the lower limit or above, there is a tendency to improve the curability of the coating film. By setting it to the upper limit or below, visible light absorption can be reduced, thereby tending to improve brightness.

[0457] The aforementioned upper and lower limits can be combined arbitrarily. For example, the content of (D) photopolymerization initiator in the total solids component of the colored resin composition is preferably 0.5 to 10% by mass, more preferably 0.8 to 9% by mass, even more preferably 1.0 to 8% by mass, and particularly preferably 1.2 to 7% by mass.

[0458] In the coloring resin composition of the present invention, the proportion of photopolymerization initiator (d1) is not particularly limited, but it is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, further preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, and preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, and particularly preferably 3% by mass or less. By setting it to the lower limit or above, there is a tendency to improve the curability of the coating film during low-temperature pre-baking. By setting it to the upper limit or below, visible light absorption can be reduced, thereby tending to improve brightness.

[0459] The aforementioned upper and lower limits can be combined arbitrarily. For example, the proportion of photopolymerization initiator (d1) in the total solids component of the colored resin composition is preferably 0.5 to 7% by mass, more preferably 0.8 to 5% by mass, even more preferably 1.0 to 4% by mass, and particularly preferably 1.2 to 3% by mass.

[0460] [1-5] Other solid components

[0461] In the coloring resin composition of the present invention, solid components other than those described above may be further incorporated as needed. Examples of such components include photopolymerizable monomers, dispersants, dispersing aids, surfactants, and antioxidants.

[0462] [1-5-1] Photopolymerizable monomers

[0463] There are no particular limitations on the photopolymerizable monomers, as long as they are low-molecular-weight compounds capable of polymerization. Preferably, they are compounds capable of addition polymerization (hereinafter referred to as "olefin compounds") having at least one olefin double bond. olefin compounds are compounds with olefin double bonds that are added polymerized and cured by the action of a photopolymerization initiator when the coloring resin composition of the present invention is irradiated by active light. It should be noted that the monomer in the present invention refers to a concept relative to so-called high-molecular-weight substances, encompassing not only monomers in the narrow sense but also dimers, trimers, and oligomers.

[0464] In this invention, it is particularly desirable to use polyfunctional olefin monomers having two or more olefinic double bonds per molecule. The number of olefinic double bonds in the polyfunctional olefin monomer is not particularly limited, but is generally two or more, preferably four or more, more preferably five or more, and even more preferably eight or less, more preferably seven or less. Setting the value to the lower limit or above tends to result in high sensitivity. Setting the value to the upper limit or below tends to improve solubility in solvents.

[0465] Examples of olefinic 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 of unsaturated carboxylic acids with polycarboxylic acids and the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and other polyhydroxy compounds, and olefinic compounds having a carbamate skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth)acryloyl group.

[0466] Examples of acrylates that are aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glyceryl acrylate. Additionally, examples include methacrylates formed by replacing the acrylic portion with a methacrylic acid portion, itaconic acid esters formed by replacing the acrylic acid portion with an itaconic acid portion, crotonic acid esters formed by replacing the crotonic acid portion with a crotonic acid portion, and maleic acid esters formed by replacing the maleic acid portion with a maleic acid portion.

[0467] Examples of esters that are aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and pyrogallol triacrylate.

[0468] Esters obtained by the esterification reaction of unsaturated carboxylic acids with polycarboxylic acids and polyhydroxy compounds do not necessarily have to be a single substance; they can also be mixtures. Representative examples include condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0469] Examples of alkenyl compounds with a carbamate skeleton obtained by reacting polyisocyanate compounds with hydroxyl compounds containing (meth)acryloyl groups include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, which react with hydroxyl compounds containing (meth)acryloyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, and 3-hydroxy(1,1,1-trimethylacryloyloxymethyl)propane.

[0470] Furthermore, olefinic compounds used in this invention, such as acrylamides like ethylene bisacrylamide, allyl esters like diallyl phthalate, and vinyl compounds like divinyl phthalate, are also useful.

[0471] The alkene compound can be a monomer having an acid value. Preferably, the monomer having an acid value is a polyfunctional monomer that is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, or that has an acid group formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of the aliphatic polyhydroxy compound. Particularly preferred are polyfunctional monomers that are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, or that have an acid group formed by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxyl group of pentaerythritol and / or dipentaerythritol.

[0472] These monomers can be used alone, but since it is difficult to use a single compound in manufacturing, two or more can be mixed together.

[0473] Polyfunctional monomers without acid groups can also be combined with polyfunctional monomers with acid groups as needed to be used as monomers.

[0474] The preferred acid value for polyfunctional monomers with acid groups is 0.1 to 40 mg KOH / g, particularly preferably 5 to 30 mg KOH / g. Setting the acid value to the lower limit or above tends to improve developing and dissolving properties. Setting it to the upper limit or below 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 acid group values ​​of all polyfunctional monomers to be within the above-mentioned range.

[0475] In this invention, a more preferred polyfunctional monomer having an acid group is a mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinates manufactured by Toa Synthetic Co., Ltd. and sold under the name TO1382. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Additionally, the polyfunctional monomer described in paragraphs

[0056] and

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

[0476] In this invention, from the viewpoint of improving the chemical resistance of pixels and the straightness of pixel edges, the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195971 is preferred. From the viewpoint of balancing coating sensitivity and shortening development time, the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195974 is preferred.

[0477] When the coloring resin composition of the present invention contains a photopolymerizable monomer, the proportion of the photopolymerizable monomer is not particularly limited. Preferably, it accounts for 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and particularly preferably 40% by mass or less. By setting the content to the lower limit or above, there is a tendency to improve the curability of the coating film. By setting the content to the upper limit or below, there is a tendency to ensure the flatness of the coating film surface.

[0478] The aforementioned upper and lower limits can be combined arbitrarily. For example, the proportion of photopolymerizable monomers in the total solids component of the coloring resin composition is preferably 5-60% by mass, more preferably 8-50% by mass, even more preferably 10-45% by mass, and particularly preferably 12-40% by mass.

[0479] [1-5-2] Dispersants, dispersing aids

[0480] When the coloring resin composition of the present invention contains a pigment as a colorant (A), it is preferable to contain a dispersant in order to stably disperse the pigment. When a high molecular weight dispersant is used, excellent dispersion stability over time is achieved, and therefore it is preferred.

[0481] Examples of polymeric dispersants include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants. Examples of these dispersants by trade name include, for example, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK), Disparlon (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the dispersants described in Japanese Patent Application Publication No. 2013-119568.

[0482] From the viewpoint of dispersibility and storage stability, block copolymers having functional groups containing nitrogen atoms are preferred among polymeric dispersants, and acrylic block copolymers are more preferred.

[0483] As block copolymers having functional groups containing nitrogen atoms, AB block copolymers and / or BAB block copolymers are preferred, consisting of A blocks having quaternary ammonium salt groups and / or amino groups in the side chains and B blocks not having quaternary ammonium salt groups and / or amino groups.

[0484] As functional groups containing nitrogen atoms, examples include primary amino, secondary amino, tertiary amino, and quaternary ammonium groups. From the viewpoint of dispersibility and storage stability, it is preferable to have primary amino, secondary amino, or tertiary amino groups, and more preferably, tertiary amino groups.

[0485] The structure of the repeating unit with tertiary amino groups in the above block copolymer is not particularly limited. From the viewpoint of dispersibility and storage stability, the repeating unit shown in the following general formula (1) is preferred.

[0486]

[0487] In the above formula (1), R 1 and R 2 Each is independently a hydrogen atom, optionally an alkyl group with substituents, optionally an aryl group with substituents, or optionally an aralkyl group with substituents, R 1 and R 2 They can be arbitrarily bonded together to form a ring structure. R 3 X is a hydrogen atom or a methyl group. X is a divalent linking group.

[0488] The number of carbon atoms in the optional alkyl group with substituents in formula (1) above is not particularly limited, but is generally 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. The alkyl group in formula (1) above can be either straight-chain or branched. The alkyl group in formula (1) above can contain cyclic structures such as cyclohexyl or cyclohexylmethyl.

[0489] The number of carbon atoms of the optional aryl group with substituents in formula (1) above 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. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being more preferred.

[0490] The number of carbon atoms in the optional aralkyl group with substituents in formula (1) above is not particularly limited, but is generally 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. Examples of aralkyl groups include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl being preferred, and phenylmethyl and phenylethyl being more preferred.

[0491] From the perspectives of dispersibility, storage stability, electrical reliability, and developability, as R 1and R 2 Each of the alkyl groups is preferably substituted, more preferably methyl or ethyl.

[0492] As a substituent optionally present in the alkyl, aralkyl, or aryl group of the above formula (1), examples include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0493] In the above equation (1), R is... 1 With R 2 The ring structure formed by mutual bonding can be exemplified by, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a fused ring formed by the fusion of two of these. The nitrogen-containing heterocyclic ring is preferably non-aromatic, and more preferably a saturated ring. Specifically, examples of nitrogen-containing heterocyclic rings described below (IV) are provided.

[0494]

[0495] These ring structures may optionally have substituents.

[0496] In formula (1) above, the divalent linking group X can be, for example, an alkylene group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -CONH-R. 13 -base, -COOR 14 -Base (where R) 13 and R 14 It is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms. Preferably -COOR 14 -base.

[0497] The proportion of the repeating unit shown in formula (1) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, even more preferably 15 mol% or more, particularly preferably 20% 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.

[0498] The upper and lower limits mentioned above can be combined arbitrarily. For example, the proportion of the repeating unit shown in formula (1) in all repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 70 mol%, particularly preferably 20 to 50%, and most preferably 25 to 40 mol%. Within the above range, there is a tendency to balance dispersion stability and high brightness.

[0499] From the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability, the above-mentioned block copolymer preferably has repeating units as shown in the following formula (2).

[0500]

[0501] In equation (2) above, R 10 It is ethylene or propylene, R 11 R is an alkyl group that is optionally substituted. 12 It can be a hydrogen atom or a methyl group. n is an integer from 1 to 20.

[0502] R in equation (2) above 11 The number of carbon atoms of the optional alkyl group with substituents is not particularly limited, but is generally 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.

[0503] The aforementioned upper and lower limits can be combined arbitrarily. For example, R in equation (2) above... 11 The alkyl group in the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 2 to 4.

[0504] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. R in formula (2) above... 11 The alkyl group can be either straight-chain or branched. R in formula (2) above... 11 The alkyl group may optionally include cyclic structures such as cyclohexyl or cyclohexylmethyl.

[0505] R is the value of equation (2) above. 11 The alkyl group may optionally have substituents, such as halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0506] From the viewpoint of compatibility and dispersibility with binder components such as solvents, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.

[0507] The aforementioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 5 is even more preferred.

[0508] The proportion of the repeating unit shown in formula (2) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.

[0509] The above upper and lower limits can be combined arbitrarily. For example, the proportion of the repeating unit shown in formula (2) in all repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%. Within the above range, there is a tendency to take into account both compatibility with binder components such as solvents and dispersion stability.

[0510] Furthermore, from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability, the block copolymers described above preferably have repeating units as shown in the following formula (3).

[0511]

[0512] In equation (3) above, R 8 R can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent. 9 It can be a hydrogen atom or a methyl group.

[0513] R in equation (3) above 8 The number of carbon atoms in the optional alkyl group with substituents is not particularly limited, but is generally 1 or more, preferably 10 or less, and more preferably 6 or less. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. R in the above formula (3) 8 The alkyl group can be either straight-chain or branched. R in formula (3) above... 8 The alkyl group may optionally include cyclic structures such as cyclohexyl or cyclohexylmethyl.

[0514] R in equation (3) above 8 The number of carbon atoms in the optional aryl group with substituents is not particularly limited, but is generally 6 or more, preferably 16 or less, and more preferably 12 or less. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being more preferred.

[0515] R in equation (3) above 8 The number of carbon atoms in the optional aralkyl group with substituents is not particularly limited, but is generally 7 or more, preferably 16 or less, and more preferably 12 or less. Examples of aralkyl groups include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl being preferred, and phenylmethyl and phenylethyl being more preferred.

[0516] From the perspective of solvent compatibility and dispersion stability, R 8 Preferably alkyl or aralkyl, more preferably methyl, ethyl or phenylmethyl.

[0517] As R 8 The alkyl group may optionally have substituents, such as halogen atoms or alkoxy groups. The aryl or aralkyl group may optionally have substituents, such as chain-like alkyl groups, halogen atoms, or alkoxy groups. R 8 The chain-like alkyl groups shown also include any of the straight-chain and branched forms.

[0518] The proportion of the repeating unit shown in formula (3) in all repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less.

[0519] The upper and lower limits mentioned above can be combined arbitrarily. For example, the proportion of the repeating unit shown in formula (3) in all repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and even more preferably 50 to 70 mol%. Within the above range, there is a tendency to balance dispersion stability and high brightness.

[0520] The block copolymers described above may also have repeating units other than those shown in general formula (1), general formula (2), and general formula (3). Examples of such repeating units include repeating units derived from styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonic glycidyl ether; and N-methacryloylmorpholine.

[0521] From the viewpoint of further improving dispersibility, the block copolymer is preferably a block copolymer comprising an A block having a repeating unit as shown in the above general formula (1) and a B block not having a repeating unit as shown in the above general formula (1), and more preferably an AB block copolymer or a BAB block copolymer. The B block preferably has repeating units as shown in the above general formula (2) and repeating units as shown in the above general formula (3).

[0522] Block A may contain repeating units other than those shown in the general formula (1) above. Examples of such repeating units include repeating units derived from (meth)acrylate monomers, as described above. The content of repeating units other than those shown in the general formula (1) in Block A is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, Block A does not contain repeating units other than those shown in the general formula (1) above.

[0523] The B block may contain repeating units other than those shown in general formula (2) and general formula (3). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acryloyl chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonic glycidyl ether; and N-methacryloylmorpholine. The content of repeating units in the B block other than those shown in general formula (2) and general formula (3) is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, the B block does not contain repeating units other than those shown in general formula (2) and general formula (3).

[0524] From a dispersibility point of view, the acid value of the above block copolymer is preferably low, and particularly preferably 0 mg KOH / g.

[0525] 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 105 mg KOH / g or more, and also preferably 150 mg KOH / g or less, more preferably 130 mg KOH / g or less.

[0526] The aforementioned upper and lower limits can be combined arbitrarily. For example, the amine value of the block copolymer is preferably 30-150 mgKOH / g, more preferably 50-150 mgKOH / g, even more preferably 70-150 mgKOH / g, even more preferably 90-130 mgKOH / g, particularly preferably 100-130 mgKOH / g, and most preferably 105-130 mgKOH / g.

[0527] The amine value represents the amine value converted from the effective solid component, expressed as the mass of KOH equivalent to the amount of alkali per 1g of solid component.

[0528] The molecular weight of the block copolymer described above, measured by weight-average molecular weight (Mw), is preferably in the range of 1,000 to 30,000. Within this range, dispersion stability becomes good, and there is a tendency for dried foreign matter to be generated when applying using a slit nozzle.

[0529] The block copolymers described above can be manufactured by known methods. For example, they can be manufactured by living polymerization of the monomers used to introduce the repeating units described above. As living polymerization methods, known methods described below can be used: for example, Japanese Patent Application Publication No. 9-62002; Japanese Patent Application Publication No. 2002-31713; P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); B.C. Anderson, G.D. Andrews et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al. al, Polym.J.17,977(1985), 18,1037(1986); Koichi Uezu, Koichi Hatada, Polymer Processing, 36,366(1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46,189(1989); M. Kuroki, T. Aida, J. Am. Chem. Soc, 109,4737(1987); Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43,300(1985); DY Sogoh, WRHertler et al, Macromolecules, 20,1473(1987), etc.

[0530] When the coloring resin composition of the present invention contains a dispersant, the proportion of the dispersant is not particularly limited. In the total solids content of the coloring resin composition, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less. Setting the content to the lower limit or above tends to improve dispersibility and storage stability. Setting the content to the upper limit or below tends to improve electrical reliability and developability.

[0531] The aforementioned upper and lower limits can be combined arbitrarily. For example, the proportion of dispersant in the total solids of the coloring resin composition 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.

[0532] When the coloring resin composition of the present invention contains pigment and dispersant, the proportion of dispersant is not particularly limited. It is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less.

[0533] The aforementioned upper and lower limits can be combined arbitrarily. For example, the content ratio of the dispersant relative to 100 parts by weight of pigment is preferably 0.5 to 70 parts by weight, more preferably 5 to 70 parts by weight, even more preferably 10 to 50 parts by weight, even more preferably 15 to 40 parts by weight, and particularly preferably 20 to 30 parts by weight. By setting it within the above range, there is a tendency to obtain a coloring resin composition with excellent dispersion stability and high brightness.

[0534] When the coloring resin composition of the present invention contains pigments, in order to improve the dispersibility and dispersion stability of the pigments, pigment derivatives may be included as dispersing aids, for example. Examples of pigment derivatives include derivatives of azo, phthalocyanine, quinacrine, benzimidazolone, quinophthalone, isoindolineone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, pyrene, diketopyrrolopyrrole, and dioxazine pigments.

[0535] Examples of substituents used in pigment derivatives include sulfonic acid groups, sulfonamide groups, quaternary salts of sulfonamide groups, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups. These substituents can be bonded to the pigment skeleton via, for example, alkyl, aryl, or heterocyclic groups, or directly. Sulfonamide groups, quaternary salts of sulfonamide groups, and sulfonic acid groups are preferred substituents, with sulfonic acid groups being more preferred.

[0536] It can be a pigment skeleton with multiple substituents, or it can be a mixture of compounds with different numbers of substitutions.

[0537] Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinoline pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacrine pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[0538] [1-5-3] Surfactants

[0539] When the coloring resin composition of the present invention contains a surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used. From the viewpoint of minimizing the possibility of adversely affecting the various properties of the coloring resin composition of the present invention, nonionic surfactants are preferred.

[0540] When the coloring resin composition of the present invention contains a surfactant, the proportion of the surfactant is not particularly limited. It is generally used in the total solids content of the coloring resin composition in the range of 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and generally 10% by mass or less, preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0541] The aforementioned upper and lower limits can be combined arbitrarily. For example, the content of surfactant in the total solids of the coloring resin composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, even more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.3% by mass.

[0542] [2] Preparation of coloring resin composition

[0543] When preparing a coloring resin composition containing pigment as a colorant, pigment, solvent, and dispersant are weighed in predetermined amounts, and the pigment-containing colorant is dispersed in a dispersion treatment step to prepare a pigment dispersion. As described above, it is preferable to use, for example, a dispersing aid and / or a dispersing resin in combination in the dispersion treatment step.

[0544] In the dispersion process, for example, a paint shaker, sand mill, ball mill, roller mill, stone mill, jet mill, or homogenizer can be used. This dispersion process micronizes the colorant, thereby improving the coating characteristics of the coloring resin composition and increasing the transmittance of the pixels on the finished color filter substrate. When using a sand mill for dispersion, glass beads or zirconia beads with a diameter of 0.1 to several mm are preferably used.

[0545] The temperature for dispersion is typically set above 0°C, preferably above room temperature, and typically below 100°C, preferably below 80°C. For example, it can be set to 0–100°C, 0–80°C, or room temperature to 80°C. The appropriate time varies depending on the composition of the pigment dispersion and the size of the sand mill, etc., so the dispersion time can be adjusted accordingly.

[0546] A homogeneous dispersion solution is prepared by mixing a solvent, an alkali-soluble resin, a photopolymerization initiator, and other components not mentioned above, as needed, into the pigment dispersion obtained through the dispersion treatment process. It should be noted that fine dust particles may sometimes be introduced during the dispersion treatment and mixing processes; therefore, it is preferable to filter the obtained pigment dispersion solution using a filter or similar device.

[0547] When preparing a coloring resin composition that does not contain pigment, the colorant, solvent, alkali-soluble resin, photopolymerization initiator, and other components not mentioned above, if used as needed, can be mixed to obtain a homogeneous solution. It is preferable to filter the obtained solution using a filter or the like.

[0548] [3] Fabrication of color filter substrate

[0549] The color filter of the present invention has pixels formed using the coloring resin composition of the present invention.

[0550] [3-1] Transparent substrate (support)

[0551] As for the transparent substrate of a color filter, its material is not particularly limited, as long as it is transparent and has suitable strength. Examples include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets made of polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic resin, or various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred.

[0552] To improve surface properties such as adhesion, the transparent substrate and the black matrix forming substrate may be subjected to various resin film formation processes, such as corona discharge treatment, ozone treatment, silane coupling agent, or urethane resin, as needed. The thickness of the transparent substrate is typically set to 0.05 mm or more, preferably 0.1 mm or more, and also typically 10 mm or less, preferably 7 mm or less, for example, 0.05–10 mm, 0.1–10 mm, 0.05–7 mm, or 0.1–7 mm. Furthermore, when performing various resin film formation processes, the film thickness is typically 0.01 μm or more, preferably 0.05 μm or more, and also typically 10 μm or less, preferably 5 μm or less, for example, 0.01–10 μm, 0.05–10 μm, 0.01–5 μm, or 0.05–5 μm.

[0553] [3-2] Black Matrix

[0554] The color filter of the present invention can be manufactured by forming a black matrix on the aforementioned transparent substrate and typically further forming red, green, and blue pixel images. The coloring resin composition of the present invention is preferably used as a coating liquid for forming green or blue pixels (resist pattern) among the red, green, and blue pixels. A resist pattern forming coating liquid containing the coloring resin composition of the present invention is applied to the resin black matrix forming surface formed on the transparent substrate or to the metallic black matrix forming surface formed using a light-shielding metal material, followed by various treatments such as heating and drying, image exposure, development, and thermosetting, thereby forming a pixel image.

[0555] A black matrix is ​​formed on a transparent substrate using a light-shielding metal material or a black matrix colored resin composition. As the light-shielding metal material, chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, as well as nickel and tungsten alloys, can be used, and they can be stacked in multiple layers.

[0556] Light-shielding metal films are typically formed using sputtering. After forming the desired pattern in film form with a positive photoresist, a chromium compound is etched using a mixed etchant of cerium ammonium nitrate and perchloric acid and / or nitric acid. For other materials, an etchant appropriate to the material is used. The positive photoresist is then stripped with a special stripping agent, thereby forming a black matrix.

[0557] For example, a thin film of a light-shielding metallic material is formed on a transparent substrate using methods such as vapor deposition or sputtering. Next, a coating of a colored resin composition is formed on this light-shielding metallic film. Then, a photomask with repeating patterns such as stripes, mosaics, or triangles is used to expose and develop the coating to form a resist image. Finally, the coating can be etched to form a black matrix.

[0558] When using a photosensitive coloring resin composition for a black matrix, a coloring resin composition containing a black colorant is used to form the black matrix. For example, a coloring resin composition containing one or more black coloring materials such as carbon black, graphite, iron black, aniline black, Cyanine Black, and titanium black, or a black coloring material obtained by mixing appropriately selected red, green, and blue pigments or dyes from inorganic or organic pigments or dyes, can be used to form a black matrix by operating in the same manner as the method for forming red, green, and blue pixel images described later.

[0559] [3-3] Pixel formation

[0560] A coloring resin composition of one of the colors red, green, and blue is coated onto a transparent substrate with a black matrix. After drying, a photomask is superimposed on the coating. The image is then exposed, developed, and thermally or photocured as needed through the photomask to form a pixel image. By performing this operation on the red, green, and blue coloring resin compositions respectively, a color filter image can be formed.

[0561] The coating of the coloring resin composition for color filters can be performed using methods such as spin coating, wire rod coating, flow coating, die coating, roller coating, and spray coating. Die coating significantly reduces the amount of coating liquid used, completely eliminates the effects of mist or other impurities that occur with spin coating, and also suppresses the formation of foreign matter, making it the preferred method from a comprehensive viewpoint.

[0562] The coating thickness, measured by the dried film thickness, is typically 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and typically 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. By setting it to the lower limit or above, it is easy to increase the pigment concentration, making it easier to express the desired color. By setting it to the upper limit or below, pattern development becomes easier, and the gap can be easily adjusted during the liquid crystal cell forming process.

[0563] The aforementioned upper and lower limits can be combined arbitrarily. For example, the thickness of the coating is preferably 0.2 to 20 μm, more preferably 0.5 to 10 μm, and even more preferably 0.8 to 5 μm.

[0564] [3-4] Drying of the coating

[0565] The drying (pre-baking) of the coating film after coating the colored resin composition onto the transparent substrate can be carried out, for example, by using a drying method using a hot plate, an IR oven, a convection oven, etc., or by a decompression drying method in a decompression chamber without increasing the temperature.

[0566] Typically, in drying methods using hot plates, IR ovens, convection ovens, etc., the material is reheated after pre-drying for further drying.

[0567] The pre-drying conditions can be selected based on the type of solvent and the performance of the dryer used.

[0568] The drying temperature for pre-drying is typically above 40°C, preferably above 50°C, and typically below 80°C, preferably below 70°C, for example, 40–80°C, 40–70°C, 50–80°C, or 50–70°C.

[0569] The pre-drying time is typically 15 seconds or more, preferably 30 seconds or more, and typically less than 5 minutes, preferably less than 3 minutes, for example, 15 seconds to 5 minutes, 30 seconds to 5 minutes, 15 seconds to 3 minutes, or 30 seconds to 3 minutes.

[0570] The preferred temperature for re-drying is a temperature higher than the pre-drying temperature.

[0571] The drying temperature for re-drying is typically above 50°C, preferably above 70°C, and typically below 200°C, preferably below 160°C, and particularly preferably below 130°C, for example, 50–200°C, 50–160°C, 50–130°C, 70–200°C, 70–160°C, or 70–130°C.

[0572] The drying time for re-drying also depends on the heating temperature, and is usually more than 10 seconds, preferably more than 15 seconds, and usually less than 10 minutes, preferably less than 5 minutes, for example, 10 seconds to 10 minutes, 15 seconds to 10 minutes, 10 seconds to 5 minutes, and 15 seconds to 5 minutes.

[0573] When the drying temperature is below the upper limit mentioned above, sufficient adhesion to the transparent substrate can be obtained. On the other hand, it is less likely to induce thermal polymerization caused by the decomposition of the adhesive resin and less likely to produce poor development.

[0574] [3-5] Exposure process

[0575] Image exposure is performed by overlaying a negative matrix pattern onto a coating of the coloring resin composition and irradiating it with an ultraviolet or visible light source through the mask pattern. To prevent a decrease in sensitivity of the photopolymerizable layer caused by oxygen, an oxygen-blocking layer, such as a polyvinyl alcohol layer, can be formed on the photopolymerizable layer before exposure, as needed. The light source used in the above image exposure is not particularly limited. Examples of light sources include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, etc.; and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, etc. When using light of a specific wavelength for irradiation, optical filters can also be used.

[0576] [3-6] Developing process

[0577] After exposing a coating film using the coloring resin composition of the present invention to an image using the aforementioned light source, development is performed using an aqueous solution containing a surfactant and an alkaline compound, thereby forming an image on a substrate to manufacture the color filter of the present invention. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes, or pigments.

[0578] Examples of basic compounds include inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds can be used alone or in combination of two or more.

[0579] Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aromatic ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkylesters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0580] Examples of organic solvents include isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents can be used in combination with aqueous solutions.

[0581] There are no particular restrictions on the developing conditions. The developing temperature is generally above 10°C, preferably above 15°C, more preferably above 20°C, and generally below 50°C, preferably below 45°C, more preferably below 40°C. For example, 10–50°C, 10–45°C, 10–40°C, 15–50°C, 15–45°C, 15–40°C, 20–50°C, 20–45°C, and 20–40°C are preferred. The developing method can be based on any of the following: immersion developing, spray developing, brush developing, ultrasonic developing, etc.

[0582] [3-7] Thermosetting treatment

[0583] The developed color filter is subjected to heat curing treatment.

[0584] The temperature during the thermosetting process is typically above 100°C, preferably above 150°C, and typically below 280°C, preferably below 250°C, for example, 100–280°C, 100–250°C, 150–280°C, or 150–250°C.

[0585] The time for thermosetting is between 5 minutes and 60 minutes.

[0586] Through this series of processes, a patterned image of one color is formed. This process is repeated sequentially to pattern black, red, green, and blue, thus forming a color filter. It should be noted that the order in which these four colors are patterned is not limited to the order described above.

[0587] [3-8] Formation of transparent electrodes

[0588] The color filter of the present invention can directly form transparent electrodes such as ITO on the image and be used as part of a color display, liquid crystal display device, etc. However, in order to improve surface smoothness and durability, a surface coating such as polyamide or polyimide can also be provided on the image as needed. In addition, in some applications such as planar orientation type driving mode (IPS mode), transparent electrodes are sometimes not formed.

[0589] [4] Image display device (panel)

[0590] The image display device of the present invention includes the color filter of the present invention. Examples of image display devices include liquid crystal display devices and organic EL display devices.

[0591] [4-1] Liquid Crystal Display Device

[0592] The liquid crystal display device is manufactured as follows: an alignment film is formed on the color filter of the present invention, and spacers are dispersed on the alignment film. This film is then bonded to an opposing substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell and connected to an opposing electrode, thereby manufacturing the device. The alignment film is preferably a resin film such as polyimide. When forming the alignment film, gravure printing and / or flexographic printing are typically used, and the thickness of the alignment film is set to several tens of nm. After curing the alignment film by thermal firing, a surface treatment is performed by ultraviolet irradiation or by using a rubbing cloth to process it into a surface state that allows adjustment of the liquid crystal tilt.

[0593] The spacers can be spacers of a size corresponding to the gap between the opposing substrates, typically 2–8 μm. Alternatively, photosensitive spacers made of a transparent resin film can be formed on the color filter substrate using photolithography and used in place of the spacers. Array substrates are commonly used as opposing substrates, and thin-film transistor substrates are particularly suitable.

[0594] The gap between the liquid crystal display cell and the opposing substrate varies depending on the application of the liquid crystal display device, and is typically selected within the range of 2μm to 8μm. After bonding with the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, thus sealing the area around the liquid crystal cell.

[0595] After the sealed liquid crystal cell is cut into panel units, it is depressurized in a vacuum chamber. The liquid crystal injection port is then immersed in liquid crystal and leaks into the chamber, thereby injecting the liquid crystal into the liquid crystal cell.

[0596] The pressure reduction level inside the liquid crystal cell is typically 1×10⁻⁶. -2 Pa or higher, preferably 1×10 -3 The above, in addition, usually 1×10 -7 Pa or below, preferably 1×10 -6 The range below Pa, for example, 1×10 -2 ~1×10 -7 Pa, 1×10 -2 ~1×10 -6 Pa, 1×10 -3 ~1×10 -7 1×10 -3 ~1×10 -6 .

[0597] Preferably, the liquid crystal cell is heated during decompression. The heating temperature is typically above 30°C, preferably above 50°C, and typically below 100°C, preferably below 90°C, for example, 30–100°C, 30–90°C, 50–100°C, or 50–90°C.

[0598] The temperature rise during decompression is typically maintained within a range of 10 to 60 minutes, followed by immersion in liquid crystal. The liquid crystal injection port of the liquid crystal cell is then sealed by curing with UV-curable resin, thus completing the liquid crystal display device (panel).

[0599] There is no particular limitation on the type of liquid crystal; it can be any of the currently known liquid crystals, such as aromatic liquid crystals, aliphatic liquid crystals, and polycyclic compounds, or any of the following: lyotropic liquid crystals and thermotropic liquid crystals. As thermotropic liquid crystals, known examples include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals; any of these can be used.

[0600] [4-2] Organic EL display device

[0601] Organic EL display devices having the color filter of the present invention, for example, Figure 1 As shown, a pixel 20 is formed on a transparent support substrate 10 using the coloring resin composition of the present invention. An organic light emitter 500 is stacked on the blue filter on which the pixel 20 is formed, with an organic protective layer 30 and an inorganic oxide film 40 in between, thereby enabling the fabrication of a multi-colored organic EL element.

[0602] Examples of stacking methods for the organic light emitter 500 include: forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 sequentially on the upper surface of a color filter; and attaching the organic light emitter 500 formed on another substrate to an inorganic oxide film 40.

[0603] The organic EL element 100 manufactured in this way can be used in both passive and active driven organic EL display devices.

[0604] Example

[0605] The present invention will now be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples without departing from its spirit.

[0606] <Phalocyanine dye A>

[0607] Phthalocyanine dye A with the following chemical structure was synthesized using Example 30 based on Japanese Patent Application Publication No. 05-345861.

[0608]

[0609] <Xanton series dye A>

[0610]

[0611] Under a nitrogen atmosphere, N-acetamide phenol (13.0 g, 86 mmol) and 1,4-dibromobutane (30.6 mL, 258 mmol) were dissolved in acetone (200 mL), followed by the addition of potassium carbonate (23.8 g, 172 mmol). The mixture was stirred under reflux for 16 hours. The reaction solution was cooled to room temperature, and after filtering out the potassium carbonate, hexane (200 mL) was added. The resulting solid was filtered off and dried to give compound 1 (26.2 g).

[0612]

[0613] Compound 2 (4.59 g, 8 mmol) and compound 1 (8.0 g, 28 mmol), synthesized by the method described in Japanese Patent Application Publication No. 2013-253168, were dissolved in N,N'-dimethylformamide (50 mL), and potassium carbonate (3.3 g, 24 mmol) was added. The mixture was stirred at 80 °C for 16 hours. After cooling to room temperature, the reaction solution was added to water (100 mL). The obtained solid was filtered off and purified by silica gel column chromatography (chloroform / methanol = 100 / 0 to 90 / 10 (v / v)). The purified solid was then dried under vacuum at 10 mmHg and 70 °C for 24 hours to obtain xanthonite dye A (6.5 g, yield 65%).

[0614] <Xanton series dyes B>

[0615]

[0616] Xanton-based dye B was synthesized using the method described in Japanese Patent Application Publication No. 2020-23660.

[0617] <Dispersant A>

[0618] This is a methacrylic acid-based AB block copolymer composed of A blocks with nitrogen-containing functional groups and B blocks with solubilizing groups. It has repeating units shown in formula (1a), formula (2a), formula (3a), formula (4a), and formula (5a). The amine value is 120 mg KOH / g, and the acid value is less than 1 mg KOH / g.

[0619] The proportions of the repeating units shown in equations (1a), (2a), (3a), (4a) and (5a) in the total number of repeating units are less than 1 mol%, 34.5 mol%, 6.9 mol%, 13.8 mol%, and 6.9 mol%, respectively.

[0620]

[0621] <Dispersant B>

[0622] This is a methacrylic acid-based AB block copolymer composed of A blocks with nitrogen-containing functional groups and B blocks with solubilizing groups. It has repeating units shown in formula (1a), formula (2a), formula (3a), formula (4a), and formula (5a). The amine value is less than 1 mg KOH / g, and the acid value is less than 1 mg KOH / g.

[0623] The proportions of the repeating units shown in equations (1a), (2a), (3a), (4a) and (5a) in the total repeating units are 34.5 mol%, less than 1 mol%, 6.9 mol%, 13.8 mol%, and 6.9 mol%, respectively.

[0624]

[0625] <Dispersion Resin A>

[0626] Prepare a separable flask with a condenser to serve as the reaction vessel. Add 400 parts by weight of propylene glycol monomethyl ether acetate, purge with nitrogen, and then heat in an oil bath while stirring to raise the temperature of the reaction vessel to 90°C.

[0627] On the other hand, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of tert-butyl peroxide-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were added to the monomer tank, while 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were added to the chain transfer agent tank. After the temperature of the reaction tank stabilized at 90°C, the additives were started dropwise from the monomer tank and the chain transfer agent tank to initiate polymerization. The addition was carried out dropwise for 135 minutes while maintaining the temperature at 90°C. After the addition was completed, the temperature was raised to 110°C after 60 minutes.

[0628] After maintaining the mixture at 110°C for 3 hours, a gas inlet tube was installed on a separable flask, and bubbling of a gas mixture of oxygen / nitrogen = 5 / 95 (v / v) was initiated. Next, 39.6 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethylamine were added to the reaction vessel, and the reaction was continued at 110°C for 9 hours under these conditions.

[0629] After cooling to room temperature, dispersion resin A was obtained with a weight-average molecular weight (Mw) of 9000 converted from polystyrene using GPC and an acid value of 101 mg KOH / g.

[0630] <Alkali-soluble resin A>

[0631] For 145 parts by mass of propylene glycol monomethyl ether acetate, the mixture was stirred while purging with nitrogen and heated to 120°C. Then, 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate, and 10 parts by mass of monomethacrylate with a tricyclic decane backbone (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and the mixture was stirred continuously at 120°C for 2 hours. Next, the reaction vessel was changed to air purging, and 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 50 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. Then, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was continued at 120°C for 3.5 hours. The resulting alkali-soluble resin A had a weight-average molecular weight (Mw) of 9000 converted from polystyrene by GPC, and an acid value of 25 mg KOH / g.

[0632] <Alkali-soluble resin B>

[0633] For 145 parts by mass of propylene glycol monomethyl ether acetate, the mixture was stirred while purging with nitrogen and heated to 120°C. Then, 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of monomethacrylate with a tricyclic decane backbone (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and the mixture was stirred continuously at 120°C for 2 hours. Next, the reaction vessel was changed to air purging, and 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 27 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. Then, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was continued at 120°C for 3.5 hours. The resulting alkali-soluble resin B had a weight-average molecular weight (Mw) of 8000 converted from polystyrene by GPC, and an acid value of 80 mg KOH / g.

[0634] <Preparation of Green Dye Dispersion A>

[0635] As shown in Table 1, 9.9 parts by weight of phthalocyanine dye A, 0.1 parts by weight of dispersant A (converted to solids), 72.0 parts by weight of propylene glycol monomethyl ether acetate (containing solvent from dispersant A), 18.0 parts by weight of propylene glycol monomethyl ether, and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing green dye dispersion A.

[0636] <Preparation of Green Pigment Dispersion A>

[0637] As shown in Table 1, 13.9 parts by weight of CI pigment green 58, 1.9 parts by weight of dispersant A (based on solids content), 4.2 parts by weight of dispersion resin A (based on solids content), 80.0 parts by weight of propylene glycol monomethyl ether acetate as solvent (also including solvent from dispersant A and solvent from dispersion resin A), and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing green pigment dispersion A.

[0638] <Preparation of Yellow Pigment Dispersion A>

[0639] As shown in Table 1, 11.4 parts by weight of CI Pigment Yellow 138, 2.9 parts by weight of dispersant A (based on solids content), 5.7 parts by weight of dispersion resin A (based on solids content), 76.0 parts by weight of propylene glycol monomethyl ether acetate (as solvent, also including solvent from dispersant A and solvent from dispersion resin A), 4.0 parts by weight of propylene glycol monomethyl ether, and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing yellow pigment dispersion A.

[0640] [Table 1]

[0641]

[0642] <Preparation of Blue Pigment Dispersion A>

[0643] As shown in Table 2, 12.4 parts by weight of CI Pigment Blue 15:6, 3.5 parts by weight of dispersant B (based on solids content), 4.1 parts by weight of dispersion resin A (based on solids content), 56.0 parts by weight of propylene glycol monomethyl ether acetate as solvent (including solvent from dispersant B and solvent from dispersion resin A), 24.0 parts by weight of propylene glycol monomethyl ether, and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing blue pigment dispersion A.

[0644] <Preparation of Purple Dye Dispersion A>

[0645] As shown in Table 2, 11.5 parts by weight of xanthan dye A, 4.6 parts by weight of dispersant B (converted to solids content), 3.9 parts by weight of dispersing resin A (converted to solids content), 76.0 parts by weight of propylene glycol monomethyl ether acetate (also including solvent from dispersant B and solvent from dispersing resin A), 4.0 parts by weight of propylene glycol monomethyl ether, and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing purple dye dispersion A.

[0646] [Table 2]

[0647]

[0648] <Preparation of Red Dye Dispersion A>

[0649] As shown in Table 3, 9.7 parts by weight of CI pigment red 177, 2.4 parts by weight of xanthan dye B, 3.1 parts by weight of dispersant B (based on solids content), 4.8 parts by weight of dispersion resin A (based on solids content), 72.0 parts by weight of propylene glycol monomethyl ether acetate (also including solvent from dispersant B and solvent from dispersion resin A), 8.0 parts by weight of propylene glycol monomethyl ether, and 225 parts by weight of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container and dispersed using a paint shaker for 6 hours. After dispersion, the beads were separated from the dispersion using a filter, thereby preparing red dye dispersion A.

[0650] [Table 3]

[0651]

[0652] <Photopolymerizable monomer A>

[0653] A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0654] <Photopolymerizable monomer B>

[0655] Polyethoxylated tetrahydroxymethylmethane tetraacrylate (NK ESTER ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0656] <Photopolymerization Initiator A>

[0657] Oxime ester compounds having the following chemical structures.

[0658]

[0659] <Photopolymerization Initiator B>

[0660] Oxime ester compounds having the following chemical structures.

[0661] (Methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxovalerate)

[0662]

[0663] <Antioxidant A>

[0664] Irganox 1010: Hindered phenolic antioxidant (manufactured by BASF)

[0665] <Chain transfer agent A>

[0666] Pentaerythritol tetra(3-mercaptopropionate) (manufactured by Starch Chemical Company)

[0667] <Surfactant A>

[0668] MEGAFAC F-554 (manufactured by DIC)

[0669] <Preparation of Coloring Resin Compositions>

[0670] The coloring resin composition was prepared by mixing the components listed in Tables 4, 5, and 6 at the stated solid content ratios. It should be noted that propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used to achieve a total solid content of 18.0% by mass in the coloring resin composition. The resulting coloring resin composition had a PGMEA / PGME mixing ratio (by mass) of 90 / 10.

[0671] [Table 4]

[0672]

[0673] [Table 5]

[0674]

[0675] [Table 6]

[0676]

[0677] <Determination of Color Characteristics>

[0678] The aforementioned coloring resin composition was applied to a 50 mm square, 0.7 mm thick glass substrate (AN100, manufactured by AGC) using spin coating, dried under reduced pressure, and then pre-baked on a hot plate at 90°C for 90 seconds. Next, it was heated using a 2 kW high-pressure mercury lamp at 40 mJ / cm². 2Exposure, illuminance 30mW / cm 2 Perform full-area exposure. Then, develop using a 0.04% (w / w) potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Next, develop at 1 kg / cm². 2 The substrate is then subjected to a 10-second spray water wash under high water pressure. Next, it undergoes a 20-minute thermosetting process at 230°C in a clean oven to produce the colored substrate.

[0679] For the green-colored substrates of Examples 1-2 and Comparative Examples 1-2, the transmission spectra were measured using a Hitachi U-3310 spectrophotometer, and the luminance at a chromaticity of sy = 0.578 under C light source was calculated. The results are shown in Table 4.

[0680] Similarly, the luminance of the blue-colored substrates of Example 3 and Comparative Example 3 at a chromaticity of sy = 0.101 under light source C was calculated. The results are shown in Table 5.

[0681] Similarly, the luminance of the red-colored substrates of Example 4 and Comparative Example 4 at a chromaticity of sx = 0.686 under light source C was calculated. The results are shown in Table 6.

[0682] <Evaluation of Pattern Formation>

[0683] The above-mentioned coloring resin composition was applied to a 50mm square, 0.7mm thick glass substrate (manufactured by AGC, AN100) using a spin coating method. It should be noted that in Examples 1-2 and Comparative Examples 1-2, the spin speed was adjusted to a chromaticity (sy) of 0.578 after thermosetting. In Example 3 and Comparative Example 3, the spin speed was adjusted to a chromaticity (sy) of 0.101 after thermosetting. Furthermore, in Example 4 and Comparative Example 4, the spin speed was adjusted to a chromaticity (sx) of 0.686 after thermosetting.

[0684] Each coating was pre-baked at 70°C for 90 seconds. Then, it was heated using a 2kW high-pressure mercury lamp at 40mJ / cm². 2 Exposure, illuminance 30mW / cm 2 Exposure was performed through an exposure mask with a circular cover of 30 μm in diameter. Then, development was performed for 60 seconds using a 0.04% (w / w) potassium hydroxide aqueous solution at a developer temperature of 23°C. Following this, development was carried out at 1 kg / cm². 2 The substrate was subjected to a 10-second spray water wash under high water pressure. Then, it underwent a heat curing process at 230°C for 20 minutes to produce patterned substrate A. The diameter (μm) of the holes in the pattern (hole diameter A) was measured using an optical microscope for the resulting patterned substrate A.

[0685] Then, in the above-described process of pattern substrate A, the pre-baking temperature was changed from 70°C to 90°C, and pattern substrate B was fabricated under the same conditions. For the obtained pattern substrate B, the diameter (μm) of the holes in the pattern (hole diameter B) was measured using an optical microscope.

[0686] The effect of pre-baking temperature on the pore diameter was calculated using pore size A and pore size B, serving as an indicator of temperature dependence. The results of the pore size pre-baking temperature dependence (=│(pore size A - pore size B)[μm] / (90-70)[℃]│) are shown in Tables 4, 5, and 6. The smaller the pore size pre-baking temperature dependence, the smaller the impact of pre-baking temperature changes on sensitivity, and the more precisely the linewidth can be adjusted; therefore, this is preferred.

[0687] As shown in Table 4, compared with the coloring resin composition containing CI pigment green 58 (pigment) in Comparative Example 1, the brightness is improved when phthalocyanine dye (1) is used as in Comparative Example 2. However, due to the use of phthalocyanine dye (1), the pre-baking temperature dependence of pore size becomes greater.

[0688] As can be seen from Comparative Examples 1 and 2, the pre-baking temperature dependence of pore size increases due to the use of dyes as colorants.

[0689] Generally, regardless of the type of colorant, there is a lot of residual solvent in the low-temperature range of 70°C during pre-baking. Therefore, it is believed that the film thickness will increase, the distance between polymeric groups will increase, thus reducing sensitivity, resulting in insufficient curing and larger pore size.

[0690] Comparative Example 1 contains pigments but no dyes. Therefore, the pigments have a low affinity for the developer, thus inhibiting the penetration of the developer into the pigment-containing coating. Over-development is also less likely in low-temperature regions where curing is insufficient. Consequently, the pore size is less susceptible to change due to variations in pre-baking temperature, exhibiting low pre-baking temperature dependence, and it is considered that no pre-baking temperature dependence issue will arise.

[0691] On the other hand, Comparative Example 2 contains a dye composition, thus exhibiting high affinity for the developer, which is believed to promote the dissolution of the coating in the developer. Furthermore, it is considered that the dye has a larger specific surface area than the pigment, making it easier for the photopolymerization initiator to undergo free radical deactivation on the colorant surface. It can be argued that, due to these factors, in Comparative Example 2, at a low-temperature region such as a pre-baking temperature of 70°C, not only is the dissolution of the coating in the developer promoted, but the free radical deactivation of the photopolymerization initiator is also promoted, resulting in larger pore sizes and thus a greater dependence of pore size on the pre-baking temperature.

[0692] In contrast, Examples 1 and 2 maintained high brightness and had low dependence on the pre-baking temperature of the aperture.

[0693] Examples 1 and 2 are examples in which the carbazole-based photopolymerization initiator B in Comparative Example 2 is replaced with the photopolymerization initiator (d1) shown in Formula (I) above. It can be considered that in the photopolymerization initiator (d1), the group bonded to the (keto)oxime ester group is a low-reactivity indole ring. Therefore, compared with the photopolymerization initiator B, which has a highly reactive carbazole ring, the decomposition and reaction rate are slower and free radicals are continuously and intermittently generated. Thus, free radical deactivation is less likely to occur in low-temperature regions with a lot of residual solvent, such as a pre-baking temperature of 70°C. As a result, the curability of the coating film is improved and the dependence of pore size on the pre-baking temperature is reduced.

[0694] Furthermore, as can be seen from the comparison between Example 3 and Comparative Example 3 and the comparison between Example 4 and Comparative Example 4, similarly to the comparison between Example 1 and Comparative Example 2, even oxalite dyes (10) with a skeleton different from phthalocyanine dyes (1) can achieve the effect of improving the pre-baking temperature dependence of pore size by using the photopolymerization initiator (d1) shown in the above formula (I).

[0695] The present invention has been described in detail using specific methods, but those skilled in the art will of course make various changes and modifications without departing from the intent and scope of the present invention.

[0696] Explanation of reference numerals in the attached figures

[0697] 10 Transparent support substrate

[0698] 20 pixels

[0699] 30 Organic protective layer

[0700] 40 Inorganic oxide film

[0701] 50 transparent anode

[0702] 51 Hole Injection Layer

[0703] 52 Hole Transport Layer

[0704] 53. Emissive Layer

[0705] 54 Electron Injection Layer

[0706] 55 Cathode

[0707] 100 Organic EL Components

[0708] 500 Organic Light-Emitting Organoluminescent Materials

Claims

1. A coloring resin composition, characterized in that, It contains (A) colorant, (B) solvent, (C) alkali-soluble resin and (D) photopolymerization initiator. The colorant (A) comprises a phthalocyanine dye having the chemical structure shown in the following general formula (1). The content of the photopolymerization initiator (D) in the total solids component of the colored resin composition is 0.5% by mass or more and 10% by mass or less. The (D) photopolymerization initiator comprises the photopolymerization initiator (d1) shown in the following general formula (I). The photopolymerization initiator (d1) in the total solids composition of the colored resin composition accounts for 0.5% by mass or more. In equation (1), A 1 ~A 16 Each of these groups independently represents a hydrogen atom, a halogen atom, or a group represented by the general formula (2) below, wherein A 1 ~A 16 One or more of them represent the groups shown in the following general formula (2), In formula (2), X represents a divalent linking group, the benzene ring in formula (2) can be optionally equipped with any substituents, and * represents a linking bond. In equation (I), R d1 This indicates an alkyl group optionally having a substituent or an aromatic cyclogroup optionally having a substituent. R d2 This indicates an alkyl group optionally having a substituent or an aromatic cyclogroup optionally having a substituent. p represents 0 or 1. R d3 This indicates an aromatic cyclic group with optional substituents.

2. The coloring resin composition according to claim 1, wherein, In the above formula (1), A 1 ~A 16 Six or more in the character represent fluorine atoms.

3. A coloring resin composition, characterized in that, It contains (A) colorant, (B) solvent, (C) alkali-soluble resin and (D) photopolymerization initiator. The colorant (A) comprises a zeatin dye having the chemical structure shown in the following general formula (10), The content of the photopolymerization initiator (D) in the total solids component of the colored resin composition is 0.5% by mass or more and 10% by mass or less. The (D) photopolymerization initiator comprises the photopolymerization initiator (d1) shown in the following general formula (I). The photopolymerization initiator (d1) in the total solids composition of the colored resin composition accounts for 0.5% by mass or more. In equation (10), R a1 ~R a4 Each can independently represent an alkyl group optionally having a substituent or an aromatic cyclogroup optionally having a substituent. R a5 Indicates -SO3 - or -COO - , n represents an integer from 1 to 5. In equation (I), R d1 This indicates an alkyl group optionally having a substituent or an aromatic cyclogroup optionally having a substituent. R d2 This indicates an alkyl group optionally having a substituent or an aromatic cyclogroup optionally having a substituent. p represents 0 or 1. R d3 This indicates an aromatic cyclic group with optional substituents.

4. The coloring resin composition according to any one of claims 1 to 3, wherein, In the photopolymerization initiator (d1), R d3 It is a benzene ring with one free valence and optionally substituents.

5. The coloring resin composition according to any one of claims 1 to 3, wherein, The colorant (A) is present in an amount of 15% by mass or more in the total solids.

6. The coloring resin composition according to any one of claims 1 to 3, wherein, The proportion of the photopolymerization initiator (d1) in the total solids content is more than 1.0% by mass.

7. A color filter having pixels made using the coloring resin composition according to any one of claims 1 to 6.

8. An image display device having the color filter of claim 7.

Images