Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device

Abstract

Provided is a photosensitive coloring composition that reduces the occurrence of surface roughness on an electrode after heat treatment. The photosensitive coloring composition of the present invention comprises (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, wherein the coloring agent (a) comprises a compound represented by the specific general formula (I), a geometric isomer of the compound, a salt of the compound, or a salt of a geometric isomer of the compound, and the dispersant (f) comprises an acrylic copolymer (f1) comprising repeating units represented by the specific general formulas (1), (2), and (3) and having no repeating units containing a quaternary ammonium group, and wherein the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less relative to the total solid content of the photosensitive coloring composition.

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition, a cured product, an organic electroluminescent element, and an image display device.

[0002] This application claims priority based on Japanese Patent Application No. 2020-162460 filed in Japan on September 28, 2020, and Japanese Patent Application No. 2021-024490 filed in Japan on February 18, 2021, the contents of which are incorporated herein by reference. Background Art

[0003] Liquid crystal displays (LCDs) utilize the property of liquid crystal molecules to switch their arrangement depending on the voltage applied to the liquid crystals. The components that make up the LCD cell are often formed using methods such as photolithography, which utilize photosensitive compositions. These photosensitive compositions facilitate the formation of fine structures and the processing of substrates for large screens, leading to a continued expansion in their application.

[0004] Image display devices containing organic electroluminescent elements (also called organic electroluminescence or organic EL) are attracting attention as next-generation flat panel displays (FPDs) due to their excellent visual recognition and responsiveness, including contrast and viewing angle, low power consumption, thinness and lightness, and the flexibility of the display body.

[0005] An organic electroluminescent element has a structure in which an organic layer, including a light-emitting layer or various functional layers, is sandwiched between a pair of electrodes, at least one of which is light-transmitting. Image display devices display images by driving a panel in which an organic electroluminescent element is placed at each pixel.

[0006] Conventionally, such organic electroluminescent elements are manufactured by forming banks on a substrate and then laminating a light-emitting layer or various functional layers in the region surrounded by the banks.

[0007] When forming a light-emitting layer or the like in a region surrounded by partition walls, a vapor deposition method is mainly used in which a material is sublimated in a vacuum state and adhered to a substrate to form a film.

[0008] In recent years, wet film formation methods such as cast film, spin coating, and inkjet printing have attracted attention. Inkjet printing, in particular, can reduce uneven film thickness when forming large areas and, by applying the coating layer in separate layers, achieves higher-definition displays, reduces material usage, and improves yield, making it suitable for forming organic layers in large panels.

[0009] As a method for easily forming partition walls, a method of forming the partition walls by photolithography using a photosensitive composition is known. In addition, as a method for imparting light-shielding properties to the partition walls and suppressing light leakage between pixels, a method of adding a colorant to the photosensitive composition is known.

[0010] Patent Document 1 describes a colored photosensitive resin composition that suppresses the generation of outgassing by using a specific organic black pigment and an alkali-soluble resin.

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: International Publication No. 2018 / 101314 Summary of the Invention

[0014] Problems to be solved by the invention

[0015] Organic electroluminescent devices come in two types: top-emitting and bottom-emitting. In the top-emitting mode, a reflective electrode, such as silver, is used as the electrode, and a cured material, such as a partition wall, is formed thereon. During heat treatment, the components of the photosensitive composition react, sometimes causing corrosion or migration of the metal electrode. If the electrode surface has irregularities (hereinafter referred to as surface roughness), the light-emitting layer cannot be uniformly formed in these areas, potentially causing display defects due to short circuits and other factors in the organic electroluminescent device.

[0016] The present inventors conducted studies and found that the colored photosensitive resin composition described in Patent Document 1 causes surface roughness of an electrode, which is problematic in practical use.

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition that reduces surface roughness of an electrode after heat treatment, thereby providing an organic light-emitting element and an image display device that are free of display defects and have high reliability.

[0018] Solutions for solving problems

[0019] The present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by using specific dispersants and colorants, thereby completing the present invention.

[0020] That is, the gist of the present invention is as follows.

[0021] [1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant.

[0022] The colorant (a) contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound,

[0023] The dispersant (f) contains an acrylic copolymer (f1), wherein the acrylic copolymer (f1) contains at least repeating units represented by the following general formulas (1), (2), and (3) and does not contain a repeating unit containing a quaternary ammonium group.

[0024] Moreover, content of the chlorine atom in the photosensitive coloring composition is 0.05 mass % or less with respect to the total solid content of the photosensitive coloring composition.

[0025]

[0026] (In formula (I), R 1 and R 6 are independently a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom,

[0027] R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R 10 Independent of all others, hydrogen atoms, halogen atoms, R 11 、COOH、COOR 11 、COO - 、CONH2、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH2、OOCNHR 11 、OOCNR 11 R 12 、NO2、NH2、NHR 11 NR 11 R 12 、NHCOR 12 NR 11 COR 12 、N=CH2、N=CHR 11 、N=CR 11 R 12 , SH, SR 11 、SOR 11 、SO2R 11 、SO3R 11 、SO3H、SO3- 、SO2NH2、SO2NHR 11 or SO2NR 11 R 12 ,

[0028] Choose from R 2 With R 3 、R 3 With R 4 、R 4 With R 5 、R 7 With R 8 、R 8 With R 9 and R 9 With R 10 At least one of the groups of combinations may also be directly bonded to each other or bonded via an oxygen atom, a sulfur atom, NH or NR 11 The bridges are bonded to each other,

[0029] R 11 and R 12 Each of them is independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0030]

[0031] (In formula (1), R 31 is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent,

[0032] R 32 is a hydrogen atom or a methyl group,

[0033] * indicates a connection key.)

[0034]

[0035] (In formula (2), R 33 is methylene, ethylene or propylene, R 34 is an alkyl group optionally having a substituent, R 35 is a hydrogen atom or a methyl group,

[0036] n is an integer from 1 to 20,

[0037] * indicates a connection key.)

[0038]

[0039] (In formula (3), R 36 and R 37are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 36 With R 37 optionally bonded to each other to form a ring structure,

[0040] R 38 is a hydrogen atom or a methyl group,

[0041] Z is a divalent linking group,

[0042] * indicates a connection key.)

[0043] [2] The photosensitive coloring composition according to [1], wherein the colorant (a) contains an organic coloring pigment.

[0044] [3] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant.

[0045] The optical density of the coating film formed by curing the photosensitive coloring composition per 1 μm of film thickness is 0.5 or more,

[0046] The dispersant (f) contains an acrylic copolymer (f1), wherein the acrylic copolymer (f1) contains at least repeating units represented by the following general formulas (1), (2), and (3) and does not contain a repeating unit containing a quaternary ammonium group.

[0047] Moreover, content of the chlorine atom in the photosensitive coloring composition is 0.05 mass % or less with respect to the total solid content of the photosensitive coloring composition.

[0048]

[0049] (In formula (1), R 31 It is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

[0050] R 32 is a hydrogen atom or a methyl group.

[0051] * indicates a connection key.)

[0052]

[0053] (In formula (2), R 33 is methylene, ethylene or propylene, R 34 is an alkyl group optionally having a substituent, R 35 is a hydrogen atom or a methyl group.

[0054] n is an integer from 1 to 20.

[0055] * indicates a connection key.)

[0056]

[0057] (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 36 With R 37 They are optionally bonded to each other to form a ring structure.

[0058] R 38 is a hydrogen atom or a methyl group.

[0059] Z is a divalent linking group.

[0060] * indicates a connection key.)

[0061] [4] The photosensitive coloring composition according to [3], wherein the colorant (a) contains at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and violet pigments.

[0062] [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the acrylic copolymer (f1) is a block copolymer.

[0063] [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the acrylic copolymer (f1) has an amine value of 90 mgKOH / g or more.

[0064] [7] The photosensitive coloring composition according to any one of [1] to [6], comprising 10% by mass or more of the coloring agent (a) relative to the total solid content of the photosensitive coloring composition.

[0065] [8] The photosensitive coloring composition according to any one of [1] to [7], which is used for forming partition walls of an organic electroluminescent element.

[0066] [9] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [8].

[0067]

[10] An organic electroluminescent device comprising the cured product described in [9].

[0068]

[11] An image display device comprising the organic electroluminescent element described in

[10] .

[0069] Effects of the Invention

[0070] According to the present invention, a photosensitive coloring composition can be provided in which the surface roughness of an electrode is less likely to be generated after heat treatment. DETAILED DESCRIPTION

[0071] The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist of the invention.

[0072] In the present invention, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

[0073] The term "(co)polymer" includes both homopolymers and copolymers, and the terms "acid (anhydride)" and "(anhydrous) acid" include both acids and their anhydrides.

[0074] In the present invention, the "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid or a (co)polymer containing a (meth)acrylate having a carboxyl group.

[0075] In the present invention, the term "monomer" is a term contrasted with a so-called high molecular substance (polymer), and means to include not only monomers in a narrow sense but also dimers, trimers, and oligomers.

[0076] In the present invention, the "total solids content" refers to the amount of all components contained in the photosensitive coloring composition or pigment dispersion, excluding the solvent. Components other than the solvent may be liquid at room temperature and are not included in the solvent but are included in the total solids content.

[0077] In the present invention, the "weight average molecular weight" refers to a polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).

[0078] In the present invention, "amine value" refers to the amine value calculated based on the effective solid content, unless otherwise specified. It is expressed as the mass of KOH equivalent to the amount of alkali per 1g of the dispersant solid content. The measurement method will be described later. "Acid value" refers to the acid value calculated based on the effective solid content, unless otherwise specified. It is calculated by neutralization titration.

[0079] Regarding pigments, "CI" refers to Color Index.

[0080] In this specification, percentages and parts expressed by "mass" have the same meaning as percentages and parts expressed by "weight".

[0081] [Photosensitive coloring composition]

[0082] The photosensitive coloring composition of the present invention contains:

[0083] (a) Colorants

[0084] (b) Alkali-soluble resin

[0085] (c) Photopolymerization initiator

[0086] (d) Ethylenically unsaturated compounds

[0087] (e) Solvent

[0088] (f) A dispersant is an essential component.

[0089] As a first embodiment, at least one selected from the group consisting of a compound represented by general formula (I), a geometric isomer of the compound represented by general formula (I), a salt of the compound represented by general formula (I), or a salt of a geometric isomer of the compound represented by general formula (I) is contained as (a) a colorant.

[0090] As a second aspect, the coating film formed by curing the photosensitive coloring composition of the present invention has an optical density of 0.5 or more per 1 μm of film thickness.

[0091] Furthermore, other ingredients such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors may be included as needed. Generally, each ingredient is used in a state of being dissolved or dispersed in a solvent.

[0092] (a) Colorants

[0093] The photosensitive coloring composition of the present invention contains (a) a coloring agent. By containing the (a) coloring agent, appropriate light absorptivity can be obtained, and in particular, appropriate light shielding properties can be obtained when used to form a light shielding member such as a partition wall.

[0094] In the first embodiment, at least one selected from the group consisting of a compound represented by general formula (I), a geometric isomer of the compound represented by general formula (I), a salt of the compound represented by general formula (I), and a salt of a geometric isomer of the compound represented by general formula (I) is contained as the (a) colorant.

[0095] The compound represented by general formula (I) (hereinafter referred to as "Compound (I)") is an organic black pigment. It is speculated that its rigid skeleton containing an aromatic ring prevents chlorine-containing gases generated during heat treatment from penetrating the coating film. Furthermore, its high UV transmittance facilitates photocuring of the applied photosensitive composition, which is beneficial in these respects.

[0096]

[0097] In formula (I), R 11 and R 16 each independently represents a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom;

[0098] R 12 、R 13 、R 14 、R 15 、R 17 、R 18 、R 19 and R 20 Each independently represents a hydrogen atom, a halogen atom, R 21 、COOH、COOR 21 、COO - 、CONH2、CONHR 21 、CONR 21 R 22 、CN、OH、OR 21 、COCR 21 、OOCNH2、OOCNHR 21 、OOCNR 21 R 22 、NO2、NH2、NHR 21 NR 21 R 22 、NHCOR 22 NR 21 COR 22 、N=CH2、N=CHR 21 、N=CR 21 R 22 ,SH,SR 21 、SOR 21 、SO2R 21 、SO3R 21 、SO3H、SO3 - 、SO2NH2、SO2NHR 21 or SO2NR 21 R 22 ;

[0099] Choose from R 12 With R 13 、R 13 With R 14 、R 14 With R 15 、R 17 With R 18 、R 18 With R 19 and R 19 With R 20At least one of the groups of combinations is optionally directly bonded to each other or bonded via an oxygen atom, a sulfur atom, NH or NR 21 The bridges are bonded to each other;

[0100] R 21 and R 22 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.

[0101] Compound (I) and its geometric isomers have the following core structure (wherein the substituents in the structural formula are omitted), and the trans-trans isomer is likely to be the most stable.

[0102]

[0103] When compound (I) is anionic, a salt in which its charge is compensated by any known suitable cation is preferably used. The cation is, for example, a metal, organic, inorganic, or metal-organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Furthermore, when the geometric isomers of compound (I) are anionic, the same salt is preferably used.

[0104] The following substituents are preferred among the substituents in the general formula (I) and their definitions because they tend to increase the shielding ratio. This is because the following substituents are believed to have no absorption and do not affect the hue of the pigment.

[0105] R 12 、R 14 、R 15 、R 17 、R 19 and R 20 Each independently preferably is a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

[0106] R 13 and R 18 Each is independently preferably a hydrogen atom, NO2, OCH3, OC2H5, a bromine atom, a chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H or SO3 - , further preferably a hydrogen atom or SO3H, particularly preferably a hydrogen atom.

[0107] R 11 and R 16 Each independently is preferably a hydrogen atom, CH3 or CF3, more preferably a hydrogen atom.

[0108] Preferably selected from R11 With R 16 、R 12 With R 17 、R 13 With R 18 、R 14 With R 19 and R 15 With R 20 At least one of the combinations is the same, and more preferably R 11 With R 16 Same, R 12 With R 17 Same, R 13 With R 18 Same, R 14 With R 19 Same, and R 15 With R 20 same.

[0109] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl, and dodecyl.

[0110] Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, adamantane-1-yl, and adamantane-2-yl.

[0111] Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1,4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl, and dodecenyl.

[0112] Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4(10)-thujden-10-yl, 2-norbornene-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcaradien-3-yl, and camphenyl.

[0113] Examples of the alkynyl group having 2 to 12 carbon atoms 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, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, and 1-dodecyn-12-yl.

[0114] The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0115] The compound represented by the general formula (I) is preferably a compound containing at least one selected from the group consisting of a compound represented by the following general formula (II) (hereinafter also referred to as "compound (II)") and geometric isomers of compound (II).

[0116]

[0117] Examples of such compounds include Irgaphor (registered trademark) Black S 0100CF (trade name, manufactured by BASF).

[0118] The organic black pigment is preferably dispersed by the method described below before use. In addition, the presence of a sulfonic acid derivative of compound (I) or a sulfonic acid derivative of a geometric isomer of compound (I), particularly a sulfonic acid derivative of compound (II) or a sulfonic acid derivative of a geometric isomer of compound (II), during dispersion may improve dispersibility and storage properties.

[0119] In the first embodiment of the present invention, the colorant (A) may contain other colorants in addition to the compound of general formula (I). As the other colorant, a pigment is preferably used, and the pigment may be an organic pigment or an inorganic pigment. From the viewpoint of high resistance and low dielectric constant, an organic pigment is more preferred, and in particular, the organic coloring pigment described below is further preferred.

[0120] Among organic coloring pigments, compound (I) and blue pigments are preferably used from the viewpoint of making the transmittance in the high wavelength region of the visible light range more uniform. Pigment Blue B60, 15:6, and 16 are preferred, and Pigment Blue B60 is more preferred.

[0121] On the other hand, from the viewpoint of making the transmittance in the entire visible light region more uniform, it is preferred to use at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and violet pigments in addition to compound (I).

[0122] In the second embodiment, the optical density per 1 μm of the coating film formed by curing the photosensitive coloring composition of the present invention (hereinafter sometimes referred to as "OD per unit film thickness") is 0.5 or more. By containing (a) the coloring agent and adjusting the OD per unit film thickness to the above lower limit or more, the light-shielding properties of the resulting cured product, particularly the partition walls, are improved.

[0123] The OD per unit film thickness can be calculated by measuring the optical density and film thickness of a coating film formed by curing the photosensitive coloring composition and dividing the optical density by the film thickness. The coating film preparation conditions are not particularly limited, and for example, the conditions described in the Examples below can be employed.

[0124] In order to make the OD per unit film thickness equal to or greater than the above lower limit, for example, the type of (a) the colorant and the content ratio thereof in the total solid content can be appropriately adjusted.

[0125] In the second aspect of the present invention, the type of the (a) colorant that can be used in the photosensitive coloring composition is not particularly limited, and either a pigment or a dye may be used. Among these, pigments are preferably used from the viewpoint of durability.

[0126] The pigment contained in the (a) colorant may be a single type or two or more types. In particular, two or more types are preferably used from the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness.

[0127] The type of pigment that can be used as the colorant (a) is not particularly limited, and examples thereof include organic coloring pigments and black pigments. Here, organic coloring pigments refer to organic pigments that exhibit colors other than black, and examples thereof include red pigments, orange pigments, blue pigments, violet pigments, green pigments, and yellow pigments.

[0128] Among pigments, organic coloring pigments are preferably used from the viewpoint of high resistance and low dielectric constant. In addition, compound (I) or other black pigments are preferably used from the viewpoint of light-shielding properties.

[0129] The organic coloring pigment can be used alone or in combination of two or more. In particular, from the viewpoint of making the OD per unit film thickness be 0.5 or more, it is more preferred to use in combination organic coloring pigments of different colors, and further preferably to use a combination of organic coloring pigments that exhibit a color close to black.

[0130] The chemical structure of these organic coloring pigments is not particularly limited, and examples thereof include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of usable pigments are shown below by pigment index number. The "CI" in "CI Pigment Red 2" and the like listed below refers to the Color Index.

[0131] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149 , 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232 , 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, and 276. From the viewpoint of light-shielding properties and dispersibility, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are preferably used, and CI Pigment Red 177, 209, 224, and 254 are more preferably used. From the viewpoint of dispersibility and light-shielding properties, CI Pigment Red 177, 254, and 272 are preferred. When the photosensitive coloring composition is cured by ultraviolet light, red pigments with low ultraviolet absorption rates are preferred. From this viewpoint, CI Pigment Red 254 and 272 are more preferred.

[0132] Examples of orange pigments include CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79. From the viewpoint of dispersibility and light-shielding properties, CI Pigment Orange 13, 43, 64, and 72 are preferred. When curing the photosensitive coloring composition with ultraviolet light, orange pigments with low ultraviolet absorption are preferred. From this viewpoint, CI Pigment Orange 64 and 72 are more preferred.

[0133] Examples of the blue pigment 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. From the viewpoint of light-shielding properties, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferably used, and CI Pigment Blue 15:6 is more preferably used. From the viewpoint of dispersibility and light-shielding properties, CI Pigment Blue 15:6, 16, and 60 are preferred. When the photosensitive coloring composition is cured by ultraviolet light, a blue pigment with a low ultraviolet absorption rate is preferred. From this viewpoint, CI Pigment Blue 60 is more preferred.

[0134] Examples of violet pigments include CI Pigment Violet 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. From the viewpoint of light-shielding properties, CI Pigment Violet 19, 23, and 29 are preferred, and CI Pigment Violet 23 is more preferred. From the viewpoint of dispersibility and light-shielding properties, CI Pigment Violet 23 and 29 are preferred. When curing the photosensitive coloring composition with ultraviolet light, violet pigments with low ultraviolet absorption are preferred, and from this viewpoint, CI Pigment Violet 29 is more preferred.

[0135] Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59. Preferably, CI Pigment Green 7 and 36 are used.

[0136] Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134 4, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. Preferred examples include CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185, and more preferred examples include CI Pigment Yellow 83, 138, 139, 150, and 180.

[0137] From the viewpoint of light-shielding properties of the cured product and control of shape and height difference, at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments is preferred.

[0138] From the viewpoint of light-shielding properties of the cured product and control of shape and height difference, it is preferred that at least one of the following pigments be contained.

[0139] Red pigment: CI Pigment Red 177, 254, 272

[0140] Orange pigment: CI Pigment Orange 43, 64, 72

[0141] Blue pigment: CI Pigment Blue 15:6, 60

[0142] Purple pigment: CI Pigment Violet 23, 29

[0143] When two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited. However, from the viewpoint of light-shielding properties, it is preferred to use in combination at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and violet pigments.

[0144] The combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, examples include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment.

[0145] As the pigment, in addition to organic coloring pigments and the organic black pigment represented by the general formula (I), organic black pigments and inorganic black pigments can also be used.

[0146] Examples of organic black pigments other than the organic black pigment represented by general formula (I) include aniline black and perylene black.

[0147] Examples of the inorganic black pigment include those described in International Publication No. 2018 / 101314.

[0148] When using these colorants, if the colorant contains chlorine atoms, the amount added can be adjusted so as not to excessively increase the amount of chlorine.

[0149] These pigments are preferably dispersed and used so as to have an average particle size of usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. The standard for the average particle size is the number of pigment particles.

[0150] In the photosensitive coloring composition of the present invention, the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed on a sufficiently diluted photosensitive coloring composition (generally, the pigment concentration is adjusted to approximately 0.005 to 0.2% by mass by dilution. However, if there is a recommended concentration for the measurement equipment, this concentration is used). The measurement is performed at 25°C.

[0151] In the photosensitive coloring composition of the second embodiment of the present invention, colorants such as organic coloring pigments and black pigments may be used alone or in combination of two or more.

[0152] In addition to the above-mentioned organic coloring pigments and black pigments, dyes can also be used. As dyes that can be used as colorants, for example, dyes described in International Publication No. 2018 / 101314 can be mentioned.

[0153] <(b) Alkali-soluble resin>

[0154] The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, novolac resins, and polyvinylphenol resins. Among them, the following are preferably used from the viewpoint of excellent platemaking properties:

[0155] (b1) Epoxy (meth)acrylate resin

[0156] (b2) Acrylic copolymer resin.

[0157] These can be used alone or in combination of two or more.

[0158] <(b1) Epoxy (meth)acrylate resin>

[0159] (b1) Epoxy (meth)acrylate resins are resins obtained by reacting an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion, and further reacting the hydroxyl group generated with a compound having two or more substituents capable of reacting with the hydroxyl group, such as a polybasic acid and / or its anhydride.

[0160] Before reacting the polybasic acid and / or its anhydride with the hydroxyl group, a compound having two or more substituents capable of reacting with the hydroxyl group is reacted and then the polybasic acid and / or its anhydride is reacted. The resin obtained in this way is also included in the above-mentioned (b1) epoxy (meth)acrylate resin.

[0161] Resins obtained by further reacting the carboxyl groups of the resin obtained by the above reaction with a compound having a reactive functional group are also included in the above-mentioned (b1) epoxy (meth)acrylate resins.

[0162] As described above, epoxy (meth)acrylate resins do not substantially have epoxy groups in their chemical structure and are not limited to "(meth)acrylates." However, since they use epoxy compounds (epoxy resins) as raw materials and are represented by "(meth)acrylates," they are named as such according to custom.

[0163] As the (b1) epoxy (meth)acrylate resin used in the present invention, from the viewpoint of developability and reliability, it is particularly preferred to use the following epoxy (meth)acrylate resin (b1-1) and / or epoxy (meth)acrylate resin (b1-2) (hereinafter sometimes referred to as "carboxyl group-containing epoxy (meth)acrylate resin").

[0164] Furthermore, as the epoxy (meth)acrylate resin (b1), from the viewpoint of outgassing, a resin having an aromatic ring in its main chain can be more preferably used.

[0165] <Epoxy (meth)acrylate resin (b1-1)>

[0166] An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, optionally reacting an isocyanate group-containing compound, and then further reacting a polybasic acid and / or an anhydride thereof.

[0167] <Epoxy (meth)acrylate resin (b1-2)>

[0168] An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, optionally reacting an isocyanate group-containing compound, and then further reacting a polyol and a polybasic acid and / or an anhydride thereof.

[0169] Here, epoxy resin also comprises the raw material compound before forming the resin by thermosetting, and as this epoxy resin, can suitably select to use from known epoxy resin.In addition, epoxy resin can use the compound that phenolic compound and epihalohydrin reaction obtain.As phenolic compound, preferably 2 yuan or the compound with phenolic hydroxyl group more than 2 yuan can be monomer and can also be polymer.

[0170] As the type of epoxy resin becoming a raw material, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolac type epoxy resin, an epoxy resin which is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin, an adamantyl-containing epoxy resin, a fluorene type epoxy resin can be preferably used. Among these, those having an aromatic ring in the main chain can be more preferably used.

[0171] Preferred epoxy resins include, for example, bisphenol A epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828," "jER-1001," "jER-1002," and "jER-1004" manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol A epoxy resin with epichlorohydrin (e.g., "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76°C)), bisphenol F resins (e.g., "jER807," "EP-4001," "EP-4002," and "EP-4004" manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting an alcoholic hydroxyl group of a bisphenol F epoxy resin with epichlorohydrin (e.g., "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 350, softening point: 66°C)), bisphenol S epoxy resins, and biphenyl glycidyl ether (e.g., "YX-4000" manufactured by Mitsubishi Chemical Corporation). Phenol novolac type epoxy resins (e.g., "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Corporation, and "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o-, m-, and p-) cresol novolac type epoxy resins (e.g., "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenol methane type epoxy resins (e.g., "EPPN (registered trademark, hereinafter the same)-501", "EPPN-502", and "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins (e.g., "Celloxide (registered trademark, hereinafter the same) 2021P", "Celloxide Epoxy resins such as "EHPE" (EHPE), epoxy resins obtained by glycidylating a phenolic resin produced by the reaction of dicyclopentadiene and phenol (e.g., "EXA-7200" manufactured by DIC Corporation and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (B1) to (B4). Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B2), "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd., which is an epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nippon Steel & Sumigin Chemical Co., Ltd., which is an epoxy resin represented by the following general formula (B4).

[0172]

[0173] In the above general formula (B1), a is an average value and represents a number from 0 to 10, and R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.

[0174] It should be noted that the presence of multiple R 111 They may be the same or different.

[0175]

[0176] In the above general formula (B2), b1 and b2 are each independently an average value and represent a number from 0 to 10, and R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. 121 They may be the same or different.

[0177]

[0178] In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), wherein the molecular structure contains one or more adamantane structures, and c represents 2 or 3.

[0179]

[0180] In the above general formulas (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 Each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.

[0181]

[0182] In the above general formula (B4), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R 143 and R 144 Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer greater than or equal to 0.

[0183] Among these, the epoxy resin represented by any one of the general formulas (B1) to (B4) is preferably used.

[0184] Examples of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, monocarboxylic acids such as (meth)acrylic acid substituted with a haloalkyl group, an alkoxy group, a halogen group, a nitro group or a cyano group, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2-(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxyethyl Acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, monomers of products obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid, or monomers obtained by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to hydroxyalkyl (meth)acrylates or pentaerythritol tri(meth)acrylate, (meth)acrylic acid dimers, etc.

[0185] Among these, (meth)acrylic acid is particularly preferred from the viewpoint of sensitivity.

[0186] Known methods can be used to add an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin. For example, the α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be reacted with the epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150°C. Examples of esterification catalysts include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride.

[0187] The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two or more.

[0188] The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of epoxy groups in the epoxy resin. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used to be above the above lower limit, there is a tendency to suppress insufficient introduction of unsaturated groups, and the subsequent reaction with the polybasic acid and / or its anhydride is also likely to proceed sufficiently. On the other hand, by setting it below the above upper limit, it is seen that the residual unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and the curing characteristics tend to be improved.

[0189] Examples of the polybasic acid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0190] Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

[0191] The addition reaction of the polybasic acid and / or its anhydride can be carried out using a known method, and the target product can be obtained by continuing the reaction under the same conditions as the addition reaction of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin. The amount of the polybasic acid and / or its anhydride component added is preferably such that the acid value of the generated carboxyl group-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mg KOH / g, and more preferably such that the acid value is in the range of 20 to 140 mg KOH / g. When the amount is above the above lower limit, the alkali developability tends to be improved. When the amount is below the above upper limit, the curing performance tends to be improved.

[0192] During the addition reaction of the polybasic acid and / or its anhydride, a polyfunctional alcohol (polyol) such as trimethylolpropane, di(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc. can be added to introduce a multi-branched structure. In this case, the order of mixing the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. By heating, the polybasic acid and / or its anhydride reacts with any hydroxyl group present in the mixture of the reaction product of the epoxy resin and the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the polyfunctional alcohol.

[0193] The use of a polyol can increase the molecular weight of the epoxy (meth)acrylate resin (b1) and introduce branches into the molecule, thereby tending to achieve a balance between molecular weight and viscosity. Furthermore, the rate of acid group introduction into the molecule can be increased, tending to facilitate a balance between sensitivity and adhesion.

[0194] Examples of the carboxyl group-containing epoxy (meth)acrylate resins include, in addition to the aforementioned examples, those described in Korean Patent Publication No. 10-2013-0022955.

[0195] The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 15000, and further preferably 2000 to 15000. By setting it to above the above lower limit, there is a tendency to suppress excessive solubility in the developer. By setting it to below the above upper limit, there is a tendency for solubility in the developer to become good.

[0196] The acid value of the carboxyl group-containing epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Furthermore, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, further preferably 80 mgKOH / g to 130 mgKOH / g, and further preferably 100 mgKOH / g to 130 mgKOH / g. By setting it to above the above lower limit, there is a tendency for the development solubility to be improved and the resolution to be good. By setting it as below the said upper limit, there exists a tendency for the residual film rate of a photosensitive coloring composition to become favorable.

[0197] The chemical structure of the epoxy (meth)acrylate resin is not particularly limited. From the viewpoint of developability and reliability, it is preferred to contain an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (b1-I) (hereinafter sometimes referred to as "(b1-I) epoxy (meth)acrylate resin"). and / or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (b1-II) (hereinafter sometimes referred to as "(b1-II) epoxy (meth)acrylate resin").

[0198]

[0199] In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a connecting bond.

[0200] The benzene ring in formula (b1-I) may be further substituted by any substituent.

[0201]

[0202] In formula (b1-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a connecting bond.

[0203] <(b1-I) Epoxy (meth)acrylate resin>

[0204] First, the epoxy (meth)acrylate resin having the partial structure represented by the general formula (b1-I) will be described in detail.

[0205]

[0206] In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a connecting bond.

[0207] The benzene ring in formula (b1-I) may be further substituted by any substituent.

[0208] (R 12 )

[0209] In the above formula (b1-I), R 12represents a divalent hydrocarbon group which may have a substituent.

[0210] Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked together.

[0211] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. Of these, linear aliphatic groups are preferred from the perspective of developer solubility. On the other hand, cyclic aliphatic groups are preferred from the perspective of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is generally 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits may be arbitrarily combined. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 1 to 10 are even more preferred. By setting the value above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the value below the upper limit, resolution tends to be improved, sensitivity degradation and film reduction during development tend to be easily suppressed.

[0212] Examples of the divalent linear aliphatic group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Of these, methylene is preferred from the perspective of rigidity of the skeleton.

[0213] Examples of the divalent branched aliphatic group include structures in which the above-mentioned divalent linear aliphatic group has, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group as a side chain.

[0214] The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 12 or less, preferably 10 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1 to 12, more preferably 1 to 10, and even more preferably 2 to 10. By setting the number of rings above the above lower limit, a strong film tends to be formed, and adhesion to the substrate tends to be improved. By setting the number of rings below the above upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0215] Examples of the divalent cyclic aliphatic group include groups formed by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene ring, a dicyclopentane ring, etc. Among these, groups formed by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring are preferred from the viewpoint of the rigidity of the skeleton.

[0216] Examples of the substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Of these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0217] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10. By setting the above lower limit value or more, it is easy to obtain a strong film, it is less likely to produce surface roughness during development, and the adhesion to the substrate tends to be improved. By setting the above upper limit value or less, there is a tendency to improve the resolution and easily suppress the sensitivity deterioration and film reduction during development.

[0218] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0219] In addition, the aromatic heterocyclic ring in the aromatic heterocyclic group can be a monocyclic ring or a condensed ring. As the aromatic heterocyclic group, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring can be enumerated.

[0220] Among these, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0221] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Of these, unsubstituted groups are preferred from the viewpoint of development solubility.

[0222] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups.

[0223] The number of divalent aliphatic groups is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number at or above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0224] The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number at or above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0225] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups include groups represented by the following formulas (b1-IA) to (b1-IF). Among these, groups represented by the following formula (b1-IA) are preferred from the perspectives of skeleton rigidity and membrane hydrophobization.

[0226]

[0227] In the above formula (b1-I), k represents 1 or 2. From the viewpoint of adhesion and patterning properties, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2. (b1-I) Epoxy (meth)acrylate may contain both partial structures in which k is 1 and partial structures in which k is 2.

[0228] The phenyl ring in formula (b1-I) is optionally further substituted by any substituent. Examples of acceptable substituents on the phenyl ring in formula (b1-I) include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. When the phenyl ring in formula (b1-I) has a substituent, the number of the substituent is not particularly limited and may be one or more than two.

[0229] From the viewpoint of patterning properties, the benzene ring in formula (b1-I) is preferably unsubstituted.

[0230] From the viewpoint of ease of synthesis, the partial structure represented by formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1).

[0231]

[0232] In formula (b1-I-1), R 11 、R 12 and k have the same meanings as in the above formula (b1-I), R X represents a hydrogen atom or a polyacid residue, and * represents a connecting bond.

[0233] The benzene ring in formula (b1-I-1) may be further substituted by any substituent.

[0234] The polybasic acid residue refers to a monovalent group formed by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0235] From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0236] The benzene ring in formula (b1-I-1) may be further substituted with any substituent. As the substituent, the substituents listed for the benzene ring in formula (b1-I) can be preferably used.

[0237] The partial structure represented by the formula (b1-I-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-I) may be one type or two or more types. For example, R X For hydrogen atoms and R X A polyacid residue.

[0238] The number of partial structures represented by the formula (b1-I) contained in one molecule of the epoxy (meth)acrylate resin (b1-I) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, and even more preferably 15 or less. It is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0239] The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1-I) as measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and most preferably 5,000 or more. It is usually 30,000 or less, preferably 20,000 or less, and more preferably 15,000 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 1,500 to 20,000, even more preferably 1,500 to 15,000, and even more preferably 2,000 to 15,000. When the value is greater than or equal to the lower limit, the residual film rate of the photosensitive coloring composition tends to be improved. When the value is less than or equal to the upper limit, the solubility in the developer tends to be improved.

[0240] (b1-1) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Furthermore, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, further preferably 80 mgKOH / g to 130 mgKOH / g, and further preferably 100 mgKOH / g to 130 mgKOH / g. By setting it to above the above lower limit, there is a tendency for the development solubility to improve and the resolution to become better. By setting it as below the said upper limit, there exists a tendency for the residual film rate of a photosensitive coloring composition to become favorable.

[0241] Specific examples of (b1-I) epoxy (meth)acrylate resins are listed below. In the examples, * represents a connecting bond.

[0242]

[0243]

[0244] <(b1-II) Epoxy (meth)acrylate resin>

[0245] The epoxy (meth)acrylate resin having the partial structure represented by the above-mentioned general formula (b1-II) will be described in detail.

[0246]

[0247] In formula (b1-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a connecting bond.

[0248] (R 14 )

[0249] In the above general formula (b1-II), R 14 It represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

[0250] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0251] The number of rings in the aliphatic cyclic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of rings at or above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number of rings at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be suppressed.

[0252] The number of carbon atoms in the aliphatic cyclic group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. Any combination of the above upper and lower limits is possible. For example, it is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting the carbon atoms at or above the above lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the carbon atoms at or below the above upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be suppressed.

[0253] Examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isobornane, adamantane, and cyclododecane. Of these, adamantane is preferred from the viewpoint of the residual film rate and resolution of the photosensitive coloring composition.

[0254] The number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and generally 10 or less, preferably 5 or less, more preferably 4 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 4, even more preferably 2 to 4, and particularly preferably 3 to 4. By setting the number above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be suppressed.

[0255] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more. Furthermore, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 4 to 40, more preferably 6 to 40, further preferably 8 to 30, further preferably 10 to 20, and particularly preferably 12 to 15. By setting the number above the lower limit, a strong film is easily obtained, and surface roughness that occurs during development is less likely to occur. By setting the number below the upper limit, patterning properties tend to be improved.

[0256] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Among these, the fluorene ring is preferred from the viewpoint of patterning properties.

[0257] The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.

[0258] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. Of these, linear aliphatic groups are preferred from the perspective of development solubility. On the other hand, cyclic aliphatic groups are preferred from the perspective of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is generally 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits may be arbitrarily combined. For example, 1 to 25 are preferred, 3 to 20 are more preferred, and 6 to 15 are even more preferred. By setting the value above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the value below the upper limit, resolution tends to be improved, sensitivity degradation and film reduction during development tend to be easily suppressed.

[0259] Examples of the divalent linear aliphatic group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Of these, methylene is preferred from the viewpoint of the rigidity of the skeleton.

[0260] Examples of the divalent branched aliphatic group include a structure in which the above-mentioned divalent linear aliphatic group has a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or tert-butyl group as a side chain.

[0261] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of rings at or above the lower limit, a strong film tends to be formed, and adhesion to the substrate tends to be improved. By setting the number of rings at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0262] Examples of divalent cyclic aliphatic groups include groups formed by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, groups formed by removing two hydrogen atoms from an adamantane ring are preferred from the perspective of skeleton rigidity.

[0263] Examples of the substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Of these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0264] Examples of the divalent aromatic ring group include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups. The carbon number is generally 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. For example, it is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. By setting the carbon number above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the carbon number below the upper limit, resolution is improved, sensitivity degradation and film reduction during development tend to be easily suppressed.

[0265] The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.

[0266] The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

[0267] Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Of these, unsubstituted groups are preferred from the viewpoint of development solubility.

[0268] Examples of the group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups include groups in which one or more of the above-mentioned divalent aliphatic groups are linked to one or more of the above-mentioned divalent aromatic ring groups.

[0269] The number of divalent aliphatic groups is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number at or above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0270] The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number at or above the lower limit, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0271] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic ring groups include groups represented by formulas (b1-IA) to (b1-IF). Among these, groups represented by formula (b1-IC) are preferred from the perspectives of skeleton rigidity and membrane hydrophobization.

[0272] For these divalent hydrocarbon groups, the bonding method of the cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a method in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted by a cyclic hydrocarbon group as a side chain, and a method in which a cyclic hydrocarbon group as a side chain is constituted by including one carbon atom of an aliphatic group.

[0273] (R 15 、R 16 )

[0274] In the general formula (b1-II), R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent.

[0275] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. Of these, linear aliphatic groups are preferred from the perspective of development solubility, while cyclic aliphatic groups are preferred from the perspective of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is generally 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. For example, it is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10. By setting the above lower limit value or more, a strong film is easily obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting the above upper limit value or less, the resolution tends to be improved and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0276] Examples of the divalent linear aliphatic group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Of these, methylene is preferred from the viewpoint of the rigidity of the skeleton.

[0277] Examples of the divalent branched aliphatic group include structures in which the above-mentioned divalent linear aliphatic group has, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group as a side chain.

[0278] The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 12 or less, preferably 10 or less. For example, it is preferably 1 to 12, more preferably 2 to 10. By setting the number of rings above the lower limit, a strong film tends to be formed, and adhesion to the substrate tends to be improved. By setting the number of rings below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0279] Examples of divalent cyclic aliphatic groups include groups formed by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, or a dicyclopentadiene ring. Among these, groups formed by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring are preferred from the perspective of skeleton rigidity.

[0280] Examples of the substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Of these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

[0281] (m, n)

[0282] In general formula (b1-II), m and n each independently represent an integer of 0 to 2. When the number is greater than or equal to the lower limit, patterning suitability tends to be improved and surface roughness that occurs during development tends to be less likely to occur. Furthermore, when the number is less than or equal to the upper limit, developability tends to be improved. From the perspective of developability, m and n are preferably 0. On the other hand, from the perspective of patterning suitability and surface roughness that occurs during development, m and n are preferably 1 or greater.

[0283] From the viewpoint of adhesion to the substrate, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1).

[0284]

[0285] In formula (b1-II-1), R 13 、R 15 、R 16 , m and n have the same meanings as in formula (b1-II), R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer of 1 or greater, and * represents a connecting bond. The benzene ring in formula (b1-II-1) may be further substituted with any substituent.

[0286] (R α )

[0287] In the general formula (b1-II-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent.

[0288] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0289] The number of rings in the aliphatic cyclic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 6 or less, preferably 4 or less, and more preferably 3 or less. For example, it is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 2 to 3. By setting the number of rings at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number of rings at or below the upper limit, patterning properties tend to be improved.

[0290] The number of carbon atoms in the aliphatic cyclic group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits may be arbitrarily combined. For example, the number is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting the number at or above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, patterning properties tend to be improved.

[0291] Examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isobornane, adamantane, and cyclododecane. Of these, adamantane is preferred from the perspective of strong film properties.

[0292] The number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and generally 10 or less, preferably 5 or less. The above upper and lower limits may be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5. By setting the number above the lower limit, a strong film tends to be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number below the upper limit, patterning properties tend to be improved.

[0293] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is generally 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits may be arbitrarily combined. For example, the number is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. By setting the number above the lower limit, a strong film is easily obtained and the surface roughness that occurs during development is less likely to occur. Furthermore, by setting the number below the upper limit, patterning properties tend to be improved.

[0294] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of developer solubility.

[0295] Examples of substituents that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Of these, unsubstituted groups are preferred from the perspective of ease of synthesis.

[0296] p represents an integer greater than or equal to 1, preferably greater than or equal to 2, and preferably less than or equal to 3. For example, p is preferably from 1 to 3, and more preferably from 2 to 3. When p is greater than or equal to the above lower limit, the film curing degree and the residual film rate tend to be improved. When p is less than or equal to the above upper limit, the developability tends to be improved.

[0297] Among these, R α It is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0298] The phenyl ring in formula (b1-II-1) is optionally further substituted by any substituent. As acceptable substituents on the phenyl ring in formula (b1-II-1), for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy can be mentioned. When the phenyl ring in formula (b1-II-1) has a substituent, the number of the substituent is not particularly limited and can be 1 or more.

[0299] From the viewpoint of patterning properties, the benzene ring in formula (b1-II-1) is preferably unsubstituted.

[0300] Specific examples of the partial structure represented by formula (b1-II-1) are listed below.

[0301]

[0302]

[0303] From the viewpoint of skeleton rigidity and membrane hydrophobization, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2).

[0304]

[0305] In formula (b1-II-2), R 13 、R 15 、R 16 , m and n have the same meanings as in formula (b1-II), R β represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a connecting bond.

[0306] The benzene ring in formula (b1-II-2) may be further substituted by any substituent.

[0307] (R β )

[0308] In formula (b1-II-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent.

[0309] Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

[0310] The number of rings in the aliphatic cyclic group is not particularly limited, but is generally 1 or more, preferably 2 or more, and generally 10 or less, preferably 5 or less. For example, it is preferably 1 to 10, more preferably 2 to 5. By setting the number at or above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be suppressed.

[0311] The number of carbon atoms in the aliphatic cyclic group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The above upper and lower limits may be arbitrarily combined. For example, the number is preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30. By setting the number at or above the lower limit, film roughening during development tends to be suppressed. By setting the number at or below the upper limit, resolution tends to be improved, and sensitivity degradation and film reduction during development tend to be easily suppressed.

[0312] Examples of the aliphatic ring in the aliphatic cyclic group include cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isobornane, adamantane, and cyclododecane. Of these, adamantane is preferred from the viewpoint of film reduction and resolution during development.

[0313] On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is generally 1 or more, preferably 2 or more, more preferably 3 or more, and generally 10 or less, preferably 5 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5. By setting the number above the lower limit, a strong film tends to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number below the upper limit, sensitivity degradation and film reduction tend to be suppressed, and resolution tends to be improved.

[0314] Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. Furthermore, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15. By setting the number above the lower limit, a strong film is easily obtained and surface roughness that occurs during development is less likely to occur. By setting the number below the upper limit, resolution is improved and sensitivity degradation and film reduction are easily suppressed.

[0315] Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of developability.

[0316] Examples of substituents that the cyclic hydrocarbon group may have include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups having 1 to 5 carbon atoms, such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. Of these, unsubstituted groups are preferred from the perspective of ease of synthesis.

[0317] Among these, R β It is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.

[0318] On the other hand, from the perspective of patterning characteristics, R β A divalent aromatic ring group is preferred, and a divalent fluorene ring group is more preferred.

[0319] The phenyl ring in formula (b1-II-2) is optionally further substituted by any substituent. As acceptable substituents on the phenyl ring in formula (b1-II-2), for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy can be mentioned. When the phenyl ring in formula (b1-II-2) has a substituent, the number of the substituent is not particularly limited and can be 1 or more than 2.

[0320] Furthermore, two benzene rings may be linked via a substituent. Examples of the substituent include divalent groups such as -O-, -S-, -NH-, and -CH2-.

[0321] From the viewpoint of patterning properties, the benzene ring in formula (b1-II-2) is preferably unsubstituted. Furthermore, from the viewpoint of less likely to cause film reduction, the benzene ring in formula (b1-II-2) is preferably substituted with a methyl group.

[0322] Specific examples of the partial structure represented by the above formula (b1-II-2) are listed below. In the examples, * represents a connecting bond.

[0323]

[0324] From the viewpoint of the coating film residual rate and patterning characteristics, the partial structure represented by formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3).

[0325]

[0326] In formula (b1-II-3), R 13 、R 14 、R 15 、R 16 , m and n have the same meanings as in formula (b1-II), R Z represents a hydrogen atom or a polyacid residue.

[0327] The polybasic acid residue is a monovalent group formed by removing one OH group from a polybasic acid. It should be noted that one more OH group may be removed and the residue may be combined with R Z Shared, that is, can be used with the help of R Z Connect a plurality of formula (b1-II-3).

[0328] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0329] Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0330] The partial structure represented by formula (b1-II-3) contained in one molecule of the epoxy (meth)acrylate resin (b1-II) may be one type or two or more types. For example, R Z For hydrogen atoms and R Z A polyacid residue.

[0331] The number of partial structures represented by formula (b1-II) contained in one molecule of the epoxy (meth)acrylate resin (b1-II) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. For example, it is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10. By setting the number at or above the lower limit, a strong film is easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the number at or below the upper limit, resolution is improved, and the tendency toward sensitivity deterioration and film reduction is easily suppressed.

[0332] The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1-II) as measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, and most preferably 5,000 or more. It is usually 10,000 or less, preferably 8,000 or less, and more preferably 7,000 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1,000 to 10,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 8,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 7,000. When the value is greater than or equal to the lower limit, the residual film rate of the photosensitive coloring composition tends to be improved. When the value is less than or equal to the upper limit, the solubility in the developer tends to be improved.

[0333] (b1-II) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, further preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Furthermore, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, further preferably 130 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g, further preferably 80 mgKOH / g to 130 mgKOH / g, and further preferably 100 mgKOH / g to 130 mgKOH / g. By setting it to above the above lower limit, there is a tendency for the developing solubility to be improved and the resolution to be improved. By setting it as below the said upper limit, there exists a tendency for the residual film rate of a photosensitive coloring composition to become favorable.

[0334] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more.

[0335] Alternatively, a portion of the carboxyl group-containing epoxy (meth)acrylate resin may be replaced with another binder resin. That is, the carboxyl group-containing epoxy (meth)acrylate resin may be used in combination with another binder resin. In this case, the proportion of the carboxyl group-containing epoxy (meth)acrylate resin in the alkali-soluble resin (b) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and is typically 100% by mass or less.

[0336] As the (b) alkali-soluble resin, from the viewpoint of compatibility with a pigment, a dispersant, etc., it is preferable to use an acrylic copolymer resin (b2), and acrylic copolymer resins described in JP-A-2014-137466 can be preferably used.

[0337] Examples of the acrylic copolymer resin include copolymers of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b2-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)").

[0338] As the unsaturated monomer (b2-1), for example, there can be mentioned: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; mono (meth)acryloyloxyalkyl) esters of polybasic acids having a valence of 2 or more, such as mono (2-(meth)acryloyloxyethyl) succinate and mono (2-(meth)acryloyloxyethyl) phthalate; mono (meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono (meth)acrylate; and p-vinylbenzoic acid.

[0339] These unsaturated monomers (b2-1) can be used alone or in combination of two or more.

[0340] Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

[0341] Styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthene and other aromatic vinyl compounds;

[0342] Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth)acrylate, polyethylene glycol (degree of polymerization 2-10) mono(meth)acrylate, polypropylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate 2,6 (Meth)acrylates such as decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, and 3-[(meth)acryloyloxymethyl]-3-ethyloxetane;

[0343] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclic [5.2.1.0 2,6 ] vinyl ethers such as decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane;

[0344] A macromonomer having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, polyn-butyl(meth)acrylate, or polysiloxane.

[0345] These unsaturated monomers (b2-2) can be used alone or in combination of two or more.

[0346] In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) within this range, a photosensitive coloring composition having excellent alkali developability and storage stability tends to be obtained.

[0347] Examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include those disclosed in JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, and JP-A-2004-101728.

[0348] The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method. For example, its structure, Mw, and Mw / Mn can be controlled by the methods disclosed in Japanese Patent Application Publication No. 2003-222717, Japanese Patent Application Publication No. 2006-259680, and International Publication No. 2007 / 029871.

[0349] Furthermore, the resins described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 can also be used.

[0350] <(c) Photopolymerization initiator>

[0351] (c) The photopolymerization initiator is a component that directly absorbs light to cause a decomposition reaction or a hydrogen abstraction reaction, thereby generating polymerization-active radicals. Additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may also be added and used as needed.

[0352] As the photopolymerization initiator, for example, metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Patent Application Laid-Open No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in Japanese Patent Application Laid-Open No. 10-39503; α-aminoalkylphenone derivatives; oxime ester compounds described in Japanese Patent Application Laid-Open No. 2000-80068 and Japanese Patent Application Laid-Open No. 2006-36750.

[0353] Examples of the metallocene compound 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-(pyrrol-1-yl)phenyl]titanium.

[0354] Examples of the hexaarylbiimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0355] Examples of the 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-furyl-1,3,4-oxadiazole.

[0356] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0357] Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0358] Oxime ester compounds are particularly effective as photopolymerization initiators from the perspectives of sensitivity and platemaking properties. For example, when using an alkali-soluble resin containing a phenolic hydroxyl group, these highly sensitive oxime ester compounds are particularly useful. Oxime ester compounds have structures that simultaneously absorb ultraviolet light, transmit light energy, and generate free radicals. Therefore, even in small amounts, they exhibit high sensitivity and are stable to thermal reactions, making it possible to produce highly sensitive photosensitive coloring compositions with small amounts.

[0359] Examples of the oxime ester compound include compounds represented by the following general formula (IV).

[0360]

[0361] In the above formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

[0362] R 21b represents an arbitrary substituent containing an aromatic ring.

[0363] R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.

[0364] n represents an integer of 0 or 1.

[0365] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. For example, it is 1 to 20, preferably 1 to 15, and more preferably 2 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group.

[0366] Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, and an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, the alkyl group is preferably unsubstituted.

[0367] As R 21a Examples of the aromatic ring group in the group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Furthermore, from the viewpoint of developability, the number of carbon atoms is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is 5 to 30, preferably 5 to 20, and more preferably 5 to 12 or less.

[0368] Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0369] Examples of the substituent that the aromatic ring group may optionally have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group formed by linking these substituents. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group formed by linking these substituents are preferred, and a linked alkoxy group is more preferred.

[0370] Among these, R21a An aromatic ring group which may have a substituent is preferred, and an aromatic ring group which has a linked alkoxy group as a substituent is more preferred.

[0371] In addition, as R 21b , and may include an optionally substituted carbazolyl group, an optionally substituted thioxanthone group, and an optionally substituted diphenyl sulfide group. Among these, an optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity, and an optionally substituted diphenyl sulfide group is preferred from the viewpoint of electrical reliability.

[0372] In addition, R 22a The number of carbon atoms in the alkanoyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less, from the viewpoint of solubility in solvents and sensitivity. For example, it is 2 to 20, preferably 2 to 15, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the alkanoyl group include acetyl, propionyl, and butyryl.

[0373] Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.

[0374] In addition, R 22a The number of carbon atoms in the aroyl group is not particularly limited, but is usually 7 or more, preferably 8 or more, and is usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility in solvents and sensitivity. For example, it is 7 to 20, preferably 7 to 15, and more preferably 8 to 10. Examples of the aroyl group include benzoyl and naphthoyl.

[0375] Examples of the substituent that the aroyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, the aroyl group is preferably unsubstituted.

[0376] Among these, from the perspective of sensitivity, R 22a An alkanoyl group which may have a substituent is preferred, an unsubstituted alkanoyl group is more preferred, and an acetyl group is further preferred.

[0377] From the viewpoint of reducing contamination of the liquid crystal layer by the colorant, it is also preferable to use the initiator described in Japanese Patent Application Laid-Open No. 2016-133574.

[0378] The photopolymerization initiator may be used alone or in combination of two or more.

[0379] In order to improve the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be mixed with the photopolymerization initiator as needed. Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open Nos. 4-221958 and 4-219756, coumarin dyes having a heterocyclic ring described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, 3-ketocoumarin compounds described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, pyrromethene dyes described in Japanese Patent Application Laid-Open No. 6-19240, and the like. A pigment having a dialkylaminobenzene skeleton as described in Japanese Patent Application Publication No. 1996-155292, Japanese Patent Application Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818.

[0380] Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. Preferred sensitizing dyes include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone and other benzophenone-based compounds; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)benzo[6,7]benzoxazole, Compounds containing a p-dialkylaminophenyl group include (p-dimethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine. Among these, 4,4'-dialkylaminobenzophenone is particularly preferred.

[0381] The sensitizing dye may be used alone or in combination of two or more.

[0382] Examples of polymerization accelerators include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate; aliphatic amines such as n-butylamine and N-methyldiethanolamine; and mercapto compounds described below. These polymerization accelerators may be used alone or in combination of two or more.

[0383] <(d) Ethylenically unsaturated compounds>

[0384] The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. By containing (d) an ethylenically unsaturated compound, the sensitivity is improved.

[0385] The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples include (meth)acrylic acid, alkyl (meth)acrylates, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyols or monohydric alcohols.

[0386] In the present invention, it is particularly preferred to use a multifunctional olefinic monomer having two or more olefinic unsaturated groups in one molecule. The number of olefinic unsaturated groups possessed by the multifunctional olefinic monomer is not particularly limited, and is generally two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 2 to 8, more preferably 2 to 7, further preferably 4 to 7, and particularly preferably 5 to 7. By setting it to above the above lower limit, there is a tendency to achieve high sensitivity, and by setting it to below the above upper limit, there is a tendency to improve solubility in solvents.

[0387] Examples of polyfunctional olefinic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polyvalent carboxylic acids.

[0388] Examples of the esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylates of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; and methacrylates obtained by converting these acrylates to methacrylates, itaconates obtained by converting these acrylates to itaconates, crotonates obtained by converting these acrylates to crotonates, and maleates obtained by converting these acrylates to maleates.

[0389] Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.

[0390] The esters obtained by the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds are not necessarily single substances, and examples thereof 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.

[0391] In addition, as the polyfunctional olefinic monomer used in the present invention, for example, urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a hydroxyl-containing (meth)acrylate, or a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound with a hydroxyl (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl-containing compounds such as divinyl phthalate are useful.

[0392] Examples of the urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, and UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, and UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), and UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).

[0393] Among these, from the viewpoint of curability, as the (d) ethylenically unsaturated compound, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, urethane (meth)acrylates, polyisocyanate compounds and hydroxyl-containing (meth)acrylates, or urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a polyol and a hydroxyl-containing (meth)acrylate are preferably used. Alkyl (meth)acrylates are more preferably used, and dipentaerythritol hexaacrylate is even more preferably used.

[0394] These may be used alone or in combination of two or more.

[0395] (e) Solvent

[0396] The photosensitive coloring composition of the present invention contains (e) a solvent. By containing (e) a solvent, the (a) coloring agent can be dispersed or dissolved in the solvent, and coating becomes easy.

[0397] The photosensitive coloring composition of the present invention generally contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and other various materials as needed, dissolved or dispersed in a solvent. Among solvents, organic solvents are preferred from the viewpoint of dispersibility and coating properties.

[0398] Among organic solvents, from the viewpoint of coating properties, those with a boiling point of 100 to 300° C. are preferably selected, and those with a boiling point of 120 to 280° C. are more preferably selected. Note that the boiling point referred to here is the boiling point at a pressure of 1013.25 hPa, and the same applies to the boiling point hereinafter.

[0399] Examples of such organic solvents include glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

[0400] Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0401] Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

[0402] Glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0403] Alkyl acetates such as cyclohexanol acetate;

[0404] Ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

[0405] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0406] Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0407] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0408] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0409] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0410] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone;

[0411] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0412] Halogenated hydrocarbons such as chlorobutane and chloropentane;

[0413] ether ketones such as methoxymethylpentyl ketone;

[0414] Nitriles such as acetonitrile and benzonitrile.

[0415] As commercially available organic solvents, for example, mineral spirits, Varsol #2, Apco #18 solvent, Apcothinner, Socal solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark. The same shall apply hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (diglyme) (all trade names) can be used.

[0416] These organic solvents may be used alone or in combination of two or more.

[0417] When forming the partition walls by photolithography, the organic solvent preferably has a boiling point of 100 to 240°C, more preferably 120 to 200°C, and even more preferably 120 to 170°C.

[0418] Among the above-mentioned organic solvents, glycol alkyl ether acetates are preferred because they have a good balance between coating properties, surface tension, etc., and have high solubility of the components in the composition.

[0419] Glycol alkyl ether acetates can be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferred as organic solvents for use in combination. Propylene glycol monomethyl ether is preferred due to the solubility of the components in the composition. Glycol monoalkyl ethers have high polarity, and excessive addition of them tends to reduce storage stability, such as increased viscosity of the resulting photosensitive coloring composition and increased pigment aggregation. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

[0420] It is also preferable to use an organic solvent with a boiling point of 150°C or higher (hereinafter sometimes referred to as a "high-boiling-point solvent"). While the use of a high-boiling-point solvent makes the photosensitive coloring composition difficult to dry, it prevents the uniform dispersion of the pigment in the composition from being disrupted during rapid drying. Specifically, it prevents foreign matter defects caused by precipitation and solidification of the colorant at the tip of the slit nozzle. Due to the high effectiveness of these solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred among the various solvents mentioned above.

[0421] When a high-boiling-point solvent is used in combination, the content of the high-boiling-point solvent in the organic solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass. By setting the content above the lower limit, there is a tendency to suppress foreign matter defects such as precipitation and solidification of the coloring material at the tip of the slit nozzle. Furthermore, by setting the content below the upper limit, a decrease in the drying speed of the composition can be suppressed, thereby tending to suppress problems such as poor tact in the reduced-pressure drying process and needle marks from pre-baking.

[0422] The high-boiling-point solvent having a boiling point of 150° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high-boiling-point solvent having a boiling point of 150° C. or higher may not be contained separately.

[0423] Preferred high-boiling-point solvents include, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glycerol triacetate.

[0424] (f) Dispersant

[0425] The photosensitive coloring composition of the present invention contains a dispersant (f). By containing the dispersant (f), the colorant (a) can be dispersed stably.

[0426] The (f) dispersant in the photosensitive coloring composition of the present invention contains an acrylic copolymer (f1) (hereinafter sometimes referred to as "dispersant (f1)") having repeating units represented by the following general formulas (1) to (3) and does not have a repeating unit containing a quaternary ammonium group.

[0427]

[0428] (In formula (1), R 31 It is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

[0429] R 32is a hydrogen atom or a methyl group.

[0430] * indicates a connection key.)

[0431]

[0432] (In formula (2), R 33 is methylene, ethylene or propylene, R 34 is an alkyl group optionally having a substituent, R 35 is a hydrogen atom or a methyl group.

[0433] n is an integer from 1 to 20.

[0434] * indicates a connection key.)

[0435]

[0436] (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 36 and R 37 They are optionally bonded to each other to form a ring structure.

[0437] R 38 is a hydrogen atom or a methyl group.

[0438] Z is a divalent linking group.

[0439] * indicates a connection key.)

[0440] The dispersant (f1) has a repeating unit represented by the following general formula (1) from the viewpoint of improving compatibility with a solvent and an alkali-soluble resin and thereby improving dispersion stability.

[0441]

[0442] (In formula (1), R 31 It is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

[0443] R 32 is a hydrogen atom or a methyl group.

[0444] * indicates a connection key.)

[0445] (R 31 )

[0446] In the above formula (1), R 31The alkyl group in the alkyl group may be a linear, branched or cyclic alkyl group. From the viewpoint of compatibility with solvents and alkali-soluble resins, a linear alkyl group is preferred, while from the viewpoint of affinity with pigments, a branched alkyl group is preferred.

[0447] 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 4 or more, and preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. The upper and lower limits described above may be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 2 to 8, and even more preferably 4 to 6. By setting the number above the lower limit, affinity for pigments tends to be improved. By setting the number below the upper limit, compatibility with solvents and alkali-soluble resins tends to be enhanced, thereby improving dispersibility.

[0448] Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl. From the viewpoint of compatibility with solvents and alkali-soluble resins, methyl and ethyl are preferred, and methyl is more preferred.

[0449] Examples of the substituent that the alkyl group may have include alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine, chlorine, and bromine; and aryl groups such as phenyl and naphthyl. From the viewpoint of compatibility with solvents and alkali-soluble resins, the alkyl group is preferably unsubstituted, while from the viewpoint of affinity for pigments, the phenyl group is preferred.

[0450] As R 31 The aryl group in includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.

[0451] The number of carbon atoms in the aryl group is not particularly limited, but is generally 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. By setting the number below the upper limit, affinity for pigments tends to improve. Examples of the aryl group include phenyl, naphthyl, and anthracenyl. From the perspective of dispersibility, phenyl and naphthyl are preferred, and phenyl is more preferred.

[0452] Examples of the substituent that the aryl group may have include alkyl groups such as methyl and ethyl groups; alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as fluorine, chlorine, and bromine atoms; aryl groups such as phenyl and naphthyl groups; and aralkyl groups such as benzyl and phenethyl groups. From the viewpoint of dispersibility, unsubstituted groups are preferred.

[0453] Among these, from the viewpoint of compatibility with solvents and alkali-soluble resins, R 31 , preferably an alkyl group which may have a substituent, more preferably a methyl group, a butyl group, an ethylhexyl group, or a benzyl group.

[0454] From the viewpoint of compatibility with the solvent and the alkali-soluble resin, the dispersant (f1) has a repeating unit represented by the following general formula (2).

[0455]

[0456] (In formula (2), R 33 is methylene, ethylene or propylene, R 34 is an alkyl group optionally having a substituent, R 35 is a hydrogen atom or a methyl group.

[0457] n is an integer from 1 to 20.

[0458] * indicates a connection key.)

[0459] In the above formula (2), R 33 It is a methylene group, an ethylene group or a propylene group, and is preferably an ethylene group from the viewpoint of compatibility with solvents and alkali-soluble resins.

[0460] In the above formula (2), R 34 It is an alkyl group which may have a substituent, and is preferably a methyl group or an ethyl group from the viewpoint of compatibility with a solvent and an alkali-soluble resin.

[0461] In the above formula (2), n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5. By setting it at or above the above lower limit, compatibility with solvents and alkali-soluble resins tends to be improved. By setting it at or below the above upper limit, affinity for pigments tends to be enhanced, and dispersibility tends to be improved.

[0462] The dispersant (f1) has a repeating unit represented by the above-mentioned general formula (3) and is preferably used from the viewpoint of roughening the surface of the electrode.

[0463]

[0464] (In formula (3), R 36 and R 37 are each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 36 and R 37 They are optionally bonded to each other to form a ring structure.

[0465] R 38 is a hydrogen atom or a methyl group.

[0466] Z is a divalent linking group.

[0467] * indicates a connection key.)

[0468] In the above formula (3), R 36 and R 37Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent. As the alkyl group optionally having a substituent or the aryl group optionally having a substituent, R in the above formula (1) can be preferably used. 31 Groups listed.

[0469] In the above formula (3), R 36 and R 37 They are optionally bonded to form a cyclic structure. Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of these rings. The nitrogen-containing heterocyclic ring is preferably non-aromatic and more preferably a saturated ring. Specifically, the following examples are given.

[0470]

[0471] (These cyclic structures may further have a substituent.

[0472] * indicates a connection key.)

[0473] (Z)

[0474] In the above formula (3), Z is a divalent linking group.

[0475] Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 39 -base, -COOR 40 - group (wherein R 39 and R 40 Each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms. From the viewpoint of dispersibility, -COOR 7 -base. R 40 Among them, from the viewpoint of temporal stability of the dispersion, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 5 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is further preferred.

[0476] The content ratio of the repeating unit represented by the general formula (1) (hereinafter sometimes referred to as "repeating unit (1)") in the dispersant (f1) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, even more preferably 50 mol% or more, and particularly preferably 60 mol% or more, and is preferably 90 mol% or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, and particularly preferably 75 mol% or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 20 mol% to 90 mol%, more preferably 30 mol% to 90 mol%, even more preferably 40 mol% to 80 mol%, even more preferably 50 mol% to 80 mol%, and particularly preferably 60 mol% to 80 mol%. When the content is greater than the above lower limit, the affinity for the pigment tends to be improved. When the content is less than the above upper limit, the compatibility with the solvent and the alkali-soluble resin tends to be improved.

[0477] The content ratio of the repeating unit represented by the general formula (2) (hereinafter sometimes referred to as "repeating unit (2)") in the dispersant (f1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 2.5 mol% or more, and particularly preferably 3 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 8 mol% or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, further preferably 1 mol% to 15 mol%, further preferably 1 mol% to 10 mol%, and particularly preferably 2 mol% to 10 mol%. By setting the content ratio above the lower limit, compatibility with solvents and alkali-soluble resins tends to improve. By setting the content ratio below the upper limit, affinity for pigments tends to improve.

[0478] The content ratio of the repeating unit represented by the general formula (3) (hereinafter sometimes referred to as "repeating unit (3)") in the dispersant (f1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, particularly preferably 30 mol% or more, and preferably 50 mol% or less, more preferably 45 mol% or less, further preferably 40 mol% or less, particularly preferably 35 mol% or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 10 mol% to 50 mol%, more preferably 20 mol% to 40 mol%, further preferably 25 mol% to 35 mol%, and particularly preferably 30 mol% to 35 mol%. By setting it to above the lower limit, there is a tendency for dispersibility to become better. By setting it to below the upper limit, there is a tendency for the temporal stability of the dispersion to become better.

[0479] The dispersant (f1) may be included in any form of random copolymerization or block copolymerization. From the viewpoint of dispersibility, a block copolymer is preferred. The block copolymer preferably comprises: an A block comprising repeating units having a solvent-philic group and a B block comprising repeating units having a pigment-adsorbing group.

[0480] When the dispersant (f1) has repeating units (1) and (2), these are preferably contained in the A block and may be contained in either a random copolymerization or a block copolymerization. Alternatively, the A block may contain two or more types of repeating units (1) and repeating units (2), in which case each repeating unit may be contained in the A block in either a random copolymerization or a block copolymerization.

[0481] The A block may contain repeating units other than the repeating units (1) and (2). Examples of such repeating units include repeating units derived from the following substances: styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acryloyl chloride; (meth)acrylamide-based monomers such as N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether and crotonic acid glycidyl ether; and N-methacryloylmorpholine.

[0482] Among these, the block copolymer comprising an A block having repeating units (1) and (2) and a B block having repeating units (3) is more preferably an AB block copolymer or an ABA block copolymer.

[0483] The amine value of the dispersant (f1) is not particularly limited, but is preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, further preferably 90 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. Furthermore, it is preferably 200 mgKOH / g or less, more preferably 160 mgKOH / g or less, further preferably 140 mgKOH / g or less, and particularly preferably 130 mgKOH / g or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 50 mgKOH / g to 200 mgKOH / g, more preferably 80 mgKOH / g to 160 mgKOH / g, further preferably 100 mgKOH / g to 140 mgKOH / g, and particularly preferably 100 mgKOH / g to 130 mgKOH / g. By setting the value above the lower limit, surface roughness of the electrode tends to be suppressed. By setting the value below the upper limit, the temporal stability of the dispersion tends to be improved. The amine value is expressed as the mass of KOH corresponding to the amount of alkali per 1 g of the solid content of the dispersant (f1).

[0484] The acid value of the dispersant (f1) is not particularly limited, but is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, further preferably 1 mgKOH / g, and particularly preferably 0 mgKOH / g from the viewpoint of dispersibility.

[0485] The weight-average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more. Furthermore, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 7,000 to 10,000. By setting the weight-average molecular weight above the lower limit, dispersibility tends to be improved. By setting the weight-average molecular weight below the upper limit, the temporal stability of the dispersion tends to be improved.

[0486] The chlorine atom content in the dispersant (f1) is not particularly limited, but is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, further preferably 0.2% by mass or less, and particularly preferably substantially free of chlorine atoms, i.e., 0.1% by mass or less. By setting the content below the upper limit, surface roughness tends to be suppressed.

[0487] The method for producing the dispersant (f1) is not particularly limited, and a known method can be used. Examples thereof include the methods described in JP-A-01-299014, JP-A-2017-019937, JP-A-2018-172530, JP-A-2018-203795, JP-A-2019-099801, and International Publication No. 2019 / 079659.

[0488] The (f) dispersant in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f1) (hereinafter sometimes referred to as “other dispersants”).

[0489] Other dispersants, for example, preferably have the following functional groups from the perspective of dispersion stability: carboxyl groups; or their salts; primary, secondary, or tertiary amino groups; quaternary ammonium salt groups; or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. Among these, dispersants having basic functional groups, such as primary, secondary, or tertiary amino groups; quaternary ammonium salt groups; or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine, are more preferred.

[0490] Furthermore, from the viewpoint of enabling dispersion with a small amount of dispersant when dispersing the pigment, a polymer dispersant is preferred.

[0491] Examples of the polymer dispersant include acrylic dispersants other than the dispersant (f1), urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants formed from a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0492] Examples of such polymer dispersants include trade names EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0493] Examples of urethane-based and acrylic-based polymer dispersants include DISPERBYK 160 to 166, and 182 series (all urethane-based), DISPERBYK 2000, 2001, and BYK-LPN 21116 (all acrylic-based) (all manufactured by BYK-Chemie).

[0494] The other dispersants may be used alone or in combination of two or more.

[0495] <Other ingredients in the photosensitive coloring composition>

[0496] The photosensitive coloring composition of the present invention may contain, in addition to the above-mentioned components, additives such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors.

[0497] (1) Adhesion enhancer

[0498] In order to improve the adhesion with the substrate, the photosensitive coloring composition of the present invention may contain an adhesion improver. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound, etc. are preferred.

[0499] As the type of silane coupling agent, various silane coupling agents such as epoxy-based, (meth)acrylic-based, and amino-based silane coupling agents may be used alone or in combination of two or more thereof.

[0500] Examples of the silane coupling agent include (meth)acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane; epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; and isocyanatesilanes such as 3-isocyanatepropyltriethoxysilane. Epoxysilane-based silane coupling agents are particularly preferred.

[0501] As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphoric acid esters are preferred, and substances represented by the following general formula (g1), (g2) or (g3) are preferred.

[0502]

[0503] In the above general formulas (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.

[0504] These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

[0505] (2) Surfactants

[0506] The photosensitive coloring composition of the present invention may contain a surfactant in order to improve coating properties.

[0507] As the surfactant, various surfactants can be used, such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. Among them, nonionic surfactants are preferably used from the perspective of low possibility of adverse effects on various properties. Among them, fluorine-based and silicon-based surfactants are effective from the perspective of coating properties.

[0508] Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Shin-Etsu Silicones), F-470, F-475, F-478, F-554, and F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Dow Corning Toray Industries, Ltd.), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unicar Co., Ltd.), and FC4430 (manufactured by 3M Co., Ltd.).

[0509] The surfactant may be used alone or in combination of two or more in any combination and ratio.

[0510] (3) Pigment derivatives

[0511] The photosensitive coloring composition of the present invention may further contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.

[0512] Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, pyrenone, diketopyrrolopyrrole, and dioxazine derivatives, among which phthalocyanine and quinophthalone derivatives are preferred.

[0513] Examples of substituents in the pigment derivative include sulfonic acid groups, sulfonamide groups, and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, and amide groups, which are directly or via alkyl groups, aryl groups, heterocyclic groups, and the like, and are preferably sulfonic acid groups. A single pigment skeleton may be substituted with multiple of these substituents.

[0514] Examples of pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.

[0515] (4) Mercapto compounds

[0516] Furthermore, in order to improve the adhesion to the substrate, a mercapto compound may be added as a polymerization accelerator.

[0517] Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butylene glycol dimercaptopropionate, butylene glycol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), and the like. Heterocyclic mercapto compounds and aliphatic polyfunctional mercapto compounds such as 1,4-bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. These may be used alone or in combination of two or more.

[0518] (5) Inhibitor

[0519] From the perspective of controlling the shape of the cured product, the photosensitive coloring composition of the present invention may contain a polymerization inhibitor. It is believed that the inclusion of a polymerization inhibitor inhibits radical polymerization of the lower layer of the coating film, thereby controlling the taper angle (the angle between the support and the cured product in the cross section of the cured product).

[0520] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol (BHT). Among these, 2,6-di-tert-butyl-4-methylphenol is preferred from the perspective of shape control. Furthermore, hydroquinone monomethyl ether and methylhydroquinone are preferred from the perspective of particularly excellent safety for the human body.

[0521] The polymerization inhibitor may be used alone or in combination of two or more.

[0522] When producing (b) the alkali-soluble resin, the resin may contain a polymerization inhibitor, which may be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor in the resin, a polymerization inhibitor that is the same as or different from the polymerization inhibitor may be added during the production of the photosensitive resin composition.

[0523] When the photosensitive coloring composition contains a polymerization inhibitor, the content ratio is not particularly limited, but is generally 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and generally 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less, relative to the total solid content of the photosensitive coloring composition. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.0005% by mass to 0.3% by mass, more preferably 0.001% by mass to 0.2% by mass, and even more preferably 0.01% by mass to 0.1% by mass. When the content is above the lower limit, the shape of the cured product tends to be controlled. When the content is below the upper limit, the desired sensitivity tends to be maintained.

[0524] <Content ratio of each component in the photosensitive coloring composition>

[0525] The content ratio of the colorant (a) in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total solids content, and 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 25% by mass or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, even more preferably 15% to 40% by mass, even more preferably 15% to 30% by mass, and particularly preferably 15% to 25% by mass. When the content is above the lower limit, light-shielding properties tend to be ensured. When the content is below the upper limit, the amount of dispersant can be reduced, and surface roughness tends to be suppressed.

[0526] In the first embodiment, the content ratio of compound (I) in the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, relative to the total solid content of the photosensitive coloring composition, and is generally 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5% by mass to 70% by mass, more preferably 20% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass. By setting it above the lower limit, there is a tendency to suppress the loss of ultraviolet light required for curing and improve light-shielding properties. By setting it below the upper limit, there is a tendency to reduce the amount of dispersant and suppress surface roughness.

[0527] In the first embodiment, when the colorant (a) comprises compound (I) and other pigments, the total content ratio thereof is not particularly limited. The content ratio of compound (I) in the colorant (a) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and further preferably 30% to 70% by mass. By setting it to above the above lower limit, there is a tendency for light-shielding properties to be improved and a hue close to black to be achieved. By setting it to below the above upper limit, there is a tendency for residue to be reduced during development and for reliability to be improved during element production.

[0528] In the first embodiment, when the colorant (a) comprises compound (I) and an organic coloring pigment, the total content ratio thereof is not particularly limited. The content ratio of compound (I) in the colorant (a) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and further preferably 30% to 70% by mass. By setting it to above the above lower limit, there is a tendency for light-shielding properties to be improved and a hue close to black to be achieved. By setting it to below the above upper limit, there is a tendency for residue to be reduced during development and for reliability to be improved during element production.

[0529] When the photosensitive coloring composition contains an organic coloring pigment, the content ratio is not particularly limited. However, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more relative to the total solid content of the photosensitive coloring composition. Furthermore, it is generally 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5% to 70% by mass, more preferably 20% to 70% by mass, even more preferably 20% to 60% by mass, and particularly preferably 20% to 50% by mass. When the content is above the lower limit, light-shielding properties tend to be improved. When the content is below the upper limit, the amount of dispersant can be reduced, and surface roughness tends to be suppressed.

[0530] When (a) colorant includes red pigment and / or orange pigment, the total content ratio of red pigment and orange pigment is not particularly limited. In (a) colorant, it is preferably 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 40% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5% by mass to 40% by mass, more preferably 8% by mass to 40% by mass, further preferably 10% by mass to 30% by mass, particularly preferably 12% by mass to 20% by mass. By setting it to above the above lower limit, there is a tendency to achieve a hue close to black. By setting it to below the above upper limit, there is a tendency to become highly sensitive.

[0531] When (a) the colorant includes a blue pigment and / or a purple pigment, the total content of the blue pigment and the purple pigment is not particularly limited. In (a) the colorant, it is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and preferably 95% by mass or less, more preferably 92% by mass or less, particularly preferably 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 30% to 95% by mass, more preferably 50% to 95% by mass, further preferably 70% to 92% by mass, and particularly preferably 80% to 90% by mass. By setting it to above the above lower limit, there is a tendency to achieve a hue close to black. By setting it to below the above upper limit, there is a tendency for sensitivity and light-shielding properties to become good.

[0532] (a) When the colorant includes a red pigment and / or an orange pigment and includes a blue pigment and / or a violet pigment, the content ratio of the red pigment and / or the orange pigment relative to the content of the blue pigment and / or the violet pigment is not particularly limited, and is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, particularly preferably 8% by mass or more, and preferably 300% by mass or less, more preferably 100% by mass or less, particularly preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1% by mass to 300% by mass, more preferably 3% by mass to 100% by mass, further preferably 5% by mass to 100% by mass, and particularly preferably 8% by mass to 50% by mass. By setting it to above the above lower limit, there is a tendency to suppress the transmission of blue light and improve light-shielding properties. By setting it to below the above upper limit, there is a tendency to achieve a hue close to black.

[0533] When the photosensitive coloring composition contains an organic black pigment, its content ratio is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more, relative to the total solids content of the photosensitive coloring composition. Furthermore, it is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 3% to 60% by mass, more preferably 5% to 60% by mass, even more preferably 10% to 50% by mass, and particularly preferably 20% to 40% by mass. When the content is above the lower limit, light-shielding properties tend to be improved. When the content is below the upper limit, the amount of dispersant can be reduced, and surface roughness tends to be suppressed.

[0534] When the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content ratio is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more relative to the total solid content of the photosensitive coloring composition. Furthermore, it is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1% to 30% by mass, more preferably 3% to 20% by mass, and even more preferably 3% to 10% by mass. When the content is above the lower limit, light-shielding properties tend to be improved. When the content is below the upper limit, a cured product with high resistance and low dielectric constant tends to be formed.

[0535] When (a) the colorant includes a black pigment and an organic coloring pigment, the total content ratio thereof is not particularly limited. The content ratio of the black pigment in (a) the colorant is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, and further preferably 30% to 70% by mass. By setting it to above the above lower limit, there is a tendency for light-shielding properties to be improved and a hue close to black to be achieved. By setting it to below the above upper limit, there is a tendency for residue to be reduced during development and for reliability to be improved during element production.

[0536] The content ratio of the (b) alkali-soluble resin is not particularly limited, but is generally 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more, and is generally 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total solid content of the photosensitive coloring composition of the present invention. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5% to 80% by mass, more preferably 10% to 70% by mass, even more preferably 20% to 60% by mass, even more preferably 30% to 60% by mass, particularly preferably 30% to 55% by mass, and particularly preferably 40% to 55% by mass. By setting the content ratio above the above lower limit, a decrease in the solubility of the unexposed portion in the developer solution can be suppressed, which tends to suppress development defects. By setting the content to be equal to or less than the upper limit, appropriate sensitivity can be maintained, dissolution of the exposed portion by the developer can be suppressed, and reduction in pattern clarity and adhesion can be suppressed.

[0537] The content ratio of the (b1) epoxy (meth)acrylate resin is not particularly limited, but is generally 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 30% by mass or more, particularly preferably 40% by mass or more, and generally 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less, relative to the total solid content of the photosensitive coloring composition of the present invention. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5% to 80% by mass, more preferably 10% to 70% by mass, further preferably 20% to 60% by mass, further preferably 30% to 60% by mass, particularly preferably 30% to 55% by mass, and particularly preferably 40% to 55% by mass. By setting it above the lower limit, the solubility of the unexposed portion in the developer tends to be ensured. By setting it to the said upper limit value or less, there exists a tendency to maintain appropriate sensitivity, suppress the dissolution of the exposed part by a developer, and suppress the fall of the clarity and adhesiveness of a pattern.

[0538] The content ratio of the epoxy (meth) acrylate resin (b1) contained in the (b) alkali-soluble resin is not particularly limited, and is generally 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and generally 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20% to 90% by mass, more preferably 30% to 80% by mass, and further preferably 40% to 80% by mass. By setting it to above the above lower limit, there is a tendency to ensure the solubility of the unexposed portion with respect to the developer. By setting it to below the above upper limit, there is a tendency to maintain appropriate sensitivity, suppress the dissolution of the exposed portion due to the developer, and suppress the reduction in the clarity and adhesion of the pattern.

[0539] The content ratio of the (c) photopolymerization initiator is not particularly limited, but is generally 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is generally 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less, relative to the total solid content of the photosensitive coloring composition of the present invention. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 0.1% by mass to 15% by mass, more preferably 0.5% by mass to 15% by mass, even more preferably 1% by mass to 10% by mass, even more preferably 2% by mass to 8% by mass, and particularly preferably 3% by mass to 6% by mass. By setting the content ratio above the lower limit, a decrease in sensitivity tends to be suppressed. By setting the content ratio below the upper limit, a decrease in solubility of the unexposed portion in the developer solution tends to be suppressed, and poor development tends to be suppressed.

[0540] When a polymerization accelerator is used together with the photopolymerization initiator (c), the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more, typically 10% by mass or less, and preferably 5% by mass or less, relative to the total solids content of the photosensitive coloring composition of the present invention. Furthermore, the polymerization accelerator is preferably used in a ratio of typically 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (c). By setting the content of the polymerization accelerator above the lower limit, a decrease in sensitivity to exposure light tends to be suppressed. By setting the content below the upper limit, a decrease in solubility of the unexposed portion in the developer tends to be suppressed, thereby suppressing development defects.

[0541] When a sensitizing dye is used together with the (c) photopolymerization initiator, the content ratio thereof is not particularly limited, but is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, relative to the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity.

[0542] The content ratio of the (d) ethylenically unsaturated compound is not particularly limited, but is generally 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total solid content of the photosensitive coloring composition of the present invention. Furthermore, it is generally 30% by mass or less, preferably 25% by mass or less, and even more preferably 20% by mass or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1% to 30% by mass, more preferably 5% to 20% by mass, and even more preferably 10% to 20% by mass. By setting the content ratio above the lower limit, there is a tendency to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developer, and suppress reduction in pattern clarity and adhesion. By setting the content ratio below the upper limit, there is a tendency to suppress increased penetration of the developer into the exposed portion, making it easier to obtain a good image.

[0543] The photosensitive coloring composition of the present invention can be prepared as a liquid by using the solvent (e) so that the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the liquid is preferably prepared so that the content is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, and even more preferably 15% by mass to 25% by mass.

[0544] (f) The content of the dispersant is not particularly limited, but is generally 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, relative to the total solids content of the photosensitive coloring composition, and is generally 20% by mass or less, 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 1% to 20% by mass, more preferably 2% to 15% by mass, even more preferably 3% to 10% by mass, and particularly preferably 3% to 7% by mass. By setting the content above the lower limit, sufficient dispersibility tends to be easily achieved. By setting the content below the upper limit, surface roughness of the electrode surface tends to be suppressed.

[0545] The content of the dispersant (f1) is not particularly limited, but is generally 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, relative to the total solid content of the photosensitive coloring composition, and is generally 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 1% to 20% by mass, more preferably 2% to 15% by mass, even more preferably 3% to 10% by mass, and particularly preferably 3% to 7% by mass. By setting it above the lower limit, sufficient dispersibility tends to be easily obtained. By setting it below the upper limit, surface roughness of the electrode surface tends to be suppressed.

[0546] The content of the dispersant (f1) is not particularly limited, but is generally 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more in the dispersant (f), and is generally 100% by mass or less. By setting the content above the lower limit, there is a tendency to suppress surface roughness of the electrode surface.

[0547] The content ratio of (f) dispersant relative to 100 parts by mass of (a) colorant is not particularly limited, but is generally 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more, and generally 50 parts by mass or less, and particularly preferably 30 parts by mass or less. The above upper and lower limits may be arbitrarily combined. For example, it is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 15 to 30 parts by mass. By setting it above the above lower limit, there is a tendency to easily obtain sufficient dispersibility. By setting it below the above upper limit, there is a tendency to suppress the surface roughness of the electrode surface.

[0548] The content ratio of the (b) alkali-soluble resin relative to 100 parts by mass of the (d) ethylenically unsaturated compound is not particularly limited, but is generally 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 250 parts by mass or more, further preferably 300 parts by mass or more, and particularly preferably 350 parts by mass or more. Furthermore, it is generally 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 450 parts by mass or less, and further preferably 400 parts by mass or less. The above upper and lower limits may be combined arbitrarily. For example, it is preferably 100 to 700 parts by mass, more preferably 200 to 700 parts by mass, further preferably 250 to 500 parts by mass, further preferably 250 to 450 parts by mass, and particularly preferably 250 to 400 parts by mass. By setting the content ratio above the lower limit, a suitable dissolution and development state without peeling or the like tends to be achieved. By setting the content ratio below the upper limit, a suitable dissolution time relative to the developer tends to be achieved.

[0549] When an adhesion improver is used, its content is not particularly limited, but is generally 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass relative to the total solid content of the photosensitive coloring composition. By setting the content above the lower limit, the adhesion-improving effect tends to be sufficiently achieved. By setting the content below the upper limit, a decrease in sensitivity and a tendency to suppress defects caused by residual residue after development can be suppressed.

[0550] When a surfactant is used, its content is not particularly limited, but is generally 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass relative to the total solid content of the photosensitive coloring composition. When the content is above the lower limit, the coating film tends to exhibit smoothness and uniformity. When the content is below the upper limit, the coating film tends to exhibit smoothness and uniformity, and deterioration of other properties tends to be suppressed.

[0551] <Chlorine Atom Content in Photosensitive Coloring Composition>

[0552] In the photosensitive coloring composition of the present invention, content of the chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less relative to the total solid content of the photosensitive coloring composition.

[0553] The formation of partition walls is accompanied by a heat treatment step (described later) to cure the photosensitive coloring composition. This process may cause surface roughness on the electrode surface. Surface roughness can be observed using an optical microscope, and the surface roughness also increases. When surface roughness develops on the electrode surface, the light-emitting layer cannot be uniformly formed in that portion, potentially causing display defects such as short circuits in the resulting organic electroluminescent element. This is presumably because chlorine atoms in the photosensitive coloring composition decompose, volatilize, or sublime during heat treatment, particularly during calcination, and act on metal electrodes such as silver, causing corrosion or etching. By keeping the chlorine atom content below a certain value, surface roughness can be suppressed.

[0554] Chlorine atoms in the photosensitive coloring composition are primarily contained in constituent materials such as (a) the colorant, (b) the alkali-soluble resin, and (f) the dispersant, and may also be contained in other materials. To ensure that the chlorine atom content falls within the specified numerical range of the present invention, the chlorine content of one constituent material may be reduced, or the composition may be designed so that the chlorine content of each material is reduced to fall within the specified numerical range.

[0555] The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is 0.05% by mass or less, preferably 0.04% by mass or less, more preferably 0.03% by mass or less, and even more preferably 0.01% by mass or less relative to the total solid content of the photosensitive coloring composition. By setting it below the upper limit, there is a tendency to suppress surface roughness of the electrode.

[0556] The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is generally 0.0005% by mass or more, preferably 0.001% by mass or more, and more preferably 0.002% by mass. Setting the content above the lower limit is effective for simplifying purification when producing each constituent material.

[0557] The above upper and lower limits may be arbitrarily combined. For example, it is preferably 0.0005 to 0.05 mass%, more preferably 0.0005 to 0.04 mass%, further preferably 0.001 to 0.03 mass%, and particularly preferably 0.002 to 0.01 mass%.

[0558] The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 100 μg / g or less, more preferably 80 μg / g or less, further preferably 50 μg / g or less, further preferably 30 μg / g or less, and particularly preferably 10 μg / g or less, relative to the total mass of the photosensitive coloring composition including the solvent. When the content is below the upper limit, the surface roughness of the electrode tends to be suppressed.

[0559] The chlorine atom content in the photosensitive coloring composition is not particularly limited, but is usually 0.5 μg / g or more, preferably 1.0 μg / g or more, and more preferably 2.0 μg / g or more. Setting the content above the lower limit is effective for simplifying purification when producing each constituent material.

[0560] The above upper and lower limits may be arbitrarily combined. For example, the content is preferably 0.5 to 100 μg / g, more preferably 0.5 to 80 μg / g, further preferably 1.0 to 50 μg / g, still further preferably 1.0 to 30 μg / g, and particularly preferably 2.0 to 10 μg / g.

[0561] The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.20% by mass or less, more preferably 0.15% by mass or less, further preferably 0.10% by mass or less, further preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less relative to 100% by mass of the content of the colorant (a) in the photosensitive coloring composition. When it is below the upper limit, the surface roughness of the electrode tends to be suppressed.

[0562] The chlorine atom content in the photosensitive coloring composition is not particularly limited, but is generally 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.010% by mass. Setting the content above the lower limit is effective for enabling simple purification during production of each constituent material.

[0563] The above upper and lower limits may be arbitrarily combined. For example, the content of the colorant (a) relative to 100% by mass of the photosensitive coloring composition is preferably 0.001 to 0.20% by mass, more preferably 0.001 to 0.15% by mass, further preferably 0.005 to 0.10% by mass, further preferably 0.005 to 0.05% by mass, and particularly preferably 0.010 to 0.03% by mass.

[0564] The content of chlorine atoms in the photosensitive coloring composition can be measured by, for example, combustion ion chromatography.

[0565] <Physical Properties of Photosensitive Coloring Composition>

[0566] In the photosensitive coloring composition of the present invention, the optical density (OD) per 1 μm film thickness of the coating film is not particularly limited in the first embodiment, but is preferably 0.5 or greater. In the second embodiment, it is 0.5 or greater. It is more preferably 0.7 or greater, further preferably 1.0 or greater, even more preferably 1.3 or greater, and particularly preferably 1.5 or greater. It is usually 4.0 or less, preferably 3.0 or less, and more preferably 2.0 or less. The above upper and lower limits may be arbitrarily combined. In either the first and second embodiments, for example, it is preferably 0.5 to 4.0, more preferably 0.7 to 4.0, even more preferably 1.0 to 3.0, even more preferably 1.3 to 3.0, and particularly preferably 1.5 to 2.0. By setting it above the lower limit, sufficient light-shielding properties tend to be achieved. By setting it below the upper limit, the surface roughness of the electrode tends to be improved.

[0567] The optical density (OD) per 1 μm of the coating film thickness can be measured using a coating film formed by curing the photosensitive coloring composition of the present invention, and can be measured using a coating film formed by heat curing at 230° C. for 20 minutes.

[0568] Optical density refers to the transmitted light density, which expresses the spectral sensitivity characteristics of the light-receiving portion using the ISO visual density standard (ISO 5-3). Typically, a CIE (International Commission on Illumination) A illuminant is used as the light source. An example of an instrument that can be used for transmitted light density measurement is the X-Rite 361T(V) from Sakata INX Engineering Co., Ltd.

[0569] <Method for producing photosensitive coloring composition>

[0570] The photosensitive coloring composition of the present invention can be prepared according to a conventional method.

[0571] Generally, the colorant (a) is preferably dispersed in advance using a paint shaker, sand mill, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. The dispersion process can finely divide the colorant (a) into microparticles, thereby improving the coating properties of the resist.

[0572] The dispersion treatment is usually preferably performed in a system using (a) a colorant, (e) a solvent, and (f) a dispersant in combination with part or all of (b) an alkali-soluble resin (hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as a "pigment dispersion"). In particular, when a polymer dispersant is used as the (f) dispersant, the thickening over time of the obtained pigment dispersion and photosensitive coloring composition can be suppressed, that is, the dispersion stability is excellent, which is preferred.

[0573] Therefore, in the step of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.

[0574] As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion, those described as examples that can be used in the photosensitive coloring composition can be preferably adopted. In addition, as the content ratio of each colorant in the (a) colorant in the pigment dispersion, the content ratio described as the content ratio in the photosensitive coloring composition can also be preferably adopted.

[0575] When dispersing a liquid containing all the components to be blended into the colored resin composition, the highly reactive components may be modified by the heat generated during the dispersion process. Therefore, it is preferable to perform the dispersion process using a system containing a polymer dispersant.

[0576] When dispersing the colorant (a) using a sand mill, glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferably used. Regarding the dispersion process conditions, the temperature is generally between 0°C and 100°C, preferably between room temperature and 80°C. The appropriate dispersion time varies depending on the composition of the liquid and the size of the dispersion process apparatus, and can be adjusted as appropriate. The standard for dispersion is to control the gloss of the pigment dispersion so that the 20-degree specular gloss (JIS Z8741) of the photosensitive coloring composition falls within the range of 50 to 300. Low gloss of the photosensitive coloring composition generally indicates insufficient dispersion, resulting in residual coarse pigment (coloring material) particles, which may lead to inadequate developability, adhesion, and resolution. If the dispersion process is performed to a gloss value exceeding the above range, the pigment will break up, resulting in a large number of ultrafine particles, which tends to impair dispersion stability.

[0577] The dispersed particle size of the pigment dispersed in the pigment dispersion is generally 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method.

[0578] Next, the pigment dispersion obtained by the above dispersion treatment is mixed with the other components contained in the photosensitive coloring composition to form a uniform solution or dispersion. During the production process of the photosensitive coloring composition, fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive coloring composition through a filter or the like.

[0579] [cured material]

[0580] The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention. The cured product obtained by curing the photosensitive coloring composition of the present invention can be preferably used as a partition wall.

[0581] [Next door]

[0582] The photosensitive coloring composition of the present invention can be preferably used to form partition walls, particularly partition walls for partitioning the organic layer of an organic electroluminescent element. Examples of organic layers used in organic electroluminescent elements include organic layers for hole injection layers, hole transport layers, or hole transport layers on hole injection layers, as described in JP-A-2016-165396.

[0583] Next, the partition wall using the photosensitive coloring composition of the present invention will be described according to its production method.

[0584] (1) Support

[0585] As a support for forming the partition wall, its material is not particularly limited as long as it has suitable strength. A substrate is mainly used, and as a material, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone and other thermoplastic resin sheets; epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins and other thermosetting resin sheets, various glasses. Among them, from the viewpoint of heat resistance, glass and heat-resistant resins are preferred. In addition, there are cases where transparent electrodes such as ITO and IZO or metal electrodes such as silver, gold, platinum, aluminum, and magnesium are formed on the surface of the substrate. In addition to the above-mentioned substrates, it can also be formed on a TFT array.

[0586] To improve surface properties such as adhesion, the support may be subjected to, for example, corona discharge treatment, ozone treatment, or treatment for forming a thin film of various resins such as a silane coupling agent or a urethane resin, as needed.

[0587] The thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. In addition, when thin film formation of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0588] (2) Partition wall

[0589] The photosensitive coloring composition of the present invention is used for the same applications as known photosensitive coloring compositions for color filters. Hereinafter, the case of using the composition as partition walls will be described according to a specific example of a partition wall formation method using the photosensitive coloring composition of the present invention.

[0590] Typically, a photosensitive coloring composition is applied in a film or pattern onto the substrate where the partition walls are to be formed by coating or other methods, and the solvent is dried off. Patterning is then performed by methods such as photolithography, which involves exposure and development. Additional exposure and thermal curing are then performed as needed to form the partition walls on the substrate.

[0591] (3) Formation of partition walls

[0592] [1] Supply method to substrate

[0593] The photosensitive coloring composition of the present invention is usually supplied to the substrate in a state dissolved or dispersed in a solvent. The supply method can be conventionally known methods, such as spin coating, wire bar coating, flow coating, die coating, roller coating, and spray coating. Alternatively, the composition can be supplied in a pattern by, for example, inkjet or printing. Die coating is preferred from a comprehensive perspective because it significantly reduces the amount of coating liquid used and eliminates the effects of droplets deposited during spin coating, suppressing the generation of foreign matter.

[0594] The coating amount varies depending on the intended use. For example, in the case of partition walls, the coating is typically applied to a dry film thickness of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dry film thickness, or the height of the final partition walls, is uniform across the entire substrate. By minimizing variations, the light-emitting layer can be uniformly formed, which can prevent display defects during light emission.

[0595] When partitions having different heights are formed at once by photolithography using the photosensitive coloring composition of the present invention, the heights of the partitions finally formed will vary.

[0596] It should be noted that as the substrate, a well-known substrate such as a glass substrate or an array substrate can be used. The surface of the substrate is preferably flat.

[0597] [2] Drying method

[0598] After supplying the photosensitive coloring composition onto the substrate, drying is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. A reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may also be combined.

[0599] Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. The drying time is generally selected from the range of 15 seconds to 5 minutes at a temperature of 40°C to 130°C, and preferably from the range of 30 seconds to 3 minutes at a temperature of 50°C to 110°C, depending on the type of solvent component, the performance of the dryer used, etc.

[0600] [3] Exposure method

[0601] Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating the film with ultraviolet or visible light through the mask pattern. When using an exposure mask for exposure, methods can be used, such as placing the exposure mask close to the coating film of the photosensitive coloring composition or positioning the exposure mask at a distance from the coating film of the photosensitive coloring composition and projecting the exposure light through the exposure mask. Scanning exposure using a laser without using a mask pattern can also be used. If necessary, to prevent oxygen-induced sensitivity reduction of the photopolymerizable layer, exposure can be performed in a deoxygenated atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

[0602] As a preferred embodiment of the present invention, when simultaneously forming partition walls of varying heights by photolithography, an exposure mask is used, for example, comprising a light-shielding portion (0% transmittance) and a plurality of openings (moderately transparent openings) whose average transmittance is lower than that of the opening with the highest average transmittance (fully transparent openings). This method utilizes the difference in average transmittance between the moderately transparent openings and the fully transparent openings, i.e., the difference in exposure, to produce a difference in residual film rate.

[0603] Methods for producing medium-transmittance apertures using a matrix-shaped light-shielding pattern with tiny polygonal light-shielding units are known, for example. Also known are methods for producing apertures using films of materials such as chromium, molybdenum, tungsten, or silicon as absorbers to control transmittance.

[0604] The light source used for the exposure is not particularly limited. Examples include lamp sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps; and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When irradiating with light of a specific wavelength, a filter may be used.

[0605] The filter may be a type that can control the transmittance of the exposure wavelength using a thin film, and the material in this case may include, for example, Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, and Al.

[0606] The exposure dose is not particularly limited, but is usually 1 mJ / cm 2 More than, preferably 5mJ / cm 2 More preferably, 10 mJ / cm 2 Above, usually 300mJ / cm 2 Below, preferably 200mJ / cm 2 Less than 150 mJ / cm 2 the following.

[0607] In the proximity exposure method, the distance between the exposure object and the mask pattern is not particularly limited, but is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[0608] [4] Development method

[0609] After the exposure, an image pattern can be formed on the substrate by developing with an aqueous solution of a basic compound or an organic solvent. The aqueous solution of the basic compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.

[0610] Examples of the alkaline compound include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be a mixture of two or more.

[0611] Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinates; and amphoteric surfactants such as alkylbetaines and amino acids.

[0612] Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Furthermore, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.

[0613] The development conditions are not particularly limited, but the development temperature is usually 10 to 50° C., preferably 15 to 45° C., and more preferably 20 to 40° C. The development method includes, for example, immersion development, spray development, brush development, and ultrasonic development.

[0614] [5] Additional exposure and thermal curing treatment

[0615] The developed substrate can be subjected to additional exposure as needed using the same method as the above-described exposure method. After development or additional exposure, a thermal curing treatment (also known as baking) can also be performed. Regarding thermal curing conditions, the temperature is preferably 100°C to 280°C, more preferably 150°C to 250°C, and the time is 5 minutes to 60 minutes.

[0616] When the photosensitive coloring composition of the present invention is used as partition walls, the size and shape thereof can be appropriately adjusted according to the specifications of the organic electroluminescent element to be used. The height of the partition walls formed from the photosensitive coloring composition of the present invention is usually about 0.5 to 10 μm.

[0617] In addition, from the perspective of light-shielding properties, the optical density (OD) per 1 μm of the partition wall of the present invention is preferably 0.7 or more, more preferably 1.2 or more, further preferably 1.5 or more, and particularly preferably 1.8 or more. In addition, it is preferably 4.0 or less, more preferably 3.0 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.7 to 4.0, more preferably 1.2 to 4.0, further preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. Here, the optical density (OD) is a value measured by the method described below.

[0618] [Organic electroluminescent element]

[0619] The organic electroluminescent device of the present invention includes the cured product of the present invention, for example, partition walls.

[0620] For example, various organic electroluminescent devices can be manufactured using a substrate having a partition wall pattern manufactured using the above method. The method for forming the organic electroluminescent device is not particularly limited, but preferably, the organic layer of pixels, etc., is formed by a wet process such as evaporation, casting, spin coating, or inkjet printing after forming a partition wall pattern on the substrate using the above method, thereby manufacturing the organic electroluminescent device. The evaporation method is to sublimate the functional material under a vacuum state and adhere it to the area surrounded by the partition wall on the substrate to form a film.

[0621] Examples of the types of organic electroluminescent elements include bottom emission type and top emission type.

[0622] Bottom-emitting devices can be produced, for example, by forming partitions on a glass substrate laminated with a transparent electrode, and then laminating a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in the openings defined by the partitions. On the other hand, top-emitting devices can be produced, for example, by forming partitions on a glass substrate laminated with a metal electrode layer as a reflective layer, and then laminating an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in the openings defined by the partitions.

[0623] Examples of the light-emitting layer include organic electroluminescent layers described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Furthermore, quantum dots described in Japanese Patent Nos. 5653387 and 5653101 may also be used.

[0624] The layer structure is not limited thereto. From the perspective of luminous efficiency, for example, a stacked structure consisting of two or more hole transport layers and two or more electron transport layers may be used. The thickness of each layer is not particularly limited, but is generally 1 to 500 nm from the perspective of luminous efficiency and brightness.

[0625] The organic electroluminescent element can be formed by distinguishing RGB colors for each opening, or two or more colors can be stacked in one opening. From the perspective of improving reliability, the organic electroluminescent element can have a sealing layer. The sealing layer has the function of preventing moisture in the air from being adsorbed on the organic electroluminescent element, thereby reducing the luminous efficiency. From the perspective of improving light extraction efficiency, the organic electroluminescent element can have a low-reflection film at the interface between it and the air. By configuring a low-reflection film at the interface between the air and the element, it is expected to reduce the refractive index difference and suppress reflection at the interface. For such a low-reflection film, technologies such as moth-eye structure and super multilayer film can be applied.

[0626] When organic electroluminescent elements are used as pixels in an image display device, it is necessary to prevent light from the light-emitting layers of certain pixels from leaking to other pixels. In addition, when electrodes, etc. are made of metal, it is necessary to prevent the degradation of image quality associated with reflection of external light. Therefore, it is preferable to impart light-shielding properties to the partition walls that constitute the organic electroluminescent elements.

[0627] In addition, in organic electroluminescent elements, since it is necessary to give electrodes on the upper surface and lower surface of the partition wall, from the viewpoint of insulation, the partition wall is preferably high resistance and low dielectric constant. Therefore, in order to give light-shielding property to the partition wall, when using a colorant, it is preferred to use the above-mentioned organic pigment of high resistance and low dielectric constant.

[0628] [Image Display Device]

[0629] Examples of the image display device of the present invention include an organic EL display device having partition walls formed of the cured product of the present invention and the organic electroluminescent element of the present invention.

[0630] As long as the organic EL display device includes the above-mentioned organic electroluminescent element, there is no particular limitation on the type and structure of the image display device. For example, an actively driven organic electroluminescent element can be used and assembled according to a conventional method. For example, it can be formed using the method described in "Organic EL Display" (OHM Co., Ltd., published on August 20, 2001, by Shizuo Tokito, Chiba Andachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light can be combined with a color filter to display an image, or organic electroluminescent elements with different luminescent colors such as RGB can be combined to display an image.

[0631] [illumination]

[0632] Organic electroluminescent devices comprising the cured product of the present invention can be used for lighting. There are no particular limitations on the type and structure of the lighting device; the organic electroluminescent device comprising the cured product of the present invention can be assembled using conventional methods. The organic electroluminescent device can employ either a simple matrix drive system or an active matrix drive system.

[0633] In order to make the lighting emit white light, an organic electroluminescent element that emits white light can also be used. In addition, the organic electroluminescent elements with different luminous colors can be combined to make the colors mixed to form white, or the color mixing ratio can be adjusted to give a color adjustment function.

[0634] Example

[0635] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist of the present invention.

[0636] The constituent components of the photosensitive coloring compositions used in the following Examples and Comparative Examples, and their evaluation methods are as follows.

[0637] <Alkali-soluble resin-I>

[0638] 300 parts by mass of "XD1000" (a polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent weight 252) manufactured by Nippon Kayaku Co., Ltd., 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and 255 parts by mass of propylene glycol monomethyl ether acetate were added to a reaction vessel and stirred at 100°C until the acid value reached 3.0 mgKOH / g. Subsequently, 145 parts by mass of tetrahydrophthalic anhydride was added, and the mixture was reacted at 120°C for 4 hours. The resulting alkali-soluble resin I had a weight-average molecular weight (Mw) of 2600 and an acid value of 106 mgKOH / g as measured by GPC.

[0639] <Alkali-soluble resin-II>

[0640]

[0641] 50.0 parts by mass of the epoxy compound (epoxy equivalent weight 248) with the above structure, 14.2 parts by mass of acrylic acid, 52.6 parts by mass of methoxybutyl acetate, 1.29 parts by mass of triphenylphosphine, and 0.044 parts by mass of p-methoxyphenol were added to a flask equipped with a thermometer, a stirrer, and a condenser. The mixture was reacted at 90°C with stirring until the acid value reached 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

[0642] The epoxy acrylate solution was added to a flask equipped with a thermometer, a stirrer, and a condenser while slowly heating to 105° C. to allow the reaction to proceed. 42.9 parts by mass of methoxybutyl acetate, 1.98 parts by mass of trimethylolpropane (TMP), 24.9 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 5.39 parts by mass of tetrahydrophthalic anhydride (THPA) were added to the flask. The mixture was stirred and then slowly heated to 105° C. to allow the reaction to proceed.

[0643] When the resin solution became transparent, it was diluted with methoxybutyl acetate to adjust the solid content to 50% by mass, thereby obtaining an alkali-soluble resin (II) having an acid value of 100 mgKOH / g and a weight average molecular weight (Mw) of 12,000.

[0644] <Alkali-soluble resin-III>

[0645] "ZCR-8035H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 7000, acid value = 82 mgKOH / g) has a partial structure represented by the following formula (C-1).

[0646]

[0647] <Pigment-I>

[0648] Irgaphor (registered trademark) Black S 0100CF manufactured by BASF (having the chemical structure represented by the following formula (2)).

[0649]

[0650] <Pigment-II>

[0651] CI Pigment Orange 64

[0652] <Pigment-III>

[0653] CI Pigment Violet 29

[0654] Pigment IV

[0655] CI Pigment Blue 60

[0656] Dispersant I

[0657] A methacrylic acid-based AB diblock copolymer composed of an A block containing repeating units having a solvophilic group and a B block containing repeating units having a pigment-adsorbing group. The copolymer has repeating units of formulas (a) to (f). Its amine value is 120 mgKOH / g. Its weight-average molecular weight is 9,000. The dispersant contains substantially no chlorine atoms.

[0658] The content ratios of the repeating units of the following formulae (a) to (f) in all repeating units are (a) 33.3 mol%, (b) 13.3 mol%, (c) 6.7 mol%, (d) 6.7 mol%, (e) 6.7 mol%, and (f) 33.3 mol%, respectively.

[0659] A block

[0660]

[0661] B block

[0662]

[0663] <Dispersant-II>

[0664] A methacrylic acid-based AB diblock copolymer composed of an A block containing repeating units having a solvophilic group and a B block containing repeating units having a pigment-adsorbing group. The copolymer has repeating units of formulas (h) to (n). Its amine value is 70 mgKOH / g. Its weight-average molecular weight before quaternization of the amino groups is 9000. The chlorine content of the dispersant is 2.1% by mass.

[0665] The content ratios of the repeating units of the following formulae (h) to (n) in all the repeating units are respectively (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, (k) 6.7 mol%, (1) 6.7 mol%, (m) 24.0 mol%, and (n) 9.3 mol%.

[0666] A block

[0667]

[0668] B block

[0669]

[0670] <Solvent-I>

[0671] PGMEA: Propylene glycol monomethyl ether acetate

[0672] <Solvent-II>

[0673] MB: 3-methoxy-1-butanol

[0674] <Solvent-III>

[0675] MBA: 3-methoxybutyl acetate

[0676] <Photopolymerization Initiator-I>

[0677] Oxime ester-based photopolymerization initiator having the following chemical structure.

[0678]

[0679] <Ethylenically unsaturated compounds>

[0680] DPHA-40H: Urethane acrylate manufactured by Nippon Kayaku Co., Ltd.

[0681] Surfactants

[0682] DIC Corporation MEGAFAC F-559

[0683] <Evaluation of viscosity>

[0684] The viscosity of the prepared pigment dispersion was measured using a RE-85L viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23° C., 20 rpm).

[0685] <Determination of chlorine atom content>

[0686] The chlorine atom content in the photosensitive coloring composition was determined by combustion ion chromatography (CIC) using a combustion absorption ion chromatograph (CIC) apparatus AQF2100H manufactured by MITSUBISHI CHEMICAL ANALYTECH (currently Nittoseiko Analytech Co., Ltd.) using a calibration curve method.

[0687] <Measurement of optical density per unit film thickness (unit OD value)>

[0688] The optical density per unit film thickness was measured according to the following procedure.

[0689] First, the prepared photosensitive coloring composition was applied to a glass substrate using a spin coater to a film thickness of 1.5 μm after baking. After drying under reduced pressure for 1 minute, it was dried on a hot plate at 100°C for 120 seconds. The resulting coating was exposed without using an exposure mask. As the irradiation light source, an intensity of 40 mW / cm at a wavelength of 365 nm was used. 2 The exposure dose of the high-pressure mercury lamp was set to 50 mJ / cm 2Next, the resist-coated substrate 1 was obtained by heat-curing in an oven at 230° C. for 30 minutes.

[0690] The optical density (OD value) of the resulting resist-coated substrate 1 was measured using a 361T(V) transmission densitometer manufactured by X-Rite (light source color temperature: approximately 2850K (equivalent to CIE standard illuminant A), spectral sensitivity characteristics of the light-receiving portion: ISO visual density under ISO 5-3 standards). The film thickness was measured using VertScan(R) 2.0, a non-contact surface and layer profile measurement system manufactured by Ryoka Systems Inc. The optical density (OD value) per unit film thickness (1 μm) (unit OD value) was calculated from the optical density (OD value) and film thickness. It should be noted that the OD value is a numerical value indicating light-shielding ability, with larger values indicating higher light-shielding properties.

[0691] <Evaluation of electrode surface roughness>

[0692] On an electrode substrate on which a 60 nm thick silver thin film was deposited on the entire surface of a glass substrate, each photosensitive coloring composition was applied using a spin coater to a film thickness of 1.5 μm after baking. After drying under reduced pressure for 1 minute, it was dried on a hot plate at 100°C for 120 seconds. Then, using a photomask capable of forming a square opening pattern of 50 μm on the resulting coated substrate, a high-pressure mercury lamp was used to expose the film at a wavelength of 330 nm or less and an exposure interval of 5 μm. 2 The light intensity at a wavelength of 365nm is 40mW / cm 2 Next, spray development was performed at 25°C for 60 seconds at a developer pressure of 0.05 MPa using a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution as a developer. The developer was then rinsed off with pure water to stop development, and the film was washed with a water spray for 60 seconds.

[0693] Through these operations, the openings were developed and removed to obtain an electrode substrate with patterned partition walls. The patterned substrate was heated (baked) in an oven at 230° C. for 30 minutes to cure the pattern.

[0694] The electrode substrate with a 50 μm opening pattern was observed with an optical microscope at 200x magnification to check for any shape changes (surface roughness) on the electrode surface within the opening pattern. The degree of surface roughness was ranked in order of A, B, and C, with A being the best.

[0695] A: After heating and curing, the electrode surface does not suffer from surface roughness.

[0696] B: After heat curing, some surface roughness was generated on the electrode surface, but it was acceptable and poses no practical problem.

[0697] C: After heat curing, the electrode surface has visible bumps and depressions, resulting in a rough surface. This is problematic in practical use and is unacceptable.

[0698] <Evaluation of Luminescence Characteristics>

[0699] On a substrate formed by depositing a 70nm thick indium tin oxide (ITO) transparent conductive film on glass using conventional photolithography and hydrochloric acid etching to form an anode, each photosensitive coloring composition was applied using a spin coater to a film thickness of 1.5μm after baking. After drying under reduced pressure for 1 minute, it was dried on a hot plate at 100°C for 120 seconds. The resulting coated substrate was then exposed to 50mJ / cm2 of light using an exposure mask (a mask having multiple rectangular cover portions (40μm long x 80μm wide) at a pitch of 60μm long and 100μm wide) using a high-pressure mercury lamp with a wavelength cut off of 330nm or less at an exposure interval of 5μm. 2 At this time, the light intensity at a wavelength of 365nm is 40mW / cm 2 Next, spray development was performed at 25°C for 60 to 120 seconds using a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution as a developer at a developer pressure of 0.05 MPa. The developer was then rinsed off with pure water to terminate development, and the film was then washed with a water spray for 60 seconds. The spray development time was set to at least 1.2 times the time required to dissolve and remove the unexposed portions of the coating film.

[0700] Through these operations, the openings were developed and removed to obtain an electrode substrate with patterned partition walls. The patterned substrate was heated (baked) in an oven at 230° C. for 30 minutes to cure the pattern.

[0701] <Fabrication of organic electroluminescent elements>

[0702] On the entire surface of the electrode substrate on which the partition walls are patterned, molybdenum oxide with a film thickness of 10 nm as a hole injection layer, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-9H-fluorene-2-amine with a film thickness of 60 nm as a hole transport layer, tris(8-hydroxyquinoline)aluminum with a film thickness of 60 nm as a light-emitting layer, 8-hydroxyquinoline lithium with a film thickness of 1 nm as an electron injection layer, and aluminum with a film thickness of 80 nm as a cathode are sequentially stacked by vacuum evaporation to produce an organic electroluminescent element.

[0703] Next, a desiccant is placed in the recessed portion of a sealing glass having a central recess, and a UV-curable resin is applied to the frame surrounding the recessed portion. The sealing glass is positioned so that the recessed portion completely covers the organic electroluminescent element on the electrode substrate. The sealing glass is then bonded to the electrode substrate, and the UV-curable resin is irradiated with UV light to cure, sealing the hollow structure. This produces a device for evaluating the organic electroluminescent element.

[0704] <Evaluation of Light Emitting Characteristics of Organic Electroluminescent Devices>

[0705] The current density of the fabricated device was measured at 10 mA / cm 2 The voltage value (driving voltage) when the DC current is flowing.

[0706] When the cell is made, the current density is 10 mA / cm 2 Voltage value when power is on (driving voltage):

[0707] A: Voltage below 6.5V,

[0708] B: The voltage is higher than 6.5V.

[0709] Next, the current density was 50 mA / cm at 60°C. 2 The time (h) from the initial luminance to the value reaching 90% of the initial luminance when the fabricated element was driven at a constant current with a direct current of 100 Å was defined as the driving life.

[0710] Time until the brightness reaches 90% of the initial brightness (lifespan):

[0711] A: Longer than 25 hours,

[0712] B: Less than 25 hours.

[0713] <Preparation of Pigment Dispersions 1 to 3>

[0714] The pigment, dispersant, alkali-soluble resin and solvent listed in Table 1 were mixed in the mass ratio listed in Table 1. The mixture was dispersed in a paint shaker at 25 to 45°C for 3 hours. Zirconia beads were added in an amount 2.5 times the mass of the dispersion. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare pigment dispersions 1 to 3.

[0715] It should be noted that the amount of solvent in Table 1 also includes the amount of solvent derived from the dispersant and the alkali-soluble resin. Table 1 also shows the viscosity evaluation results of the pigment dispersion measured by the above-mentioned method.

[0716] [Table 1]

[0717]

[0718] [Examples 1, 2, Comparative Example 1]

[0719] The components were added so that the solid content of each component in the total solid content was the value shown in Table 2. A solvent was further added so that PGMEA / MB / MBA = 72 / 20 / 8 and the total solid content was 17% by mass, and the mixture was stirred and dissolved to prepare photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1. The chlorine atom content, unit OD value, and electrode surface roughness evaluation results measured by the above method are shown in Tables 2 and 3.

[0720] [Table 2]

[0721]

[0722] In the substrate using the photosensitive coloring composition of Comparative Example 1, it was confirmed that the silver (electrode) surface had unevenness and roughness. This is believed to be because the amount of chlorine atoms contained in Dispersant-II is large, so the photosensitive coloring composition also contains a large amount of chlorine atoms. Chlorine-containing gas is generated during baking, which reacts with the silver (electrode) surface to form unevenness on the surface.

[0723] On the other hand, in the substrate using the photosensitive coloring composition of Example 1, no unevenness was observed on the silver (electrode) surface. This is believed to be because Dispersant-1 contains no chlorine atoms, and as a result, the content in the photosensitive coloring composition is also low, so the silver (electrode) surface does not become rough, and a normal electrode substrate is obtained.

[0724] Regarding the light-emitting characteristics of the organic electroluminescent element, Example 1 showed a longer life than Comparative Example 1. This is considered to be because the reduction in the amount of chlorine suppressed the temporal degradation of the light-emitting element.

[0725] [Table 3]

[0726]

[0727] For the substrate using the photosensitive coloring composition of Example 2, the unevenness of the silver (electrode) surface was at a level that was substantially non-problematic. The reason why Example 1 was better in terms of the roughness of the silver (electrode) surface than Example 2 is believed to be that Pigment-I has a rigid skeleton containing an aromatic ring, so even a trace amount of chlorine atoms is not released outside the film.

[0728] Regarding the light-emitting characteristics of the organic electroluminescent element, the initial driving voltage of Example 2 was lower and good, and better than that of Example 1.

Claims

1. A photosensitive coloring composition, characterized in that It contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. The colorant (a) contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of a geometric isomer of the compound, The dispersant (f) contains an acrylic copolymer (f1), wherein the acrylic copolymer (f1) contains at least repeating units represented by the following general formulas (1), (2), and (3) and does not contain a repeating unit containing a quaternary ammonium group. Furthermore, the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less relative to the total solid content of the photosensitive coloring composition. In formula (I), R 1 and R 6 are independently a hydrogen atom, CH3, CF3, a fluorine atom or a chlorine atom, R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R 10 Independent of all others, hydrogen atoms, halogen atoms, R 11 、COOH、COOR 11 、COO - 、CONH2、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH2、OOCNHR 11 、OOCNR 11 R 12 、NO2、NH2、NHR 11 NR 11 R 12 、NHCOR 12 NR 11 COR 12 、N=CH2、N=CHR 11 、N=CR 11 R 12 , SH, SR 11 、SOR 11 、SO2R 11 、SO3R 11 、SO3H、SO3 - 、SO2NH2、SO2NHR 11 or SO2NR 11 R 12 , Choose from R 2 With R 3 、R 3 With R 4 、R 4 With R 5 、R 7 With R 8 、R 8 With R 9 and R 9 With R 10 At least one of the groups of combinations may also be directly bonded to each other or bonded via an oxygen atom, a sulfur atom, NH or NR 11 The bridges are bonded to each other, R 11 and R 12 are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms, In formula (1), R 31 is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 32 is a hydrogen atom or a methyl group, * indicates a connection key, In formula (2), R 33 is methylene, ethylene or propylene, R 34 is an alkyl group optionally having a substituent, R 35 is a hydrogen atom or a methyl group, n is an integer from 1 to 20, * indicates a connection key, In formula (3), R 36 and R 37 are each independently an alkyl group, R 38 is a hydrogen atom or a methyl group, Z is a divalent linking group, * indicates a connection key.

2. The photosensitive coloring composition according to claim 1, wherein The (a) colorant contains an organic coloring pigment.

3. A photosensitive coloring composition, characterized in that It contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. The coating film formed by curing the photosensitive coloring composition has an optical density of 0.5 or more per 1 μm of film thickness. The dispersant (f) contains an acrylic copolymer (f1), wherein the acrylic copolymer (f1) contains at least repeating units represented by the following general formulas (1), (2), and (3) and does not contain a repeating unit containing a quaternary ammonium group. Furthermore, the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less relative to the total solid content of the photosensitive coloring composition. In formula (1), R 31 is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, R 32 is a hydrogen atom or a methyl group, * indicates a connection key, In formula (2), R 33 is methylene, ethylene or propylene, R 34 is an alkyl group optionally having a substituent, R 35 is a hydrogen atom or a methyl group, n is an integer from 1 to 20, * indicates a connection key, In formula (3), R 36 and R 37 are each independently an alkyl group, R 38 is a hydrogen atom or a methyl group, Z is a divalent linking group, * indicates a connection key.

4. The photosensitive coloring composition according to claim 3, wherein The (a) colorant includes at least one selected from the group consisting of red pigments and orange pigments and at least one selected from the group consisting of blue pigments and violet pigments.

5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein The acrylic copolymer (f1) is a block copolymer. The photosensitive coloring composition according to any one of claims 1 to 4, wherein The acrylic copolymer (f1) has an amine value of 90 mgKOH / g or more.

7. The photosensitive coloring composition according to claim 5, wherein The acrylic copolymer (f1) has an amine value of 90 mgKOH / g or more.

8. The photosensitive coloring composition according to any one of claims 1 to 4, wherein The (a) colorant is contained in an amount of 10% by mass or more based on the total solid content of the photosensitive coloring composition.

9. The photosensitive coloring composition according to claim 5, wherein The (a) colorant is contained in an amount of 10% by mass or more based on the total solid content of the photosensitive coloring composition.

10. The photosensitive coloring composition according to claim 6, wherein The (a) colorant is contained in an amount of 10% by mass or more based on the total solid content of the photosensitive coloring composition.

11. The photosensitive coloring composition according to claim 7, wherein The (a) colorant is contained in an amount of 10% by mass or more based on the total solid content of the photosensitive coloring composition. 12 . The photosensitive coloring composition according to claim 1 , which is used for forming partition walls of an organic electroluminescent element. The photosensitive coloring composition according to claim 5 , which is used for forming partition walls of an organic electroluminescent element. The photosensitive coloring composition according to claim 6 , which is used for forming partition walls of an organic electroluminescent element. The photosensitive coloring composition according to claim 7 , which is used for forming partition walls of an organic electroluminescent element. The photosensitive coloring composition according to claim 8 , which is used for forming partition walls of an organic electroluminescent element. 17 . The photosensitive coloring composition according to claim 9 , which is used for forming partition walls of an organic electroluminescent element. 18 . A cured product obtained by curing the photosensitive coloring composition according to claim 1 . An organic electroluminescent device comprising the cured product according to claim 18. 20 . An image display device comprising the organic electroluminescent element according to claim 19 .

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