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

Abstract

The invention provides a photosensitive coloring composition, a cured product, an organic electroluminescent element and an image display device, wherein surface roughness of an electrode is less generated after heat treatment. The photosensitive coloring composition comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent and (f) a dispersant, and is characterized in that the colorant (a) contains a compound represented by a specific general formula (I), a geometric isomer of the compound, a salt of the compound or a salt of the geometric isomer of the compound; the dispersant (f) contains an acrylic copolymer (f1) which contains repeating units represented by specific general formulae (1), (2) and (3) and does not have a repeating unit containing a quaternary ammonium group, and the content of chlorine atoms in the photosensitive colored composition is 0.05 mass% or less with respect to the total solid content of the photosensitive colored composition.

Description

[0001] This application is a divisional application of the application filed on September 27, 2021, with application number 202180064110.2 and entitled "Photosensitive Coloring Composition, Cured Product, Organic Electroluminescent Element and Image Display Device". Technical Field

[0002] This invention relates to photosensitive coloring compositions, cured products, organic electroluminescent elements, and image display devices.

[0003] 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 Technology

[0004] Liquid crystal displays (LCDs) utilize the property that the arrangement of liquid crystal molecules changes depending on the voltage applied or removed to the liquid crystal. Most of the components that make up an LCD cell are formed using methods employing photosensitive compositions, such as photolithography. These photosensitive compositions easily form fine structures, and the processing of substrates for large-screen applications is also relatively easy; for these reasons, their applications are expanding.

[0005] Image display devices incorporating organic electroluminescent elements (also known as organic EL) are attracting significant attention as the next generation of flat panel displays (FPDs) due to their superior visual recognition and responsiveness, such as contrast and viewing angle, low power consumption, thin and lightweight design, and flexible display body.

[0006] Organic electroluminescent elements have the following structure: an organic layer containing a light-emitting layer or various functional layers is sandwiched between a pair of electrodes, at least one of which is transparent. Image display devices display images by driving a panel in which organic electroluminescent elements are disposed at each pixel.

[0007] Organic electroluminescent devices have traditionally been manufactured by forming spacers (banks) on a substrate and then stacking light-emitting layers or various functional layers within the area surrounded by the spacers.

[0008] When forming a light-emitting layer or the like within a region surrounded by partition walls, the following vapor deposition method is mainly used: the material is sublimated and attached to the substrate under vacuum, thereby forming a film.

[0009] In addition, in recent years, wet processes such as casting, spin coating, and inkjet printing have attracted much attention for film formation. In particular, inkjet printing can reduce film thickness unevenness when forming large areas, and can achieve high precision in displays, reduce material consumption, and improve yield by coating separately. Therefore, it is suitable as a film formation method for organic layers in large panels.

[0010] As a method for easily forming spacers, a method using a photosensitive composition to form them by photolithography is known. Additionally, as a method for imparting light-blocking properties to the spacers and suppressing light leakage between pixels, a method of containing a colorant in the photosensitive composition is known.

[0011] Patent Document 1 discloses a coloring photosensitive resin composition that suppresses the generation of escape gases by using a specific organic black pigment and an alkali-soluble resin.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: International Publication No. 2018 / 101314 Summary of the Invention

[0015] The problem the invention aims to solve

[0016] Organic light-emitting diodes (OLEDs) exist in both top-emitting and bottom-emitting panel configurations. In the case of top-emitting OLEDs, reflective electrodes such as silver are used as electrodes, and spacers or other cured materials are formed on them. During heat treatment, the components in the photosensitive composition react, sometimes causing corrosion or migration of the metal electrodes. When unevenness (hereinafter referred to as surface roughness) occurs on the electrode surface, the light-emitting layer cannot be uniformly formed in that area, which may lead to display defects such as short circuits when manufacturing OLEDs.

[0017] The inventors conducted research and found that the coloring photosensitive resin composition described in Patent Document 1 causes surface roughness of the electrode, which poses a practical problem.

[0018] The present invention was made in view of the above circumstances, and its object is to provide a photosensitive coloring composition that produces less surface roughness in the electrodes after heat treatment, and to provide an organic light-emitting element and an image display device with high reliability and no display defects.

[0019] Solution for solving the problem

[0020] The inventors conducted in-depth research and found that the above-mentioned problems could be solved by using specific dispersants and colorants, thus completing the present invention.

[0021] That is, the gist of the present invention is as described below.

[0022] [1] A photosensitive coloring composition, characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an olefinic unsaturated compound, (e) a solvent, and (f) a dispersant.

[0023] The colorant described above (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 above compound, a salt of the above compound, and a salt of a geometric isomer of the above compound.

[0024] The dispersant (f) described above contains an acrylic copolymer (f1), which contains at least repeating units represented by the following general formulas (1), (2) and (3) and does not have repeating units containing quaternary ammonium groups.

[0025] Furthermore, the chlorine atom content in the photosensitive coloring composition is less than 0.05% by mass relative to the total solid content of the photosensitive coloring composition.

[0026]

[0027] (In formula (I), R) 1 and R 6 Each atom can be independently composed of a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom.

[0028] R 2 R 3 R 4 R 5 R 7 R 8 R 9 and R 10 Independent of all others, consisting of hydrogen atoms, halogen atoms, and 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 12N=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 ,

[0029] Choose freely 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 combination in the group may also be directly bonded to each other or through oxygen atoms, sulfur atoms, NH or NR atoms. 11 The bridges are interlocked.

[0030] R 11 and R 12 Independently, they are alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, or alkynyl groups having 2 to 12 carbon atoms.

[0031]

[0032] (In equation (1), R) 31 It can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent.

[0033] R 32 It can be a hydrogen atom or a methyl group.

[0034] * indicates a connection key.

[0035]

[0036] (In equation (2), R) 33 It is methylene, ethylene, or propylene, R 34 R is an alkyl group that is optionally substituted. 35 It can be a hydrogen atom or a methyl group.

[0037] n is an integer from 1 to 20.

[0038] * indicates a connection key.

[0039]

[0040] (In equation (3), R) 36 and R 37 Each is independently a hydrogen atom, optionally an alkyl group with substituents, optionally an aryl group with substituents, or optionally an aralkyl group with substituents, R 36 With R 37 They can be arbitrarily bonded together to form a ring structure.

[0041] R 38 It can be a hydrogen atom or a methyl group.

[0042] Z is a divalent linker.

[0043] * indicates a connection key.

[0044] [2] The photosensitive coloring composition according to [1], wherein the colorant (a) above comprises an organic coloring pigment.

[0045] [3] A photosensitive coloring composition, characterized in that it contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an olefinic unsaturated compound, (e) a solvent, and (f) a dispersant.

[0046] The optical density of the coating film cured from the above-mentioned photosensitive coloring composition is 0.5 or higher per 1 μm film thickness.

[0047] The dispersant (f) described above contains an acrylic copolymer (f1), which contains at least repeating units represented by the following general formulas (1), (2) and (3) and does not have repeating units containing quaternary ammonium groups.

[0048] Furthermore, the chlorine atom content in the photosensitive coloring composition is less than 0.05% by mass relative to the total solid content of the photosensitive coloring composition.

[0049]

[0050] (In equation (1), R) 31 It can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent.

[0051] R 32 It can be a hydrogen atom or a methyl group.

[0052] * indicates a connection key.

[0053]

[0054] (In equation (2), R)33 It is methylene, ethylene, or propylene, R 34 R is an alkyl group that is optionally substituted. 35 It can be a hydrogen atom or a methyl group.

[0055] n is an integer from 1 to 20.

[0056] * indicates a connection key.

[0057]

[0058] (In equation (3), R) 36 and R 37 Each is independently a hydrogen atom, optionally an alkyl group with substituents, optionally an aryl group with substituents, or optionally an aralkyl group with substituents, R 36 With R 37 They can be selectively bonded together to form a ring structure.

[0059] R 38 It can be a hydrogen atom or a methyl group.

[0060] Z is a divalent linker.

[0061] * indicates a connection key.

[0062] [4] The photosensitive coloring composition according to [3], wherein the colorant (a) comprises at least one selected from the group consisting of red pigment and orange pigment and at least one selected from the group consisting of blue pigment and purple pigment.

[0063] [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the acrylic copolymer (f1) is a block copolymer.

[0064] [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the amine value of the acrylic copolymer (f1) is 90 mg KOH / g or more.

[0065] [7] The photosensitive coloring composition according to any one of [1] to [6], wherein the colorant described above (a) comprises 10% by mass or more relative to the total solid content of the photosensitive coloring composition.

[0066] [8] The photosensitive coloring composition according to any one of [1] to [7] is used to form the spacer wall of an organic electroluminescent element.

[0067] [9] A cured product formed by curing the photosensitive coloring composition described in any one of [1] to [8].

[0068]

[10] An organic electroluminescent element comprising the cured material described in [9].

[0069]

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

[10] .

[0070] The effects of the invention

[0071] According to the present invention, a photosensitive coloring composition is provided in which the electrode produces less surface roughness after heat treatment. Detailed Implementation

[0072] The following describes specific embodiments of the present invention; however, the present invention is not limited to the following embodiments and can be implemented with various modifications within its scope.

[0073] In this invention, "(meth)acrylic acid" refers to "acrylic acid and / or methacrylic acid", and "(meth)acrylate" and "(meth)acryloyl" are the same.

[0074] "(Co)polymer" refers to both homopolymer and copolymer, while "acid (anhydride)" and "(anhydrous)...acid" refer to both acid and its anhydride.

[0075] In this invention, "acrylic resin" refers to a (co)polymer containing (meth)acrylic acid or a (co)polymer containing (meth)acrylate having a carboxyl group.

[0076] In this invention, "monomer" is a term relative to so-called high molecular weight substances (polymers), and it includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.

[0077] In this invention, "total solids content" refers to the total amount of all components, excluding solvents, contained in the photosensitive coloring composition or pigment dispersion. Components other than solvents may be liquids at room temperature; these components are not included in the solvent but are included in the total solids content.

[0078] In this invention, "weight-average molecular weight" refers to the weight-average molecular weight (Mw) of polystyrene obtained by GPC (gel permeation chromatography).

[0079] In this invention, "amine value" unless otherwise stated refers to the amine value calculated based on the effective solid content, expressed as the mass of KOH equivalent to the amount of alkali per 1g of dispersant solid content. The determination method will be described later. "Acid value" unless otherwise stated refers to the acid value calculated based on the effective solid content, determined by neutralization titration.

[0080] Regarding pigments, "CI" refers to the Color Index.

[0081] In this specification, the percentages and parts expressed as "mass" have the same meaning as the percentages and parts expressed as "weight".

[0082] [Photosensitive coloring composition]

[0083] The photosensitive coloring composition of the present invention contains:

[0084] (a) Coloring agent

[0085] (b) Alkali-soluble resins

[0086] (c) Photopolymerization initiator

[0087] (d) Unsaturated olefinic compounds

[0088] (e) Solvent

[0089] (f) Dispersants are an essential component.

[0090] As a first method, at least one of the following is used as a colorant: a compound selected from the group consisting of a compound of general formula (I), a geometric isomer of the compound of general formula (I), a salt of the compound of general formula (I), or a salt of a geometric isomer of the compound of general formula (I).

[0091] As a second method, the optical density of the coating film formed by curing the photosensitive coloring composition of the present invention is 0.5 or more per 1 μm film thickness.

[0092] In addition, depending on the requirements, it may also include other compounding components such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors. Usually, each compounding component is used in a dissolved or dispersed state in a solvent.

[0093] <(a) Colorant>

[0094] The photosensitive coloring composition of the present invention contains (a) a colorant. By containing (a) a colorant, moderate light absorption can be obtained, and moderate light blocking properties can be obtained, especially when used for forming light-shielding members such as spacers.

[0095] In the first method, at least one of the following is selected as the colorant: a compound of general formula (I), a geometric isomer of the compound of general formula (I), a salt of the compound of general formula (I), and a salt of the geometric isomer of the compound of general formula (I).

[0096] The compound represented by general formula (I) (hereinafter also referred to as "compound (I)") is an organic black pigment. It is speculated that the rigid skeleton containing aromatic rings makes it difficult for chlorine-containing gases generated during heat treatment to penetrate into the coating. Furthermore, its high ultraviolet transmittance facilitates photocuring of the coated photosensitive composition, which is advantageous in these aspects.

[0097]

[0098] In equation (I), R 11 and R 16 Each can independently represent a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom;

[0099] 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, and 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 ;

[0100] Choose freely R 12 With R 13 R13 With R 14 R 14 With R 15 R 17 With R 18 R 18 With R 19 and R 19 With R 20 At least one combination in the group may be directly bonded to each other or through oxygen, sulfur, NH or NR atoms. 21 The bridges are interlocked;

[0101] R 21 and R 22 Each can be independently represented as 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.

[0102] Compound (I) and its geometric isomers have the following core structures (where substituents in the structural formulas have been omitted), with the trans-trans isomer likely to be the most stable.

[0103]

[0104] When compound (I) is anionic, it is preferably a salt formed by compensating for its charge with any known suitable cation, such as a metal, organic, inorganic, or organometallic 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.

[0105] Based on the tendency to improve the hiding power, the following substituents are preferred among the substituents of general formula (I) and their definitions. This is because the following substituents are considered to have no absorption and do not affect the hue of the pigment.

[0106] R 12 R 14 R 15 R 17 R 19 and R 20 Each atom is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and is more preferably a hydrogen atom.

[0107] R 13 and R 18 Each of the following is preferably an independent hydrogen atom, NO2, OCH3, OC2H5, bromine atom, chlorine atom, CH3, C2H5, N(CH3)2, N(CH3)(C2H5), N(C2H5)2, α-naphthyl, β-naphthyl, SO3H or SO3- Further preferred are hydrogen atoms or SO3H, with hydrogen atoms being particularly preferred.

[0108] R 11 and R 16 Each atom is preferably a hydrogen atom, CH3 or CF3, and more preferably a hydrogen atom.

[0109] Preferred selection of free R 11 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 combination in the group is the same, 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.

[0110] Alkyl groups having 1 to 12 carbon atoms are, for example, 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, or dodecyl.

[0111] Cycloalkyl groups having 3 to 12 carbon atoms include, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, norcaryl, caryl, menthyl, norpinyl, pinyl, adamantane-1-yl, or adamantane-2-yl.

[0112] Alkenes having 2 to 12 carbon atoms are, for example, 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, or dodecenyl.

[0113] Cycloalkenyl groups with 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 1-p-menthene-8-yl, 4(10)-thujene-10-yl, 2-norbornen-1-yl, 2,5-norbornadien-1-yl, 7,7-dimethyl-2,4-norcarbapen-3-yl or camphenyl.

[0114] Examples of alkynyl groups with 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-octyne-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-dodecyn-12-yl.

[0115] Halogen atoms can be, for example, fluorine, chlorine, bromine, or iodine atoms.

[0116] The compound represented by the above general formula (I) is preferably a compound comprising at least one of the following groups: the compound represented by the general formula (II) below (hereinafter also referred to as "compound (II)") and the geometric isomers of compound (II).

[0117]

[0118] Examples of such compounds include, for instance, Irgaphor (registered trademark) Black S 0100CF (manufactured by BASF).

[0119] The organic black pigment is preferably used after dispersion using the method described later. In addition, the presence of sulfonic acid derivatives of compound (I) or geometric isomers of compound (I), especially sulfonic acid derivatives of compound (II) or geometric isomers of compound (II), during dispersion may sometimes improve dispersibility and shelf life.

[0120] In the first aspect of the present invention, (A) the colorant may contain other colorants besides compounds of general formula (I). Pigments are preferred as other colorants, and these pigments can be either organic or inorganic. From the viewpoint of high electrical resistance and low dielectric constant, organic pigments are more preferred, and particularly, organic coloring pigments described later are even more preferred.

[0121] From the viewpoint of making the transmittance more uniform in the high wavelength region of the visible light spectrum, compound (I) and a blue pigment are preferred in organic coloring pigments. Pigment Blue B60, 15:6, and 16 are preferred, and Pigment Blue B60 is more preferred.

[0122] On the other hand, from the viewpoint of making the overall transmittance of the visible light region more uniform, it is preferable to use at least one of the group consisting of red and orange pigments and at least one of the group consisting of blue and purple pigments, in addition to using compound (I).

[0123] In the second embodiment, the optical density (hereinafter sometimes referred to as "OD per unit film thickness") of the coating film cured by the photosensitive coloring composition of the present invention is 0.5 or more per 1 μm film thickness. By containing (a) the colorant and making the OD per unit film thickness at or above the aforementioned lower limit value, the light-shielding property of the cured product, especially the spacer wall, is improved.

[0124] The optical density (OD) per unit film thickness can be calculated by measuring the optical density and film thickness of the coating formed by curing the photosensitive coloring composition, and then dividing the optical density by the film thickness. The coating preparation conditions are not particularly limited; for example, the conditions described in the examples described later can be used.

[0125] In order to make the OD per unit film thickness above the lower limit mentioned above, for example, the type of colorant and its content in the total solids content can be appropriately adjusted.

[0126] In the second aspect of the invention, the type of colorant (a) that can be used in the photosensitive coloring composition is not particularly limited; pigments or dyes can be used. Of these, pigments are preferred from the viewpoint of durability.

[0127] (a) The pigment contained in the colorant may be a single type or two or more types. In particular, from the viewpoint of balancing uniform light blocking in the visible area and OD per unit film thickness, two or more types are preferred.

[0128] There is no particular limitation on the types of pigments that can be used as colorants in (a), but examples include organic pigments and black pigments. Here, organic pigments refer to organic pigments that exhibit colors other than black, such as red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0129] From the viewpoint of high electrical resistance and low dielectric constant, organic coloring pigments are preferred in pigments. Furthermore, from the viewpoint of light-blocking properties, compound (I) or other black pigments are preferred.

[0130] Organic coloring pigments can be used alone or in combination of two or more. In particular, from the viewpoint of achieving an OD of 0.5 or more per unit film thickness, it is more preferable to use organic coloring pigments of different colors in combination, and even more preferable to use a combination of organic coloring pigments that exhibit a color close to black.

[0131] The chemical structure of these organic coloring pigments is not particularly limited, and examples include azo, phthalocyanine, quinacrine, benzimidazolone, isoindolinone, dioxazine, indanisole, and perylene series. Below, specific examples of usable pigments are shown using pigment index numbers. In the following examples such as "CI Pigment Red 2," "CI" refers to the Color Index.

[0132] As red pigments, examples of CI pigments include: 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 The following are examples of pigments: 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, 276. From the viewpoint of light-blocking and dispersibility, CI pigment red 48 is preferably listed as follows: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254. CI pigment red 177, 209, 224, 254 is further preferred. From the perspective of dispersibility and light-blocking properties, CI pigment red 177, 254, and 272 are preferred. When using ultraviolet light to cure the photosensitive coloring composition, as a red pigment, it is preferred to have a low ultraviolet absorption rate. From this point of view, CI pigment red 254 and 272 are more preferred.

[0133] Examples of orange pigments include CI pigments 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 viewpoints of dispersibility and opacity, CI pigments Orange 13, 43, 64, and 72 are preferred. When using ultraviolet light to cure the photosensitive coloring composition, pigments with low ultraviolet absorption are preferred as orange pigments; from this viewpoint, CI pigments Orange 64 and 72 are more preferred.

[0134] Examples of CI Pigment Blues include 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-blocking properties, CI Pigment Blues 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, and CI Pigment Blue 15:6 is even more preferred. From the perspective of dispersibility and light-blocking properties, CI Pigment Blue 15:6, 16, and 60 are preferred. When using ultraviolet light to cure the photosensitive coloring composition, as a blue pigment, a pigment with low ultraviolet absorption rate is preferred. From this point of view, CI Pigment Blue 60 is more preferred.

[0135] Examples of suitable purple pigments include CI pigments 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. From the viewpoint of light-blocking properties, CI pigments 19, 23, and 29 are preferred, with CI pigment 23 being even more preferred. From the perspectives of dispersibility and light-blocking properties, CI pigments 23 and 29 are preferred. When using ultraviolet light to cure the photosensitive coloring composition, a pigment with low ultraviolet absorption is preferred as the purple pigment; from this viewpoint, CI pigment 29 is more preferred.

[0136] Examples of green pigments include CI pigments green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, and 59. CI pigments green 7 and 36 are preferred examples.

[0137] As a yellow pigment, examples of CI pigments include: 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, 13 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, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. CI pigment yellows 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferably listed, and CI pigment yellows 83, 138, 139, 150, and 180 are even more preferably listed.

[0138] From the viewpoint of controlling the light-blocking properties of the cured material and the differences in shape and height, at least one of the following pigments is preferably selected from the group consisting of red, orange, blue and purple pigments.

[0139] From the viewpoint of controlling the light-blocking properties of the cured product and the differences in shape and height, it is preferable to contain at least one of the following pigments.

[0140] Red pigments: CI Pigment Red 177, 254, 272

[0141] Orange pigments: CI pigments orange 43, 64, 72

[0142] Blue pigment: CI Pigment Blue 15:6,60

[0143] Purple pigments: CI pigments purple 23 and 29

[0144] Regarding the combination of two or more organic coloring pigments, there are no particular limitations on the combination of organic coloring pigments. From the viewpoint of light-blocking properties, it is preferable to use at least one pigment selected from the group consisting of red and orange pigments and at least one pigment selected from the group consisting of blue and purple pigments.

[0145] There are no particular limitations on color combinations. From the perspective of light-blocking properties, examples include combinations of red and blue pigments, blue and orange pigments, and blue, orange, and purple pigments.

[0146] As a pigment, in addition to organic coloring pigments and organic black pigments as shown in general formula (I), organic black pigments and inorganic black pigments can also be used.

[0147] Examples of organic black pigments other than those shown in general formula (I) include aniline black and perylene black.

[0148] Examples of inorganic black pigments include those described in International Publication No. 2018 / 101314.

[0149] When using these colorants, if the colorant contains chlorine atoms, the amount added can be adjusted to avoid excessive chlorine content.

[0150] These pigments are preferably used in a manner where the average particle size is typically 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the average particle size is based on the number of pigment particles.

[0151] It should be noted that in the photosensitive coloring composition of the present invention, the average particle size of the pigment is a value obtained by measuring the pigment particle size using dynamic light scattering (DLS). The particle size determination is performed on a sufficiently diluted photosensitive coloring composition (typically, dilution is performed to adjust the pigment concentration to approximately 0.005–0.2% by mass. However, if a recommended concentration is available on the measuring device, that concentration is used). The determination is performed at 25°C.

[0152] In the photosensitive coloring composition of the second aspect of the present invention, one type of colorant such as organic coloring pigment or black pigment may be used alone, or two or more types may be used in combination.

[0153] In addition to the aforementioned organic pigments and black pigments, dyes may also be used. Examples of dyes that can be used as colorants include those described in International Publication No. 2018 / 101314.

[0154] <(b) Alkali-soluble resins>

[0155] As for the alkali-soluble resin used in this invention (b), there is no particular limitation as long as it contains carboxyl or hydroxyl groups, and examples include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, phenolic varnish resins, and polyvinylphenol resins. From the viewpoint of excellent plate-making properties, the following are preferred:

[0156] (b1) Epoxy (meth)acrylate resins

[0157] (b2) Acrylic copolymer resins.

[0158] These can be used individually or in combination of two or more.

[0159] <(b1) Epoxy (meth)acrylate resins>

[0160] (b1) Epoxy (meth)acrylate resin is a resin 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 part, and then reacting the hydroxyl group generated therefrom with a compound having two or more substituents that can react with a polybasic acid and / or its anhydride.

[0161] Before reacting a polybasic acid and / or its anhydride with a hydroxyl group, a compound having two or more substituents capable of reacting with a hydroxyl group is reacted, and then the polybasic acid and / or its anhydride are reacted. The resulting resin is also included in the above-mentioned (b1) epoxy (meth)acrylate resins.

[0162] Resins obtained by further reacting the carboxyl groups of the resin obtained through the above reaction with compounds having reactive functional groups are also included in the above (b1) epoxy (meth) acrylate resins.

[0163] In this way, epoxy (meth)acrylate resins do not actually have epoxy groups in their chemical structure and are not limited to "(meth)acrylate", but because they are made from epoxy compounds (epoxy resins) and are represented by "(meth)acrylate", they are named in this way by convention.

[0164] From the viewpoint of developability and reliability, the epoxy (meth) acrylate resin (b1) used in this invention 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-containing epoxy (meth) acrylate resin").

[0165] Furthermore, from the viewpoint of escaping gases, it is preferable to use an epoxy (meth)acrylate resin, which has an aromatic ring in the main chain.

[0166] <Epoxy (meth)acrylate resin (b1-1)>

[0167] An alkali-soluble resin obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group to an epoxy resin, and optionally reacting an isocyanate-containing compound with a further reaction of a polybasic acid and / or its anhydride.

[0168] <Epoxy (meth)acrylate resins (b1-2)>

[0169] An alkali-soluble resin is obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group to an epoxy resin, and optionally by reacting an isocyanate-containing compound with a polyol and a polyacid and / or its anhydride.

[0170] Here, epoxy resin also includes the raw material compound that forms the resin before thermal curing, and this epoxy resin can be suitably selected from known epoxy resins. Alternatively, the epoxy resin can be a compound obtained by reacting a phenolic compound with a surface haloalcohol. As the phenolic compound, compounds with two or more phenolic hydroxyl groups are preferred, and these can be monomers or polymers.

[0171] The types of epoxy resins used as raw materials may preferably include, for example, cresol varnish-type epoxy resins, phenol varnish-type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenol methane type epoxy resins, biphenol varnish-type epoxy resins, naphthol varnish-type epoxy resins, epoxy resins that are products of the further reaction of dicyclopentadiene with phenol or cresol and epihaloalcohols, adamantyl-containing epoxy resins, and fluorene type epoxy resins. Among these, those with an aromatic ring in the main chain may be preferred.

[0172] Preferred epoxy resins include, for example, bisphenol A type epoxy resins (e.g., "jER828", "jER-1001", "jER-1002", "jER-1004", etc. manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting the hydroxyl groups of bisphenol A type epoxy resin with epichlorohydrin (e.g., "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type epoxy resins (e.g., "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), epoxy resins obtained by reacting the hydroxyl groups of bisphenol F type epoxy resin with epichlorohydrin (e.g., "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resins, and biphenyl glycidyl ether (e.g., "YX-4000" manufactured by Mitsubishi Chemical Corporation). Phenolic varnish-type epoxy resins (e.g., "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152" and "EP-154" manufactured by Mitsubishi Chemical Co., Ltd., and "DEN-438" manufactured by Dowchemical Co., Ltd.), (ortho-, meta-, and para-)cresol varnish-type epoxy resins (e.g., "EOCN-102S", "EOCN-1020", and "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (e.g., "TEPIC" manufactured by Nissan Chemical Co., Ltd.), pyromellitic methane-type epoxy resins (e.g., "EPPN-501", "EPPN-502", and "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy resins (e.g., "Celloxide 2021P" and "Celloxide" manufactured by Daicel Co., Ltd.). EHPE), epoxy resins obtained by glycidizing phenolic resin generated by the reaction of dicyclopentadiene and phenol (e.g., "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), and epoxy resins represented by the following general formulas (B1) to (B4). Specifically, examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy resin represented by the following general formula (B2), "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4).

[0173]

[0174] In the above general formula (B1), a is the average value, representing a number from 0 to 10, and R... 111 Each can independently represent 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.

[0175] It should be noted that multiple R molecules exist within a single molecule. 111 They can be the same or different.

[0176]

[0177] In the above general formula (B2), b1 and b2 are each independent averages, representing numbers from 0 to 10, and R... 121 Each of these can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. It should be noted that multiple R groups present in one molecule... 121 They can be the same or different.

[0178]

[0179] In the above general formula (B3), X represents the linking group shown in the following general formula (B3-1) or (B3-2), wherein the molecular structure contains more than one adamantane structure, and c represents 2 or 3.

[0180]

[0181] In the above general formulas (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 Each of the following independently represents an optional adamantyl group with substituents, a hydrogen atom, an optional alkyl group with 1 to 12 carbon atoms with substituents, or an optional phenyl group with substituents; * indicates a connecting bond.

[0182]

[0183] In the above general formula (B4), p and q each independently represent integers from 0 to 4, and R 141 and R 142 Each independently represents an alkyl or halogen atom having 1 to 4 carbon atoms, R 143 and R 144 Each of the two groups independently represents an alkylene group having 1 to 4 carbon atoms, and x and y independently represent integers greater than 0.

[0184] Among these, epoxy resins represented by any of the general formulas (B1) to (B4) are preferred.

[0185] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with a carboxyl group include: (meth)acrylic acid, crotonic acid, o-, m-, or p-vinylbenzoic acid, monocarboxylic acids with α-haloalkyl, alkoxy, halogen, nitro, or cyano substitutions at the α-position of (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, etc. Monomers of methacryloyloxypropyl phthalic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid, 2-(meth)acryloyloxybutyl hydrogen phthalic acid, 2-(meth)acryloyloxybutyl phthalic acid, 2-(meth)acryloyloxybutyl maleic acid, monomers of products obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerol to (meth)acrylic acid, or monomers of acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to hydroxyalkyl methacrylate or pentaerythritol tri(meth)acrylate, and (meth)acrylic acid dimers, etc.

[0186] Of these, (meth)acrylic acid is particularly preferred from the perspective of sensitivity.

[0187] As a method for adding α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups to epoxy resin, known methods can be used. For example, α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups can be reacted with epoxy resin in the presence of an esterification catalyst at a temperature of 50–150°C. As esterification catalysts used herein, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.

[0188] The components of epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group and esterification catalyst can be selected one by one, or two or more can be used in combination.

[0189] Regarding the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group used, it is preferably in the range of 0.5 to 1.2 equivalents relative to the epoxy group of the epoxy resin, and more preferably in the range of 0.7 to 1.1 equivalents. By using the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group at or above the above-mentioned lower limit, there is a tendency to suppress insufficient introduction of unsaturated groups, and the subsequent reaction with polybasic acids and / or their anhydrides is also more likely to proceed sufficiently. On the other hand, by setting it to the above-mentioned upper limit or below, it is evident that the residue of unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group can be suppressed, and the curing properties are more likely to be improved.

[0190] Examples of polybasic acids and / or their anhydrides include, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, methylmethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and their anhydrides.

[0191] Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides are preferred. Tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride are particularly preferred.

[0192] The addition reaction of polybasic acids and / or their anhydrides can be carried out using known methods. The reaction can be continued under the same conditions as the addition reaction of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to epoxy resins to obtain the target product. The amount of addition of the polybasic acid and / or its anhydride is preferably such that the acid value of the resulting carboxyl-containing epoxy (meth)acrylate resin is in the range of 10 to 150 mg KOH / g, and more preferably in the range of 20 to 140 mg KOH / g. Values ​​above the lower limit tend to improve alkali developability. Values ​​below the upper limit tend to improve curing performance.

[0193] In addition reactions of polybasic acids and / or their anhydrides, polyfunctional alcohols (polyols) such as trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol can be added to introduce multibranched structures. In this case, the mixing order of the polybasic acid and / or its anhydride with the polyfunctional alcohol is not particularly restricted. By heating, the polybasic acid and / or its anhydride undergo an addition reaction with any hydroxyl group present in the reaction product of epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups, and a mixture of polyfunctional alcohols.

[0194] By using polyols, the molecular weight of (b1) epoxy (meth)acrylate resin can be increased, and branches can be introduced into the molecule, thus tending to achieve a balance between molecular weight and viscosity. Furthermore, the introduction rate of acid groups into the molecule can be increased, tending to easily achieve a balance between sensitivity, adhesion, etc.

[0195] In addition to the examples mentioned above, other examples of carboxyl-containing epoxy (meth)acrylate resins include those described in Korean Patent Publication No. 10-2013-0022955.

[0196] The weight-average molecular weight (Mw) of polystyrene, as determined by gel permeation chromatography (GPC) of carboxyl-containing epoxy (meth)acrylate resins, is typically 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 typically 30000 or less, preferably 20000 or less, more preferably 15000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1000 to 30000 is preferred, more preferably 1500 to 20000, further preferably 1500 to 15000, and even more preferably 2000 to 15000. By setting the value above the lower limit, the tendency for excessive solubility relative to the developer can be suppressed. By setting the value below the upper limit, the solubility relative to the developer tends to become good.

[0197] The acid value of the carboxyl-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. It is also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, further preferably 130 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20 mg KOH / g to 200 mg KOH / g, more preferably 60 mg KOH / g to 150 mg KOH / g, further preferably 80 mg KOH / g to 130 mg KOH / g, and even more preferably 100 mg KOH / g to 130 mg KOH / g. By setting it to the above lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting the value below the aforementioned upper limit, the residual film rate of the photosensitive coloring composition tends to become better.

[0198] The chemical structure of epoxy (meth)acrylate resins is not particularly limited. From the viewpoint of developability and reliability, epoxy (meth)acrylate resins having a partial structure shown in the following general formula (b1-I) (hereinafter sometimes simply referred to as "(b1-I) epoxy (meth)acrylate resins") and / or epoxy (meth)acrylate resins having a partial structure shown in the following general formula (b1-II) (hereinafter sometimes simply referred to as "(b1-II) epoxy (meth)acrylate resins").

[0199]

[0200] In equation (b1-I), R 11 R represents a hydrogen atom or a methyl group. 12 This indicates a divalent hydrocarbon group with optional substituents, k indicates 1 or 2, and * indicates a linking bond.

[0201] The benzene ring in formula (b1-I) may be further substituted with any substituents.

[0202]

[0203] In equation (b1-II), R 13 Each can independently represent a hydrogen atom or a methyl group, R 14 R represents a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. 15 and R 16 Each of the following independently represents a divalent aliphatic group with optional substituents, m and n independently represent integers from 0 to 2, and * represents a linking bond.

[0204] <(b1-I) Epoxy (Meth)acrylate Resins>

[0205] First, the epoxy (meth)acrylate resins having the partial structure shown in the general formula (b1-I) will be described in detail.

[0206]

[0207] In equation (b1-I), R 11 R represents a hydrogen atom or a methyl group. 12 This indicates a divalent hydrocarbon group with optional substituents, k indicates 1 or 2, and * indicates a linking bond.

[0208] The benzene ring in formula (b1-I) may be further substituted with any substituents.

[0209] (R 12 )

[0210] In the above formula (b1-I), R 12This indicates a divalent hydrocarbon group that is optionally substituted.

[0211] Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic cyclic groups, and groups formed by connecting one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups.

[0212] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is typically 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-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, more preferably 1 to 15, and even more preferably 1 to 10. By setting the value to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness during development, and has a better adhesion to the substrate. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film loss during development.

[0213] Examples of divalent, linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Among these, methylene is preferred from the viewpoint of skeletal rigidity.

[0214] Examples of divalent branched aliphatic groups include structures with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains on the aforementioned divalent straight-chain aliphatic groups.

[0215] 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. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferred, 1 to 10 is more preferred, and 2 to 10 is even more preferred. By setting the value to the lower limit or above, there is a tendency to form a robust film and improve substrate adhesion. By setting the value to the upper limit or below, there is a tendency to improve resolution and easily suppress sensitivity degradation and film reduction during development.

[0216] Examples of divalent cyclic aliphatic groups include those formed by removing two hydrogen atoms from rings such as cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoboronane, adamantane, cyclododecane, dicyclopentadiene, and dicyclopentane. From the viewpoint of skeletal rigidity, groups formed by removing two hydrogen atoms from dicyclopentadiene, dicyclopentane, or adamantane are preferred.

[0217] Examples of substituents that can be chosen as divalent aliphatic groups include: alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0218] Examples of divalent aromatic cyclic groups include divalent aromatic hydrocarbon cyclic groups and divalent aromatic heterocyclic groups. The number of carbon atoms is typically 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-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 20 is preferred, more preferably 5 to 15, and even more preferably 6 to 10. By setting the value to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness during development, and has a tendency to improve adhesion to the substrate. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film loss during development.

[0219] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having two free valences. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0220] Furthermore, the aromatic heterocyclic group can be either a monocyclic or fused ring. Examples of aromatic heterocyclic groups include: furan rings with two free valences, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazol rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazol rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazine rings, quinoxaline rings, phenanthridine rings, primidine rings, quinazoline rings, quinazoline rings, and azurite rings.

[0221] From the viewpoint of patterning properties, benzene rings or naphthalene rings with two free valences are preferred, and benzene rings with two free valences are more preferred.

[0222] Examples of substituents that can be optionally present in the divalent aromatic cyclic group include hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of reproducibility and solubility, unsubstituted substituents are preferred.

[0223] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups, examples include groups formed by linking one or more of the aforementioned divalent aliphatic groups to one or more of the aforementioned divalent aromatic cyclic groups.

[0224] The number of divalent aliphatic groups is not particularly limited, but is generally 1 or more, preferably 2 or more, 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, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness that occurs during development, and has a tendency to improve adhesion to the substrate. By setting it to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film size during development.

[0225] The number of divalent aromatic ring groups is not particularly limited, but is generally 1 or more, preferably 2 or more, 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, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness that occurs during development, and has a tendency to improve adhesion to the substrate. By setting it to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film size during development.

[0226] Examples of groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups include those represented by formulas (b1-IA) to (b1-IF). Among these, groups represented by formula (b1-IA) are preferred from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

[0227]

[0228] In the above formula (b1-I), k represents 1 or 2. From the viewpoint of adhesion and patternability, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2. The (b1-I) epoxy (meth)acrylate may contain both a partial structure with k = 1 and a partial structure with k = 2.

[0229] The benzene ring in formula (b1-I) may be further substituted with any substituents. Examples of acceptable substituents on the benzene ring in formula (b1-I) include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. When the benzene ring in formula (b1-I) has substituents, the number of substituents is not particularly limited; it may be one or more than two.

[0230] From the perspective of patterning properties, the benzene ring in formula (b1-I) is preferably unsubstituted.

[0231] From the viewpoint of ease of synthesis, the partial structure shown in formula (b1-I) is preferably the partial structure shown in formula (b1-I-1) below.

[0232]

[0233] In equation (b1-I-1), R 11 R 12 And k has the same meaning as in the above formula (b1-I), R X * indicates a hydrogen atom or a polybasic acid residue, and * indicates a linking bond.

[0234] The benzene ring in formula (b1-I-1) may be further substituted with any substituents.

[0235] A polybasic acid residue is a monovalent group formed by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, nethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0236] From the perspective of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0237] The benzene ring in formula (b1-I-1) may be further substituted with any substituents. As substituents, the substituents listed for the benzene ring in formula (b1-I) may be preferred.

[0238] One molecule of (b1-I) epoxy (meth)acrylate resin may contain one or more of the structures represented by the above formula (b1-I-1), for example, it may be mixed with R. X For hydrogen atoms and R X It consists of polyacid residues.

[0239] Furthermore, the number of partial structures represented by the above formula (b1-I) contained in one molecule of (b1-I) epoxy (meth)acrylate resin 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. Preferably 1 to 20, more preferably 1 to 15, and more preferably 3 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation and film reduction during development.

[0240] (b1-I) The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC), is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, generally 30000 or less, preferably 20000 or less, and more preferably 15000 or less. The above-mentioned 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 even more preferably 2000 to 15000. By setting it to the lower limit or above, the residual film rate of the photosensitive coloring composition tends to become better. By setting it to the upper limit or below, the solubility relative to the developer tends to become better.

[0241] (b1-I) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. It is also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 130 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20 mg KOH / g to 200 mg KOH / g, more preferably 60 mg KOH / g to 150 mg KOH / g, further preferably 80 mg KOH / g to 130 mg KOH / g, and even more preferably 100 mg KOH / g to 130 mg KOH / g. By setting it to the above lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting the value below the aforementioned upper limit, the residual film rate of the photosensitive coloring composition tends to become better.

[0242] The following are specific examples of (b1-I) epoxy (meth)acrylate resins. It should be noted that * in the examples represents a connecting bond.

[0243]

[0244]

[0245] <(b1-II) Epoxy (Meth)acrylate Resins>

[0246] The epoxy (meth)acrylate resins having the partial structures shown in the above general formula (b1-II) are described in detail.

[0247]

[0248] In equation (b1-II), R 13 Each can independently represent a hydrogen atom or a methyl group, R 14 R represents a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. 15 and R 16 Each of the following independently represents a divalent aliphatic group with optional substituents, m and n independently represent integers from 0 to 2, and * represents a linking bond.

[0249] (R 14 )

[0250] In the above general formula (b1-II), R 14 This indicates a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain.

[0251] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0252] The number of rings in the aliphatic ring 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, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting it to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation and film reduction during development.

[0253] The aliphatic ring group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation and film reduction during development.

[0254] Examples of aliphatic rings among aliphatic ring groups include cyclohexane rings, cycloheptane rings, cyclodecane rings, cyclododecane rings, norbornane rings, isobornane rings, adamantane rings, and cyclododecane rings. Among these, adamantane rings are preferred from the viewpoint of residual film yield and resolution of the photosensitive coloring composition.

[0255] 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-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, further preferably 1 to 4, even more preferably 2 to 4, and particularly preferably 3 to 4. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation and film reduction during development.

[0256] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic cyclic group is typically 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more. It is also preferred to have 40 or fewer carbon atoms, more preferably 30 or fewer, further preferably 20 or fewer, and particularly preferably 15 or fewer. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 carbon atoms are preferred, more preferably 6 to 40, further preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is more likely that the patterning characteristics become better.

[0257] Examples of aromatic rings in aromatic cyclic groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylene rings, pyrene rings, and benzo[a]pyrene rings. The options include triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings. From the perspective of patterning properties, fluorene rings are preferred.

[0258] The divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but can be exemplified by: divalent aliphatic groups, divalent aromatic cyclic groups, and groups formed by connecting one or more divalent aliphatic groups with one or more divalent aromatic cyclic groups.

[0259] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is typically 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-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 25 is preferred, more preferably 3 to 20, and even more preferably 6 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness during development, and has a better adhesion to the substrate. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film loss during development.

[0260] Examples of divalent, linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Among these, methylene is preferred from the viewpoint of skeletal rigidity.

[0261] Examples of divalent branched aliphatic groups include structures with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains on the aforementioned divalent straight-chain aliphatic groups.

[0262] 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 even more preferably 3 or less. For example, 1 to 10 is preferred, 1 to 5 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the value to the lower limit or above, there is a tendency to form a robust film and improve substrate adhesion. By setting the value to the upper limit or below, there is a tendency to improve resolution and easily suppress sensitivity degradation and film reduction during development.

[0263] Examples of divalent cyclic aliphatic groups include groups formed by removing two hydrogen atoms from the rings of cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoboronane, adamantane, and cyclododecane. From the viewpoint of skeletal rigidity, groups formed by removing two hydrogen atoms from the adamantane ring are preferred.

[0264] Examples of substituents that can be chosen as divalent aliphatic groups include: alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0265] Examples of divalent aromatic cyclic groups include divalent aromatic hydrocarbon cyclic groups and divalent aromatic heterocyclic groups. The number of carbon atoms is typically 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, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness during development, and has a tendency to improve adhesion to the substrate. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film loss during development.

[0266] The aromatic hydrocarbon ring in a divalent aromatic hydrocarbon cyclic group can be a monocyclic or fused ring. Examples of aromatic hydrocarbon cyclic groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, and benzo[a]pyrene rings, all having two free valences. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, and fluorene rings.

[0267] Aromatic heterocyclic groups can be monocyclic or fused rings. Examples of aromatic heterocyclic groups include: furan rings with two free valences, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, carbazole rings, pyrroloimidazolium rings, pyrrolopyrazole rings, pyrrolopyrrole rings, thienopyrrole rings, thienothiophene rings, furanolopyrrole rings, furanolofuran rings, thienofuran rings, benzoisoxazole rings, benzoisothiazolium rings, benzimidazole rings, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, borazolinium rings, quinoxaline rings, phenanthridine rings, benzimidazole rings, piridine rings, quinazoline rings, quinazolineone rings, and azurite rings. From the viewpoint of patterning properties, benzene rings or naphthalene rings with two free valences are preferred, and benzene rings with two free valences are more preferred.

[0268] Examples of substituents that can be optionally present in the divalent aromatic cyclic group include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. From the viewpoint of reproducibility and solubility, unsubstituted substituents are preferred.

[0269] As a group formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups, examples include groups formed by linking one or more of the aforementioned divalent aliphatic groups to one or more of the aforementioned divalent aromatic cyclic groups.

[0270] The number of divalent aliphatic groups is not particularly limited, but is generally 1 or more, preferably 2 or more, 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, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness that occurs during development, and has a tendency to improve adhesion to the substrate. By setting it to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film size during development.

[0271] The number of divalent aromatic ring groups is not particularly limited, but is generally 1 or more, preferably 2 or more, 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, further preferably 1 to 3, and particularly preferably 2 to 3. By setting it to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness that occurs during development, and has a tendency to improve adhesion to the substrate. By setting it to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film size during development.

[0272] Groups formed by linking one or more divalent aliphatic groups to one or more divalent aromatic cyclic groups can be exemplified by groups represented by formulas (b1-IA) to (b1-IF) above. Among these, groups represented by formula (b1-IC) above are preferred from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

[0273] For these divalent hydrocarbon groups, there is no particular limitation on the bonding mode of the cyclic hydrocarbon group as a side chain. Examples include: a hydrogen atom of an aliphatic group or an aromatic cyclic group being replaced by a cyclic hydrocarbon group as a side chain, or a cyclic hydrocarbon group consisting of a carbon atom of an aliphatic group.

[0274] (R 15 R 16 )

[0275] In general formula (b1-II), R 15 and R 16 Each can be independently represented as a divalent aliphatic group with a substituent.

[0276] Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred; conversely, from the viewpoint of reducing developer penetration into the exposed area, cyclic aliphatic groups are preferred. The number of carbon atoms is typically 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, 1 to 20 is preferred, more preferably 3 to 15, and even more preferably 6 to 10. By setting the value to the lower limit or above, it is easier to obtain a robust film, less prone to surface roughness during development, and has a better adhesion to the substrate. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation, and reduce film loss during development.

[0277] Examples of divalent, linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Among these, methylene is preferred from the viewpoint of skeletal rigidity.

[0278] Examples of divalent branched aliphatic groups include structures with methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl as side chains on the aforementioned divalent straight-chain aliphatic groups.

[0279] 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, 1 to 12 is preferred, and 2 to 10 is more preferred. By setting the value to the lower limit or above, there is a tendency to form a robust film and improve substrate adhesion. By setting the value to the upper limit or below, there is a tendency to improve resolution and easily suppress sensitivity degradation and film reduction during development.

[0280] Examples of divalent cyclic aliphatic groups include those formed by removing two hydrogen atoms from cyclohexane, cycloheptane, cyclodecane, cyclododecane, norbornane, isoborane, adamantane, cyclododecane, and dicyclopentadiene rings. From the viewpoint of skeletal rigidity, groups formed by removing two hydrogen atoms from dicyclopentadiene or adamantane rings are preferred.

[0281] Examples of substituents that can be chosen as divalent aliphatic groups include: alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0282] (m, n)

[0283] In general formula (b1-II), m and n each independently represent integers from 0 to 2. By setting them to the lower limit or above, there is a tendency for patterning suitability to improve and for surface roughness to occur during development to be less likely to occur. Conversely, by setting them to the upper limit or below, there is a tendency for developability to improve. From the viewpoint of developability, it is preferable that m and n are 0. On the other hand, from the viewpoint of patterning suitability and surface roughness that occurs during development, it is preferable that m and n are 1 or above.

[0284] From the viewpoint of ensuring a tight seal on the substrate, the partial structure shown in general formula (b1-II) is preferably the partial structure shown in general formula (b1-II-1) below.

[0285]

[0286] In equation (b1-II-1), R 13 R 15 R 16 , m and n have the same meaning as in equation (b1-II), R α The symbol represents a monovalent cyclic hydrocarbon group with optional substituents, p represents an integer greater than 1, and * represents a linking bond. The benzene ring in formula (b1-II-1) may be further substituted with any substituents.

[0287] (R α )

[0288] In general formula (b1-II-1), R α It represents a cyclic hydrocarbon group with a 1-valent valence that is optionally substituted.

[0289] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0290] The number of rings in the aliphatic ring 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, 1 to 6 is preferred, 1 to 4 is more preferred, 1 to 3 is even more preferred, and 2 to 3 is particularly preferred. By setting the value to the lower limit or above, it is easier to obtain a strong film and less likely to produce surface roughness that occurs during development. By setting the value to the upper limit or below, it is more likely to have good patterning properties.

[0291] The aliphatic ring group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is more likely that patterning characteristics become better.

[0292] Examples of aliphatic rings among aliphatic cyclic groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Among these, the adamantane ring is preferred from the viewpoint of robust membrane properties.

[0293] 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-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is more likely that the patterning characteristics become better.

[0294] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic cyclic group is typically 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-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferred, more preferably 5 to 20, and even more preferably 6 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development; conversely, by setting the value to the upper limit or below, it is more likely to have good patterning properties.

[0295] Aromatic rings, including benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings, can be listed as aromatic rings. Among these, fluorene rings are preferred from the viewpoint of developing and solubility.

[0296] Examples of substituents that can be optionally present in the cyclic hydrocarbon group include: alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0297] p represents an integer greater than or equal to 1, preferably greater than or equal to 2, and further preferably less than or equal to 3. For example, 1 to 3 is preferred, and 2 to 3 is more preferred. By setting it to the lower limit value or above, there is a tendency for the film curing degree and residual film rate to become better. By setting it to the upper limit value or below, there is a tendency for the developability to become better.

[0298] Of these, from the perspective of robust film curing, R α Preferably, it is a monovalent aliphatic cyclic group, more preferably adamantyl alkyl.

[0299] The benzene ring in formula (b1-II-1) may optionally be further substituted with any substituents. Examples of acceptable substituents on the benzene ring in formula (b1-II-1) include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. When the benzene ring in formula (b1-II-1) has substituents, the number of substituents is not particularly limited; it may be one or more.

[0300] From the perspective of patterning properties, the benzene ring in formula (b1-II-1) is preferably unsubstituted.

[0301] The following are specific examples of some of the structures shown in formula (b1-II-1).

[0302]

[0303]

[0304] From the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane, the partial structure shown in general formula (b1-II) is preferably the partial structure shown in general formula (b1-II-2) below.

[0305]

[0306] In equation (b1-II-2), R 13 R 15 R 16 , m and n have the same meaning as in equation (b1-II), R β The symbol represents a divalent cyclic hydrocarbon group with optional substituents, and * represents a linking bond.

[0307] The benzene ring in formula (b1-II-2) may be further substituted with any substituents.

[0308] (R β )

[0309] In equation (b1-II-2), R β This indicates a divalent cyclic hydrocarbon group that may be optionally substituted.

[0310] As cyclic hydrocarbon groups, aliphatic cyclic groups or aromatic cyclic groups can be listed.

[0311] The number of rings in the aliphatic ring 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, 1 to 10 is preferred, and 2 to 5 is more preferred. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation and film reduction during development.

[0312] The aliphatic cyclic group typically has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 6 to 35, and even more preferably 8 to 30. By setting the value above the lower limit, there is a tendency to suppress film roughness during development. By setting the value below the upper limit, there is a tendency to improve resolution and easily suppress decreased sensitivity and film reduction during development.

[0313] Examples of aliphatic rings that can be classified as aliphatic ring groups include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Among these, adamantane ring is preferred from the viewpoint of reducing film size and improving resolution during development.

[0314] 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-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is easier to suppress sensitivity degradation, reduce film size, and improve resolution.

[0315] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. Furthermore, the number of carbon atoms in the aromatic cyclic group is typically 4 or more, preferably 6 or more, more preferably 8 or more, and even more preferably 10 or more. It is also preferred to have 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferred, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15. By setting the value to the lower limit or above, it is easier to obtain a robust film and less prone to surface roughness that occurs during development. By setting the value to the upper limit or below, it is easier to improve resolution and suppress sensitivity degradation and film reduction.

[0316] Examples of aromatic rings that can be considered as aromatic ring groups include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and fluorene rings. Among these, fluorene rings are preferred from the viewpoint of radioactivity.

[0317] Examples of substituents that can be optionally present in the cyclic hydrocarbon group include: alkyl groups with 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, and isopentyl; alkoxy groups with 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl groups; nitro groups; cyano groups; and carboxyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0318] Among these, from the perspective of inhibition due to membrane reduction and resolution, R β Preferably, it is a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group.

[0319] On the other hand, from the perspective of patterning characteristics, R β Preferably, it is a divalent aromatic cyclic group, more preferably a divalent fluorene cyclic group.

[0320] The benzene ring in formula (b1-II-2) may optionally be further substituted with any substituents. Examples of acceptable substituents on the benzene ring in formula (b1-II-2) include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy. When the benzene ring in formula (b1-II-2) has substituents, the number of substituents is not particularly limited; it may be one or more.

[0321] Furthermore, the two benzene rings can be linked by substituents. Examples of substituents in this case include divalent groups such as -O-, -S-, -NH-, and -CH2-.

[0322] From the viewpoint of patterning properties, the benzene ring in formula (b1-II-2) is preferably unsubstituted. Furthermore, from the viewpoint of minimizing film loss, the benzene ring in formula (b1-II-2) is preferably substituted with a methyl group.

[0323] The following are specific examples of some of the structures shown in equation (b1-II-2). It should be noted that * in the examples represents a connecting key.

[0324]

[0325] From the viewpoint of coating residual film rate and patterning characteristics, the partial structure shown in formula (b1-II) is preferably the partial structure shown in formula (b1-II-3) below.

[0326]

[0327] In equation (b1-II-3), R 13 R 14 R 15 R 16 , m and n have the same meaning as in equation (b1-II), R Z It represents a hydrogen atom or a polyacid residue.

[0328] A polybasic acid residue is a monovalent group formed by removing one OH group from a polybasic acid. It should be noted that it is also possible to remove another OH group and combine it with the R group in other molecules shown in formula (b1-II-3). Z Shared, that is, can be achieved by using R Z Connect multiple equations (b1-II-3).

[0329] Examples of polybasic acids include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, methyltetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0330] 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.

[0331] One molecule of (b1-II) epoxy (meth)acrylate resin may contain one or more of the structures shown in formula (b1-II-3), for example, it may contain R. Z For hydrogen atoms and R Z It consists of polyacid residues.

[0332] The number of partial structures represented by formula (b1-II) contained in one molecule of (b1-II) epoxy (meth)acrylate resin 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 it to the lower limit or above, it is easier to obtain a strong film and less prone to surface roughness that occurs during development. By setting it to the upper limit or below, the resolution is improved and it is easier to suppress the tendency of decreased sensitivity and film reduction.

[0333] (b1-II) The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC), is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, even more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, generally 10000 or less, preferably 8000 or less, more preferably 7000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 10000, more preferably 1500 to 10000, further preferably 1500 to 8000, even more preferably 2000 to 8000, and particularly preferably 2000 to 7000. By setting it to the lower limit or above, the residual film rate of the photosensitive coloring composition tends to become better. By setting it to the upper limit or below, the solubility relative to the developer tends to become better.

[0334] The acid value of the (b1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 60 mg KOH / g or more, even more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. It is also preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, further preferably 130 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20 mg KOH / g to 200 mg KOH / g, more preferably 60 mg KOH / g to 150 mg KOH / g, further preferably 80 mg KOH / g to 130 mg KOH / g, and even more preferably 100 mg KOH / g to 130 mg KOH / g. By setting it to the above lower limit or above, there is a tendency for improved developing solubility and better resolution. By setting the value below the aforementioned upper limit, the residual film rate of the photosensitive coloring composition tends to become better.

[0335] Carboxyl-containing epoxy (meth)acrylate resins can be used alone or in combination of two or more resins.

[0336] Alternatively, a portion of the carboxyl-containing epoxy (meth)acrylate resin can be replaced with other adhesive resins. That is, the carboxyl-containing epoxy (meth)acrylate resin can be used in combination with other adhesive resins. In this case, it is preferable that the proportion of the carboxyl-containing epoxy (meth)acrylate resin in (b) the alkali-soluble resin is 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 typically 100% by mass or less.

[0337] As for (b) alkali-soluble resin, from the viewpoint of compatibility with pigments, dispersants, etc., (b2) acrylic copolymer resin is preferred, and the acrylic copolymer resin described in Japanese Patent Application Publication No. 2014-137466 is preferred.

[0338] Examples of acrylic copolymer resins include copolymers of an olefinic unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b2-1)") with other olefinic unsaturated monomers that can be copolymerized (hereinafter referred to as "unsaturated monomer (b2-2)").

[0339] Examples of unsaturated monomers (b2-1) include: 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 mesoconic acid; mono[(meth)acryloyloxyalkyl] esters of polybasic acids with two or more members, such as succinate mono[2-(meth)acryloyloxyethyl] ester and phthalate mono[2-(meth)acryloyloxyethyl] ester; mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxylated polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

[0340] These unsaturated monomers (b2-1) can be used alone or in combination of two or more.

[0341] Examples of unsaturated monomers (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

[0342] Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene;

[0343] Methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, benzyl methacrylate, 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 methacrylate, isobornyl methacrylate, tricyclohexyl methacrylate [5.2.1.0] 2,6 Decane-8-yl ester, (meth)acrylate dicyclopentenyl ester, glyceryl mono(meth)acrylate, (meth)acrylate 4-hydroxyphenyl ester, p-cumylphenol ethylene oxide modified (meth)acrylate, (meth)acrylate glycidyl ester, 3,4-epoxycyclohexyl meth(meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane and other (meth)acrylates;

[0344] Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0] 2,6 Vinyl ethers such as decane-8-yl vinyl ether, pentacyclic pentadecyl vinyl ether, and 3-(vinyloxymethyl)-3-ethyloxetane;

[0345] Macromonomers with mono(meth)acryloyl groups at the ends of polymer molecular chains such as polystyrene, poly(meth)acrylate, poly(n-butyl)methacrylate, and polysiloxane.

[0346] These unsaturated monomers (b2-2) can be used alone or in combination of two or more.

[0347] In the copolymer of unsaturated monomer (b2-1) and unsaturated monomer (b2-2), the copolymerization ratio of unsaturated monomer (b2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing unsaturated monomer (b2-1) within such a range, there is a tendency to obtain a photosensitive coloring composition with excellent alkali developability and storage stability.

[0348] Examples of copolymers of unsaturated monomer (b2-1) and unsaturated monomer (b2-2) include those disclosed in Japanese Patent Application Publication Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.

[0349] The copolymer of unsaturated monomer (b2-1) and unsaturated monomer (b2-2) can be manufactured by known methods, for example, by controlling its structure, Mw, and Mw / Mn 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.

[0350] In addition, the resins described in International Publication No. 2016 / 194619 and International Publication No. 2017 / 154439 may also be used.

[0351] <(c) Photopolymerization initiators>

[0352] (c) Photopolymerization initiators are components that directly absorb light to induce decomposition or hydrogen abstraction reactions, generating polymerization-active free radicals. Polymerization accelerators (chain transfer agents), sensitizing pigments, and other additives may also be added or used as needed.

[0353] Examples of photopolymerization initiators include: metallocene compounds, including ditectonic compounds, as described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197; hexaaryl biimidazole derivatives as described in Japanese Patent Application Publication No. 2000-56118; halomethylated oxadiazole derivatives and halomethyltriazine derivatives as described in Japanese Patent Application Publication No. 10-39503; α-aminoalkyl phenyl ketone derivatives; and oxime ester compounds as described in Japanese Patent Application Publication Nos. 2000-80068 and 2006-36750.

[0354] Examples of metallocene compounds include: bis(cyclopentadienyl)dichloride, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-tetrafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorophenyl)titanium, bis(cyclopentadienyl)bis(2,6-difluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4-difluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and bis(cyclopentadienyl)-[2,6-difluoro-3-(pyrrolo-1-yl)phenyl]titanium.

[0355] Examples of hexaaryl biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0356] Examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6”-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0357] Examples of halomethyltriazine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)triazine.

[0358] Examples of α-aminoalkylphenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0359] Oxime ester compounds are effective as photopolymerization initiators, particularly in terms of sensitivity and printability. For example, they are especially useful when using alkali-soluble resins containing phenolic hydroxyl groups. Because oxime ester compounds simultaneously possess structures that absorb ultraviolet light, transfer light energy, and generate free radicals, they exhibit high sensitivity even in small quantities and are thermally stable, enabling the production of highly sensitive photosensitive coloring compositions in small amounts.

[0360] Examples of oxime ester compounds include those represented by the general formula (IV) below.

[0361]

[0362] In equation (IV) above, R 21a Represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic cyclogroup optionally having a substituent.

[0363] R 21b It represents any substituent containing an aromatic ring.

[0364] R 22a This indicates an alkyl acyl group or an aromatic acyl group that may optionally have a substituent.

[0365] n represents an integer that is either 0 or 1.

[0366] R 21a The number of carbon atoms in the alkyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in the solvent, it is generally 1 or more, preferably 2 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less. For example, it is 1 to 20, preferably 1 to 15, more preferably 2 to 10. Examples of alkyl groups include methyl, ethyl, propyl, and cyclopentylethyl.

[0367] Examples of substituents that may be optionally present in the alkyl group include: aromatic cycloalgides, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl or N-acetyl-N-acetoxyamino groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0368] As R 21a The aromatic ring group in the composition can include aromatic hydrocarbon ring groups and aromatic heterocyclic ring groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but from the viewpoint of solubility in the photosensitive coloring composition, it is preferably 5 or more. Furthermore, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, it is 5 to 30, preferably 5 to 20, and more preferably 5 to 12 or less.

[0369] Examples of aromatic cyclic groups include phenyl, naphthyl, pyridyl, and furanyl. From the viewpoint of reproducibility, phenyl or naphthyl is preferred, and phenyl is more preferred.

[0370] Examples of substituents that can be optionally present in an aromatic cyclic group include: hydroxyl, carboxyl, halogen atom, amino, amide, alkyl, alkoxy, and groups formed by the linkage of these substituents. From the viewpoint of reproducibility, alkyl, alkoxy, and groups formed by the linkage of these substituents are preferred, and alkoxy groups formed by the linkage of these substituents are more preferred.

[0371] Of these, from the perspective of imaging, R21a Preferably, it is an aromatic cyclic group with optional substituents, and more preferably, it is an aromatic cyclic group with linked alkoxy groups as substituents.

[0372] Additionally, as R 21b Examples of substituted carbazole groups, substituted thioxanone groups, and substituted diphenyl sulfide groups include those optionally substituted. Of these, the optionally substituted carbazole group is preferred from the viewpoint of sensitivity, and the optionally substituted diphenyl sulfide group is preferred from the viewpoint of electrical reliability.

[0373] Additionally, R 22a The number of carbon atoms in the alkyl acyl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is generally 2 or more, preferably 3 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. 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 alkyl acyl groups include acetyl, propionyl, and butyryl.

[0374] Examples of substituents that can be optionally present on the alkyl acyl group include aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0375] Additionally, R 22a The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is generally 7 or more, preferably 8 or more, and generally 20 or less, preferably 15 or less, more preferably 10 or less. For example, it is 7 to 20, preferably 7 to 15, more preferably 8 to 10. Examples of aryl groups include benzoyl and naphthyl.

[0376] Examples of substituents that can be optionally present in the aryl group include hydroxyl, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0377] Of these, from the perspective of sensitivity, R 22a Preferably, the alkanoyl group has a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

[0378] From the perspective of reducing contamination of the liquid crystal layer caused by colorants, it is also preferable to use the initiator described in Japanese Patent Application Publication No. 2016-133574.

[0379] Photopolymerization initiators can be used alone or in combination of two or more.

[0380] To improve sensing sensitivity, photopolymerization initiators can be combined with sensitizing pigments and polymerization accelerators corresponding to the wavelength of the image exposure light source, as needed. Examples of sensitizing pigments include: xanthones as described in Japanese Patent Application Publication Nos. 4-221958 and 4-219756; heterocyclic coumarin pigments as described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; 3-ketocoumarin compounds as described in Japanese Patent Application Publication Nos. 3-239703 and 5-289335; pyrrolemethylammonium pigment as described in Japanese Patent Application Publication Nos. 6-19240; and Japanese Patent Application Publication Nos. 47-2528 and 54. Pigments having a dialkylaminobenzene skeleton as described in Japanese Published Publications No. 155292, 45-37377, 48-84183, 52-112681, 58-15503, 60-88005, 59-56403, 2-69, 57-168088, 5-107761, 5-210240, and 4-288818.

[0381] Among these sensitizing pigments, amino-containing sensitizing pigments are preferred, and compounds having both an amino and a phenyl group within the same molecule are more preferred. Examples of preferred sensitizing pigments include, for instance, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; benzophenone-based compounds such as 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, and 2,5-bis(p-diethylaminophenyl)benzoxazole. Compounds containing p-dialkylaminophenyl, such as (p-dimethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)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, are preferred. Among these, 4,4'-dialkylaminobenzophenone is particularly preferred.

[0382] Sensitizing pigments can be used alone or in combination of two or more.

[0383] As polymerization accelerators, examples of aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate; aliphatic amines such as n-butylamine and N-methyldiethanolamine; and thiol compounds described later can be used. A single polymerization accelerator can be used alone, or two or more can be used in combination.

[0384] <(d) Unsaturated Alkenes>

[0385] The photosensitive coloring composition of the present invention comprises (d) olefinic unsaturated compounds. Sensitivity is improved by including (d) olefinic unsaturated compounds.

[0386] The olefinically unsaturated compounds used in this invention are compounds having at least one olefinically unsaturated group within their molecules. Specifically, examples include: (meth)acrylic acid, alkyl (meth)acrylates, acrylonitrile, styrene, carboxylic acids having one olefinically unsaturated bond, and monoesters of polyols or monohydric alcohols.

[0387] In this invention, a polyfunctional olefin monomer having two or more olefin unsaturated groups per molecule is particularly preferred. The number of olefin unsaturated groups in the polyfunctional olefin monomer is not particularly limited, but is generally two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, two to eight groups are preferred, more preferably two to seven, further preferably four to seven, and particularly preferably five to seven. By setting the value to the lower limit or above, there is a tendency to achieve high sensitivity; by setting the value to the upper limit or below, there is a tendency to improve solubility in solvents.

[0388] Examples of polyfunctional olefin 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 reactions of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.

[0389] Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, etc., methacrylates formed by changing these acrylates to methacrylates, itaconic acid esters formed by changing them to itaconic acid esters, crotonic acid esters formed by changing them to crotonic acid esters, and maleic acid esters formed by changing them to maleic acid esters.

[0390] Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, pyrogallol triacrylate, and other acrylates and methacrylates of aromatic polyhydroxy compounds.

[0391] As esters are obtained through the esterification reaction of polycarboxylic acids and unsaturated carboxylic acids with polyhydroxy compounds, they do not necessarily have to be a single substance. Examples include: condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; and condensates of acrylic acid, adipic acid and butanediol and glycerol.

[0392] Furthermore, as polyfunctional olefin monomers used in this invention, such as urethane (meth)acrylates obtained by reacting polyisocyanate compounds with hydroxy (meth)acrylates or polyisocyanate compounds with polyols and hydroxy (meth)acrylates; epoxy acrylates such as addition reaction products of polyepoxides with hydroxy (meth)acrylates or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and vinyl compounds such as divinyl phthalate are useful.

[0393] Examples of urethane (meth)acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoesha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Co., Ltd.).

[0394] From the viewpoint of curability, as (d) olefinic unsaturated compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth) acrylates, urethane (meth) acrylates obtained by reacting polyisocyanate compounds with hydroxyl-containing (meth) acrylates or polyisocyanate compounds with polyols and hydroxyl-containing (meth) acrylates are preferred, alkyl (meth) acrylates are more preferred, and dipentaerythritol hexaacrylate is even more preferred.

[0395] These can be used individually or in combination of two or more.

[0396] <(e) Solvent>

[0397] The photosensitive coloring composition of the present invention comprises (e) a solvent. By comprising (e) a solvent, (a) a colorant can be dispersed or dissolved in the solvent, and coating becomes easier.

[0398] The photosensitive coloring compositions of the present invention typically use (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an olefinic unsaturated compound, (f) a dispersant, and various other materials as needed, dissolved or dispersed in a solvent. From the viewpoint of dispersibility and coatability, organic solvents are preferred.

[0399] From the viewpoint of coatability, organic solvents with a boiling point of 100–300°C are preferred, and those with a boiling point of 120–280°C are more preferred. It should be noted that the boiling point referred to here is the boiling point at a pressure of 1013.25 hPa, and the same applies to boiling points in the following text.

[0400] Examples of such organic solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and other diethylene glycol monoalkyl ethers;

[0401] Dialkyl ethers of glycols, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0402] Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, and other diol alkyl ether acetates;

[0403] Diol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate;

[0404] Alkyl acetates such as cyclohexanol acetate;

[0405] Ethers such as pentylene, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0406] Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;

[0407] Ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol, and other monohydric or polyhydric alcohols;

[0408] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0409] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane;

[0410] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0411] 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, γ-butyrolactone, and other chain or cyclic esters;

[0412] Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0413] Halogenated hydrocarbons such as chlorobutane and chloropentane;

[0414] Ether ketones such as methoxymethylpentanone;

[0415] Nitriles such as acetonitrile and benzonitrile.

[0416] Commercially available organic solvents may include, for example: mineral oil, Varsol#2, Apco#18 solvent, Apcothinner, Socal solvent No.1 and No.2, Solvesso#150, ShellTS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“cellosolve” is a registered trademark. The same applies hereinafter.), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diethylene glycol dimethyl ether (diglyme) (all trade names).

[0417] These organic solvents can be used alone or in combination of two or more.

[0418] When forming the spacer wall using photolithography, the organic solvent preferably has a boiling point of 100 to 240°C, more preferably a boiling point of 120 to 200°C, and even more preferably a boiling point of 120 to 170°C.

[0419] Among the aforementioned organic solvents, diol alkyl ether acetates are preferred from the perspective of good balance of coatability and surface tension, and high solubility of the constituent components in the composition.

[0420] Diol alkyl ether acetates can be used alone or in combination with other organic solvents. As organic solvents used in combination, monoalkyl glycol ethers are particularly preferred. Propylene glycol monomethyl ether is preferred based on the solubility of the components in the composition. Monoalkyl glycol ethers are highly polar; if added in excessive amounts, there is a tendency for pigments to aggregate and for the resulting photosensitive coloring composition to increase in viscosity, leading to decreased storage stability. Therefore, the proportion of monoalkyl glycol ethers in the solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

[0421] It is also preferable to use organic solvents with boiling points of 150°C or higher (hereinafter, sometimes referred to as "high-boiling-point solvents"). By using high-boiling-point solvents in combination, although the photosensitive coloring composition becomes more difficult to dry, it has the effect of preventing the uniform dispersion of pigments in the composition from being destroyed under rapid drying conditions. That is, it has the effect of preventing foreign matter defects caused by the precipitation and curing of colorants at the tip of the slit nozzle, for example. From the perspective of such high effectiveness, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred among the various solvents mentioned above.

[0422] When using high-boiling-point solvents in combination, the content of high-boiling-point solvents 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 to the lower limit or above, it is possible to suppress the tendency for foreign matter defects to occur, such as due to the precipitation and curing of coloring materials at the tip of the slit nozzle. In addition, by setting the content to the upper limit or below, it is possible to suppress the slowing down of the drying rate of the composition, thereby suppressing problems such as poor cycle time of the vacuum drying process and pin marks from pre-baking.

[0423] The high-boiling-point solvent with a boiling point above 150°C can be a glycol alkyl ether acetate, or it can be a glycol alkyl ether. In this case, it is not necessary to contain any additional high-boiling-point solvent with a boiling point above 150°C.

[0424] Among the various solvents mentioned above, examples of preferred high-boiling-point solvents include diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and glyceryl triacetate.

[0425] <(f) Dispersant>

[0426] The photosensitive coloring composition of the present invention contains (f) a dispersant. By containing (f) a dispersant, the (a) colorant can be stably dispersed.

[0427] The dispersant (f) in the photosensitive coloring composition of the present invention contains an acrylic copolymer (f1) having repeating units shown in the following general formulas (1) to (3) (hereinafter sometimes referred to as "dispersant (f1)"), and does not have repeating units containing quaternary ammonium groups.

[0428]

[0429] (In equation (1), R) 31 It can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent.

[0430] R 32It can be a hydrogen atom or a methyl group.

[0431] * indicates a connection key.

[0432]

[0433] (In equation (2), R) 33 It is methylene, ethylene, or propylene, R 34 R is an alkyl group that is optionally substituted. 35 It can be a hydrogen atom or a methyl group.

[0434] n is an integer from 1 to 20.

[0435] * indicates a connection key.

[0436]

[0437] (In equation (3), R) 36 and R 37 Each is independently a hydrogen atom, optionally an alkyl group with substituents, optionally an aryl group with substituents, or optionally an aralkyl group with substituents, R 36 and R 37 They can be selectively bonded together to form a ring structure.

[0438] R 38 It can be a hydrogen atom or a methyl group.

[0439] Z is a divalent linker.

[0440] * indicates a connection key.

[0441] From the viewpoint of improving the compatibility with solvents and alkali-soluble resins to improve dispersion stability, the dispersant (f1) has repeating units as shown in the following general formula (1).

[0442]

[0443] (In equation (1), R) 31 It can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent.

[0444] R 32 It can be a hydrogen atom or a methyl group.

[0445] * indicates a connection key.

[0446] (R 31 )

[0447] In the above equation (1), R is... 31The alkyl group in the form of the alkyl group can be linear, branched or cyclic. From the viewpoint of compatibility with solvents and alkali-soluble resins, linear alkyl groups are preferred. From the viewpoint of affinity for pigments, branched alkyl groups are preferred.

[0448] 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 above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, more preferably 2 to 8, and even more preferably 4 to 6. By setting the value above the lower limit, there is a tendency to improve the affinity for pigments. By setting the value below the upper limit, there is a tendency to improve compatibility with solvents and alkali-soluble resins, and to improve dispersibility.

[0449] Examples of alkyl groups 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.

[0450] Examples of substituents that may be optionally present in the alkyl group 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, unsubstituted groups are preferred, and from the viewpoint of affinity for pigments, phenyl groups are preferred.

[0451] As R 31 The aryl group in the text can be categorized into monovalent aromatic hydrocarbon cyclic groups and monovalent aromatic heterocyclic groups.

[0452] 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 it to the above upper limit value, there is a tendency to improve the affinity for pigments. Examples of aryl groups include phenyl, naphthyl, and anthracene, and from the viewpoint of dispersibility, phenyl and naphthyl are preferred, and phenyl is more preferred.

[0453] Examples of substituents that can be optionally present in the aryl group include: alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine, chlorine, and bromine; aryl groups such as phenyl and naphthyl; and aralkyl groups such as benzyl and phenethyl. From the viewpoint of dispersibility, unsubstituted groups are preferred.

[0454] Among these, from the perspective of compatibility with solvents and alkali-soluble resins, R... 31 Preferably, alkyl groups with substituents are selected, more preferably methyl, butyl, ethylhexyl, or benzyl.

[0455] From the viewpoint of compatibility with solvents and alkali-soluble resins, the dispersant (f1) has repeating units as shown in the following general formula (2).

[0456]

[0457] (In equation (2), R) 33 It is methylene, ethylene, or propylene, R 34 R is an alkyl group that is optionally substituted. 35 It can be a hydrogen atom or a methyl group.

[0458] n is an integer from 1 to 20.

[0459] * indicates a connection key.

[0460] In equation (2) above, R 33 The solvent is methylene, ethylene, or propylene; from the viewpoint of compatibility with solvents and alkali-soluble resins, ethylene is preferred.

[0461] In equation (2) above, R 34 The alkyl group can be optionally substituted, and from the viewpoint of compatibility with solvents and alkali-soluble resins, methyl or ethyl groups are preferred.

[0462] In formula (2) above, n is an integer from 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 to the lower limit value or above, there is a tendency to improve the compatibility with solvents and alkali-soluble resins. By setting it to the upper limit value or below, there is a tendency to improve the affinity and dispersibility of pigments.

[0463] The dispersant (f1) has repeating units as shown in the general formula (3) above. From the viewpoint of surface roughness of the electrode, it is preferred to use it.

[0464]

[0465] (In equation (3), R) 36 and R 37 Each is independently a hydrogen atom, optionally an alkyl group with substituents, optionally an aryl group with substituents, or optionally an aralkyl group with substituents, R 36 and R 37 They can be selectively bonded together to form a ring structure.

[0466] R 38 It can be a hydrogen atom or a methyl group.

[0467] Z is a divalent linker.

[0468] * indicates a connection key.

[0469] In equation (3) above, R 36 and R 37Each of the following is 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. As an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, R in formula (1) above is preferably used. 31 List of functional groups.

[0470] In equation (3) above, R 36 and R 37 The ring structure is formed by optional bonding between the rings. Examples of ring structures include: 5- to 7-membered nitrogen-containing heterocyclic monocyclic rings or fused rings formed by the condensation of two of these. The nitrogen-containing heterocyclic rings are preferably not aromatic, and more preferably saturated rings. Specifically, the following examples can be cited.

[0471]

[0472] (These ring structures may optionally have substituents.)

[0473] * indicates a connection key.

[0474] (Z)

[0475] In the above formula (3), Z is a divalent linking group.

[0476] Examples of divalent linking groups include: single bonds, alkylene groups with 1 to 10 carbon atoms, aryl groups with 6 to 12 carbon atoms, and -CONH-R. 39 -base, -COOR 40 -Base (where R) 39 and R 40 Each group is independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms. From a dispersibility viewpoint, -COOR is preferred. 7 -base. R 40 From the viewpoint of the long-term stability of the dispersion, alkylene groups having 1 to 10 carbon atoms are preferred, alkylene groups having 1 to 5 carbon atoms are more preferred, and alkylene groups having 1 to 3 carbon atoms are even more preferred.

[0477] The proportion of the repeating unit (hereinafter sometimes referred to as "repeating unit (1)") shown in general formula (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, particularly preferably 60 mol% or more, and preferably 90 mol% or less, more preferably 85 mol% or less, further preferably 80 mol% or less, particularly preferably 75 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 20 mol% to 90 mol%, more preferably 30 mol% to 90 mol%, further preferably 40 mol% to 80 mol%, even more preferably 50 mol% to 80 mol%, and particularly preferably 60 mol% to 80 mol%. By setting it to the lower limit or above, there is a tendency to improve the affinity for pigments. By setting it to the upper limit or below, there is a tendency to improve the compatibility with solvents and alkali-soluble resins.

[0478] The proportion of the repeating unit (hereinafter sometimes referred to as "repeating unit (2)") shown in the above general formula (f1) 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, particularly preferably 3 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 15 mol% or less, even more preferably 10 mol% or less, and particularly preferably 8 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, further preferably 1 mol% to 15 mol%, even more preferably 1 mol% to 10 mol%, and particularly preferably 2 mol% to 10 mol%. By setting it to the lower limit or above, there is a tendency to improve compatibility with solvents and alkali-soluble resins. By setting it to the upper limit or below, there is a tendency to improve affinity with pigments.

[0479] The proportion of the repeating unit (hereinafter sometimes referred to as "repeating unit (3)") shown in the general formula (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 can be combined arbitrarily. 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 the lower limit or above, there is a tendency for the dispersibility to become better. By setting it to the upper limit or below, there is a tendency for the stability of the dispersion over time to become better.

[0480] The dispersant (f1) can be included in any manner, such as random copolymerization or block copolymerization. From the viewpoint of dispersibility, block copolymers are preferred. Block copolymers preferably include: A blocks containing repeating units having solubilizing groups and B blocks containing repeating units having pigment adsorption groups.

[0481] When the dispersant (f1) has repeating units (1) and repeating units (2), they are preferably contained in block A, and can be contained in any manner, such as random copolymerization or block copolymerization. In addition, block A may contain two or more types of repeating units (1) and repeating units (2), and in this case, each repeating unit can be contained in block A in any manner, such as random copolymerization or block copolymerization.

[0482] Block A may contain repeating units other than repeating units (1) and (2). Examples of such repeating units include repeating units from the following substances: styrene, α-methylstyrene and other styrene monomers; (meth)acryloyl chloride and other (meth)acrylate monomers; (meth)acrylamide, N-hydroxymethylacrylamide and other (meth)acrylamide monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic glycidyl ether; N-methacryloylmorpholine.

[0483] Among these, the block copolymers comprising A blocks having repeating units (1) and (2) repeating units and B blocks having repeating units (3) are more preferably AB block copolymers or ABA block copolymers.

[0484] The amine value of the dispersant (f1) is not particularly limited, but is preferably 50 mg KOH / g or more, more preferably 80 mg KOH / g or more, further preferably 90 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. It is also preferably 200 mg KOH / g or less, more preferably 160 mg KOH / g or less, further preferably 140 mg KOH / g or less, and particularly preferably 130 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 50 mg KOH / g to 200 mg KOH / g, more preferably 80 mg KOH / g to 160 mg KOH / g, further preferably 100 mg KOH / g to 140 mg KOH / g, and particularly preferably 100 mg KOH / g to 130 mg KOH / g. By setting it to the lower limit or above, there is a tendency to suppress surface roughness of the electrode. By setting it to the upper limit or below, there is a tendency to improve the stability of the dispersion over time. The amine value is expressed as the mass of KOH equivalent to the amount of alkali per 1g of the solid component of the dispersant (f1).

[0485] The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10 mg KOH / g or less, more preferably 5 mg KOH / g or less, even more preferably 1 mg KOH / g, and particularly preferably 0 mg KOH / g.

[0486] 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. It is also preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. 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 it to the lower limit or above, the dispersibility tends to be improved. By setting it to the upper limit or below, the stability of the dispersion over time tends to be improved.

[0487] The content of chlorine atoms 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, even more 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 it to the above-mentioned upper limit value or less, there is a tendency to suppress surface roughness.

[0488] The method for manufacturing the dispersant (f1) is not particularly limited, and known methods can be used. Examples include: Japanese Patent Application Publication No. 01-299014, Japanese Patent Application Publication No. 2017-019937, Japanese Patent Application Publication No. 2018-172530, Japanese Patent Application Publication No. 2018-203795, Japanese Patent Application Publication No. 2019-099801, and International Publication No. 2019 / 079659.

[0489] The dispersant (f) in the photosensitive coloring composition of the present invention may contain dispersants other than dispersant (f1) (hereinafter sometimes referred to as "other dispersants").

[0490] As other dispersants, from the perspective of dispersion stability, dispersants having the following functional groups are preferred, for example: carboxyl groups; or their bases; primary, secondary, or tertiary amino groups; quaternary ammonium base groups; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. More preferably, dispersants have basic functional groups, such as primary, secondary, or tertiary amino groups; quaternary ammonium base groups; or groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine.

[0491] Furthermore, from the viewpoint that a small amount of dispersant can be used to disperse pigments, polymeric dispersants are preferred.

[0492] Examples of polymeric dispersants include: acrylic dispersants other than dispersant (f1), urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants formed from monomers with amino groups and macromonomers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0493] Examples of such polymeric dispersants include, for instance, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), DISPARLON (registered trademark, manufactured by Kusunoki Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd., KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0494] Examples of urethane and acrylic polymeric dispersants include: DISPERBYK 160-166, 182 series (all urethane), DISPERBYK 2000, 2001, and BYK-LPN21116 (all acrylic) (all manufactured by BYK-Chemie).

[0495] Other dispersants can be used in one form or in combination of two or more.

[0496] <Other coordinating components of the photosensitive coloring composition>

[0497] In addition to the above-mentioned components, the photosensitive coloring composition of the present invention may also be appropriately combined with additives such as silane coupling agents, adhesion enhancers, surfactants, pigment derivatives, photoacid generators, crosslinking agents, thiol compounds, and polymerization inhibitors.

[0498] (1) Adhesion enhancer

[0499] To improve adhesion to the substrate, the photosensitive coloring composition of the present invention may contain an adhesion enhancer. Preferably, the adhesion enhancer is a silane coupling agent or a phosphate-containing compound.

[0500] As a type of silane coupling agent, one of various silane coupling agents, such as epoxy, (meth)acrylic, and amino, can be used alone or in combination of two or more.

[0501] Examples of silane coupling agents include: (meth)acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane and 3-epoxypropoxypropyltriethoxysilane; ureosilanes such as 3-ureopropyltriethoxysilane; and isocyanate silanes such as 3-isocyanatepropyltriethoxysilane. Epoxy silane coupling agents are particularly preferred.

[0502] As a phosphate-containing compound, it is preferred to contain (meth)acryloyl phosphate esters, and preferably substances represented by the following general formulas (g1), (g2) or (g3).

[0503]

[0504] In the above general formulas (g1), (g2), and (g3), R 51 Represents a hydrogen atom or a methyl group, where l and l' are integers from 1 to 10, and m is 1, 2, or 3.

[0505] These phosphate-containing compounds can be used alone or in combination of two or more.

[0506] (2) Surfactants

[0507] To improve coatability, the photosensitive coloring composition of the present invention may contain a surfactant.

[0508] As surfactants, various surfactants can be used, such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among them, nonionic surfactants are preferred from the perspective of minimizing the possibility of adverse effects on various properties. From the perspective of coatability, fluorinated and silicone surfactants are effective.

[0509] 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, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin Industries), L-77 (manufactured by Unika Corporation), and FC4430 (manufactured by 3M).

[0510] One surfactant can be used, or two or more surfactants can be used in any combination and ratio.

[0511] (3) Pigment derivatives

[0512] To improve dispersibility and shelf life, the photosensitive coloring composition of the present invention may also contain pigment derivatives as dispersing aids.

[0513] Examples of pigment derivatives include: azo-based, phthalocyanine-based, quinacrine-based, benzimidazolone-based, quinacrine-based, isoindolineone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, pyrene-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives, with phthalocyanine-based and quinacrine-based derivatives being preferred.

[0514] Examples of substituents used in pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimide methyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., which are directly or indirectly bonded to the pigment skeleton via alkyl, aryl, heterocyclic, or other groups. Sulfonic acid groups are preferred. Furthermore, multiple such substituents can be substituted onto a single pigment skeleton.

[0515] Examples of pigment derivatives include: sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinoline ketone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacrine, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These can be used individually or in combination of two or more.

[0516] (4) Thiol compounds

[0517] In addition, to improve the adhesion to the substrate, thiol compounds can be added as polymerization accelerators.

[0518] Examples of thiol compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butylene dimercaptopropionate, butylene dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butylene dimercaptopropionate, trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis(3-mercaptobutyrate), and butylene glycol bis(3-mercaptopropionate). Heterocyclic thiol compounds and aliphatic polyfunctional thiol compounds, such as 3-mercaptobutyrate, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(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, can be used. These can be used alone or in combination with two or more compounds.

[0519] (5) Polymerization inhibitors

[0520] From the viewpoint 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 by containing a polymerization inhibitor, the free radical polymerization of the underlying layer of the coating is hindered, thereby controlling the cone angle (the angle between the support and the cured product in the cross-section of the cured product).

[0521] Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred. Furthermore, from the viewpoint of particularly excellent safety for human health, hydroquinone monomethyl ether and methyl hydroquinone are preferred.

[0522] A single polymerization inhibitor can be used alone, or two or more can be mixed together.

[0523] In the manufacture of (b) alkali-soluble resin, the resin may sometimes contain a polymerization inhibitor, which can be used as the polymerization inhibitor of the present invention. Alternatively, in addition to the polymerization inhibitor in the resin, the same or different polymerization inhibitors may be added during the manufacture of the photosensitive resin composition.

[0524] When a photosensitive coloring composition contains a polymerization inhibitor, its content is not particularly limited, but it 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, more preferably 0.1% by mass or less, relative to the total solid content of the photosensitive coloring composition. The above-mentioned 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. By setting it to the lower limit or above, there is a tendency to be able to control the shape of the cured product. By setting it to the upper limit or below, there is a tendency to be able to maintain the required sensitivity.

[0525] <Proportion of each component in the photosensitive coloring composition>

[0526] The proportion 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, further preferably 15% by mass or more, and even more preferably 20% by mass or more relative to the total solids content. It is also preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5% to 50% by mass, more preferably 10% to 40% by mass, further preferably 15% to 40% by mass, even more preferably 15% to 30% by mass, and particularly preferably 15% to 25% by mass. By setting it to the lower limit or above, there is a tendency to ensure light-blocking properties. By setting it to the upper limit or below, there is a tendency to reduce the dispersion dose and suppress surface roughness.

[0527] In the first embodiment, the content of compound (I) in the photosensitive coloring composition relative to the total solid content of 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, and particularly preferably 20% by mass or more. 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-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5% to 70% by mass, more preferably 20% to 70% by mass, further preferably 20% to 60% by mass, and particularly preferably 20% to 50% by mass. By setting it to the lower limit or above, there is a tendency to suppress the loss of ultraviolet light required for curing and improve the opacity. By setting it to the upper limit or below, there is a tendency to reduce the dispersion dosage and suppress surface roughness.

[0528] In the first method, when (a) the colorant contains compound (I) and other pigments, the total proportion of their contents is not particularly limited. The proportion of compound (I) in (a) the colorant is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Furthermore, it is 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 even more preferably 30% to 70% by mass. By setting it to the lower limit or above, there is a tendency to improve light-blocking properties and achieve a near-black hue. By setting it to the upper limit or below, there is a tendency to reduce residue during development and improve the reliability of component manufacturing.

[0529] In the first method, when (a) the colorant comprises compound (I) and organic pigment, the total proportion of their contents is not particularly limited. The proportion of compound (I) in (a) the colorant is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. Furthermore, it is 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 even more preferably 30% to 70% by mass. By setting it to the lower limit or above, there is a tendency to improve light-blocking properties and achieve a near-black hue. By setting it to the upper limit or below, there is a tendency to reduce residue during development and improve the reliability of component manufacturing.

[0530] When the photosensitive coloring composition contains organic coloring pigments, the proportion of these pigments is not particularly limited. However, relative to the total solid content of the photosensitive coloring composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. 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-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5% to 70% by mass, more preferably 20% to 70% by mass, further preferably 20% to 60% by mass, and particularly preferably 20% to 50% by mass. By setting it to the lower limit or above, there is a tendency to improve light-blocking properties. By setting it to the upper limit or below, there is a tendency to reduce the dispersion dosage and suppress surface roughness.

[0531] When the colorant contains red and / or orange pigments, the total proportion of red and orange pigments is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more in the colorant. Additionally, it is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5% to 40% by mass, more preferably 8% to 40% by mass, further preferably 10% to 30% by mass, and particularly preferably 12% to 20% by mass. By setting it to the lower limit or above, there is a tendency to achieve a near-black hue. By setting it to the upper limit or below, there is a tendency to achieve high sensitivity.

[0532] When the colorant contains blue and / or purple pigments, the total proportion of blue and purple pigments is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more in the colorant. It is also preferably 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 30% to 95% by mass is preferred, more preferably 50% to 95% by mass, further preferably 70% to 92% by mass, and particularly preferably 80% to 90% by mass. By setting the value above the lower limit, there is a tendency to achieve a near-black hue. By setting the value below the upper limit, there is a tendency to improve sensitivity and opacity.

[0533] (a) When the colorant contains red and / or orange pigments and blue and / or purple pigments, the proportion of red and / or orange pigments relative to the content of blue and / or purple pigments is not particularly limited, but 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% to 300% by mass, more preferably 3% to 100% by mass, further preferably 5% to 100% by mass, and particularly preferably 8% to 50% by mass. By setting it to the lower limit or above, there is a tendency to suppress the transmission of blue light and improve the light-blocking property. By setting it to the upper limit or below, there is a tendency to achieve a hue close to black.

[0534] When the photosensitive coloring composition contains an organic black pigment, its content ratio is not particularly limited. However, relative to the total solid content of the photosensitive coloring composition, it is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more. Additionally, 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-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 3% to 60% by mass, more preferably 5% to 60% by mass, further preferably 10% to 50% by mass, and particularly preferably 20% to 40% by mass. By setting it to the lower limit or above, there is a tendency to improve light-blocking properties. When it is below the upper limit, there is a tendency to reduce the dispersion dosage and suppress surface roughness.

[0535] When the photosensitive coloring composition contains carbon black as an inorganic black pigment, its content ratio is not particularly limited. However, relative to the total solid content of the photosensitive coloring composition, it is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. 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-mentioned 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. By setting it to the lower limit or above, there is a tendency to improve light-blocking properties. By setting it to the upper limit or below, there is a tendency to form a cured product with high resistance and low dielectric constant.

[0536] (a) When the colorant contains black pigment and organic pigment, the total proportion of both is not particularly limited. The proportion of black pigment in the colorant is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. It is also 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, 10% to 90% by mass is preferred, more preferably 20% to 80% by mass, and even more preferably 30% to 70% by mass. By setting the value to the lower limit or above, there is a tendency to improve light-blocking properties and achieve a near-black hue. By setting the value to the upper limit or below, there is a tendency to reduce residue during development and improve the reliability of component manufacturing.

[0537] (b) The content of the 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, further preferably 30% by mass or more, particularly preferably 40% by mass or more, and generally 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 55% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5% to 80% by mass, more preferably 10% to 70% by mass, further preferably 20% to 60% by mass, even more preferably 30% to 60% by mass, particularly preferably 30% to 55% by mass, and especially preferably 40% to 55% by mass. By setting it to the above-mentioned lower limit or above, it is possible to suppress the decrease in solubility of the unexposed portion relative to the developer and suppress poor development. By setting the value below the aforementioned upper limit, there is a tendency to maintain appropriate sensitivity, suppress the dissolution of the exposed area due to the developer, and suppress the reduction in the clarity and adhesion of the pattern.

[0538] (b1) The content of 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, especially preferably 30% by mass or more, particularly preferably 40% by mass or more, generally 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 55% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferred to be 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, even more preferably 30% by mass to 60% by mass, especially preferably 30% by mass to 55% by mass, particularly preferably 40% by mass to 55% by mass. By setting it to the above-mentioned lower limit value or above, there is a tendency to ensure the solubility of the unexposed portion relative to the developer. By setting the value below the aforementioned upper limit, there is a tendency to maintain appropriate sensitivity, suppress the dissolution of the exposed area due to the developer, and suppress the reduction in the clarity and adhesion of the pattern.

[0539] (b) The proportion of (b1) epoxy (meth)acrylate resin contained in the alkali-soluble resin is not particularly limited, but 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, 20% to 90% by mass is preferred, more preferably 30% to 80% by mass, and even more preferably 40% to 80% by mass. By setting the value above the lower limit, there is a tendency to ensure the solubility of the unexposed portion relative to the developer. By setting the value below the upper limit, there is a tendency to maintain suitable sensitivity, suppress the dissolution of the exposed portion due to the developer, and suppress the reduction in pattern clarity and adhesion.

[0540] (c) The proportion of the 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, further preferably 2% by mass or more, and even more preferably 3% by mass or more, and 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-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1% to 15% by mass, more preferably 0.5% to 15% by mass, further preferably 1% to 10% by mass, even more preferably 2% to 8% by mass, and particularly preferably 3% to 6% by mass. By setting it to the lower limit or above, there is a tendency to suppress the decrease in sensitivity. By setting it to the upper limit or below, there is a tendency to suppress the decrease in the solubility of the unexposed portion relative to the developer and to suppress poor development.

[0541] When using the polymerization accelerator in conjunction with (c) the photopolymerization initiator, the content ratio of the polymerization accelerator is not particularly limited, but it 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 solid content of the photosensitive coloring composition of the present invention. Furthermore, it is preferable to use the polymerization accelerator 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 ratio of the polymerization accelerator to the lower limit or above mentioned above, there is a tendency to suppress the decrease in sensitivity to exposure light. By setting it to the upper limit or below mentioned above, there is a tendency to suppress the decrease in solubility of the unexposed portion relative to the developer and suppress poor development.

[0542] When the sensitized pigment is used in conjunction with (c) the photopolymerization initiator, there is no particular limitation on its content ratio. From the point of view of sensitivity, the content relative to the total solid content in the photosensitive coloring composition is generally 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

[0543] (d) The proportion of the olefinic 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. It is also generally 30% by mass or less, preferably 25% by mass or less, and even more preferably 20% by mass or less. The above-mentioned upper and lower limits can 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 it to the lower limit or above, there is a tendency to maintain suitable sensitivity, suppress the dissolution of the exposed portion due to the developer, and suppress the reduction of pattern clarity and adhesion. By setting it to the upper limit or below, there is a tendency to suppress the increased penetration of the developer into the exposed portion and easily obtain a good image.

[0544] The photosensitive coloring composition of the present invention, by using solvent (e), can be prepared into a liquid with a total solid content of preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, the liquid can be prepared in a manner preferably 5% to 50% by mass, more preferably 10% to 30% by mass, and further preferably 15% to 25% by mass.

[0545] (f) The proportion 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 solid content of the photosensitive coloring composition. It is also 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-mentioned upper and lower limits can 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 to the lower limit or above, there is a tendency to easily obtain sufficient dispersibility. By setting it to the upper limit or below, there is a tendency to suppress surface roughness of the electrode surface.

[0546] The proportion of dispersant (f1) is not particularly limited, but it 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. It is also 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-mentioned upper and lower limits can 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 to the lower limit or above, there is a tendency to easily obtain sufficient dispersibility. By setting it to the upper limit or below, there is a tendency to suppress surface roughness of the electrode surface.

[0547] The proportion of dispersant (f1) is not particularly limited, but it 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 addition, it is generally 100% by mass or less. By setting it to the above-mentioned lower limit or above, there is a tendency to suppress the surface roughness of the electrode surface.

[0548] (f) The proportion of the dispersant relative to 100 parts by mass of (a) the colorant is not particularly limited, but is generally 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, generally 50 parts by mass or less, and particularly preferably 30 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 5 to 50 parts by mass is preferred, more preferably 10 to 50 parts by mass, and even more preferably 15 to 30 parts by mass. By setting the value to the lower limit or above, there is a tendency to easily obtain sufficient dispersibility. By setting the value to the upper limit or below, there is a tendency to suppress surface roughness of the electrode surface.

[0549] (b) The proportion of alkali-soluble resin relative to 100 parts by weight of (d) olefinic unsaturated compound is not particularly limited, but is generally 100 parts by weight or more, preferably 200 parts by weight or more, more preferably 250 parts by weight or more, further preferably 300 parts by weight or more, and particularly preferably 350 parts by weight or more. It is also generally 700 parts by weight or less, preferably 500 parts by weight or less, more preferably 450 parts by weight or less, and further preferably 400 parts by weight or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 700 parts by weight, more preferably 200 to 700 parts by weight, further preferably 250 to 500 parts by weight, even more preferably 250 to 450 parts by weight, and particularly preferably 250 to 400 parts by weight. By setting it to the lower limit or above, there is a tendency to achieve a suitable dissolution and development state without peeling, etc. By setting it to the upper limit or below, there is a tendency to obtain a suitable dissolution time relative to the developer.

[0550] When using an adhesion enhancer, its content is not particularly limited, but it is typically 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 it to the lower limit or above, there is a tendency to obtain a sufficient adhesion enhancement effect. By setting it to the upper limit or below, there is a tendency to suppress defects such as decreased sensitivity and residual residue after development.

[0551] When using a surfactant, its content is not particularly limited, but it is typically 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. By setting it to the lower limit or above, the coating film tends to exhibit smoothness and uniformity. By setting it to the upper limit or below, the coating film tends to exhibit smoothness and uniformity while also suppressing deterioration of other properties.

[0552] <Chlorine atom content in the photosensitive coloring composition>

[0553] In the case of the photosensitive coloring composition of the present invention, 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.

[0554] During the fabrication of the spacer, a process described later involves heat treatment to cure the photosensitive coloring composition. Sometimes, this process can cause surface roughness on the electrode surface. This roughness can be observed using an optical microscope, and the surface roughness itself is also increased. When surface roughness occurs on the electrode surface, a light-emitting layer cannot be formed uniformly in that area, potentially causing display defects such as short circuits when fabricating organic electroluminescent elements. It is speculated that this is because, during heat treatment, especially calcination, chlorine atoms in the photosensitive coloring composition decompose, volatilize, or sublimate, acting on metal electrodes such as silver and causing corrosion or etching. By setting the chlorine atom content below a certain value, surface roughness can be suppressed.

[0555] The chlorine atoms in the photosensitive coloring composition are mainly contained in constituent materials such as (a) colorants, (b) alkali-soluble resins, and (f) dispersants, and sometimes also in other materials. In order to keep the chlorine atom content within the specified range of the present invention, the chlorine content of one constituent material can be reduced, or it can be designed in a way that reduces the chlorine content in each material to be within the specified range.

[0556] The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.05% by mass or less, more 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 to the above-mentioned upper limit value or less, there is a tendency to suppress the surface roughness of the electrode.

[0557] 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 it to the above lower limit or above is effective for easy purification during the manufacture of each constituent material.

[0558] The aforementioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.0005 to 0.05% by mass, more preferably 0.0005 to 0.04% by mass, even more preferably 0.001 to 0.03% by mass, and particularly preferably 0.002 to 0.01% by mass.

[0559] 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, even more preferably 30 μg / g or less, and particularly preferably 10 μg / g or less, relative to the total mass of the photosensitive coloring composition containing the solvent. By setting it to the above-mentioned upper limit value or less, there is a tendency to suppress the surface roughness of the electrode.

[0560] The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is generally 0.5 μg / g or more, preferably 1.0 μg / g or more, and more preferably 2.0 μg / g or more. Setting it to the lower limit or above is effective for easy purification during the manufacture of each constituent material.

[0561] The aforementioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.5 to 100 μg / g, more preferably 0.5 to 80 μg / g, further preferably 1.0 to 50 μg / g, even more preferably 1.0 to 30 μg / g, and particularly preferably 2.0 to 10 μg / g.

[0562] 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, even more preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less, relative to the content of the colorant (a) in the photosensitive coloring composition. By setting it to the above-mentioned upper limit value or less, there is a tendency to suppress the surface roughness of the electrode.

[0563] The content of chlorine atoms 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. By setting it to a lower limit or above, it is effective to facilitate purification when manufacturing each constituent material.

[0564] The aforementioned upper and lower limits can be combined arbitrarily. For example, the content of the colorant (a) in 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, even more preferably 0.005 to 0.05% by mass, and particularly preferably 0.010 to 0.03% by mass.

[0565] The chlorine atom content in the photosensitive coloring composition can be determined, for example, by combustion ion chromatography.

[0566] <Physical Properties of Photosensitive Coloring Compositions>

[0567] Regarding the photosensitive coloring composition of the present invention, the optical density (OD) per 1 μm film thickness is not particularly limited in the first embodiment, but is preferably 0.5 or more. In the second embodiment, it is 0.5 or more. More preferably, it is 0.7 or more, further preferably 1.0 or more, even more preferably 1.3 or more, particularly preferably 1.5 or more, generally 4.0 or less, preferably 3.0 or less, more preferably 2.0 or less. The above-mentioned upper and lower limits can be combined arbitrarily. In either the first or second embodiment, for example, it is preferably 0.5 to 4.0, more preferably 0.7 to 4.0, further 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 to the above-mentioned lower limit value or above, there is a tendency to obtain sufficient light-blocking properties. By setting it to the above-mentioned upper limit value or below, there is a tendency to improve the surface roughness of the electrode.

[0568] The optical density (OD) per 1 μm film thickness of the coating can be measured using a coating formed by curing the photosensitive coloring composition of the present invention, or using a coating formed by heating and curing at 230°C for 20 minutes.

[0569] Optical density refers to the transmitted optical density expressed as ISO visual density in ISO 5-3 standard, representing the spectral sensitivity characteristics of the receiving part. Typically, an A-level light source as specified by the CIE (International Commission on Illumination) is used as the light source. An example of an instrument suitable for measuring transmitted optical density is the X-Rite 361T(V) from SAKATA INX ENG.CO.,LTD.

[0570] <Method for manufacturing photosensitive coloring composition>

[0571] The photosensitive coloring composition of the present invention can be prepared by conventional methods.

[0572] Typically, (a) the colorant is preferably pre-dispersed using a paint shaker, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, etc. Through dispersion treatment, (a) the colorant is micronized, thus improving the coating properties of the resist.

[0573] The dispersion treatment is generally preferably carried out in a system that uses (a) a colorant, (e) a solvent, and (f) a dispersant, and part or all of (b) an alkali-soluble resin (hereinafter, the mixture supplied for the dispersion treatment and the composition obtained by the dispersion treatment are sometimes referred to as "pigment dispersion"). In particular, if a polymeric dispersant is used as the dispersant (f), the thickening of the resulting pigment dispersion and photosensitive coloring composition over time can be suppressed, i.e., excellent dispersion stability is achieved, and therefore preferred.

[0574] Therefore, in the process of manufacturing a photosensitive coloring composition, it is preferable to manufacture a pigment dispersion containing at least (a) a colorant, (e) a solvent and (f) a dispersant.

[0575] As for (a) the colorant, (e) the solvent, and (f) the dispersant that can be used in the pigment dispersion, examples described as those that can be used in a photosensitive coloring composition are preferred. Furthermore, as for the content ratio of each colorant in (a) the pigment dispersion, the content ratio described as that in the photosensitive coloring composition is also preferred.

[0576] When dispersing a liquid containing all the components to be incorporated into a coloring resin composition, highly reactive components may be modified due to the exothermic reaction generated during the dispersion process. Therefore, it is preferable to perform the dispersion process using a system containing a polymeric dispersant.

[0577] When dispersing (a) the colorant using a sand mill, glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferred. Regarding dispersion conditions, the temperature is typically 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 apparatus, and can be adjusted accordingly. 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 reaches a range of 50 to 300. Low gloss in the photosensitive coloring composition usually indicates insufficient dispersion and residual coarse pigment (coloring material) particles, which may lead to insufficient developability, adhesion, and resolution. If dispersion is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated due to pigment breakage, which may actually impair dispersion stability.

[0578] The particle size of pigments dispersed in pigment dispersions is typically 0.03–0.3 μm, which can be determined by dynamic light scattering.

[0579] Next, the pigment dispersion obtained through the above dispersion treatment is mixed with the other components contained in the photosensitive coloring composition to prepare a homogeneous solution or dispersion. During the manufacturing process of the photosensitive coloring composition, since fine dust sometimes mixes into the liquid, it is desirable to filter the obtained photosensitive coloring composition using a filter or the like.

[0580] [cured material]

[0581] By curing the photosensitive coloring composition of the present invention, a cured product of the present invention can be obtained. The cured product obtained by curing the photosensitive coloring composition of the present invention can preferably be used as a spacer.

[0582] [Block]

[0583] The photosensitive coloring composition of the present invention is preferably used to form spacers, particularly spacers for dividing organic layers of organic electroluminescent elements. Examples of organic layers for use in organic electroluminescent elements include, for instance, the organic layers described in Japanese Patent Application Publication No. 2016-165396, which are used for hole injection layers, hole transport layers, or hole transport layers on hole injection layers.

[0584] Next, the spacer wall using the photosensitive coloring composition of the present invention will be described according to its manufacturing method.

[0585] (1) Support

[0586] As a support for forming the spacers, the material is not particularly limited as long as it has suitable strength. The main material used is a substrate, and examples of suitable materials include: sheets of polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone; thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic acid resin; and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred. Additionally, 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 substrate surface. Besides the substrates mentioned above, these electrodes can also be formed on TFT arrays.

[0587] To improve surface properties such as adhesion, the support can also be subjected to various resin film formation treatments, such as corona discharge treatment, ozone treatment, silane coupling agents, and urethane resins, as needed.

[0588] The thickness of the substrate is typically 0.05 to 10 mm, preferably 0.1 to 7 mm. Furthermore, when performing thin film formation processes with various resins, the film thickness is typically 0.01 to 10 μm, preferably 0.05 to 5 μm.

[0589] (2) partition wall

[0590] The photosensitive coloring composition of the present invention is used for the same purposes as the known photosensitive coloring compositions for color filters. Hereinafter, the use as a spacer will be described according to a specific example of a method for forming a spacer using the photosensitive coloring composition of the present invention.

[0591] Typically, a photosensitive coloring composition is applied to the substrate to which spacers are to be formed in a film or pattern by means of coating or other methods, and the solvent is dried off. Next, a pattern is formed by methods such as photolithography with exposure and development. Afterward, additional exposure and thermal curing are performed as needed, thereby forming spacers on the substrate.

[0592] (3) Formation of partition walls

[0593] [1] Method of supplying substrate

[0594] The photosensitive coloring composition of the present invention is typically supplied to a substrate in a dissolved or dispersed state in a solvent. As a method of supply, it can be performed using conventionally known methods, such as spin coating, wire bar coating, flow coating, die coating, roll coating, and spray coating. Alternatively, it can be supplied in a patterned manner using, for example, inkjet printing or printing. Among these methods, die coating significantly reduces the amount of coating liquid used and completely eliminates the effects of droplets and other contaminants that occur with spin coating, thus suppressing the formation of foreign matter; therefore, it is preferred from a comprehensive viewpoint.

[0595] The coating amount varies depending on the application. For example, in the case of spacers, the coating is typically applied at a thickness of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm, based on the dried film thickness. It is important that the dried film thickness or the final height of the spacers is uniform across the entire substrate. By reducing variations, a uniform light-emitting layer can be fabricated, suppressing display defects during light emission.

[0596] When using the photosensitive coloring composition of the present invention to form spacers of different heights in a single step by photolithography, the final heights of the spacers will be different.

[0597] It should be noted that known substrates such as glass substrates and array substrates can be used as the substrate. The substrate surface is preferably planar.

[0598] [2] Drying method

[0599] Drying after supplying the photosensitive coloring composition to the substrate is preferably performed using drying methods such as hot plate drying, IR oven drying, or convection oven drying. Alternatively, a vacuum drying method can be used, where drying is performed in a vacuum chamber without increasing the temperature.

[0600] The drying conditions can be selected appropriately based on the type of solvent and the performance of the dryer used. The drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40℃ to 130℃, preferably within the range of 30 seconds to 3 minutes at a temperature of 50℃ to 110℃.

[0601] [3] Exposure method

[0602] Exposure is performed by overlaying a negative mask pattern onto a coating of the photosensitive coloring composition and irradiating it with an ultraviolet or visible light source through the mask pattern. When using an exposure mask, methods include placing the exposure mask close to the coating of the photosensitive coloring composition; or placing the exposure mask away from the coating of the photosensitive coloring composition and projecting exposure light through the mask. Alternatively, a scanning exposure method using a laser can be employed without a mask pattern. Depending on the need, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, 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.

[0603] As a preferred embodiment of the present invention, when spacers of different heights are formed simultaneously by photolithography, an exposure mask is used, for example, which has a light-blocking portion (0% transmittance) and a plurality of openings whose average transmittance is less than that of the opening with the highest average transmittance (fully transparent opening) (medium-transmittance opening). This method utilizes the difference in average transmittance between the medium-transmittance opening and the fully transparent opening, i.e., the difference in exposure, to generate a difference in residual film yield.

[0604] Methods for creating medium-transmittance openings are known, for example, by using a matrix-like light-blocking pattern with tiny polygonal light-blocking units. Additionally, methods for controlling transmittance by using films made of materials such as chromium-based, molybdenum-based, tungsten-based, or silicon-based materials as absorbers are known.

[0605] There are no particular limitations on the light source used in the above exposure. Examples of light sources include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, etc.; and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When irradiating and using light of a specific wavelength, filters can also be used.

[0606] As a filter, it can be of the type in which the transmittance of the exposure wavelength can be controlled by a thin film. Examples of materials in this case include: Cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, and Al.

[0607] There is no specific limit to the exposure level; it is usually 1 mJ / cm². 2 The above, preferably 5mJ / cm 2 The above, and more preferably, is 10 mJ / cm 2 The above is typically 300 mJ / cm 2 The following, preferably, is 200 mJ / cm 2 The following, and more preferably, is 150 mJ / cm 2 the following.

[0608] When using a near-exposure method, the distance between the object to be exposed and the mask pattern is not particularly limited, but is generally 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and generally 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[0609] [4] Development method

[0610] After the above exposure, an image pattern can be formed on the substrate by developing it with an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, surfactants, organic solvents, buffers, complexing agents, dyes, or pigments.

[0611] Examples of basic compounds include: 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, ammonium hydroxide, and other inorganic basic compounds; and 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), choline, and other organic basic compounds. These basic compounds can be mixtures of two or more.

[0612] Examples of surfactants include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinates; and amphoteric surfactants such as alkyl betaines and amino acids.

[0613] Examples of organic solvents include isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents can also be used in combination. Furthermore, organic solvents can be used alone or in combination with water or aqueous solutions of alkaline compounds.

[0614] There are no particular restrictions on the conditions for the developing process. Generally, the developing temperature is 10°C to 50°C, preferably 15°C to 45°C, and more preferably 20°C to 40°C. Developing methods may include, for example, immersion developing, spray developing, brush developing, and ultrasonic developing.

[0615] [5] Additional exposure and thermosetting treatment

[0616] After development, the substrate can be further exposed using the same method as described above. After development or further exposure, a heat curing process (also known as calcination) can be performed. Regarding the heat curing conditions, the preferred temperature is 100°C to 280°C, more preferably 150°C to 250°C, and the time is 5 minutes to 60 minutes.

[0617] When the photosensitive coloring composition of the present invention is used to form a spacer, its size, shape, etc. can be appropriately adjusted according to the specifications of the organic electroluminescent element in which it is used. The height of the spacer formed by the photosensitive coloring composition of the present invention is usually about 0.5 to 10 μm.

[0618] Furthermore, from the viewpoint of light-shielding properties, the optical density (OD) per 1 μm of the spacer 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. Additionally, it is preferably 4.0 or less, more preferably 3.0 or less. The above-mentioned upper and lower limits can be combined arbitrarily. 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 later.

[0619] [Organic electroluminescent element]

[0620] The organic electroluminescent element of the present invention comprises the cured material of the present invention, such as a spacer wall.

[0621] For example, various organic light-emitting elements can be manufactured using a substrate with a spacer pattern created by the above method. The method for forming the organic light-emitting element is not particularly limited, but it is preferable to manufacture the organic light-emitting element by forming an organic layer such as a pixel using a wet process such as vapor deposition, casting, spin coating, or inkjet printing after forming a spacer pattern on the substrate using the above method. The vapor deposition process involves sublimating the functional material under vacuum and depositing it onto the area enclosed by the spacers on the substrate to form a film.

[0622] Types of organic electroluminescent elements include bottom-emitting and top-emitting types.

[0623] Bottom-emitting types can be fabricated, for example, by forming spacers on a glass substrate with stacked transparent electrodes, and stacking a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer in the openings surrounded by the spacers. On the other hand, top-emitting types can be fabricated, for example, by forming spacers on a glass substrate with stacked metal electrode layers as reflective layers, and stacking an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer in the openings surrounded by the spacers.

[0624] It should be noted that, as the light-emitting layer, organic electroluminescent layers described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent Publication No. 5734681 can be used. Alternatively, quantum dots described in Japanese Patent Publication No. 5653387 and Japanese Patent Publication No. 5653101 can also be used.

[0625] The layer composition is not limited to this. From the perspective of luminous efficiency, it can be a stacked structure consisting of two or more hole transport layers and two or more electron transport layers. The thickness of each layer is not particularly limited, but from the perspective of luminous efficiency and brightness, it is usually 1 to 500 nm.

[0626] Organic light-emitting diodes (OLEDs) can be formed by separating each of the RGB colors in each opening, or by layering two or more colors in a single opening. From a reliability perspective, OLEDs can incorporate a sealing layer. This sealing layer prevents moisture from the air from adsorbing onto the OLED, thus preventing a decrease in luminous efficiency. From a light extraction efficiency perspective, OLEDs can have a low-reflection film at their air interface. By configuring a low-reflection film at the air-element interface, it is expected to reduce the refractive index difference and suppress reflection at the interface. For such low-reflection films, techniques such as moth-eye structures and multilayer films can be applied.

[0627] When organic electroluminescent elements are used as pixels in an image display device, it is necessary to prevent light from the light-emitting layer of some pixels from leaking into other pixels. Furthermore, when the electrodes are made of metal, it is necessary to prevent the degradation of image quality associated with the reflection of external light. Therefore, it is preferable to give the spacers constituting the organic electroluminescent elements light-shielding properties.

[0628] Furthermore, in organic electroluminescent elements, since electrodes need to be provided on the upper and lower surfaces of the spacer walls, from the viewpoint of insulation, it is preferable that the spacer walls have high resistance and low dielectric constant. Therefore, in order to impart light-shielding properties to the spacer walls, when using colorants, it is preferable to use the aforementioned organic pigments with high resistance and low dielectric constant.

[0629] [Image display device]

[0630] As an image display device of the present invention, an organic EL display device having a spacer wall containing the cured material of the present invention and an organic electroluminescent element of the present invention can be cited.

[0631] Organic EL display devices only need to include the aforementioned organic electroluminescent elements. There are no particular restrictions on the type or structure of the image display device. For example, active-drive organic electroluminescent elements can be used and assembled according to conventional methods. For example, they can be formed using the methods described in "Organic EL Display" (OHM Corporation, published August 20, 2016, authored by Shizushi Tokito, Chinatsu Adachi, and Hideyuki Murata). For example, an image can be displayed by combining an organic electroluminescent element that emits white light with a color filter, or by combining organic electroluminescent elements that emit different colors such as RGB.

[0632] [illumination]

[0633] Organic electroluminescent elements 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; organic electroluminescent elements comprising the cured product of the present invention can be used and assembled according to conventional methods. The organic electroluminescent element can be a simple matrix-driven element or an active matrix-driven element.

[0634] To produce white light, organic electroluminescent elements that emit white light can also be used. Alternatively, the system can be configured by combining organic electroluminescent elements that emit different colors so that the colors are mixed to produce white, or it can be configured to allow adjustment of the color mixing ratio, thus providing a color-tuning function.

[0635] Example

[0636] The present invention will be described in more detail below with examples and comparative examples, but it is not limited to the following examples as long as it does not depart from the spirit of the present invention.

[0637] The components of the photosensitive coloring compositions used in the following examples and comparative examples, as well as their evaluation methods, are described below.

[0638] <Alkali-soluble resin-I>

[0639] 300 parts by weight of "XD1000" (a polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252) manufactured by Nippon Kayaku Co., Ltd., 87 parts by weight of acrylic acid, 0.2 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 255 parts by weight of propylene glycol monomethyl ether acetate were added to a reaction vessel and stirred at 100°C until the acid value reached 3.0 mg KOH / g. Then, 145 parts by weight of tetrahydrophthalic anhydride were added, and the reaction was carried out 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 mg KOH / g, as determined by GPC.

[0640] <Alkali-soluble Resin-II>

[0641]

[0642] 50.0 parts by mass of the epoxy compound with the above structure (epoxy equivalent 248), 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, stirrer, and condenser. The mixture was stirred and reacted at 90°C until the acid value reached below 5 mg KOH / g. The reaction took 12 hours to obtain an epoxy acrylate solution.

[0643] For the above epoxy acrylate solution, 42.9 parts by mass of methoxybutyl acetate, 1.98 parts by mass of trimethylolpropane (TMP), 24.9 parts by mass of biphenyl dianhydride (BPDA), and 5.39 parts by mass of tetrahydrophthalic anhydride (THPA) were added to a flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was stirred while being slowly heated to 105°C to carry out the reaction.

[0644] When the resin solution becomes transparent, it is diluted with methoxybutyl acetate to adjust the solid content to 50% by mass, thus obtaining an alkali-soluble resin (II) with an acid value of 100 mg KOH / g and a weight-average molecular weight (Mw) of 12000.

[0645] <Alkali-soluble resin-III>

[0646] ZCR-8035H (weight-average molecular weight Mw = 7000, acid value = 82 mg KOH / g), manufactured by Nippon Kayaku Co., Ltd., has a partial structure as shown in the following formula (C-1).

[0647]

[0648] <Pigment-I>

[0649] BASF Corporation, Irgaphor (registered trademark) Black S 0100CF (with the chemical structure shown in formula (2) below).

[0650]

[0651] <Pigment-II>

[0652] CI Pigment Orange 64

[0653] <Pigment-III>

[0654] CI Pigment Violet 29

[0655] <Pigment-IV>

[0656] CI Pigment Blue 60

[0657] <Dispersant-I>

[0658] A methacrylic acid-based AB diblock copolymer composed of A blocks containing repeating units with solubilizing groups and B blocks containing repeating units with pigment-adsorbing groups. It has repeating units of formulas (a) to (f) below. The amine value is 120 mg KOH / g. The weight-average molecular weight is 9000. The dispersant is substantially free of chlorine atoms.

[0659] The proportions of the repeating units in the following formulas (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.

[0660] A block

[0661]

[0662] B segment

[0663]

[0664] <Dispersant-II>

[0665] A methacrylic acid-based AB diblock copolymer composed of A blocks containing repeating units with solubilizing groups and B blocks containing repeating units with pigment-adsorbing groups. It has repeating units of the following formulas (h) to (n). The amine value is 70 mg KOH / g. The weight-average molecular weight of the amino group before quaternization is 9000. The chlorine content in the dispersant is 2.1% by mass.

[0666] The proportions of the repeating units in the following formulas (h) to (n) in all repeating units are (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, (k) 6.7 mol%, (l) 6.7 mol%, (m) 24.0 mol%, and (n) 9.3 mol%, respectively.

[0667] A block

[0668]

[0669] B segment

[0670]

[0671] <Solvent-I>

[0672] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0673] <Solvent-II>

[0674] MB: 3-Methoxy-1-butanol

[0675] <Solvent-III>

[0676] MBA: 3-Methoxybutyl Acetate

[0677] <Photopolymerization Initiator-I>

[0678] Oxime ester photopolymerization initiators having the following chemical structures.

[0679]

[0680] <Unsaturated Alkenes>

[0681] DPHA-40H: Carbamate acrylate manufactured by Nippon Kayaku Co., Ltd.

[0682] <surfactants>

[0683] DIC Corporation MEGAFAC F-559

[0684] <Viscosity Evaluation>

[0685] The viscosity of the prepared pigment dispersion was measured using a RE-85L viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23℃, 20rpm).

[0686] <Determination of Chlorine Atom Content>

[0687] The determination was performed using combustion ion chromatography. The chlorine atom content in the photosensitive coloring composition was quantified using a combustion absorption ion chromatography (CIC) instrument AQF2100H from MITSUBISHI CHEMICAL ANALYTECH (now Nittoseiko Analytech Co., Ltd.) via a standard curve method.

[0688] <Determination of optical density per unit film thickness (unit OD value)>

[0689] The optical density per unit film thickness was determined according to the following steps.

[0690] First, the prepared photosensitive coloring composition was spin-coated onto a glass substrate to a thickness of 1.5 μm after calcination. After vacuum drying for 1 minute, it was dried on a hot plate at 100°C for 120 seconds. The resulting coating was then exposed without an exposure mask. An intensity of 40 mW / cm² at a wavelength of 365 nm was used as the illumination source. 2 The high-pressure mercury lamp was set to an exposure dose of 50 mJ / cm. 2Next, the substrate is heated and cured in an oven at 230°C for 30 minutes to obtain the resist-coated substrate 1.

[0691] The optical density (OD value) of the obtained 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 light source A), spectral sensitivity characteristics of the light-receiving part: ISO visual density under ISO 5-3 standard). The film thickness was measured using a VertScan(R) 2.0 non-contact surface-layer profile shape measurement system manufactured by Ryoka Systems Inc. The optical density (OD value) per unit film thickness (1μm) was calculated from the optical density (OD value) and the film thickness. It should be noted that the OD value represents the light-blocking ability; the larger the value, the higher the light-blocking ability.

[0692] <Electrode Surface Roughness Evaluation>

[0693] On an electrode substrate with a 60 nm thick silver film deposited on its entire surface on a glass substrate, various photosensitive coloring compositions were coated using a spin coater to achieve a 1.5 μm thick film after calcination. After vacuum drying for 1 minute, the film was dried at 100°C for 120 seconds using a hot plate. Then, using a photomask capable of forming a square opening pattern with a side length of 50 μm on the resulting coated substrate, a high-pressure mercury lamp was used to select wavelengths below 330 nm, with an exposure gap of 5 μm and an exposure rate of 50 mJ / cm². 2 The ultraviolet light was exposed. The light intensity at a wavelength of 365nm was 40mW / cm². 2 Next, using a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution as the developer, the developer was sprayed at 25°C for 60 seconds at a water pressure of 0.05 MPa. After that, the developer was rinsed off with pure water and the development was stopped. The mixture was then washed with a water rinse spray for 60 seconds.

[0694] These operations remove the openings by developing, resulting in an electrode substrate with patterned spacer walls. The patterned substrate is then heated (calcined) in an oven at 230°C for 30 minutes to solidify the pattern.

[0695] The electrode substrate with a 50 μm opening pattern was observed using an optical microscope at 200x magnification to confirm whether there were any shape changes (surface roughness) on the electrode surface within the opening pattern. The degree of surface roughness was ranked in the order of A, B, C, with A representing the best.

[0696] A: After heat curing, the electrode surface did not become rough.

[0697] B: After heat curing, some surface roughness was produced on the electrode surface, but this is not a problem in practical use and is acceptable.

[0698] C: After heat curing, the electrode surface shows unevenness, resulting in a rough surface, which is problematic in practical use and unacceptable.

[0699] <Evaluation of Luminescent Properties>

[0700] On a substrate where an indium tin oxide (ITO) transparent conductive film with a thickness of 70 nm was deposited on glass and an anode was formed using conventional photolithography and hydrochloric acid etching, various photosensitive coloring compositions were coated using a spin coater to a film thickness of 1.5 μm after calcination. After vacuum drying for 1 minute, the substrate was dried on a hot plate at 100°C for 120 seconds. Then, on the resulting coated substrate, an exposure mask (a mask with multiple rectangular coverings (40 μm x 80 μm) spaced 60 μm vertically and 100 μm horizontally) was used with a high-pressure mercury lamp that cut off wavelengths below 330 nm at an exposure gap of 5 μm and an exposure rate of 50 mJ / cm². 2 The light was exposed to ultraviolet light. At this time, the light intensity at a wavelength of 365nm was 40mW / cm². 2 Next, using a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution as the developer, spray development was performed at 25°C for 60–120 seconds at a water pressure of 0.05 MPa. Afterward, the developer was rinsed off with pure water to stop development, followed by a 60-second water rinse spray. The spray development time was set to be at least 1.2 times the time required to dissolve and remove the unexposed areas of the coating.

[0701] These operations remove the openings by developing, resulting in an electrode substrate with patterned spacer walls. The patterned substrate is then heated (calcined) in an oven at 230°C for 30 minutes to solidify the pattern.

[0702] <Fabrication of Organic Electroluminescent Components>

[0703] An organic electroluminescent element is fabricated by sequentially layering molybdenum oxide (10 nm thick) as a hole injection layer, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2-amine (60 nm thick) as a hole transport layer, tris(8-hydroxyquinoline)aluminum (60 nm thick) as a light-emitting layer, lithium 8-hydroxyquinoline (1 nm thick) as an electron injection layer, and aluminum (80 nm thick) as a cathode on the entire surface of an electrode substrate with patterned spacer walls.

[0704] Then, a desiccant is applied to the recess of the sealing glass with a central concavity, and a UV-curable resin is applied to the frame portion surrounding the concavity. The sealing glass is configured such that its concavity completely covers the organic electroluminescent element on the electrode substrate. The sealing glass is then attached to the electrode substrate, and the UV-curable resin is irradiated with UV light to cure it, thereby sealing the hollow structure and fabricating a device for evaluating organic electroluminescent elements.

[0705] <Evaluation of the luminescent properties of organic electroluminescent devices>

[0706] The current density of the fabricated component was measured to be 10 mA / cm². 2 The voltage value (driving voltage) when the DC current is applied.

[0707] During the box manufacturing process, a current density of 10 mA / cm² was used. 2 Voltage value when powered on (driving voltage):

[0708] A: Voltage below 6.5V

[0709] B: The voltage is higher than 6.5V.

[0710] Next, measurements were taken at 60°C with a current density of 50 mA / cm². 2 The time (h) from the initial brightness to 90% of the initial brightness when the fabricated component is driven by a constant current DC current is taken as the drive life.

[0711] Lifespan (time before initial brightness reaches 90%):

[0712] A: Longer than 25 hours.

[0713] B: Less than 25 hours.

[0714] <Preparation of Pigment Dispersions 1-3>

[0715] The pigments, dispersants, alkali-soluble resins, and solvents listed in Table 1 are mixed at the mass ratios specified in Table 1. The mixture is then dispersed using a paint shaker at 25–45°C for 3 hours. As beads, [the mixture is used...]. Zirconia beads were added to a dispersion solution at a ratio of 2.5 times their mass. After dispersion, the beads were separated from the dispersion solution using a filter, thereby preparing pigment dispersion solutions 1-3.

[0716] It should be noted that the solvent amounts in Table 1 also include the amounts of solvent from the dispersant and the alkali-soluble resin. Additionally, the viscosity evaluation results of the pigment dispersions measured using the above method are shown in Table 1.

[0717] [Table 1]

[0718]

[0719] [Example 1, Example 2, Comparative Example 1]

[0720] Each component was added in such a manner that the proportion of each solid component in the total solid content was as shown in Table 2. Solvent was then added with a PGMEA / MB / MBA ratio of 72 / 20 / 8 and a total solid content of 17% by mass. The mixture was stirred until dissolved, thereby preparing the photosensitive coloring compositions of Examples 1, 2, and Comparative Example 1. Furthermore, the evaluation results of the chlorine atom content, unit OD value, and electrode surface roughness measured using the above method are shown in Tables 2 and 3.

[0721] [Table 2]

[0722]

[0723] For substrates using the photosensitive coloring composition of Comparative Example 1, it was confirmed that the silver (electrode) surface became uneven and rough. This is believed to be because the dispersant-II contains a large number of chlorine atoms, and therefore the photosensitive coloring composition also contains a large number of chlorine atoms. During calcination, chlorine-containing gas is generated, which reacts with the silver (electrode) surface and forms unevenness on the surface.

[0724] On the other hand, no unevenness was observed on the silver (electrode) surface in the substrate using the photosensitive coloring composition of Example 1. This is believed to be because dispersant-I contains no chlorine atoms, resulting in a low content of chlorine in the photosensitive coloring composition. Therefore, the silver (electrode) did not develop a rough surface, and a normal electrode substrate was obtained.

[0725] Regarding the luminescence characteristics of the organic electroluminescent element, Example 1 showed a longer lifespan compared to Comparative Example 1. This is believed to be due to the suppression of time-related degradation of the luminescent element by reducing the chlorine content.

[0726] [Table 3]

[0727]

[0728] For the substrate using the photosensitive coloring composition of Example 2, the unevenness of the silver (electrode) surface is also at a substantially problem-free level. It can be considered that the reason why the silver (electrode) surface roughness is better than that of Example 1 compared to Example 2 is that pigment-I has a rigid skeleton containing aromatic rings, so even trace amounts of chlorine atoms are not released outside the film.

[0729] Regarding the light-emitting characteristics of the organic electroluminescent element, the initial driving voltage of Example 2 is reduced, which is good. Furthermore, it is better than Example 1.

Claims

1. A photosensitive coloring composition, characterized in that, It contains (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) olefinic unsaturated compound, (e) solvent and (f) 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), which contains at least repeating units represented by general formulas (1), (2) and (3) and does not have repeating units containing quaternary ammonium groups. Furthermore, the chlorine atom content in the photosensitive coloring composition is less than 0.05% by mass relative to the total solid content of the photosensitive coloring composition. In equation (I), R 1 and R 6 Each atom can be independently composed of a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom. R 2 R 3 R 4 R 5 R 7 R 8 R 9 and R 10 Independent of all others, consisting of hydrogen atoms, halogen atoms, and 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 freely 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 combination in the group may also be directly bonded to each other or through oxygen atoms, sulfur atoms, NH or NR atoms. 11 The bridges are interlocked. R 11 and R 12 They are independently alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, or alkynyl groups having 2 to 12 carbon atoms. In equation (1), R 31 It can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent. R 32 It can be a hydrogen atom or a methyl group. * indicates a connection key. In equation (2), R 33 It is methylene, ethylene, or propylene, R 34 R is an alkyl group that is optionally substituted. 35 It can be a hydrogen atom or a methyl group. n is an integer from 1 to 20. * indicates a connection key. In equation (3), R 36 and R 37 Each can be independently alkyl, aryl, or aralkyl. R 38 It can be a hydrogen atom or a methyl group. Z is a divalent linker. * indicates a connection key.

2. The photosensitive coloring composition according to claim 1, wherein, The chlorine atom content in the photosensitive coloring composition is less than 0.01% by mass relative to the total solid content of the photosensitive coloring composition.

3. The photosensitive coloring composition according to claim 1, wherein, The chlorine atom content in the photosensitive coloring composition is less than 0.02% by mass relative to the colorant content of the photosensitive coloring composition (100% by mass).

4. The photosensitive coloring composition according to claim 1, wherein, The colorant (a) comprises organic coloring pigments.

5. A photosensitive coloring composition, characterized in that, It contains (a) colorant, (b) alkali-soluble resin, (c) photopolymerization initiator, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant. The coating film cured from the photosensitive coloring composition has an optical density of 0.5 or higher per 1 μm film thickness. The dispersant (f) contains an acrylic copolymer (f1), which contains at least repeating units represented by general formulas (1), (2) and (3) and does not have repeating units containing quaternary ammonium groups. Furthermore, the chlorine atom content in the photosensitive coloring composition is less than 0.05% by mass relative to the total solid content of the photosensitive coloring composition. In equation (1), R 31 It can be an alkyl group with a substituent, an aryl group with a substituent, or an aralkyl group with a substituent. R 32 It can be a hydrogen atom or a methyl group. * indicates a connection key. In equation (2), R 33 It is methylene, ethylene, or propylene, R 34 R is an alkyl group that is optionally substituted. 35 It can be a hydrogen atom or a methyl group. n is an integer from 1 to 20. * indicates a connection key. In equation (3), R 36 and R 37 Each can be independently alkyl, aryl, or aralkyl. R 38 It can be a hydrogen atom or a methyl group. Z is a divalent linker. * indicates a connection key.

6. The photosensitive coloring composition according to claim 5, wherein, The chlorine atom content in the photosensitive coloring composition is less than 0.01% by mass relative to the total solid content of the photosensitive coloring composition.

7. The photosensitive coloring composition according to claim 5, wherein, The chlorine atom content in the photosensitive coloring composition is less than 0.02% by mass relative to the colorant content of the photosensitive coloring composition (100% by mass).

8. The photosensitive coloring composition according to claim 5, wherein, The colorant (a) comprises at least one selected from the group consisting of red and orange pigments and at least one selected from the group consisting of blue and purple pigments.

9. The photosensitive coloring composition according to any one of claims 1 to 8, wherein, The acrylic copolymer (f1) is a block copolymer.

10. The photosensitive coloring composition according to any one of claims 1 to 8, wherein, The amine value of the acrylic copolymer (f1) is above 90 mg KOH / g.

11. The photosensitive coloring composition according to any one of claims 1 to 8, wherein, The total solid content of the photosensitive coloring composition contains more than 10% by mass of the colorant described in (a).

12. The photosensitive coloring composition according to any one of claims 1 to 8, used to form the spacer wall of an organic electroluminescent element.

13. A cured product formed by curing the photosensitive coloring composition according to any one of claims 1 to 8.

14. An organic electroluminescent element comprising the cured material of claim 13.

15. An image display device comprising the organic electroluminescent element of claim 14.

Images