Photosensitive colored composition, cured product, particle, organic electroluminescent element, color filter, and image display device

Abstract

The invention provides a photosensitive coloring composition with excellent substrate adhesion. The photosensitive coloring composition according to the present invention contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, the dispersant (B) containing a copolymer (B1) having: a structural unit (B1-1) having a specific structure; and a structural unit (B1-2) having at least one of a tertiary amino group and a quaternary ammonium group.

Description

Technical Field

[0001] This invention relates to photosensitive coloring compositions. Furthermore, this invention relates to cured products formed by curing photosensitive coloring compositions, spacers formed from the cured products, organic electroluminescent elements having spacers, color filters, and image display devices.

[0002] This application claims priority based on Japanese Patent Application No. 2023-179679, filed in Japan on October 18, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] In recent years, in order to reduce the power consumption and widen the color gamut of displays, color filters that use luminescent nanocrystals such as quantum dots to form pixels have been studied. Among the manufacturing methods of color filters are photolithography and inkjet printing, the latter of which is known to reduce the loss of ink material (for example, see Patent Document 1).

[0004] In the case of manufacturing a color filter containing luminescent nanocrystals by inkjet printing, ink containing luminescent nanocrystals is ejected into a region (pixel section) surrounded by pre-made spacer walls to form a pixel.

[0005] Furthermore, organic light-emitting elements used in organic electroluminescent displays, etc., are manufactured by forming spacers (banks) on a substrate and stacking various functional layers within the areas surrounded by the spacers. Among the methods for stacking functional layers within the spacers, inkjet printing is known.

[0006] As a resin composition for forming spacers, photosensitive resin compositions containing a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, and a liquid repellent are known (for example, see Patent Document 2).

[0007] In addition, it is known that: coloring resin compositions with low contact angle with water and good coating unevenness are produced by using specific dispersants (e.g., see Patent Document 3); block copolymers with good dispersibility, developability, and dry resolubility; and pigment dispersion compositions containing them (e.g., see Patent Document 4).

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2019-086745

[0011] Patent Document 2: International Publication No. 2022 / 264909

[0012] Patent Document 3: Japanese Patent Application Publication No. 2018-132554

[0013] Patent Document 4: Japanese Patent Application Publication No. 2013-119568 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] However, the substrate adhesion of the photosensitive resin composition and its cured product described in Patent Document 2 is insufficient.

[0016] In the compositions described in Patent Documents 3 and 4, no substrate adhesion problem is generated due to the low film thickness.

[0017] Therefore, the object of the present invention is to provide a photosensitive coloring composition with excellent substrate adhesion.

[0018] Furthermore, the present invention aims to provide a cured product formed by curing a photosensitive coloring composition that provides excellent substrate adhesion, a spacer wall formed by the cured product, an organic electroluminescent element having the spacer wall, a color filter having the spacer wall, and an image display device having the spacer wall.

[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 a dispersant with a specific structure in the photosensitive coloring composition, thus completing the present invention.

[0021] That is, the main idea of ​​this invention is as follows.

[0022] The present invention has the following solution.

[0023] [1] A photosensitive coloring composition, characterized in that it contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, wherein the photosensitive coloring composition is used to form a spacer wall, wherein,

[0024] The content of the colorant (A) is less than 15% by mass relative to the total solid content of the photosensitive coloring composition, and the dispersant (B) contains a copolymer (B1) having at least the following (B1-1) structural units and (B1-2) structural units.

[0025] (B1-1) Structural unit: The structural unit shown in the following general formula (B1-1).

[0026] (B1-2) Structural unit: a structural unit having at least one of a tertiary amino group and a quaternary ammonium group.

[0027] [Chemical Formula 1]

[0028]

[0029] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following groups independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents. n represents an integer from 1 to 10.

[0030] * indicates a bond.

[0031] [2] A photosensitive coloring composition, characterized in that it contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, wherein,

[0032] The colorant (A) contains CI pigment violet 29.

[0033] The (B) dispersant contains a copolymer (B1) having at least the following (B1-1) and (B1-2) structural units.

[0034] (B1-1) Structural unit: The structural unit shown in the following general formula (B1-1).

[0035] (B1-2) Structural unit: a structural unit having at least one of a tertiary amino group and a quaternary ammonium group.

[0036] [Chemical Formula 2]

[0037]

[0038] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following groups independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents. n represents an integer from 1 to 10.

[0039] * indicates a bond.

[0040] [3] A photosensitive coloring composition, characterized in that it contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, wherein,

[0041] The (B) dispersant contains a copolymer (B1) having at least the following (B1-1) and (B1-2) structural units.

[0042] The photosensitive coloring composition is used to form spacer walls with a height of 5 μm or more.

[0043] (B1-1) Structural unit: The structural unit shown in the following general formula (B1-1).

[0044] (B1-2) Structural unit: a structural unit having at least one of a tertiary amino group and a quaternary ammonium group.

[0045] [Chemical Formula 3]

[0046]

[0047] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following groups independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents. n represents an integer from 1 to 10.

[0048] * indicates a bond.

[0049] [4] The photosensitive coloring composition according to any one of [1] to [3], wherein the copolymer (B1) further has the following (B1-3) structural units.

[0050] (B1-3) Structural unit: The structural unit shown in the following general formula (B1-3).

[0051] [Chemical Formula 4]

[0052]

[0053] In equation (B1-3), R 11 R represents a hydrogen atom or a methyl group. 12 Indicates ethylene or propyleneene, R 13 This indicates an alkyl group that may optionally have substituents. m represents an integer from 1 to 20. * indicates a bonded bond.

[0054] [5] According to the photosensitive coloring composition of [4], the content of the (B1-1) structural unit in the copolymer (B1) is 100 mol% and the content of the (B1-3) structural unit is 20 to 500 mol%.

[0055] [6] The photosensitive coloring composition according to any one of [1] to [5], wherein the (B1-2) structural unit in the copolymer (B1) comprises at least one of the structural unit shown in the following general formula (B1-2-1) and the structural unit shown in the following general formula (B1-2-2).

[0056] [Chemical Formula 5]

[0057]

[0058] In equation (B1-2-1), R 21 R represents a hydrogen atom or a methyl group. 22 and R23 Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, Z 1 * indicates a divalent linker. * indicates a bond.

[0059] [Chemical Formula 6]

[0060]

[0061] In equation (B1-2-2), R 24 R represents a hydrogen atom or a methyl group. 25 ~R 27 Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, X 1 Y represents a divalent linker group. - * indicates a counteracting anion. * indicates a bonded bond.

[0062] [7] The photosensitive coloring composition according to any one of [1] to [6], wherein the copolymer (B1) comprises a block copolymer.

[0063] [8] The photosensitive coloring composition according to any one of [1] to [7], wherein the photosensitive coloring composition further contains a compound having a crosslinking group and having fluorine atoms and / or siloxane chains.

[0064] [9] The photosensitive coloring composition according to any one of [1] to [8], wherein the photosensitive coloring composition further contains a solvent.

[0065]

[10] The photosensitive coloring composition according to any one of [1] to [9], wherein the photosensitive coloring composition is used for firing at a temperature below 140°C.

[0066]

[11] A cured product which is formed by curing a photosensitive coloring composition according to any one of [1] to

[10] .

[0067]

[12] A spacer wall comprising a solidified material according to

[11] .

[0068]

[13] An organic electroluminescent element having a spacer wall according to

[12] .

[0069]

[14] A color filter having a spacer wall according to

[12] and further comprising luminescent nanocrystals.

[0070]

[15] An image display device having a spacer wall according to

[12] .

[0071] Invention Effects

[0072] According to the present invention, a photosensitive coloring composition with excellent substrate adhesion can be provided. Attached Figure Description

[0073] Figure 1 This is a cross-sectional view schematically illustrating an example of a color filter equipped with the spacer wall of the present invention. Detailed Implementation

[0074] The present invention will now be described in detail. It should be noted that the following description is merely one example of an embodiment of the present invention, and the present invention is not limited to these examples as long as it does not depart from its spirit.

[0075] In this invention, the following terms have the following meanings.

[0076] “(Meth)acrylic acid” means “either or both of acrylic acid and methacrylic acid”.

[0077] "Total solids content of a photosensitive coloring composition" refers to the total amount of components in a photosensitive coloring composition excluding the solvent. Even if the components other than the solvent are liquid at room temperature, they are not included in the solvent but are included in the total solids content.

[0078] The range of values ​​represented by “~” refers to the range of values ​​recorded before and after “~” as the lower and upper limits.

[0079] "Blocking wall" refers to a dam, wall, or vessel wall.

[0080] "Weight-average molecular weight" and "number-average molecular weight" refer to the weight-average molecular weight (Mw) obtained by GPC (gel permeation chromatography) converted to polystyrene.

[0081] Unless otherwise specified, "acid value" refers to the acid value converted from the effective solid content, calculated through neutralization titration.

[0082] In this invention, the spacer can be used, for example, as a component for dividing the functional layer (organic layer, light-emitting portion) in an active-drive organic electroluminescent element. It can be used to spray ink, a material constituting the functional layer, onto the divided area (pixel area) and then dry it, thereby forming, for example, a pixel comprising the functional layer and the spacer. Furthermore, it can also be used as a component for dividing the pixel portion in a color filter containing luminescent nanocrystals. It can be used to spray ink onto the divided area and then dry it, thereby forming a pixel.

[0083] [1] Photosensitive coloring composition

[0084] The photosensitive coloring composition of the present invention contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator. The photosensitive coloring composition may further include other components as needed, such as (F) a compound, an ultraviolet absorber, a polymerization inhibitor, a thermal polymerization initiator, an amino compound, a silane coupling agent, an inorganic filler, a phosphate-based olefin monomer, and a solvent.

[0085] The first aspect of the present invention is a photosensitive coloring composition (A) in which the content of a colorant is 15% by mass or less and is used to form a spacer wall.

[0086] The second aspect of the present invention is a photosensitive coloring composition (A) containing CI pigment violet 29 as a colorant.

[0087] The photosensitive coloring composition of the third aspect of the present invention is a photosensitive coloring composition for forming spacer walls with a height of 5 μm or more.

[0088] [1-1] Components and composition of photosensitive coloring compositions

[0089] The components and their composition constituting the photosensitive coloring composition of the present invention will be described.

[0090] [1-1-1] (A) Coloring agent

[0091] The photosensitive coloring composition of the present invention contains a colorant (A). By containing the colorant (A), moderate light absorption can be obtained, particularly moderate light blocking properties in the case of its use in forming a light-shielding member including a coloring spacer. Furthermore, in the case of its use for light scattering purposes, good light scattering properties can be obtained by using a white colorant.

[0092] [1-1-1-1] First Option, Third Option

[0093] The type of colorant (A) used in the first and third embodiments of the present invention is not particularly limited; pigments or dyes can be used. From the viewpoint of durability, pigments are preferred.

[0094] (A) The colorant may contain one or more pigments. In particular, from the viewpoint of uniformly blocking light in the visible area, two or more pigments are preferred.

[0095] There is no particular limitation on the types of pigments that can be used as colorants (A), such as organic pigments and inorganic pigments. When the purpose is to achieve opacity, from the viewpoint of efficiently curing the photosensitive coloring composition by controlling the transmission wavelength, organic pigments are preferred.

[0096] Organic pigments can be categorized into organic coloring pigments and organic black pigments. Here, organic coloring pigments refer to organic pigments that are colors other than black, such as red pigments, orange pigments, blue pigments, purple pigments, green pigments, and yellow pigments.

[0097] From the viewpoint of ultraviolet absorption, organic coloring pigments are preferred among organic pigments.

[0098] Organic pigments can be used alone or in combination of two or more. When used for opaque purposes, it is more preferable to use a combination of organic pigments of different colors, and even more preferable to use a combination of organic pigments that are close to black.

[0099] The chemical structures of these organic pigments are not particularly limited; examples include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Below, specific examples of usable pigments are indicated by pigment numbers. Terms such as "CI Pigment Red 2" listed below refer to the Color Index (CI).

[0100] 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, and 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, 1 49, 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, 23 2, 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.

[0101] From the viewpoint of light-blocking and dispersibility, CI Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are preferred, and CI Pigment Red 177, 209, 224, and 254 are even more preferred.

[0102] From the perspectives of dispersibility and opacity, CI pigments Red 177, 254, and 272 are preferred. When the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use a pigment with low ultraviolet absorption as the red pigment; from this viewpoint, CI pigments Red 254 and 272 are preferred.

[0103] Examples of orange pigments include CI pigments 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.

[0104] From the viewpoints of dispersibility and light-blocking properties, CI pigments Orange 13, 43, 64, and 72 are preferred, and CI pigments Orange 43, 64, and 72 are more preferred. When the photosensitive coloring composition is cured by ultraviolet light, a pigment with low ultraviolet absorption is preferred as the orange pigment; from this viewpoint, CI pigments Orange 64 and 72 are preferred.

[0105] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0106] From the viewpoint of light-blocking properties, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferred, with CI Pigment Blue 15:6 being more preferred.

[0107] From the perspectives of dispersibility and light-blocking properties, CI Pigment Blue 15:6, 16, and 60 are preferred, and CI Pigment Blue 15:6 and 60 are more preferred. When the photosensitive coloring composition is cured by ultraviolet light, a pigment with low ultraviolet absorption is preferred as the blue pigment; from this viewpoint, CI Pigment Blue 60 is more preferred.

[0108] Examples of purple pigments include CI pigments 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0109] From the viewpoint of light-blocking properties, CI pigment violet 19 and 23 are preferred, and CI pigment violet 23 is more preferred.

[0110] From the perspectives of dispersibility and opacity, CI pigments Violet 23 and 29 are preferred. When the photosensitive coloring composition is cured by ultraviolet light, a pigment with low ultraviolet absorption is preferred as the purple pigment; from this viewpoint, CI pigment Violet 29 is preferred.

[0111] In addition to red, orange, blue, and purple pigments, other organic coloring pigments that can be used include, for example, green and yellow pigments.

[0112] 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, and 55, with CI pigments green 7 and 36 being preferred.

[0113] Examples of yellow pigments include CI pigments Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 7 5, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127, 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, more preferably CI pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and even more preferably CI pigment yellow 83, 138, 139, 150, 180.

[0114] From the viewpoint of light-blocking and ink-repelling properties, it is preferable to use at least one selected from the group consisting of red pigment, orange pigment, blue pigment, and purple pigment.

[0115] From the viewpoint of light-blocking and ink-repelling properties, it is preferable to use a product containing at least one of the following pigments.

[0116] Red pigments: CI Pigment Red 177, 254, 272.

[0117] Orange pigments: CI Pigment Orange 64, 72.

[0118] Blue pigment: CI Pigment Blue 15:6, 16, 60.

[0119] Purple pigments: CI pigments purple 23 and 29.

[0120] When using two or more organic coloring pigments, there is no particular limitation on the combination of organic coloring pigments. From the viewpoint of light blocking, it is preferable to use 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 as coloring agent (A).

[0121] 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.

[0122] From the viewpoint of the light-blocking properties of blue light, it is preferable to use a purple pigment as colorant (A).

[0123] From the viewpoint of light-blocking properties, organic black pigments are preferred as colorant (A). Examples of organic black pigments include perylene-based black pigments, aniline-based black pigments, and benzodifuranone-based black pigments.

[0124] Examples of perylene-based black pigments include: Lumogen Black (registered trademark) FK4281, K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF). Examples of aniline-based black pigments include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).

[0125] Among these, benzodifuranone-based black pigments are preferred from the perspectives of good dispersibility, developability, control of cone shape, and ink repellency.

[0126] Among benzodifuranone-based black pigments, it is preferable to use an organic black pigment (hereinafter also referred to as "organic black pigment of general formula (A1)") comprising at least one of the following groups: a compound selected from the general formula (A1) (hereinafter also referred to as "compound (A1)"), a geometric isomer of compound (A1), a salt of compound (A1) and a salt of a geometric isomer of compound (A1).

[0127] [Chemical Formula 7]

[0128]

[0129] In formula (A1), R a11 and R a16 Each can independently represent a hydrogen atom, CH3, CF3, fluorine atom, or chlorine atom; R a12 R a13 R a14 R a15R a17 R a18 R a19 and R a20 Each independently represents a hydrogen atom, a halogen atom, and R. a21 COOH, COOR a21 COO - CONH2, CONHR a21 CONR a21 R a22 CN, OH, OR a21 COCR a21 、OOCNH2、OOCNHR a21 OOCNR a21 R a22 NO2, NH2, NHR a21 NR a21 R a22 , NHCOR a22 NR a21 COR a22 N=CH2, N=CHR a21 N=CR a21 R a22 SH, SR a21 SOR a21 SO2R a21 SO3R a21 SO3H, SO3 - SO2NH2, SO2NHR a21 or SO2NR a21 R a22 Choose freely R a12 and R a13 R a13 and R a14 R a14 and R a15 R a17 and R a18 R a18 and R a19 and R a19 and R a20 At least one combination of the groups is optionally directly bonded to each other or optionally bonded through an oxygen atom, a sulfur atom, NH or NR atom. a21 Bridged and bonded together; R a21 and R a22 Each can be independently represented as an alkyl group with 1 to 12 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, a cycloalkenyl group with 3 to 12 carbon atoms, or an alkynyl group with 2 to 12 carbon atoms.

[0130] Compound (A1) and its geometric isomers have the following core structures (where substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

[0131] [Chemical Formula 8]

[0132]

[0133] When compound (A1) is anionic, it is preferable to use a salt formed by compensating for its charge with any known suitable cation, such as a metal cation, organic cation, inorganic cation, 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 (A1) are anionic, the same salt is preferred.

[0134] Among the substituents in formula (A1) and their definitions, the following groups are preferred from the perspective of having a tendency to increase the hiding power. This is because the following substituents are considered to have no absorption and will not affect the hue of the pigment.

[0135] R a12 R a14 R a15 R a17 R a19 and R a20 Each atom is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

[0136] R a13 and R a18 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.

[0137] R a11 and R a16 Each atom is preferably a hydrogen atom, CH3 or CF3, and more preferably a hydrogen atom.

[0138] Preferred selection of free R a11 With R a16 R a12 With R a17 R a13 With R a18 R a14 With R a19 and R a15With R a20 At least one combination in the group is the same, more preferably R a11 With R a16 Same, R a12 With R a17 Same, R a13 With R a18 Same, R a14 With R a19 Same, and R a15 With R a20 same.

[0139] Alkyl groups having 1 to 12 carbon atoms include, 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.

[0140] Cycloalkyl groups having 3 to 12 carbon atoms include, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thujyl, norbornyl, bornyl, norcareyl, careyl, menthyl, norpinyl, pinyl, adamantane-1-yl or adamantane-2-yl.

[0141] Alkenes with 2 to 12 carbon atoms include, for example, ethylene, 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.

[0142] 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.

[0143] 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.

[0144] Halogen atoms can be, for example, fluorine, chlorine, bromine, or iodine atoms.

[0145] The organic black pigment represented by general formula (A1) is preferably an organic black pigment comprising at least one of the group consisting of a compound represented by general formula (A2) below (hereinafter also referred to as "compound (A2)") and a geometrical isomer of compound (A2).

[0146] [Chemical Formula 9]

[0147]

[0148] Organic black pigments represented by compound (A2) include, for example, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).

[0149] The organic black pigment is preferably used by dispersion using the dispersant, solvent, and method described later. Furthermore, if a sulfonic acid derivative of compound (A1), particularly a sulfonic acid derivative of compound (A2), is present during dispersion, dispersibility and shelf life are sometimes improved; therefore, the organic black pigment preferably contains these sulfonic acid derivatives.

[0150] Inorganic black pigments can be listed as colorants in addition to these organic pigments. Furthermore, inorganic black pigments can be used in addition to organic pigments.

[0151] Inorganic black pigments include: carbon black, acetylene black, lampblack, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black is preferred from the perspective of opacity.

[0152] Examples of carbon black include the following.

[0153] Mitsubishi Chemical Group system: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #96 0, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150 , #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B.

[0154] Made by Degussa: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, ColorBlack S170.

[0155] Cabot Corporation manufactures: Monarch (registered trademark, same below) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, same below) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 550R, REGAL 660R, BLACKPEARLS 480, PEARLS 130, VULCAN (registered trademark, same below) XC72R, ELFTEX (registered trademark) -8.

[0156] Made by Birla: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN100 0. RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

[0157] Carbon black can also be resin-coated carbon black. When resin-coated carbon black is used, it improves the adhesion to the glass substrate and increases the volume resistivity.

[0158] As for the resin-coated carbon black, the carbon black described in Japanese Patent Application Publication No. 09-71733 is preferred. From the perspective of volume resistivity and dielectric constant, resin-coated carbon black is preferred.

[0159] These organic and inorganic pigments are preferably dispersed in a manner with an average particle size typically below 1 μm, more preferably below 0.5 μm, and even more preferably below 0.25 μm.

[0160] Here, the average particle size is based on the number of pigment particles.

[0161] The average particle size of the pigment is determined based on the pigment particle size measured by dynamic light scattering (DLS). The particle size determination is performed on a sufficiently diluted photosensitive coloring composition (usually diluted to a pigment concentration of approximately 0.005–0.2% by mass; if the measuring equipment recommends a concentration, that concentration is used). The determination is conducted at 25°C.

[0162] Besides organic pigments and inorganic black pigments, dyes can also be used. Examples of dyes that can be used as coloring agents include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methylene dyes.

[0163] Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, and CI Mordant Black 7.

[0164] Examples of anthraquinone dyes include CI Vat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue 60.

[0165] Examples of phthalocyanine dyes include CI Variant Blue 5.

[0166] Examples of quinone imine dyes include Basic Blue 3 and Basic Blue 9.

[0167] Examples of quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64.

[0168] Examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42.

[0169] In the first embodiment, the content of (A) colorant relative to the total solid content of the photosensitive coloring composition is 15% by mass or less, preferably 12% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. Furthermore, it is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 4% by mass or more. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, even more preferably 3 to 10% by mass, and even more preferably 4 to 8% 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, the relative increase of (C) alkali-soluble resin and (D) photopolymerizable compound results in a tendency to improve the curability, ink repellency, and substrate adhesion of the coating film.

[0170] In the third embodiment, the proportion of colorant (A) in the photosensitive coloring composition is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, even more preferably 12% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% 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 2 to 20% by mass, further preferably 3 to 15% by mass, even more preferably 4 to 15% by mass, even more preferably 4 to 12% by mass, particularly preferably 4 to 10% by mass, and most preferably 4 to 8% 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, the relative increase in alkali-soluble resin and photopolymerizable compounds results in a tendency to improve the curability, ink repellency, and substrate adhesion of the coating film.

[0171] When light scattering is desired, a portion or the total amount of colorant (A) may be a white pigment (A3). Examples of white pigments (A3) include: metal oxides such as titanium dioxide, zirconium oxide, hafnium oxide, and barium titanate; inorganic fillers such as calcium silicate, magnesium carbonate, calcium carbonate, calcium sulfate, and barium sulfate.

[0172] White pigment (A3) can be used alone or in combination with two or more.

[0173] From the viewpoint of refractive index and light scattering, metal oxides are preferred as white pigments (A3), titanium oxide, zirconium oxide, and hafnium oxide are more preferred, and titanium oxide is even more preferred.

[0174] [1-1-1-2] Second Option

[0175] In the second aspect of the invention, the photosensitive coloring composition contains CI pigment violet 29 as a colorant (A). By containing CI pigment violet 29, when used in a color filter with quantum dots, the light-blocking properties of the blue light from the backlight and the green light from adjacent pixels become good.

[0176] In the second embodiment, the photosensitive coloring composition may contain other colorants besides CI Pigment Violet 29. Examples of other usable colorants include (A) colorants other than CI Pigment Violet 29 described in the first and third embodiments.

[0177] In the second embodiment, the content of CI pigment violet 29 is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 12% by mass or less, and most preferably 10% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 50% by mass is preferred, more preferably 1 to 30% by mass, further preferably 2 to 20% by mass, even more preferably 2 to 15% by mass, particularly preferably 3 to 12% by mass, and especially preferably 4 to 10% by mass. By setting it above the lower limit, there is a tendency to ensure light-blocking properties. By setting it below the upper limit, the relative increase in alkali-soluble resin and photopolymerizable compounds leads to a tendency to improve the curability and ink-repellency of the coating film.

[0178] In the second embodiment, the proportion of CI pigment violet 29 in the colorant (A) is not particularly limited. From the viewpoint of light-blocking properties and curability of green light, it is preferably 30% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, especially preferably 80% by mass or more, and usually 100% by mass or less. For example, it is preferably 30 to 100% by mass, more preferably 45 to 100% by mass, further preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, especially preferably 70 to 100% by mass, and especially preferably 80 to 100% by mass.

[0179] [1-1-2] (B) Dispersant

[0180] The photosensitive coloring composition of the present invention contains a dispersant (B). By containing a dispersant (B), it has the effect of finely dispersing the colorant (A) and stabilizing its dispersion state.

[0181] The photosensitive coloring composition of the present invention contains a (B) dispersant comprising a copolymer (B1) as shown below. In addition to containing copolymer (B1), the (B) dispersant may also contain other dispersants besides copolymer (B1) (hereinafter also referred to as "other dispersants").

[0182] [1-1-2-1] copolymer (B1)

[0183] The copolymer (B1) has at least the following (B1-1) and (B1-2) structural units. Preferably, the copolymer (B1) contains, in addition to the (B1-1) and (B1-2) structural units, the (B1-3) structural unit described later. Furthermore, the copolymer (B1) may also contain the (B1-4) structural unit described later. Additionally, the copolymer (B1) may also contain structural units other than the (B1-1), (B1-2), (B1-3), and (B1-4) structural units (hereinafter also referred to as "other structural units").

[0184] The copolymer (B1) has solvent-affinity groups and pigment-affinity groups. The (B1-1) structural unit functions as a solvent-affinity group, and the (B1-2) structural unit functions as a pigment-affinity group.

[0185] Pigment-affinity groups readily adsorb onto pigments, while solvent-affinity groups exhibit high affinity for solvents, alkali-soluble resins, and the like. Therefore, it is hypothesized that even in a dispersed state in solution or as a cured product, the copolymer (B1) remains in a state where solvent-affinity groups are exposed on the pigment surface.

[0186] It is believed that the solvent-affinity groups exposed on the surface of the pigment readily facilitate bonding with other substances. Specifically, the (B1-1) structural unit has ester and hydroxyl groups as polar functional groups, thus further promoting bonding with the substrate surface, such as the outermost surface of glass, i.e., substrate adhesion, as a whole cured product. Therefore, the photosensitive coloring composition of the present invention exhibits excellent substrate adhesion.

[0187] <(B1-1) Structural Unit>

[0188] (B1-1) The structural unit is the structural unit shown in the following general formula (1).

[0189] [Chemical Formula 10]

[0190]

[0191] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following groups independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents. n represents an integer from 1 to 10. * represents a bond.

[0192] R in equation (B1-1) 2 and R 3 Each of the following independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents. The alkylene group can be either straight-chain or branched. R 2 Preferably, the number of carbon atoms is 2 or more. Furthermore, it is preferably 7 or less, more preferably 5 or less, and even more preferably 3 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 2 to 7, more preferably 2 to 5, and even more preferably 2 to 3. By setting it to the lower limit or above, there is a tendency for improved substrate adhesion. Furthermore, by setting it to the upper limit or below, there is a tendency for improved dispersion.

[0193] Examples of alkylene compounds include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, and n-hexylene.

[0194] R 3 Preferably, the number of carbon atoms is 2 or more, more preferably 4 or more. Furthermore, it is preferably 7 or less, more preferably 6 or less, and even more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 2 to 7 is preferred, more preferably 2 to 6, even more preferably 4 to 6, and particularly preferably 4 to 5. By setting the value above the lower limit, there is a tendency for improved substrate adhesion. Furthermore, by setting the value below the upper limit, there is a tendency for improved dispersion.

[0195] Examples of substituents include halogen atoms, alkoxy groups, and hydroxyl groups.

[0196] From the viewpoint of compatibility and dispersibility with the solvent and binder components, n is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Furthermore, n is preferably 9 or less, more preferably 7 or less, and even more preferably 6 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, n is preferably 2 to 9, more preferably 3 to 7, and even more preferably 4 to 6.

[0197] The proportion of the (B1-1) structural unit in all structural units of the copolymer (B1) is not particularly limited. From the viewpoint of dispersibility, when the total of all structural units is set to 100 mol%, that is, relative to the total number of moles of structural units in the copolymer (B1), it is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, even more preferably 0.3 mol% or more, and preferably 10 mol% or less, more preferably 5 mol% or less, even more preferably 2 mol% or less, and particularly preferably 1 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, even more preferably 0.1 to 2 mol%, particularly preferably 0.1 to 1 mol%, and most preferably 0.3 to 1 mol%.

[0198] <(B1-2) Structural Unit>

[0199] (B1-2) The structural unit is a structural unit having at least one of a tertiary amino group and a quaternary ammonium group.

[0200] By giving the copolymer (B1) a (B1-2) structural unit, there is a tendency for it to have good dispersibility and good stability in photosensitive coloring compositions and pigment dispersants.

[0201] The structural units having tertiary amino groups in the copolymer (B1) are not particularly limited, but from the viewpoint of dispersibility, it is preferred to have structural units having the following general formula (B1-2-1) (hereinafter also referred to as "(B1-2-1) structural units").

[0202] [Chemical Formula 11]

[0203]

[0204] In equation (B1-2-1), R 21 R represents a hydrogen atom or a methyl group. 22 and R 23 Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, Z 1 * indicates a divalent linker. * indicates a bond.

[0205] Furthermore, the structural units having quaternary ammonium groups in the copolymer (B1) are not particularly limited, but from the viewpoint of dispersibility, it is preferable to have structural units having the following general formula (B1-2-2) (hereinafter also referred to as "(B1-2-2) structural units").

[0206] [Chemical Formula 12]

[0207]

[0208] In equation (B1-2-2), R 24 R represents a hydrogen atom or a methyl group. 25 ~R 27 Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, X 1 Y represents a divalent linker group. - * indicates a counteracting anion. * indicates a bonded bond.

[0209] R in equation (B1-2-1) 22 and R 23 R in equation (B1-2-2) 25 ~R 27 The number of carbon atoms in the alkyl group optionally having substituents is not particularly limited, but is preferably 1 or more, and more preferably 10 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, and 1 to 6 is more preferred.

[0210] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. The alkyl group can be either straight-chain or branched. Furthermore, it can also contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0211] R in equation (B1-2-1) 22 and R 23 R in equation (B1-2-2) 25 ~R 27 The number of carbon atoms in the aryl group, which optionally has substituents, is not particularly limited, but is preferably 6 or more, and more preferably 16 or less, and even more preferably 12 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 6 to 16 is preferred, and 6 to 12 is more preferred.

[0212] Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being more preferred.

[0213] R in equation (B1-2-1) 22 and R 23 R in equation (B1-2-2) 25 ~R 27The number of carbon atoms in the optionally substituent aralkyl group is not particularly limited, but is preferably 7 or more, and more preferably 16 or less, and even more preferably 12 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 7 to 16 is preferred, and 7 to 12 is more preferred.

[0214] Examples of aralkyl groups include phenylmethyl (benzyl), phenylethyl (phenylethyl), phenylpropyl, phenylbutyl, and phenylisopropyl, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl being preferred, and phenylmethyl and phenylethyl being more preferred.

[0215] R in equation (B1-2-1) 22 and R 23 R in equation (B1-2-2) 25 ~R 27 The alkyl, aryl, or aralkyl group may optionally have substituents, such as halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups.

[0216] Of these, from the viewpoint of redissolution, R in formula (B1-2-1) is preferred. 22 and R 23 Each of the alkyl groups is preferably substituted, more preferably methyl or ethyl, and even more preferably methyl.

[0217] Furthermore, considering the dispersibility and the preservation after dispersal, R in equation (B1-2-2) 25 ~R 27 Each is preferably an alkyl group optionally having substituents or an aralkyl group optionally having substituents, more preferably methyl, ethyl, phenylmethyl or phenylethyl, and even more preferably methyl and phenylmethyl. In particular, R 25 and R 27 Preferably methyl, R 26 Phenylmethyl is preferred.

[0218] In formulas (B1-2-1) and (B1-2-2), Z acts as a divalent linking group. 1 and divalent linker X 1 Examples include alkylene groups with 1 to 10 carbon atoms, arylene groups with 6 to 12 carbon atoms, and -CONH-R. 28 -base, -COOR 29 -base (where R) 28 and R 29 It is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms, preferably -COO-R. 28 - group, more preferably -COO-C2H4- group.

[0219] In equation (B1-2-2), the counter anion Y... - For example, Cl can be listed - ,Br - I - ClO4 - BF4 - CH3COO - PF6 - CH3SO4 - C2H5SO4 - .

[0220] The proportion of the (B1-2) structural unit in all structural units of the copolymer (B1) is not particularly limited. From the viewpoint of dispersibility, when the total of all structural units is set to 100 mol%, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, even more preferably 15 to 30 mol%, and particularly preferably 20 to 30 mol%.

[0221] The proportion of the (B1-2-1) structural unit in all structural units of the copolymer (B1) is not particularly limited. From the viewpoint of dispersibility, when the total of all structural units is set to 100 mol%, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 15 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, even more preferably 15 to 30 mol%, and particularly preferably 15 to 20 mol%.

[0222] The proportion of the (B1-2-2) structural unit in all structural units of the copolymer (B1) is not particularly limited. From the viewpoint of dispersibility, when the total of all structural units is set to 100 mol%, it is preferably 1 mol% or more, more preferably 4 mol% or more, even more preferably 7 mol% or more, and preferably 40 mol% or less, more preferably 20 mol% or less, even more preferably 15 mol% or less, and particularly preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 40 mol%, more preferably 4 to 20 mol%, even more preferably 4 to 15 mol%, and particularly preferably 7 to 10 mol%.

[0223] The content ratio of the (B1-2-2) structural unit is not particularly limited. When the total content ratio of the (B1-2-2) structural unit and the (B1-2-1) structural unit is set to 100 mol%, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 35 mol% or less. Furthermore, it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and particularly preferably 30 mol% or more. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, even more preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%. By setting it to the lower limit or above, there is a tendency for the preservation after dispersion to become better. Furthermore, by setting it to the upper limit or below, there is a tendency for the dispersion to become better.

[0224] <(B1-3) Structural Unit>

[0225] (B1-3) The structural unit is the structural unit shown in the following general formula (B1-3).

[0226] By giving the copolymer (B1) a (B1-3) structural unit, the copolymer (B1) functions as a solvent-affinity group, improving the compatibility of the (B) dispersant with respect to solvent and binder components, and further enhancing the dispersion stability.

[0227] [Chemical Formula 13]

[0228]

[0229] In equation (B1-3), R 11 R represents a hydrogen atom or a methyl group. 12 Indicates ethylene or propyleneene, R 13 This indicates an alkyl group that may optionally have substituents. m represents an integer from 1 to 20. * indicates a bonded bond.

[0230] R in equation (B1-3) 13 The number of carbon atoms in the alkyl group optionally having substituents is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, 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 6.

[0231] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, or hexyl being preferred, and methyl, ethyl, propyl, or butyl being more preferred. The alkyl group can be either straight-chain or branched. Furthermore, it can also contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0232] As R 13 Substituents in the group can include, for example, halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups.

[0233] From the viewpoint of compatibility and dispersibility with the solvent and binder components, m in formula (B1-3) is preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferred, 1 to 5 is more preferred, and 2 to 5 is even more preferred.

[0234] When the copolymer (B1) contains (B1-3) structural units, the proportion of (B1-3) structural units in all structural units of the copolymer (B1) is not particularly limited. When the total of all structural units is set to 100 mol%, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and even more preferably 1 mol% or more. Furthermore, it is preferably 10 mol% or less, more preferably 8 mol% or less, and even more preferably 5 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 10 mol%, more preferably 0.5 to 8 mol%, and even more preferably 1 to 5 mol%. Within these ranges, there is a tendency to balance compatibility and dispersion stability with respect to solvent and binder components.

[0235] When the copolymer (B1) contains (B1-3) structural units, the proportion of (B1-3) structural units in the copolymer (B1) relative to the proportion of (B1-1) structural units is not particularly limited to 100 mol%, but is preferably 20 mol% or more, more preferably 50 mol% or more, even more preferably 100 mol% or more, particularly preferably 200 mol% or more, and further preferably 500 mol% or less, more preferably 400 mol% or less, and even more preferably 300 mol% or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 20 to 500 mol%, more preferably 50 to 500 mol%, even more preferably 100 to 400 mol%, and particularly preferably 200 to 300 mol%. By setting the value above the lower limit, there is a tendency for better dispersibility. Furthermore, by setting the value below the upper limit, there is a tendency for better substrate adhesion.

[0236] <(B1-4) Structural Unit>

[0237] (B1-4) The structural unit is the structural unit shown in the following general formula (B1-4).

[0238] By giving the copolymer (B1) (B1-4) structural units, which act as solvent-affinity groups, the compatibility of the (B) dispersant with respect to solvent and binder components is improved, and the dispersion stability is further enhanced.

[0239] [Chemical Formula 14]

[0240]

[0241] In equation (B1-4), R 31 R represents a hydrogen atom or a methyl group. 32 Indicates an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent. * Indicates a bonded bond.

[0242] R in equation (B1-4) 32 The number of carbon atoms in the alkyl group optionally having substituents is not particularly limited, but is preferably 1 or more, more preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 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 8.

[0243] Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. The alkyl group can be either straight-chain or branched. Furthermore, it can also contain a cyclic structure, such as cyclohexyl or cyclohexylmethyl.

[0244] R in equation (B1-4) 32 The number of carbon atoms in the aryl group, which optionally has substituents, is not particularly limited, but is preferably 6 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 6 to 16 is preferred, more preferably 6 to 12, and even more preferably 6 to 8.

[0245] Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracene, with phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl being preferred, and phenyl, methylphenyl, and ethylphenyl being more preferred.

[0246] R in equation (B1-4) 32 The number of carbon atoms in the optionally substituent aralkyl group is not particularly limited, but is preferably 7 or more, more preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 7 to 16 is preferred, more preferably 7 to 12, and even more preferably 7 to 10.

[0247] Examples of aralkyl groups include phenylmethyl (benzyl), phenylethyl (phenylethyl), phenylpropyl, phenylbutyl, and phenylisopropyl, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl being preferred, and phenylmethyl and phenylethyl being more preferred.

[0248] From the perspective of solvent compatibility and dispersion stability, as R 32 Preferably, it is an alkyl or aralkyl group, more preferably methyl, ethyl, or phenylmethyl.

[0249] As R 32 The alkyl group may optionally have substituents, such as halogen atoms and alkoxy groups.

[0250] As R 32 The aryl or aralkyl group may optionally have substituents, such as linear or branched alkyl groups, halogen atoms, and alkoxy groups.

[0251] When the copolymer (B1) contains (B1-4) structural units, from a dispersibility viewpoint, when the total number of all structural units is set to 100 mol%, the content of the (B1-4) structural units in the total number of structural units of the copolymer (B1) is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 75 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 30 to 90 mol% is preferred, more preferably 50 to 90 mol%, even more preferably 60 to 80 mol%, and particularly preferably 60 to 75 mol%.

[0252] <Other structural units>

[0253] The copolymer (B1) may also have structural units other than (B1-1), (B1-2-1), (B1-2-2), (B1-3), and (B1-4) structural units. Other structural units may include, for example, those derived from: styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acryloyl chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonic glycidyl ether; and N-methacryloylmorpholine.

[0254] The proportion of other structural units in all structural units of the copolymer (B1) is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 1 mol% or less.

[0255] <Preparation Method>

[0256] The copolymer (B1) is preferably a random copolymer, graft copolymer, or block copolymer from which the monomers that form the structural units described above are derived, and more preferably a block copolymer. By being a block copolymer, the copolymer (B1) can contain blocks with pigment affinity and blocks with solvent affinity.

[0257] These copolymers can be manufactured using known methods. For example, living polymerization methods can be used, including anionic living polymerization, cationic living polymerization, and free radical living polymerization.

[0258] In the synthesis of copolymer (B1), for example, Japanese Patent Application Publication No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.C. Anderson, G.D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al. al, Polym.J.18,1037 (1986), Koichi Uezu, Koichi Hatada, Polymer Processing, 36,366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Proceedings of the Polymer Conference, 46,189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109,4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43,300 (1985), DY Sogoh, W. R. Hertler et al, Macromolecules, 20,1473 (1987), Methods described in Japanese Patent Application Publication No. 2013-119568, Japanese Patent Application Publication No. 2017-182092, Japanese Patent Application Publication No. 2017-019937, and International Publication No. 2019 / 107020.

[0259] From the viewpoint of further improving dispersibility, the copolymer (B1) is preferably a block copolymer having A blocks and B blocks, wherein the A blocks have (B1-2-1) structural units and (B1-2-2) structural units, and the B blocks do not have (B1-2-1) structural units and (B1-2-2) structural units. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. By being a block copolymer, there is a tendency to increase the affinity for solvents, enhance the adsorption of pigments, and significantly improve the dispersing ability of the dispersant. The A-block / B-block ratio is preferably 1 / 99 to 80 / 20 (mass ratio), and more preferably 5 / 95 to 60 / 40 (mass ratio).

[0260] The amount of quaternary ammonium groups in 1g of copolymer (B1) is preferably 0.1 to 10 mmol. By setting it within this range, there is a tendency to ensure good dispersibility.

[0261] <Physical properties>

[0262] The amine value of the copolymer (B1) is preferably 1 to 100 mg KOH / g, and from the viewpoint of dispersibility, it is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, and even more preferably 50 mg KOH / g or more. Furthermore, it is preferably 90 mg KOH / g or less, more preferably 80 mg KOH / g or less, and even more preferably 75 mg KOH / g or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 100 mg KOH / g, more preferably 10 to 90 mg KOH / g, even more preferably 30 to 80 mg KOH / g, and particularly preferably 50 to 75 mg KOH / g.

[0263] The amine value of the copolymer (B1) is expressed by the mass of KOH equivalent to the amount of alkali per 1g of the solid component containing the copolymer (B1) (hereinafter also referred to as the "dispersant sample") after solvent removal, and is determined by the following method.

[0264] Accurately weigh 0.5–1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titration apparatus equipped with a pH electrode, neutralize and titrate the solution with 0.1 mol / L HClO4 acetic acid solution. Take the inflection point of the pH titration curve as the titration endpoint and calculate the amine value using the following formula.

[0265] Amine value [mgKOH / g] = (561 × V) / (W × S) [where W: represents the amount of dispersant sample weighed [g], V: represents the titration volume at the titration endpoint [mL], and S: represents the concentration of solid components in the dispersant sample [mass %].]

[0266] The acid value of copolymer (B1) also depends on the presence and type of acidic groups that contribute to its acid value. A low acid value is preferred, preferably below 10 mg KOH / g, and more preferably below 1 mg KOH / g. There is no particular limitation on the lower limit, for example, 0 mg KOH / g.

[0267] The weight-average molecular weight (Mw) of the copolymer (B1) is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more. Furthermore, it is preferably 50000 or less, more preferably 20000 or less, and further preferably 15000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 50000, more preferably 3000 to 50000, further preferably 4000 to 20000, and particularly preferably 5000 to 15000. By setting it above the lower limit, there is a tendency for better dispersibility. By setting it below the upper limit, there is a tendency for viscosity changes to be less likely.

[0268] [1-1-2-2] Other dispersants

[0269] As other dispersants, polymeric dispersants with functional groups are preferred. Furthermore, considering dispersion stability, polymeric dispersants having the following groups are preferred, for example: carboxyl, phosphate, sulfonic acid, or their salts; primary, secondary, or tertiary amino groups; quaternary ammonium salt groups; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. From the viewpoint that pigments can be dispersed with a small amount of dispersant, polymeric dispersants having the following basic functional groups are particularly preferred: primary, secondary, or tertiary amino groups; quaternary ammonium salt groups; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine.

[0270] Other dispersants include, for example: (meth)acrylic acid copolymer dispersants other than copolymer (B1), urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants containing monomers and macromonomers having amino groups, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

[0271] Other specific examples of dispersants include, for instance, trade names such as 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.).

[0272] Polymer dispersants can be used alone or in combination with two or more.

[0273] The weight-average molecular weight (Mw) of other dispersants is preferably 700 or more, more preferably 1000 or more, and further preferably 100,000 or less, more preferably 50,000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 700 to 100,000, more preferably 1000 to 50,000.

[0274] From the viewpoint of pigment dispersibility, when the dispersant (B) contains other dispersants, it is preferable to include any one or both of the following: (meth)acrylic acid copolymer dispersants other than copolymer (B1) and urethane polymeric dispersants having functional groups. It is particularly preferable to include (meth)acrylic acid copolymer dispersants other than copolymer (B1).

[0275] From the perspectives of dispersibility and preservation, polymeric dispersants with basic functional groups and either or both of polyester bonds and polyether bonds are preferred.

[0276] Other than copolymers (B1), examples of (meth)acrylic acid-based copolymer dispersants and urethane-based polymeric dispersants include DISPERBYK-160~167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116, and BYK-LPN6919 (all acrylic-based) (all manufactured by BYK-Chemie).

[0277] (B) The proportion of the dispersant is not particularly limited, but relative to the total solid content of the photosensitive coloring composition, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 8% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.5 to 3% by mass, and particularly preferably 0.5 to 2% by mass. By setting it to the lower limit or above, there is a tendency to suppress the formation of residues from agglomerates. By setting it to the upper limit or below, there is a tendency to improve ink repellency and developability.

[0278] [1-1-3] (C) Alkali-soluble resin

[0279] The photosensitive coloring composition of the present invention contains (C) an alkali-soluble resin.

[0280] In this invention, the alkali-soluble resin (C) is any alkali-soluble resin that can be developed with an alkali developer, and there is no particular limitation. Various resins having carboxyl or hydroxyl groups can be listed as alkali-soluble resins, but from the viewpoint of excellent developability, alkali-soluble resins having carboxyl groups are preferred.

[0281] Furthermore, from the viewpoint of improving substrate adhesion, alkali-soluble resins having olefin unsaturated groups are preferred. By having olefin unsaturated groups, photocuring based on exposure occurs, resulting in a more robust film.

[0282] (C) The alkali-soluble resin preferably includes the acrylic copolymer resin shown below (C1) from the viewpoint of ink repellency, preferably includes the epoxy (meth) acrylate resin (C2) from the viewpoint of pattern linearity, and preferably includes the resin (C3) from the viewpoint of curability at low temperature.

[0283] [1-1-3-1] Acrylic copolymer resin (C1)

[0284] As an acrylic copolymer resin (C1), it is preferable to have olefinic unsaturated groups on the side chain.

[0285] Furthermore, the acrylic copolymer resin (C1) preferably has the (C1-1) structural unit shown below. Preferably, in addition to having the (C1-1) structural unit, the acrylic copolymer resin (C1) also has one or more of the (C1-2), (C1-3) structural units shown below.

[0286] <(C1-1) Structural Unit>

[0287] The (C1-1) structural unit is the structural unit shown in the following general formula (C1-1).

[0288] By giving the acrylic copolymer resin (C1) a (C1-1) structural unit, there is a tendency for the membrane to maintain its flexibility and for free radicals to diffuse easily.

[0289] [Chemical Formula 15]

[0290]

[0291] In equation (C1-1), R c1 and R c2 Each atom can be represented independently as a hydrogen atom or a methyl group. * indicates a bonded bond.

[0292] In the partial structure shown in formula (C1-1), from the viewpoint of sensitivity and alkali developability, the partial structure shown in the following general formula (C1-1-1) is preferred (hereinafter also referred to as "(C1-1-1) structural unit").

[0293] [Chemical Formula 16]

[0294]

[0295] In equation (C1-1-1), R c1 and R c2 Each can independently represent a hydrogen atom or a methyl group, R X It represents a hydrogen atom or a polyacid residue.

[0296] In formula (C1-1-1), a polybasic acid residue refers to a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. 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, inner methylene tetrahydrophthalic acid, chloramphenic acid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.

[0297] 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.

[0298] The proportion of (C1-1) structural units contained in the acrylic copolymer resin (C1) is not particularly limited. However, the total molar percentage of the structural units relative to the acrylic copolymer resin (C1) is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, even more preferably 60 mol% or more, particularly preferably 70 mol% or more, especially preferably 80 mol% or more. Furthermore, it is preferably 99 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 10–99 mol%, preferably 30–95 mol%, more preferably 50–95 mol%, further preferably 60–95 mol%, even more preferably 70–95 mol%, and especially preferably 80–90 mol%. Setting the value above the lower limit tends to improve ink repellency and penetration resistance. Setting the value below the upper limit tends to improve developability.

[0299] When the acrylic copolymer resin (C1) has a (C1-1-1) structural unit, its content ratio is not particularly limited. The total molar percentage relative to the total number of structural units of the acrylic copolymer resin (C1) is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, even more preferably 60 mol% or more, particularly preferably 70 mol% or more, especially preferably 80 mol% or more, and preferably 99 mol% or less, more preferably 95 mol% or less, and even more preferably 90 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 10–99 mol%, preferably 30–95 mol%, more preferably 50–95 mol%, further preferably 60–95 mol%, even more preferably 70–95 mol%, and especially preferably 80–90 mol%. Setting the value above the lower limit tends to improve ink repellency and penetration resistance. Setting the value below the upper limit tends to improve developability.

[0300] <(C1-2) Structural Unit>

[0301] (C1-2) The structural unit is the structural unit shown in the following general formula (C1-2).

[0302] By giving the acrylic copolymer resin (C1) a (C1-2) structural unit, there is a tendency for it to have high substrate adhesion and ink repellency.

[0303] [Chemical Formula 17]

[0304]

[0305] In equation (C1-2), R c3 R represents a hydrogen atom or a methyl group. c4The term indicates an alkyl group optionally having a substituent, an aromatic cycloal group optionally having a substituent, or an alkenyl group optionally having a substituent.

[0306] In equation (C1-2), R c4 The term indicates an alkyl group optionally having a substituent, an aromatic cycloal group optionally having a substituent, or an alkenyl group optionally having a substituent.

[0307] As R c4 The alkyl group in the film can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, even more preferably 5 or more, particularly preferably 8 or more, and more preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferred, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12. By setting the value above the lower limit, there is a tendency for increased film strength and improved substrate adhesion. By setting the value below the upper limit, there is a tendency for improved developability.

[0308] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of reproducibility, dicyclopentyl or dodecyl is preferred, and dicyclopentyl is more preferred.

[0309] Examples of substituents that may be optionally present as alkyl groups include: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred, while from the viewpoint of substrate adhesion and ease of synthesis, unsubstituted groups are preferred.

[0310] As R c4 The aromatic cyclic group in the sample can be a monovalent aromatic hydrocarbon cyclic group or a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is 6 to 24, preferably 6 to 22, more preferably 6 to 20, and even more preferably 6 to 18. By setting it above the lower limit, there is a tendency to improve substrate adhesion. By setting it below the upper limit, there is a tendency to reduce residue.

[0311] Aromatic hydrocarbon rings, which are the cyclic groups of aromatic hydrocarbons, can be monocyclic or fused rings. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetraphenylene ring, pyrene ring, benzo[a]pyrene ring, cyclopentadiene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.

[0312] Aromatic heterocycles, as part of aromatic heterocyclic groups, can be monocyclic or fused rings. Examples include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazolium ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanolopyrrole ring, furanolofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazolium ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, borazolinium ring, quinoxaline ring, phenanthridine ring, naphthalene-intercalated diazoxide ring, quinazoline ring, quinazolineone ring, and azurite ring.

[0313] From the viewpoint of radioactivity, the aromatic ring in the aromatic ring group is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

[0314] Examples of substituents that may be optionally present in the aromatic cyclic group include: methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluorine, hydroxyl, amino, epoxy, polyethylene glycol, phenyl, and carboxyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred; from the viewpoint of substrate adhesion and ease of synthesis, unsubstituted groups are preferred.

[0315] As R c4 The alkenyl group in the form can be linear, branched, or cyclic. It has 2 or more carbon atoms, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is 2 to 22, preferably 2 to 20, more preferably 2 to 18, even more preferably 2 to 16, and even more preferably 2 to 14. By setting it to the lower limit or above, there is a tendency to improve substrate adhesion. By setting it to the upper limit or below, there is a tendency to reduce residue.

[0316] Examples of substituents that may be optionally present in the alkenyl group include: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, polyethylene glycol, phenyl, and carboxyl. From the viewpoint of reproducibility, hydroxyl and polyethylene glycol groups are preferred, while from the viewpoint of substrate adhesion and ease of synthesis, unsubstituted groups are preferred.

[0317] From the perspective of developability and film strength, R c4 Preferably, it is an unsubstituted alkyl group or an unsubstituted alkenyl group, and more preferably an unsubstituted alkyl group.

[0318] When the acrylic copolymer resin (C1) has (C1-2) structural units, its content ratio is not particularly limited. The total molar percentage relative to the total number of structural units of the acrylic copolymer resin (C1) is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 70 mol% or less, more preferably 50 mol% or less, even more preferably 30 mol% or less, and even more preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is 1 to 70 mol%, preferably 2 to 50 mol%, more preferably 2 to 30 mol%, and even more preferably 2 to 10 mol%. By setting it above the lower limit, there is a tendency for improved substrate adhesion and ink repellency. By setting it below the upper limit, there is a tendency for improved developability.

[0319] <(C1-3) Structural Unit>

[0320] (C1-3) The structural unit is the structural unit shown in the following general formula (C1-3).

[0321] By giving acrylic copolymer resin (C1) (C1-3) structural units, there is a tendency to improve heat resistance and film strength.

[0322] [Chemical Formula 18]

[0323]

[0324] In equation (C1-3), R c5 R represents a hydrogen atom or a methyl group. c6 This indicates an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group optionally having a substituent, a halogen atom, an alkoxy group optionally having a substituent, a mercapto group optionally having a substituent, or an alkylthio group optionally having a substituent. t represents an integer from 0 to 5. When t represents an integer greater than 2, multiple R groups... c6 They can be the same or different.

[0325] In equation (C1-3), R c6 The term indicates an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group optionally having a substituent, a halogen atom, an alkoxy group optionally having a substituent, a mercapto group optionally having a substituent, or an alkylthio group optionally having a substituent.

[0326] As R c6The alkyl group in the sample can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 3 or more, even more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it can be 1 to 20, preferably 1 to 18, more preferably 3 to 16, and even more preferably 5 to 14. By setting it to the lower limit or above, there is a tendency to improve substrate adhesion. By setting it to the upper limit or below, there is a tendency to reduce residue.

[0327] Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of reproducibility and film strength, dicyclopentyl or dodecyl is preferred, and dicyclopentyl is more preferred.

[0328] Examples of substituents that may be optionally present in the alkyl group include: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of reproducibility, unsubstituted groups are preferred.

[0329] As R c6 The alkenyl group in the form can be linear, branched, or cyclic. It has 2 or more carbon atoms, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is 2 to 22, preferably 2 to 20, more preferably 2 to 18, even more preferably 2 to 16, and even more preferably 2 to 14. Setting it to the lower limit or above tends to improve substrate adhesion. Setting it to the upper limit or below tends to improve developability.

[0330] Examples of substituents that may be optionally present in the alkenyl group include: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of improving reproducibility, unsubstituted groups are preferred.

[0331] As R c6The alkynyl group in the compound can be linear, branched, or cyclic. It has 2 or more carbon atoms, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. The upper and lower limits described above can be combined arbitrarily. For example, it is 2 to 22, preferably 2 to 20, more preferably 2 to 18, even more preferably 2 to 16, and even more preferably 2 to 14. Setting the value above the lower limit tends to improve substrate adhesion. Setting the value below the upper limit tends to improve developability.

[0332] Substituents optionally present in the alkynyl group include, for example, methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, and carboxyl groups. From the viewpoint of improving reproducibility, unsubstituted groups are preferred.

[0333] As R c6 Halogen atoms in the ink can be, for example, fluorine, chlorine, bromine, and iodine atoms. From the viewpoint of ink repellency, fluorine atoms are preferred.

[0334] As R c6 The alkoxy group in the sample can be linear, branched, or cyclic. It has 1 or more carbon atoms, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, and still more preferably 14 or less, particularly preferably 12 or less. The upper and lower limits described above can be combined arbitrarily. For example, it can be 1 to 20, preferably 1 to 18, more preferably 1 to 16, even more preferably 1 to 14, and still more preferably 1 to 12. Setting the value above the lower limit tends to improve substrate adhesion. Setting the value below the upper limit tends to improve developability.

[0335] Examples of substituents that may be optionally present in the alkoxy group include: methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of improving reproducibility, unsubstituted groups are preferred.

[0336] As R c6The alkyl thio group in the form can be linear, branched, or cyclic. It preferably has 1 or more carbon atoms, more preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it can be 1 to 20, preferably 1 to 18, more preferably 1 to 16, even more preferably 1 to 14, and even more preferably 1 to 12. Setting it above the lower limit tends to improve substrate adhesion. Setting it below the upper limit tends to improve developability.

[0337] Substituents optionally present in the alkyl group of the alkylthio group include, for example, methoxy, ethoxy, chloro, bromo, fluorine, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl. From the viewpoint of improving reproducibility, unsubstituted groups are preferred.

[0338] R c6 The term indicates an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group optionally having a substituent, a halogen atom, an alkoxy group, a hydroxyalkyl group, a mercapto group, or an alkylthio group optionally having a substituent. From the viewpoint of improving reproducibility, hydroxyl and carboxyl groups are preferred, and carboxyl groups are more preferred.

[0339] In equation (C1-3), t represents an integer from 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.

[0340] When the acrylic copolymer resin (C1) has (C1-3) structural units, its content ratio is not particularly limited. The total molar percentage of the acrylic copolymer resin (C1) structural units is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 2 mol% or more, and particularly preferably 4 mol% or more. Furthermore, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 6 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is 0.5 to 50 mol%, preferably 1 to 30 mol%, more preferably 1 to 20 mol%, further preferably 2 to 10 mol%, and even more preferably 4 to 6 mol%. Setting it above the lower limit tends to improve film uniformity. Setting it below the upper limit tends to improve developability.

[0341] <(C1-4) Structural Unit>

[0342] The (C1-4) structural unit is the structural unit shown in the following general formula (C1-4).

[0343] By giving acrylic copolymer resin (C1) (C1-4) structural units, there is a tendency to improve its developability.

[0344] [Chemical Formula 19]

[0345]

[0346] In equation (C1-4), R c7 It represents a hydrogen atom or a methyl group.

[0347] When the acrylic copolymer resin (C1) has (C1-4) structural units, its content ratio is not particularly limited. The total molar percentage relative to the total number of structural units of the acrylic copolymer resin (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it is 5 to 80 mol%, preferably 10 to 70 mol%, more preferably 20 to 60 mol%. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve ink repellency.

[0348] <Double bond equivalent>

[0349] The double bond equivalent of the acrylic copolymer resin (C1) is 400 g / mol or less, preferably 350 g / mol or less, more preferably 300 g / mol or less, and even more preferably 270 g / mol or less. Furthermore, it is preferably 80 g / mol or more, more preferably 100 g / mol or more, even more preferably 150 g / mol or more, and particularly preferably 200 g / mol or more. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is 80–400 g / mol, preferably 100–350 g / mol, more preferably 150–300 g / mol, and even more preferably 200–270 g / mol. Setting it below the upper limit tends to increase ink repellency. Setting it above the lower limit tends to increase developability.

[0350] The double bond equivalent of acrylic copolymer resin (C1) can be calculated using the following formula.

[0351] (Double bond equivalent of acrylic copolymer (C1)) = (Weight-average molecular weight of acrylic copolymer (C1)) / (Number of olefinic unsaturated double bonds per molecule of acrylic copolymer (C1))

[0352] <Physical properties>

[0353] The acid value of the acrylic copolymer resin (C1) is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, further preferably 20 mg KOH / g or more, and even more preferably 25 mg KOH / g or more. Furthermore, it is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, further preferably 90 mg KOH / g or less, even more preferably 60 mg KOH / g or less, and particularly preferably 40 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is 10–150 mg KOH / g, preferably 15–120 mg KOH / g, more preferably 20–90 mg KOH / g, further preferably 20–60 mg KOH / g, and even more preferably 20–40 mg KOH / g. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve penetration resistance and substrate adhesion.

[0354] The weight-average molecular weight (Mw) of the acrylic copolymer resin (C1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 4000 or more, even more preferably 6000 or more, particularly preferably 7000 or more. Furthermore, it is preferably 30000 or less, more preferably 20000 or less, further preferably 15000 or less, and even more preferably 10000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is 1000 to 30000, preferably 2000 to 20000, more preferably 4000 to 20000, further preferably 6000 to 15000, even more preferably 7000 to 15000, and particularly preferably 7000 to 10000. Setting it above the lower limit tends to improve substrate adhesion and impermeability. Setting it below the upper limit tends to improve developability.

[0355] (C) The proportion of acrylic copolymer resin (C1) contained in the alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it is 10 to 100% by mass, preferably 20 to 95% by mass, more preferably 30 to 90% by mass, even more preferably 40 to 85% by mass, and even more preferably 50 to 85% by mass. By setting it to the lower limit or above, there is a tendency for improved ink repellency and penetration resistance. By setting it to the upper limit or below, there is a tendency for improved developability and the ability to form fine, high-precision spacers with narrow linewidths.

[0356] When the alkali-soluble resin (C) contains acrylic copolymer resin (C1), if the alkali-soluble resin (C) contains at least one of epoxy (meth)acrylate resin (C2) and resin (C3) described later, in addition to acrylic copolymer resin (C1), when the total content ratio of acrylic copolymer resin (C1), epoxy (meth)acrylate resin (C2) and resin (C3) is set to 100% by mass, the content ratio of acrylic copolymer resin (C1) is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, and further preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the concentration is 10-99% by mass, preferably 30-95% by mass, more preferably 50-90% by mass, even more preferably 60-85% by mass, and still more preferably 70-85% by mass. Setting the concentration above the lower limit tends to improve ink repellency and penetration resistance. Setting the concentration below the upper limit tends to improve substrate adhesion.

[0357] It should be noted that, for example, the resins described in Japanese Patent Application Publication No. 8-297366 and Japanese Patent Application Publication No. 2001-89533 can be cited as examples of acrylic copolymer resins (C1).

[0358] [1-1-3-2] Epoxy (meth)acrylate resin (C2)

[0359] Epoxy (meth)acrylate resin (C2) is a resin obtained by adding an olefinically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting a compound containing an isocyanate group, and then further reacting it with a polybasic acid or its anhydride. For example, a resin obtained by ring-opening addition of the carboxyl group of an unsaturated monocarboxylic acid to the epoxy group of an epoxy resin, thereby adding an olefinically unsaturated group to the epoxy resin via an ester bond (-COO-), and then adding a carboxyl group from a polybasic acid anhydride to the hydroxyl group generated at this time. Another example is a resin obtained by simultaneously adding a polyol during the addition of the polybasic acid anhydride.

[0360] The resin obtained by further reacting the carboxyl group of the resin obtained through the above reaction with a compound having a reactive functional group is also included in the above epoxy (meth)acrylate resin (C2).

[0361] Examples of epoxy resins include: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic varnish epoxy resin, cresol phenolic varnish epoxy resin, biphenolic varnish epoxy resin, triphenol epoxy resin, polymeric epoxy resin of phenol and dicyclopentadiene, dihydroxyfluorene type epoxy resin, dihydroxyalkyloxyfluorene type epoxy resin, diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene, and diglycidyl ether of 1,1-bis(4'-hydroxyphenyl)adamantane. Epoxy resins with an aromatic ring in the main chain are preferred.

[0362] From the viewpoint of heat resistance, bisphenol A epoxy resin, phenolic varnish epoxy resin, cresol varnish epoxy resin, polymeric epoxy resin of phenol and dicyclopentadiene, and diglycidyl ether of 9,9-bis(4'-hydroxyphenyl)fluorene are preferred as epoxy resins, with bisphenol A epoxy resin being even more preferred.

[0363] As epoxy resins, the following are preferably used: bisphenol A type epoxy resins (e.g., "jER828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Group, and "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resins (e.g., "jER807", "jER4004P", "jER4005P", "jER4007P" manufactured by Mitsubishi Chemical Group, and "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., Mitsubishi Chemical...). Group's "jERYX-4000"), phenolic varnish-type epoxy resins (e.g., Nippon Kayaku Co., Ltd.'s "EPPN-201", Mitsubishi Chemical) Group's "jER152", "jER154", Dow Chemical's "DEN-438", (ortho, meta, para) cresol phenolic varnish epoxy resins (e.g., Nippon Kayaku Co.'s "EOCN-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g., Nissan Chemical Co.'s "TEPIC"), triphenol methane type epoxy resins (e.g., Nippon Kayaku Co.'s "EPPN-501", "EPPN-502", "EPPN-503"), alicyclic epoxy resins (Daicel's "CELLOXIDE 2021P", "CELLOXIDE"), etc. EHPE”), epoxy resins obtained by glycidizing phenolic resins obtained from the reaction of dicyclopentadiene and phenol (e.g., “EXA-7200” manufactured by DIC Corporation, “NC-7300” and “XD-1000” manufactured by Nippon Kayaku Co., Ltd.), biphenyl-type epoxy resins (e.g., “NC-7000” manufactured by Nippon Kayaku Co., Ltd.), “E-201” manufactured by Osaka Organic Chemical Industry Co., Ltd., more preferably “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “NC-3000” manufactured by Nippon Kayaku Co., Ltd., “ESF-300” manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and “E-201” manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0364] Epoxy resin can be used alone or in combination with two or more types.

[0365] Examples of olefinically unsaturated monocarboxylic acids include: (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, and the reaction product of (meth)acrylic acid and ε-caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.

[0366] Alkene unsaturated monocarboxylic acids can be used alone or in combination with two or more.

[0367] Examples of polybasic acids (anhydrides) include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and their anhydrides. From the viewpoint of suppressing venting from the cured product and ensuring long-term reliability, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.

[0368] Polybasic acids (anhydrides) can be used alone or in combination with two or more.

[0369] By using polyols, the molecular weight of epoxy (meth)acrylate resin (C2) can be increased, introducing branches into the molecule, and there is a tendency to achieve a balance between molecular weight and viscosity. Furthermore, there is a tendency to increase the introduction rate of acid groups into the molecule, making it easier to achieve a balance between sensitivity and substrate adhesion.

[0370] Preferred polyols include trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.

[0371] Polyols can be used alone or in combination with two or more.

[0372] In addition to the resins mentioned above, the resin described in Korean Patent Publication No. 10-2013-0022955 can also be cited as an epoxy (meth)acrylate resin (C2).

[0373] The acid value of the epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 50 mg KOH / g or more, even more preferably 70 mg KOH / g or more, particularly preferably 80 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, more preferably 180 mg KOH / g or less, further preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 110 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10–200 mg KOH / g, more preferably 30–180 mg KOH / g, further preferably 50–150 mg KOH / g, even more preferably 70–120 mg KOH / g, and particularly preferably 80–110 mg KOH / g. By setting it to the lower limit or above, there is a tendency for improved developability. By setting the value below the aforementioned upper limit, there is a tendency for increased ink repellency and film strength.

[0374] The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, particularly preferably 3500 or more, and preferably 30000 or less, more preferably 15000 or less, further preferably 10000 or less, even more preferably 8000 or less, and particularly preferably 5000 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1000 to 15000, further preferably 2000 to 10000, even more preferably 3000 to 8000, and particularly preferably 3500 to 5000. Setting the value above the lower limit tends to improve ink repellency and film strength. Setting the value below the upper limit tends to reduce residue.

[0375] [1-1-3-3] Resin (C3)

[0376] The resin (C3) is a resin having the structural unit (C3-1) shown below. Preferably, the resin (C3) further has the structural unit (C3-2) shown below in addition to the structural unit (C3-1). Furthermore, the resin (C3) may also have structural units other than the structural units (C3-1 and C3-2) (other structural units).

[0377] <(C3-1) Structural Unit>

[0378] (C3-1) The structural unit is the structural unit shown in the following general formula (C3-1).

[0379] Although the (C3-1) structural unit is not as rigid as aromatic hydrocarbons, it is a three-dimensional structure with a large volume. It is believed that due to a certain degree of flexibility, the reaction points are close to each other during photo- or thermo-curing reactions, which will not excessively hinder the curing reaction. As a result, the large volume structure after curing exhibits impermeability.

[0380] [Chemical Formula 20]

[0381]

[0382] In equation (C3-1), R c11 ~R c14 Each can independently represent a hydrogen atom or a hydrocarbon group. p represents an integer from 0 to 2. * represents a bond.

[0383] In equation (C3-1), R c11 ~R c14 Each can be independently a hydrogen atom or a hydrocarbon group. Examples of hydrocarbon groups include: alkyl, alkenyl, alkynyl, aromatic cycloyl, and aralkyl.

[0384] The alkyl group can be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 3 or more, even more preferably 6 or more, and preferably 15 or less, even more preferably 8 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 15 is preferred, more preferably 3 to 15, and even more preferably 6 to 8. Setting the value above the lower limit tends to improve penetration resistance. Setting the value below the upper limit tends to improve developability.

[0385] Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0386] The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and further preferably 10 or less, more preferably 8 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 2 to 10 is preferred, more preferably 3 to 8. By setting it above the lower limit, there is a tendency for improved permeability resistance. By setting it below the upper limit, there is a tendency for improved developability.

[0387] Examples of alkenyl groups include: ethylene, allyl, butenyl, and pentenyl.

[0388] The number of carbon atoms in the alkynyl group is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and further preferably 10 or less, more preferably 8 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 2 to 10 is preferred, more preferably 3 to 8. By setting it above the lower limit, there is a tendency for improved penetration resistance. By setting it below the upper limit, there is a tendency for improved developability.

[0389] Examples of alkynyl groups include the acetylenic group.

[0390] Examples of aromatic cyclic groups include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Furthermore, it is 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. Setting the value above the lower limit tends to improve penetration resistance. Setting the value below the upper limit tends to improve developability.

[0391] Examples of aromatic cyclic groups include: phenyl, naphthyl, anthraceneyl, tolyl, and xylyl.

[0392] The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more. Furthermore, it is 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, 5 to 20 is preferred, more preferably 6 to 15, and even more preferably 7 to 10. Setting the value above the lower limit tends to improve penetration resistance. Setting the value below the upper limit tends to improve developability.

[0393] As an aralkyl group, examples include groups obtained by replacing one hydrogen atom of the alkyl group with the aforementioned aromatic cycloalkanes.

[0394] Examples of aralkyl groups include benzyl and phenethyl.

[0395] R c11 With R c14 They can also be connected to form a ring structure, R c12 With R c13 They can also be connected to form a ring structure.

[0396] From the perspective of ease of synthesis, R is preferred. c11 ~R c14 Any one of them is a hydrogen atom, more preferably R c11 ~R c14 It consists entirely of hydrogen atoms.

[0397] p represents an integer from 0 to 2. From the perspective of imaging properties, it is preferable that n is 0.

[0398] As structural units (C3-1), structural units represented by the following general formulas (C3-1-1) to (C3-1-3) can be listed. Among them, from the viewpoint of impermeability, the structural unit represented by the following general formula (C3-1-1) is more preferred.

[0399] [Chemical Formula 21]

[0400]

[0401] In equations (C3-1-1) to (C3-1-3), * represents a bond.

[0402] <(C3-2) Structural Unit>

[0403] (C3-2) structural units are structural units with carboxyl groups.

[0404] (C3-2) The structural unit only needs to have a carboxyl group, and its structure is not particularly limited. For example, repeating units derived from carboxylic acids containing unsaturated groups and carboxylic anhydrides containing unsaturated groups can be listed.

[0405] From the viewpoint of improving developability and resistance to penetration, the structural unit shown in the following general formula (C3-2-1) is preferred as the (C3-2) structural unit (hereinafter also referred to as the "(C3-2-1) structural unit").

[0406] [Chemical Formula 22]

[0407]

[0408] In equation (C3-2-1), R c15 * Represents a hydrogen atom or an organic group. * Represents a bond.

[0409] Examples of organic groups include alkyl groups optionally having substituents and aryl groups optionally having substituents. The number of carbon atoms in the organic group is preferably 1 to 18.

[0410] In R c15 When the carbon atom is an alkyl group, the number of carbon atoms is not particularly limited, but preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more. Furthermore, it is preferably 9 or less, and even more preferably 7 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 9 is preferred, more preferably 2 to 9, and even more preferably 4 to 7.

[0411] Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0412] In R c15 When the carbon atom is aryl, the number of carbon atoms is not particularly limited, but is preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. For example, 6 to 20 is preferred, more preferably 6 to 15, and even more preferably 6 to 10.

[0413] Examples of aryl groups include: phenyl, naphthyl, anthraceneyl, tolyl, and xylyl.

[0414] Substituents that may be optionally present in alkyl and aryl groups include, for example, hydroxyl and (meth)acryloyl groups.

[0415] From the perspective of impermeability, R c15 Preferably, it is an alkyl group having (meth)acryloyl group as a substituent, more preferably an organic group represented by the following general formula (C3-2-2).

[0416] [Chemical Formula 23]

[0417]

[0418] In equation (C3-2-2), R c16 Represents a hydrogen atom or a methyl group. e represents an integer from 1 to 5. * represents a bond.

[0419] In formula (C3-2-2), e represents an integer from 1 to 5. From the viewpoint of permeability resistance, e is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0420] As a structural unit (C3-2-1), it is more preferably any one of the structural units shown in the following general formulas (C3-2-3) to (C3-2-6), and is particularly preferably a structural unit shown in the following general formula (C3-2-3) or formula (C3-2-4).

[0421] [Chemical Formula 24]

[0422]

[0423] In equations (C3-2-3) to (C3-2-6), * represents a bond.

[0424] <Other structural units>

[0425] Other structural units are structural units other than structural units (C3-1) and (C3-2).

[0426] Other structural units are not limited, but for example, the structural units shown in the following general formulas (C3-3-1) to (C3-3-5) can be listed (hereinafter also referred to as "(C3-3-1) structural unit to (C3-3-5) structural unit").

[0427] [Chemical Formula 25]

[0428]

[0429] In equation (C3-3-1), R c15 Synonymous with equation (C3-2-1), in equations (C3-3-1) and (C3-3-2), R c17 Each can be used independently to represent a hydrogen atom or a methyl group.

[0430] * indicates a bond.

[0431] [Chemical Formula 26]

[0432]

[0433] In equation (C3-3-5), R c18 * indicates an alkyl group that may optionally have substituents. * indicates a bonded bond.

[0434] As R c18 Alkyl groups optionally having substituents, such as methyl, ethyl, propyl, and benzyl.

[0435] From the viewpoint of surface smoothness and impermeability, the resin (C3) preferably has (C3-1) structural units, (C3-2) structural units and (C3-3-1) structural units, and more preferably has (C3-1) structural units, (C3-2) structural units, (C3-3-1) structural units and (C3-3-4) structural units.

[0436] <Method for manufacturing resin (C3)>

[0437] There are no particular limitations on the manufacturing method of resin (C3), and existing known methods can be used. For example, it can be produced by the methods described in International Publication No. 2016 / 194619, Japanese Patent Application Publication No. 2017-057260, and International Publication No. 2022 / 264909.

[0438] The proportion of (C3-1) structural units in the resin (C3) is not particularly limited, but the total molar percentage of the structural units relative to the resin (C3) is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 20–80 mol% is preferred, more preferably 30–70 mol%, and even more preferably 40–60 mol%. Setting the value above the lower limit tends to improve permeability resistance. Setting the value below the upper limit tends to improve developability.

[0439] When the resin (C3) has a (C3-2-1) structural unit, its content ratio is not particularly limited. The total molar percentage of the structural units of the resin (C3) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. Furthermore, it is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 40 mol% is preferred, more preferably 10 to 30 mol%, and even more preferably 15 to 20 mol%. Setting it above the lower limit tends to improve developability. Setting it below the upper limit tends to improve permeability resistance.

[0440] When the resin (C3) has a (C3-3-1) structural unit, its content ratio is not particularly limited. The total molar percentage relative to the structural units of the resin (C3) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. Furthermore, it is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 40 mol% is preferred, more preferably 10 to 30 mol%, and even more preferably 15 to 20 mol%. Setting it above the lower limit tends to improve permeability resistance. Setting it below the upper limit tends to improve developability.

[0441] When the resin (C3) has (C3-3-4) structural units, its content ratio is not particularly limited. The total molar percentage of the structural units relative to the resin (C3) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. Furthermore, it is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 40 mol% is preferred, more preferably 10 to 30 mol%, and even more preferably 15 to 20 mol%. Setting the value above the lower limit tends to make synthesis easier. Setting the value below the upper limit tends to improve permeability and developability.

[0442] When the resin (C3) has (C3-2-1) structural units, (C3-3-1) structural units, and (C3-3-4) structural units, and the total content of the (C3-2-1) structural units, (C3-3-1) structural units, and (C3-3-4) structural units in the resin (C3) is set to 100 mol%, the content of the (C3-2-1) structural units is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 10 to 90 mol% is preferred, more preferably 20 to 70 mol%, and even more preferably 30 to 50 mol%. By setting the content above the lower limit, there is a tendency for improved developability. By setting the content below the upper limit, there is a tendency for improved permeability resistance.

[0443] The acid value of the resin (C3) is not particularly limited, but is preferably 10 mg KOH / g or more, more preferably 30 mg KOH / g or more, further preferably 50 mg KOH / g or more, and preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, further preferably 100 mg KOH / g or less, and particularly preferably 80 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. For example, 10–200 mg KOH / g is preferred, more preferably 10–150 mg KOH / g, further preferably 30–100 mg KOH / g, and particularly preferably 50–80 mg KOH / g. Setting the value above the lower limit tends to improve developability. Setting the value below the upper limit tends to improve substrate adhesion.

[0444] The weight-average molecular weight (Mw) of the resin (C3) is not particularly limited, but is preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, even more preferably 5000 or more, particularly preferably 6000 or more. Furthermore, it is preferably 35000 or less, more preferably 20000 or less, further preferably 15000 or less, and particularly preferably 10000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 2000 to 35000, more preferably 3000 to 35000, further preferably 4000 to 20000, even more preferably 5000 to 15000, and particularly preferably 6000 to 10000. Setting the value above the lower limit tends to improve substrate adhesion. Setting the value below the upper limit tends to improve developability.

[0445] The double bond equivalent of the resin (C3) is not particularly limited, but is preferably 200 g / mol or more, more preferably 300 g / mol or more, further preferably 400 g / mol or more, even more preferably 500 g / mol or more, particularly preferably 600 g / mol or more. Furthermore, it is preferably 1000 g / mol or less, more preferably 800 g / mol or less, and even more preferably 700 g / mol or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 200–1000 g / mol, more preferably 300–800 g / mol, further preferably 400–700 g / mol, even more preferably 500–700 g / mol, and particularly preferably 600–700 g / mol. Setting the value above the lower limit tends to improve developability. Setting the value below the upper limit tends to improve permeability resistance.

[0446] The double bond equivalent of resin (C3) can be calculated using the same method as the double bond equivalent of acrylic copolymer resin (C1).

[0447] The content of (C) alkali-soluble resin 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, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, even more preferably 30% by mass or more, especially preferably 35% by mass or more, most preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and even more preferably 60% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, further preferably 15 to 90% by mass, even more preferably 20 to 80% by mass, especially preferably 25 to 80% by mass, even more preferably 30 to 80% by mass, particularly preferably 35 to 70% by mass, and most preferably 40 to 60% by mass. By setting it to the lower limit or above, there is a tendency to reduce residue. By setting it below the aforementioned upper limit value, there is a tendency for ink repellency to increase.

[0448] The proportion of acrylic copolymer resin (C1) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the total solids content of the photosensitive coloring composition. Furthermore, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, further preferably 20 to 50% by mass, even more preferably 30 to 50% by mass, and particularly preferably 30 to 40% by mass. By setting it to the lower limit or above, there is a tendency for improved ink repellency. By setting it to the upper limit or below, there is a tendency for improved resolution of high-precision patterns.

[0449] The content of epoxy (meth)acrylate resin (C2) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 33% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% 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, 5 to 60% by mass is preferred, more preferably 10 to 55% by mass, further preferably 20 to 50% by mass, and particularly preferably 33 to 50% by mass. By setting it to the lower limit or above, there is a tendency to improve the resolution of high-precision patterns. By setting it to the upper limit or below, there is a tendency to improve ink repellency.

[0450] The content of resin (C3) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more, relative to the total solid content of the photosensitive coloring composition. Furthermore, it is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, further preferably 20 to 50% by mass, even more preferably 25 to 50% by mass, particularly preferably 30 to 50% by mass, and most preferably 30 to 40% by mass. By setting it to the lower limit or above, there is a tendency to suppress exudation during low-temperature firing. By setting it to the upper limit or below, there is a tendency to improve developability.

[0451] [1-1-4] (D) Photopolymerizable compounds

[0452] The photosensitive coloring composition of the present invention contains a (D) photopolymerizable compound. It is believed that by including the (D) photopolymerizable compound, the curability of the coating film is improved, and in addition, the ink repellency is improved.

[0453] Examples of photopolymerizable compounds include those having one or more olefinic unsaturated bonds within the molecule. For instance, compounds having two or more olefinic unsaturated bonds within the molecule are preferred, considering their polymerizability, crosslinking properties, and ability to amplify the difference in developer solubility between the exposed and unexposed areas. The olefinic unsaturated bonds are preferably derived from (meth)acryloyloxy groups, and (meth)acrylate compounds are more preferably photopolymerizable compounds.

[0454] In this invention, it is particularly desirable to use a polyfunctional olefin monomer having two or more olefinic unsaturated bonds in a single molecule. The number of olefinic unsaturated bonds in the polyfunctional olefin monomer is not particularly limited, but is preferably two or more, more preferably three or more, even more preferably five or more, and preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 7 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 2 to 15 is preferred, more preferably 2 to 10, even more preferably 3 to 8, and particularly preferably 5 to 7. By setting the value above the lower limit, there is a tendency for increased polymerizability and improved ink repellency. By setting the value below the upper limit, there is a tendency for better developability.

[0455] Examples of photopolymerizable compounds 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.

[0456] 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, and other aliphatic polyhydroxy compounds; methacrylates obtained by replacing the acrylates of these example compounds with methacrylates; itaconic acid esters obtained by replacing the acrylates of these example compounds with itaconic acid esters; crotonic acid esters obtained by replacing the acrylates of these example compounds with crotonic acid esters; and maleic acid esters obtained by replacing the acrylates of these example compounds with maleic acid esters.

[0457] 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.

[0458] Esters, obtained through the esterification reaction of polyhydroxy compounds such as aliphatic and aromatic polyhydroxy compounds with unsaturated and polycarboxylic acids, do not necessarily have to be a single substance. Representative examples include: condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; and condensates of acrylic acid, adipic acid, butanediol, and glycerol.

[0459] In addition, useful polyfunctional olefin monomers include: urethane (meth)acrylates obtained by reacting polyisocyanate compounds with hydroxyl-containing (meth)acrylates, or polyisocyanate compounds with polyols and hydroxyl-containing (meth)acrylates; epoxy acrylates, such as addition reactions of polyepoxides with hydroxyl (meth)acrylates or (meth)acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; and compounds containing ethylene such as diethylene phthalate.

[0460] Examples of the aforementioned carbamate (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 Group).

[0461] From the viewpoint of substrate adhesion and ink repellency of the spacer relative to the substrate, the (D) photopolymerizable compound is preferably an ester or urethane (meth) acrylate of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. More preferably, it is a dicarboxylic acid anhydride adduct of trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, 2-tri(meth)acryloyloxymethyl ethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol penta(meth)acrylate, or pentaerythritol tri(meth)acrylate.

[0462] (D) Photopolymerizable compounds can be used alone or in combination with two or more.

[0463] (D) The molecular weight of the photopolymerizable compound is not particularly limited, but from the viewpoint of ink repellency and the formation of finely spaced spacers with narrow linewidths, it is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, even more preferably 300 or more, particularly preferably 400 or more, especially preferably 500 or more, preferably 1000 or less, and more preferably 700 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 1000, more preferably 150 to 1000, further preferably 200 to 1000, even more preferably 300 to 700, especially preferably 400 to 700, and particularly preferably 500 to 700.

[0464] (D) The number of carbon atoms in the photopolymerizable compound is not particularly limited, but from the viewpoint of ink repellency and residue suppression, it is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, even more preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 7 to 50, more preferably 10 to 50, further preferably 15 to 40, even more preferably 20 to 35, and particularly preferably 25 to 30.

[0465] From the viewpoint of ink repellency and forming finely spaced walls with narrow line widths, ester (meth)acrylates, epoxy (meth)acrylates, and carbamate (meth)acrylates are preferred, and pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate, etc., which are trifunctional or higher ester (meth)acrylates; and adducts of trifunctional or higher ester (meth)acrylates and anhydrides, such as 2,2,2-tri(meth)acryloyloxymethyl ethyl phthalate and dipentaerythritol penta(meth)acrylate.

[0466] From the viewpoint of improving the permeability resistance of the spacer wall, it is preferable to use ester (meth)acrylates, epoxy (meth)acrylates, and carbamate (meth)acrylates with one or more hydroxyl groups in the molecule. More preferably, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol di(meth)acrylate. Additives of acrylates, glycerol, and glycidyl methacrylate (addition number 1-3); additives of pentaerythritol and glycidyl methacrylate (addition number 1-4); additives of dipentaerythritol and glycidyl methacrylate (addition number 1-6); additives of sorbitol and glycidyl methacrylate (addition number 1-6); additives of 3-buten-1,2-diol and glycidyl acrylate (addition number 2); reactants of bisphenol diglycidyl compounds with (meth)acrylic acid and their epoxide-modified derivatives. Two or more of these can also be used in combination.

[0467] (D) The hydroxyl equivalent of the photopolymerizable compound is preferably 1200 g / mol or less, more preferably 800 g / mol or less, further preferably 600 g / mol or less, even more preferably 400 g / mol or less, particularly preferably 350 g / mol or less, and most preferably 300 g / mol or less. Furthermore, it is preferably 100 g / mol or more, more preferably 150 g / mol or more, further preferably 200 g / mol or more, and particularly preferably 225 g / mol or more. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 100–1200 g / mol, more preferably 100–800 g / mol, further preferably 150–600 g / mol, even more preferably 200–400 g / mol, particularly preferably 225–350 g / mol, and most preferably 225–300 g / mol. By setting it below the upper limit, there is a tendency for improved developability and improved resistance to penetration of the spacer walls. By setting it above the lower limit, there is a tendency for improved ink repellency.

[0468] It should be noted that "hydroxyl equivalent" is defined as the number of grams of resin having 1 equivalent of hydroxyl groups.

[0469] The proportion of the (D) photopolymerizable compound in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, most preferably 25% by mass or more, and further preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 90% by mass, more preferably 1 to 80% by mass, further preferably 5 to 80% by mass, even more preferably 10 to 70% by mass, particularly preferably 15 to 60% by mass, especially preferably 20 to 60% by mass, and most preferably 25 to 50% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to form highly fine spacers with fine linewidths.

[0470] The proportion of (D) photopolymerizable compound relative to 100 parts by mass of (C) alkali-soluble resin is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, especially preferably 50 parts by mass or more, and preferably 200 parts by mass or less, more preferably 180 parts by mass or less, further preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, especially preferably 125 parts by mass or less, even more preferably 120 parts by mass or less, and especially preferably 105 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 200 parts by weight is preferred, more preferably 5 to 180 parts by weight, further preferably 10 to 160 parts by weight, even more preferably 15 to 140 parts by weight, particularly preferably 20 to 125 parts by weight, even more preferably 25 to 125 parts by weight, even more preferably 30 to 125 parts by weight, even more preferably 30 to 120 parts by weight, and especially preferably 50 to 105 parts by weight. By setting the value above the lower limit, there is a tendency for improved ink repellency. By setting the value below the upper limit, there is a tendency to form highly fine spacers with narrow linewidths.

[0471] [1-1-5] (E) Photopolymerization initiator

[0472] The photosensitive coloring composition of the present invention contains a (E) photopolymerization initiator. The (E) photopolymerization initiator is any compound that polymerizes the (D) photopolymerizable compound by active light, for example, any compound that polymerizes the olefinic unsaturated bonds present in the (A) photopolymerizable compound, and is not particularly limited.

[0473] The photosensitive coloring composition of the present invention can use a photopolymerization initiator commonly used in the art as the (E) photopolymerization initiator. Examples of such photopolymerization initiators include: metallocene compounds containing dititanium 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, halomethyltriazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, and other free radical activators and α-aminoalkylphenyl ketone derivatives as described in Japanese Patent Application Publication Nos. 2000-80068 and 2006-36750.

[0474] Examples of metallocene compounds include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl) titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl) titanium, dicyclopentadienyl bis(2,6-difluorophenyl) titanium, dicyclopentadienyl bis(2,4-difluorophenyl) titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl) titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl) titanium, and dicyclopentadienyl[2,6-di-fluoro-3-(pyrrolo-1-yl)-phenyl] titanium.

[0475] Examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazolium dimer.

[0476] Examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)ethylidene]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)ethylidene)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

[0477] 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.

[0478] Examples of α-aminoalkylphenyl ketone derivatives include: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butane-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.

[0479] As photopolymerization initiators, oxime ester compounds are effective, particularly considering sensitivity and printability. For example, in the case of using alkali-soluble resins containing phenolic hydroxyl groups, sensitivity becomes a disadvantage, making such highly sensitive oxime ester compounds especially useful. Oxime ester compounds exhibit high quantum yields in the photoreaction and high reactivity of the generated free radicals, thus achieving high sensitivity with small quantities. Furthermore, they are thermally stable, allowing for the production of highly sensitive photosensitive coloring compositions with minimal input.

[0480] Examples of oxime ester compounds include those represented by the general formula (E1).

[0481] [Chemical Formula 27]

[0482]

[0483] In equation (E1), R e1 R represents a hydrogen atom, an alkyl group optionally having substituents, or an aromatic cyclogroup optionally having substituents. e2 R represents any substituent containing an aromatic ring. e3 This indicates an alkyl acyl group or an aromatic acyl group that may optionally have substituents. q represents an integer of 0 or 1.

[0484] R e1 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 preferably 1 or more, more preferably 2 or more, and further 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, it is preferably 1 to 20, more preferably 2 to 15, and even more preferably 2 to 10.

[0485] Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, and cyclohexylmethyl.

[0486] Substituents optionally present in the alkyl group include, for example, aromatic cyclic groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl, and N-acetyl-N-acetoxyamino. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0487] As R e1The aromatic cyclic group in the aromatic cyclic group can include aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic cyclic 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. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.

[0488] 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.

[0489] Substituents that may be optionally present in an aromatic cyclic group include, for example, hydroxyl, carboxyl, halogen, amino, amide, alkyl, alkoxy, and groups formed by linking these substituents. From the viewpoint of reproducibility, alkyl, alkoxy, and groups formed by linking them are preferred, and linked alkoxy groups are more preferred.

[0490] From a sensitivity perspective, R e1 Preferably, it is an alkyl group that optionally has substituents or an aromatic cycloal group that optionally has substituents.

[0491] As R e2 Preferably, the substituted carbazoyl group, optionally substituted thioxanone group, or optionally substituted diphenyl sulfide group, optionally substituted fluorenyl group, or optionally substituted indole group are used. From the viewpoint of sensitivity, the optionally substituted carbazoyl group is more preferred.

[0492] R e3 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 preferably 2 or more, further preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and even more preferably 5 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, and even more preferably 2 to 5.

[0493] Examples of alkyl acyl groups include acetyl, propionyl, and butyryl.

[0494] Substituents that may be optionally present on the alkyl acyl group include, for example, 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.

[0495] R e3The number of carbon atoms in the aryl group is not particularly limited, but from the viewpoint of solubility and sensitivity in solvents, it is preferably 7 or more, further 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, 7 to 20 is preferred, more preferably 7 to 15, and even more preferably 7 to 10. Examples of aryl groups include benzoyl and naphthyl.

[0496] Substituents that may be optionally present in the aryl group include, for example, hydroxyl, carboxyl, halogen, amino, amide, and alkyl groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

[0497] From a sensitivity perspective, R e3 Preferably, it is an alkyl acyl group that optionally has a substituent, more preferably an unsubstituted alkyl acyl group, and even more preferably an acetyl group.

[0498] As a photopolymerization initiator (E), for example, the photopolymerization initiators described in Japanese Patent No. 4454067, International Publication No. 2002 / 100903, International Publication No. 2012 / 45736, International Publication No. 2015 / 36910, International Publication No. 2006 / 18973, International Publication No. 2008 / 78678, Japanese Patent No. 4818458, International Publication No. 2005 / 80338, International Publication No. 2008 / 75564, International Publication No. 2009 / 131189, International Publication No. 2010 / 133077, International Publication No. 2010 / 102502, and International Publication No. 2012 / 68879 can be used.

[0499] (E) Photopolymerization initiators can be used alone or in combination of two or more.

[0500] To improve sensitivity, sensitizing pigments and polymerization accelerators corresponding to the wavelength of the image exposure light source can be added to the (E) photopolymerization initiator as needed.

[0501] Examples of sensitizing pigments include: xanthones as described in Japanese Patent Application Publications Nos. 4-221958 and 4-219756; heterocyclic coumarin pigments as described in Japanese Patent Application Publications Nos. 3-239703 and 5-289335; 3-coumarinone compounds as described in Japanese Patent Application Publications Nos. 3-239703 and 5-289335; methylene pyrrole pigments as described in Japanese Patent Application Publications No. 6-19240; and Japanese Patent Application Publications Nos. 47-2528 and 54-15529. Pigments having a dialkylaminobenzene skeleton as described in Japanese Published Publication No. 2, Japanese Published Publication No. 45-37377, Japanese Published Publication No. 48-84183, Japanese Published Publication No. 52-112681, Japanese Published Publication No. 58-15503, Japanese Published Publication No. 60-88005, Japanese Published Publication No. 59-56403, Japanese Published Publication No. 2-69, Japanese Published Publication No. 57-168088, Japanese Published Publication No. 5-107761, Japanese Published Publication No. 5-210240, and Japanese Published Publication No. 4-288818.

[0502] As sensitizing pigments, amino-containing sensitizing pigments are preferred, and compounds having both an amino group and a phenyl group within the same molecule are more preferred. For example, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone are further preferred; 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)-1,3,4- Compounds containing p-dialkylaminophenyl, such as 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, (p-diethylaminophenyl)pyrimidine, etc., are particularly preferred to be 4,4'-dialkylaminobenzophenone.

[0503] Sensitizing pigments can be used alone or in combination with two or more.

[0504] As polymerization promoters, aromatic amines such as ethyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, ethylhexyl 4-dimethylaminobenzoate, acetophenone, and phenylacetone, as well as aliphatic amines such as n-butylamine, N-methyldiethanolamine, and ethyl 2-dimethylaminobenzoate can be used.

[0505] Polymerization accelerators can be used alone or in combination with two or more.

[0506] The proportion of the (E) photopolymerization initiator in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, even more preferably 12% by mass or less, particularly preferably 10% by mass or less, particularly preferably 8% by mass or less, and most preferably 7% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, further preferably 0.1 to 15% by mass, even more preferably 1 to 12% by mass, particularly preferably 1 to 10% by mass, particularly preferably 2 to 8% by mass, and most preferably 3 to 7% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to reduce residue.

[0507] The proportion of the photopolymerization initiator (E) to the photopolymerizable compound (D) in the photosensitive coloring composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, particularly preferably 5 parts by mass or more, especially preferably 6 parts by mass or more, even more preferably 8 parts by mass or more, most preferably 10 parts by mass or more, and further preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, especially preferably 30 parts by mass or less, and most preferably 20 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 200 parts by mass, more preferably 2 to 200 parts by mass, further preferably 3 to 200 parts by mass, even more preferably 4 to 100 parts by mass, especially preferably 5 to 100 parts by mass, especially preferably 6 to 50 parts by mass, even more preferably 8 to 50 parts by mass, even more preferably 10 to 30 parts by mass, and most preferably 10 to 20 parts by mass. Setting the value above the lower limit tends to increase ink repellency. Setting the value below the upper limit tends to reduce residue.

[0508] Chain transfer agents can also be used in conjunction with photopolymerization initiators. Examples of chain transfer agents include thiol-containing compounds and carbon tetrachloride. Considering the tendency for high chain transfer efficiency, thiol-containing compounds are preferred. This is believed to be because the low SH bond energy facilitates bond breaking, hydrogen abstraction, and chain transfer reactions. The use of chain transfer agents is effective in improving sensitivity and surface curing properties.

[0509] As a thiol-containing compound, it can have multiple thiol groups within its molecule. Examples of thiol-containing compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazolin, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene, and other thiol-containing compounds with aromatic rings; hexanedithiol, decandithiol, butylene glycol bis(3-mercaptopropionate), butylene glycol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dimercaptoacetate, trimethylolpropane tri(3-mercaptopropionate), ... Alkyltrimercaptoacetate, trihydroxyethyltrimercaptopropionate, pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tri(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tri(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and other aliphatic thiol-containing compounds.

[0510] As a thiol-containing compound with an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred. As an aliphatic thiol-containing compound, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetras(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetras(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

[0511] From the perspective of sensitivity, aliphatic compounds containing thiol groups are preferred, more preferably trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and even more preferably pentaerythritol tetra(3-mercaptopropionate) and pentaerythritol tetra(3-mercaptobutyrate).

[0512] Aliphatic thiol-containing compounds can be used alone or in combination with two or more.

[0513] From the viewpoint of increasing the cone angle, it is preferable to use one or more of the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole in combination with a photopolymerization initiator as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or a combination of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole can be used.

[0514] From a sensitivity perspective, it is preferable to use one or more of the group consisting of pentaerythritol tetra(3-mercaptopropionate) and pentaerythritol tetra(3-mercaptobutyrate). Furthermore, from a sensitivity perspective, it is preferable to use a combination of one or more of the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, one or more of the group consisting of pentaerythritol tetra(3-mercaptopropionate) and pentaerythritol tetra(3-mercaptobutyrate), and a photopolymerization initiator.

[0515] When the photosensitive coloring composition of the present invention contains a chain transfer agent, the proportion of the chain transfer agent is not particularly limited. It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and even more preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, and even more preferably 2% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, further preferably 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to form finely spaced walls with narrow linewidths.

[0516] When the photosensitive coloring composition of the present invention contains a chain transfer agent, the proportion of the chain transfer agent in the photosensitive coloring composition relative to the (E) photopolymerization initiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and further preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 5 to 500 parts by mass is preferred, more preferably 10 to 300 parts by mass, further preferably 15 to 100 parts by mass, and particularly preferably 20 to 50 parts by mass. By setting the value above the lower limit, there is a tendency to improve ink repellency. By setting the value below the upper limit, there is a tendency to form highly fine spacers with fine linewidth.

[0517] [1-1-6] (F) compound

[0518] The photosensitive coloring composition of the present invention preferably contains a compound having a crosslinking group and having fluorine atoms and / or siloxane chains (hereinafter also referred to as "(F) compound"). The (F) compound can be used as a liquid repellent. By containing the (F) compound in the photosensitive coloring composition, ink repellency (hereinafter also referred to as "liquid repellency") can be imparted to the upper surface of the resulting spacer wall. If the ink repellency is excellent, then, for example, when ink is ejected by inkjet, the ink between adjacent pixel portions formed by the spacer wall can be prevented from mixing with each other.

[0519] (F) The compound preferably comprises at least one of the compounds (F1) and (F2) shown below.

[0520] Compound (F1): A resin containing fluorine atoms with crosslinking groups.

[0521] Compound (F2): A resin containing crosslinking groups and siloxane chains.

[0522] <Compound (F1)>

[0523] Crosslinking groups present in a compound (F1) can be exemplified by, for example, epoxy groups, olefinic unsaturated groups, or active groups that generate free radicals through irradiation with active energy rays.

[0524] Examples of active groups that generate free radicals through irradiation with active energy rays include benzophenone, acetophenone, α-hydroxyketone, α-aminoketone, α-diketone, and α-diketone-dialkylacetal. Among these, α-hydroxyketone is preferred from the viewpoint that the wavelength distribution of the light source used in the exposure coincides with the absorbance spectrum of the active group.

[0525] From the viewpoint of ink repellency and ink wetting spread within the pixel, compound (F1) is preferably an acrylic copolymer resin.

[0526] From the viewpoint of suppressing the outflow of fluorine-containing resin into the developer, olefinic unsaturated groups are preferred as crosslinking groups.

[0527] It can be considered that by using a fluorine-containing resin with crosslinking groups, the crosslinking reaction on the surface of the formed coating can be accelerated during exposure. The fluorine-containing resin is not easy to flow out during the development process, resulting in the spacer wall exhibiting high ink repellency.

[0528] As a resin compound containing fluorine atoms (F1), the surface orientation of the spacer wall tends to prevent ink leakage and color mixing. More specifically, the fluorine-containing groups repel ink, thus preventing ink leakage and color mixing caused by ink crossing the spacer wall and entering adjacent areas.

[0529] From the viewpoint that resins containing fluorine atoms are more likely to orient on the surface of the spacer walls, indicating higher ink repellency and further preventing ink leakage and color mixing, resins containing fluorine atoms with crosslinking groups preferably have one or more of the following: fluoroalkyl, perfluoroalkyl, fluoroalkylene, perfluoroalkylene, fluoroalkylene ether chain, perfluoroalkylene ether chain, fluoroaromatic group, and perfluoroaromatic group. Among these, from the perspective of ink repellency, resins having perfluoroalkyl, perfluoroalkylene, perfluoroalkylene ether chain, or perfluoroaromatic group are more preferred.

[0530] Examples of fluoroalkyl groups include: fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, and fluorohexyl. Examples of perfluoroalkyl groups include: perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, and perfluorohexyl.

[0531] Examples of fluoroalkylene chains include: fluoromethyl chain, fluoroethyl chain, fluoropropylene chain, fluorobutylene chain, and fluorohexylene chain. Examples of perfluoroalkylene chains include: perfluoromethyl chain, perfluoroethyl chain, perfluoropropylene chain, perfluorobutylene chain, and perfluorohexylene chain.

[0532] Examples of perfluoroalkylene ether chains include: -CF2-O-, -(CF2)2-O-, -(CF2)3-O-, -CF2-C(CF3)O-, -C(CF3)-CF2-O-, and divalent groups having these repeating units. Examples of fluoroalkylene ether chains include those obtained by substituting a portion, but not all, of the F in a perfluoroalkylene ether chain with H.

[0533] Examples of fluoroaromatic groups include: fluorophenyl, fluoronaphthyl, and fluoroanthrayl. Examples of perfluoroaromatic groups include: perfluorophenyl, perfluoronaphthyl, and perfluoroanthrayl.

[0534] Examples of resins containing fluorine atoms and having crosslinking groups include: acrylic copolymer resins having epoxy groups and perfluoroalkyl groups; acrylic copolymer resins having epoxy groups and perfluoroalkylene ether chains; acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkyl groups; acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkylene ether chains; epoxy (meth)acrylate resins having epoxy groups and perfluoroalkyl groups; epoxy (meth)acrylate resins having epoxy groups and perfluoroalkylene ether chains; epoxy (meth)acrylate resins having olefinic unsaturated groups and perfluoroalkyl groups; and epoxy (meth)acrylate resins having olefinic unsaturated groups and perfluoroalkylene ether chains. From the viewpoint of ink repellency, acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkyl groups, and acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkylene ether chains are preferred. From the viewpoint of ink wetting and spreading within the pixel, acrylic copolymer resins having olefinic unsaturated groups and perfluoroalkyl groups are further preferred.

[0535] Commercially available resins containing fluorinated atoms and crosslinking groups can include, for example, fluorinated organic compounds commercially available under the following trade names: "MEGAFACE (registered trademark, hereinafter the same) F116", "MEGAFACE F120", "MEGAFACE F142D", "MEGAFACE F144D", "MEGAFACE F150", "MEGAFACE F160", "MEGAFACE F171", "MEGAFACE F172", "MEGAFACE F173", "MEGAFACE F177", "MEGAFACE F178A", "MEGAFACE F178K", ​​"MEGAFACE F179", "MEGAFACE F183", "MEGAFACE F184", "MEGAFACE F191", "MEGAFACE F812", "MEGAFACE F815", "MEGAFACE F824", "MEGAFACE F833", "MEGAFACE RS101 ...83", "MEGAFACE F184", "MEGAFACE F183", "MEGAFACE F184", "MEGAFACE F183", "MEGAFACE F184", "MEGAFACE F183", "MEGAFACE F184", "MEGAFACE F183", "MEGAFACE F183", "MEGAFACE F183", "MEGAFACE F183", "MEGAFACE F183", "MEGAFACE F183", "MEGAFACE F183", “RS102”, “MEGAFACE RS105”, “MEGAFACE RS201”, “MEGAFACE RS202”, “MEGAFACE RS301”, “MEGAFACE RS303”, “MEGAFACE RS304”, “MEGAFACERS401”, “MEGAFACE RS402”, “MEGAFACE RS501”, “MEGAFACE RS502”, “MEGAFACE RS-72-K”, “MEGAFACE RS-78”, “MEGAFACE RS-90”, “DEFENSA (registered trademark, same below) MCF300”, “DEFENSAMCF310”, “DEFENSA MCF312”, “DEFENSA MCF323”.

[0536] As acrylic copolymer resins with olefinic unsaturated groups and perfluoroalkyl groups, “MEGAFACE RS-72-K”, “MEGAFACE RS-78”, and “MEGAFACE RS-90” are preferred.

[0537] The proportion of fluorine atoms in the resin containing fluorine atoms with crosslinking groups 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 mass of the resin containing fluorine atoms with crosslinking groups. Furthermore, it is preferably 50% by mass or less, more preferably 35% 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 50% by mass, further preferably 15 to 35% by mass, and particularly preferably 20 to 35% by mass. By setting it to the lower limit or above, there is a tendency to suppress flow to the pixel portion. By setting it to the upper limit or below, there is a tendency to exhibit a high contact angle.

[0538] The molecular weight of the fluorinated resin with crosslinking groups is not particularly limited; it can be a low molecular weight compound or a high molecular weight compound. High molecular weight compounds are preferred because they can suppress exudation during development and flowability caused by post-baking, and can suppress flow from the spacer walls. When the fluorinated resin with crosslinking groups is a high molecular weight compound, the number average molecular weight of the fluorinated resin with crosslinking groups is preferably 100 or more, more preferably 500 or more, and even more preferably 1000 or more. Furthermore, it is preferably 150,000 or less, more preferably 130,000 or less, and even more preferably 100,000 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 150,000, more preferably 500 to 130,000, and even more preferably 1,000 to 100,000.

[0539] Furthermore, the weight-average molecular weight of the fluorinated resin having crosslinking groups is preferably 1000 or more, more preferably 5000 or more, and even more preferably 10000 or more. It is also preferably 150000 or less, more preferably 130000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1000 to 150000, more preferably 5000 to 130000, and even more preferably 10000 to 130000.

[0540] For example, examples include resins containing fluorine atoms described in Japanese Patent Application Publication No. 2012-72296, Japanese Patent Application Publication No. 2012-92308, International Publication No. 2019 / 107026, Japanese Patent Application Publication No. 2021-51235, Japanese Patent Application Publication No. 2010-140043, International Publication No. 2010 / 1976, and International Publication No. 2011 / 81150.

[0541] <Compound (F2)>

[0542] As a crosslinking group in compound (F2), the crosslinking group illustrated in the description of compound (F1) is preferably used.

[0543] The siloxane chain of compound (F2) is preferably a polysiloxane represented by the following general formula (F2).

[0544] R f1 R f2 R f3 Si-O-(SiR f4 R f5 -O) r -SiR f6 R f7 R f8

[0545] (F2) (In formula (F2), R) f1 R f2 R f3 R f4 R f5 R f6 R f7 and R f8 Each can independently represent a monovalent organic group or a hydrogen atom. r is an integer greater than or equal to 0.

[0546] As a monovalent organic group, it is preferably a hydrocarbon group with 1 to 10 carbon atoms, such as: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; alkenyl groups such as ethylene, allyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and phenethyl; and substituted alkyl groups such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, and nonafluorobutylethyl. These organic groups optionally have ester bonds.

[0547] r is an integer greater than or equal to 0, preferably greater than or equal to 5, more preferably greater than or equal to 10, and further preferably less than or equal to 2000, more preferably less than or equal to 1500, even more preferably less than or equal to 1000, even more preferably less than or equal to 500, and particularly preferably less than or equal to 300. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 5 to 2000 is preferred, more preferably 5 to 1500, even more preferably 5 to 1000, even more preferably 10 to 500, and particularly preferably 10 to 300. Setting the value above the lower limit tends to increase ink repellency. Setting the value below the upper limit tends to increase the uniformity of the coating film.

[0548] Commercially available resins containing crosslinking groups and siloxane chains can be, for example, compounds sold under trade names such as "BYK-UV3500 series" manufactured by BYK-Chemie and "8SS" series manufactured by Taisei Fine Chemical.

[0549] As compounds that have crosslinking groups and contain fluorine atoms and siloxane chains, examples include those commercially available under trade names such as the "8FS" series manufactured by Taisei Fine Chemical Co., Ltd., and the "KP" series manufactured by Shin-Etsu Chemical Co., Ltd.

[0550] Compound (F2) can be a compound containing both a fluorine atom and a siloxane chain in a single molecule, or a mixture of multiple compounds (F2).

[0551] Examples of compounds (F2) include those described in Japanese Patent Application Publication No. 2004-45910, International Publication No. 2010 / 1976, and International Publication No. 2013 / 31737.

[0552] When the photosensitive coloring composition of the present invention contains compound (F), the proportion of compound (F) in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% 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 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when the ink is applied to the pixel portion after forming the spacer.

[0553] When the photosensitive coloring composition of the present invention contains compound (F1), the content ratio of compound (F1) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more relative to the total solid content of the photosensitive coloring composition. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when the ink is applied to the pixel portion after forming the spacer.

[0554] When the photosensitive coloring composition of the present invention contains compound (F2), the content ratio of compound (F2) is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% 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 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and even more preferably 0.5 to 2% by mass. By setting it to the lower limit or above, there is a tendency to improve ink repellency. By setting it to the upper limit or below, there is a tendency to easily obtain a uniform coating film when the ink is applied to the pixel portion after forming the spacer.

[0555] In the photosensitive coloring composition of the present invention, surfactants may also be used with (F) compounds. Surfactants may be used, for example, to improve the coatability of the coating liquid as a photosensitive coloring composition and the developability of the coating film, and examples include fluorinated surfactants and organosilicon surfactants that do not have crosslinking groups.

[0556] In particular, considering that it has the function of removing the residue of the photosensitive coloring composition from the unexposed part during development and also has the function of exhibiting wetting properties, organosilicon surfactants are preferred, and polyether-modified organosilicon surfactants are even more preferred.

[0557] As a fluorinated surfactant without crosslinking groups, it is preferable to have a fluoroalkyl or fluoroalkylene group at at least one of the terminals, main chain, and side chain.

[0558] Commercially available fluorinated surfactants without crosslinking groups include, for example: BM Chemie's "BM-1000" and "BM-1100"; DIC's "MEGAFACE F142D", "MEGAFACE F172", "MEGAFACE F173", "MEGAFACE F183", "MEGAFACE F470", "MEGAFACE F475", "MEGAFACE F554", and "MEGAFACE F559"; NEOS's "DFX-18"; 3M Japan's "Fluorad FC430", "Fluorad FC431", "FC-4430", and "FC4432"; and AGC's "Asahi Guard (registered trademark) AG710", "Surflon (registered trademark, hereinafter the same) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", and "Surflon...". SC-104", "Surflon SC-105", "Surflon SC-106".

[0559] Commercially available silicone surfactants include, for example: "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032 Additive", and "SH8400" manufactured by Dow Corning Toray; and "BYK 323" and "BYK 330" manufactured by BYK-Chemie.

[0560] Surfactants can be used alone or in combination of two or more. Examples include combinations of silicone surfactants and fluorinated surfactants, combinations of silicone surfactants and special polymeric surfactants, and combinations of fluorinated surfactants and special polymeric surfactants. Combinations of silicone surfactants and fluorinated surfactants are preferred.

[0561] Examples of combinations of silicone-based and fluorinated surfactants include: NEOS's "DFX-18", BYK-Chemie's "BYK-300" or "BYK-330" and AGC SeimiChemical's "S-393"; Shin-Etsu Silicone's "KP340" and DIC's "F-554" or "F-559"; Dow Corning Toray's "SH7PA" and DAIKIN's "DS-401"; and NUC's "L-77" and 3M Japan's "FC4430".

[0562] As surfactants, in addition to fluorinated surfactants and organosilicon surfactants, they can also include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0563] [1-1-7] Ultraviolet absorbers

[0564] The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The purpose of adding the ultraviolet absorber is to control the photocuring distribution by absorbing specific wavelengths of the light source used for exposure. By adding the ultraviolet absorber, for example, it is possible to obtain the effect of forming fine spacers with narrow linewidths and eliminating residues remaining in the non-exposed areas after development.

[0565] As an ultraviolet absorber, from the viewpoint of hindering the light absorption of (E) photopolymerization initiators, for example, a compound with a maximum absorption value between wavelengths of 250 nm and 400 nm can be used.

[0566] Ideally, the ultraviolet absorber should contain either or both of benzotriazole and triazine compounds. It can be argued that by including either or both of benzotriazole and triazine compounds, the light absorption rate of the initiator at the bottom of the film is reduced, and the linewidth at the bottom of the coating is decreased, thereby enabling the formation of finely spaced septa with narrow linewidths.

[0567] Examples of benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, octyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, ethylhexyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl) Ester compounds of 5-chlorobenzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionic acid with C7-9 straight-chain and branched alkyl alcohols.

[0568] Commercially available benzotriazole compounds include, for example: SUMISORB (registered trademark, hereinafter the same) 200, SUMISORB 250, SUMISORB 300, SUMISORB 340, SUMISORB 350 (manufactured by Sumitomo Chemical); JF77, JF78, JF79, JF80, JF83 (manufactured by Jōhoku Chemical Industry); TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF); EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Yung-Kuang Chemical Industry, Taiwan, China); TOMISORB (registered trademark, same below) 100, TOMISORB600 (manufactured by API Corporation); SEESORB (registered trademark, same below) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by SHIPRO KASEI KAISHA); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0569] Examples of triazine compounds include 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-octoxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 2-ethylhexyl glycidyl ether, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. From the viewpoint of ink repellency and the formation of finely spaced walls with narrow lines, hydroxyphenyl triazine compounds are preferred.

[0570] Commercially available triazine compounds include, for example: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

[0571] Other ultraviolet absorbers include, for example: benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.

[0572] For example, the following can be listed: SUMISORB130 (manufactured by Sumitomo Chemical), EVESROB10, EVESROB11, EVESROB12 (manufactured by Yung-Kuang Chemical Industry, Taiwan), TOMISORB800 (manufactured by API Corporation); SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by SHIPRO KASEI). Benzophenone compounds such as those manufactured by KAISHA; benzoic acid ester compounds such as SUMISORB400 (manufactured by Sumitomo Chemical) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; and α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthol, 1,3-dihydroxynaphthol, and 1,4-dihydroxynaphthol. Naphthalene derivatives such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; anthracene and its derivatives such as anthracene and 9,10-dihydroxyanthracene; dyes such as azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, and p-aminobenzoic acid dyes. From the viewpoint of ink repellency, cinnamic acid derivatives and naphthalene derivatives are preferred, with cinnamic acid derivatives being particularly preferred.

[0573] From the viewpoint of cone shape, either or both of benzotriazole compounds and hydroxyphenyltriazine compounds are preferred, with benzotriazole compounds being particularly preferred.

[0574] Ultraviolet absorbers can be used alone or in combination with two or more.

[0575] When the photosensitive coloring composition of the present invention contains an ultraviolet absorber, the proportion of the absorber is not particularly limited. However, relative to the total solid content of the photosensitive coloring composition, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 15% by mass, more preferably 0.05 to 15% by mass, further preferably 0.1 to 10% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 1 to 3% by mass. By setting it to the lower limit or above, there is a tendency to form highly fine spacers with narrow linewidths. By setting it to the upper limit or below, there is a tendency for increased ink repellency.

[0576] When the photosensitive coloring composition of the present invention contains an ultraviolet absorber, the proportion of the ultraviolet absorber relative to the (E) photopolymerization initiator, specifically the amount of ultraviolet absorber relative to 100 parts by mass of the (E) photopolymerization initiator, is preferably 1 part by mass or more, more preferably 10 parts by mass or more, further preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and further preferably 500 parts by mass or less, more preferably 300 parts by mass or less, even more preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 1 to 500 parts by mass is preferred, more preferably 10 to 500 parts by mass, further preferably 30 to 300 parts by mass, even more preferably 50 to 200 parts by mass, and particularly preferably 80 to 100 parts by mass. By setting the value above the lower limit, there is a tendency to form highly fine spacers with narrow linewidths. By setting the value below the upper limit, there is a tendency for increased ink repellency.

[0577] [1-1-8] Polymerization inhibitors

[0578] The photosensitive coloring composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, free radical polymerization is hindered, and therefore there is a tendency to increase the cone angle of the resulting spacer wall.

[0579] 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 polymerization inhibition ability, hydroquinone, methoxyphenol, and methyl hydroquinone are preferred, and methyl hydroquinone is more preferred.

[0580] A polymerization inhibitor can be used alone or in combination with two or more.

[0581] Alkali-soluble resins manufactured according to the method for manufacturing alkali-soluble resins according to (C) sometimes contain polymerization inhibitors. In this case, the alkali-soluble resin can be used as is with the polymerization inhibitors already present, or a polymerization inhibitor, the same or different from the one contained in the resin, can be added further during the manufacture of the photosensitive coloring composition.

[0582] When the photosensitive coloring composition contains a polymerization inhibitor, the proportion of the inhibitor is not particularly limited. However, relative to the total solids content of the photosensitive coloring composition, it is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more. Furthermore, it is preferably 0.1% by mass or less, more preferably 0.08% by mass or less, and even more preferably 0.05% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.08% by mass, and even more preferably 0.01 to 0.05% by mass. By setting it above the lower limit, there is a tendency to increase the cone angle. By setting it below the upper limit, there is a tendency to increase ink repellency.

[0583] [1-1-9] Thermal polymerization initiator

[0584] The photosensitive coloring composition of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency to increase the degree of crosslinking of the film. Examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide.

[0585] Thermal polymerization initiators can be used alone or in combination with two or more.

[0586] When a thermal polymerization initiator is used in conjunction with a photopolymerization initiator in order to improve ink repellency and increase the crosslinking density of the film, it is preferable that the total proportion of these two initiators is equal to the proportion of the photopolymerization initiator in the photosensitive coloring composition. Furthermore, from the viewpoint of ink repellency, it is preferable that the proportion of the photopolymerization initiator and the thermal polymerization initiator is 5 to 300 parts by mass relative to 100 parts by mass of the photopolymerization initiator.

[0587] [1-1-10] Amino compounds

[0588] To promote thermosetting, the photosensitive coloring composition of the present invention may contain an amino compound. When the photosensitive coloring composition of the present invention contains an amino compound, the proportion of the amino compound relative to the total solid content of the photosensitive coloring composition is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 0.5% by mass or more, more preferably 1% by mass or more. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 0.5 to 40% by mass is preferred, more preferably 1 to 30% by mass. By setting it below the upper limit, there is a tendency to maintain storage stability. By setting it above the lower limit, there is a tendency to ensure sufficient thermosetting properties.

[0589] Examples of amino compounds include, for instance, amino compounds having at least two of the following functional groups: hydroxymethyl groups, obtained by condensing and modifying them with alcohols having 1 to 8 carbon atoms. Specifically, examples include: melamine resin obtained by condensing melamine with formaldehyde; benzoguanidine resin obtained by condensing benzoguanidine with formaldehyde; glycourea resin obtained by condensing glycourea with formaldehyde; urea resin obtained by condensing urea with formaldehyde; resin obtained by co-condensing two or more of melamine, benzoguanidine, glycourea, or urea with formaldehyde; and modified resins obtained by condensing and modifying the hydroxymethyl groups of the above resins with alcohols. Melamine resin and its modified resins are preferred, and the modified resin is more preferably a modified resin with a hydroxymethyl group modification ratio of 70% or more, and even more preferably a modified resin with a hydroxymethyl group modification ratio of 80% or more.

[0590] Amino compounds can be used alone or in combination with two or more.

[0591] Examples of melamine resins and their modified resins include: CYMEL (registered trademark, hereinafter the same) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 manufactured by CYTEC; and NIKALAC (registered trademark, hereinafter the same) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 manufactured by Sanwa Chemical.

[0592] Examples of benzoguanidine resins and their modified resins include "CYMEL" 1123, 1125, and 1128 manufactured by CYTEC.

[0593] Examples of glycourea resins and their modified resins include, for example, "CYMEL" 1170, 1171, 1174, and 1172 manufactured by CYTEC; and "NIKALAC" MX-270 manufactured by Sanwa Chemical.

[0594] Examples of urea resins and their modified resins include, for example, "UFR" 65 and 300 manufactured by CYTEC Corporation (registered trademark); and "NIKALAC" MX-290 manufactured by Sanwa Chemical Corporation.

[0595] [1-1-11] Silane coupling agent

[0596] To improve substrate adhesion, the photosensitive coloring composition of the present invention may contain a silane coupling agent.

[0597] As silane coupling agents, epoxy, methacrylic, amino, and imidazole silane coupling agents can be used, among others. From the viewpoint of improving substrate adhesion, epoxy and imidazole silane coupling agents are preferred.

[0598] When the photosensitive coloring composition of the present invention contains a silane coupling agent, from the viewpoint of substrate adhesion, the proportion of the silane coupling agent is preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total solid content of the photosensitive coloring composition.

[0599] [1-1-12] Inorganic fillers

[0600] In order to improve the strength of the cured product and enhance the excellent verticality and cone angle of the coating film achieved by the moderate interaction with (C) alkali-soluble resin (formation of matrix structure), the photosensitive coloring composition of the present invention may contain an inorganic filler.

[0601] Examples of inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or substances obtained by surface treatment of these materials with various silane coupling agents. In particular, silica sol and silica sol modifiers tend to exhibit excellent dispersion stability and improved cone angle, and are therefore preferred.

[0602] The average particle size of the inorganic filler is preferably 0.005 to 2 μm, more preferably 0.01 to 1 μm. The average particle size is a value measured using a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter, etc.

[0603] When the photosensitive coloring composition of the present invention contains an inorganic filler, from the viewpoint of ink repellency, the content ratio 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, preferably 80% by mass or less, and more preferably 70% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, 5 to 80% by mass is preferred, and 10 to 70% by mass is more preferred.

[0604] [1-1-13] Phosphate-based olefinic monomers

[0605] For the purpose of imparting adhesion to the substrate, the photosensitive coloring composition of the present invention may contain phosphate alkene monomers.

[0606] As a phosphate-based olefinic monomer, phosphate esters containing (meth)acryloyloxy groups are preferred, and phosphate esters containing (meth)acryloyloxy groups as shown in the following general formulas (G1), (G2), and (G3) are even more preferred.

[0607] [Chemical Formula 28]

[0608]

[0609] In equation (G1), R g1 Represents a hydrogen atom or a methyl group. j1 represents an integer from 1 to 10, and k1 represents an integer from 1 to 3.

[0610] In equation (G2), R g2 Represents a hydrogen atom or a methyl group. j2 represents an integer from 1 to 10, and k2 represents an integer from 1 to 3.

[0611] In equation (G3), R g3 This represents a hydrogen atom or a methyl group. j3 and j4 represent integers from 1 to 10, and k3 represents integers from 1 to 3.

[0612] Phosphoalkene monomers can be used alone or in combination with two or more.

[0613] When the photosensitive coloring composition of the present invention contains a phosphate-based olefin monomer, its content relative to the total solid content of the photosensitive coloring composition is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and further preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 0.02 to 4% by mass, more preferably 0.05 to 3% by mass, even more preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass. By setting it to the lower limit or above, there is a tendency for the improvement effect on substrate adhesion to become sufficient. By setting it to the upper limit or below, there is a tendency for the deterioration of substrate adhesion to be easily suppressed.

[0614] [1-1-14] Solvent

[0615] The photosensitive coloring composition of the present invention may contain a solvent, and may be used in a state in which all components (solid components: even if the components other than the solvent are liquid at room temperature, they are still solid components) contained in the photosensitive coloring composition are dissolved or dispersed in a solvent. There are no particular limitations on the solvent, and for example, the organic solvents described below can be listed.

[0616] 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, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and other diethylene glycol monoalkyl ethers;

[0617] Dialkyl ethers of glycols, such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;

[0618] Diethylene 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, 3-methoxy-1-butyl 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 diethylene glycol alkyl ether acetates;

[0619] Diol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate, and 1,6-hexanediol diacetate;

[0620] Alkyl acetates such as cyclohexanol acetate;

[0621] Ethers such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, and dihexyl ether;

[0622] Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl pentyle ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyle ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentyle ketone;

[0623] Monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

[0624] Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

[0625] Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

[0626] Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

[0627] Chain or cyclic esters such as amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

[0628] Halogenated hydrocarbons such as butyl chloride and pentyl chloride;

[0629] Ether ketones such as methoxymethylpentanone;

[0630] Nitriles such as acetonitrile and benzonitrile;

[0631] Tetrahydrofurans, such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

[0632] Commercially available solvents include, for example: Mineral Spirit, Varsol#2, Apco#18 Solvent, Apco Thinner, Socal Solvent No.1 and No.2, Solvesso#150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellulose Solvent, Ethyl Cellulose Solvent, Ethyl Cellulose Solvent Acetate, Methyl Cellulose Solvent Acetate, and Diethylene Glycol Dimethyl Ether (diglyme) (all trade names).

[0633] The solvent is selected based on the method of using the photosensitive coloring composition according to the present invention, as it dissolves or disperses the various components contained in the photosensitive coloring composition. From the viewpoint of coatability, the boiling point of the solvent at atmospheric pressure is preferably 60–280°C, more preferably 70–260°C. Among these, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.

[0634] Solvents can be used alone or in combination with two or more.

[0635] The solvent is preferably used in such a manner that the total solid content of the photosensitive coloring composition relative to its total mass is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and further preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably used in a manner that is 10 to 50% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass. By setting it to the lower limit or above, there is a tendency to suppress the generation of uneven coating. By setting it to the upper limit or below, there is a tendency to suppress the generation of foreign matter, shrinkage, etc.

[0636] [1-2] Method for manufacturing photosensitive coloring compositions

[0637] The photosensitive coloring composition of the present invention is manufactured by mixing the components contained in the photosensitive coloring composition using a mixer.

[0638] For example, when the colorant (A) contains a solvent-free component such as a pigment, it is preferable to pre-disperse it using a paint conditioner, sand mill, ball mill, roller mill, stone mill, jet mill, homogenizer, etc. Through dispersion treatment, the colorant (A) is micronized, thereby improving the coating properties of the photosensitive coloring composition.

[0639] The dispersion treatment can be carried out in a system using (A) a colorant, a solvent, and (B) a dispersant, or in a system using (C) an alkali-soluble resin, either partially or entirely (hereinafter, the mixture supplied for the dispersion treatment and the composition obtained by the dispersion treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, if (B) a dispersant is used, the resulting ink and photosensitive coloring composition exhibit excellent dispersion stability and thickening over time is suppressed, and is therefore preferred.

[0640] In this way, in the process of manufacturing a photosensitive coloring composition, it is preferable to manufacture a pigment dispersion containing at least (A) a colorant, a solvent and (B) a dispersant.

[0641] As the colorant (A), organic solvent, and dispersant (B) that can be used in the pigment dispersion, it is preferable to use substances described as substances that can be used in the photosensitive coloring composition. The content ratio of each colorant as the colorant (A) in the pigment dispersion is preferably a ratio described as the content ratio in the photosensitive coloring composition.

[0642] When using a sand mill to disperse colorant (A), glass beads or zirconia beads with a particle size of approximately 0.1 to 8 mm are preferably used. The temperature for dispersion is preferably 0°C to 100°C, more preferably room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid and the size of the dispersion apparatus, and therefore should be adjusted accordingly. A general standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300.

[0643] The preferred particle size of the pigment dispersed in the ink is 0.03–0.3 μm, which can be determined, for example, by dynamic light scattering.

[0644] Next, the ink obtained through dispersion is mixed with other components contained in the photosensitive coloring composition to form a homogeneous solution or dispersion. During the manufacturing process of the photosensitive coloring composition, fine foreign matter may sometimes be introduced into the liquid; therefore, it is ideal to filter the obtained photosensitive coloring composition using a filter or similar means.

[0645] [2] Spare walls and their formation methods

[0646] By curing the photosensitive coloring composition of the present invention, the cured product of the present invention can be obtained.

[0647] The photosensitive coloring composition of the present invention can be used to form spacers, and is preferably used to form spacers for dividing organic layers of organic electroluminescent elements, and for dividing pixel portions in color filters containing luminescent nanocrystals. The spacers of the present invention are composed of the cured product of the present invention.

[0648] The method for forming spacers using the photosensitive coloring composition of the present invention is not particularly limited, and conventionally known methods can be used. The formation of the cured product using the photosensitive coloring composition of the present invention preferably includes at least the following steps (1) to (4).

[0649] Step (1): The step of coating a substrate with the photosensitive coloring composition of the present invention to form a coating film.

[0650] Step (2): A step of exposing at least a portion of the coating formed in step (1).

[0651] Step (3): The process of developing the coating after exposure in step (2).

[0652] Process (4): The process of firing the coating after development in process (3).

[0653] <Step (1): Step of coating a substrate with a photosensitive coloring composition to form a coating film>

[0654] Methods for supplying a photosensitive coloring composition to a substrate include, for example, inkjet printing and photolithography.

[0655] In inkjet printing, a photosensitive coloring composition, whose viscosity has been adjusted by dilution with a solvent, is used as ink. Ink droplets are jetted onto a substrate along a predetermined spacer pattern, thereby coating the photosensitive coloring composition onto the substrate to form an uncured spacer pattern. The uncured spacer pattern is then exposed to light, forming cured spacers on the substrate. The exposure of the uncured spacer pattern is performed in the same manner as the exposure process in photolithography, except that a mask is not used.

[0656] In photolithography, a photosensitive coloring composition is coated onto the entire surface of the area of ​​the substrate where spacers are to be formed to form a photosensitive coloring composition layer. After the photosensitive coloring composition layer formed according to the prescribed spacer pattern is exposed, the exposed photosensitive coloring composition layer is developed to form spacers on the substrate.

[0657] In the photolithography process, the photosensitive coloring composition is coated onto a substrate. Contact transfer coating equipment such as roller coaters, reverse coaters, and bar coaters, as well as non-contact coating equipment such as spin coaters (rotary coating equipment) and curtain flow coaters are used to coat the photosensitive coloring composition onto the substrate on which spacers are to be formed.

[0658] After the photosensitive coloring composition is supplied to the substrate, it is preferable to dry it to form a coating film. Drying is preferably carried out by using a heating plate, an IR (Infrared Ray) oven, or a convection oven. A depressurization drying method, in which drying is performed in a depressurized chamber without increasing the temperature, can also be used.

[0659] The drying conditions can be appropriately selected based on the type of solvent and the performance of the dryer used. The drying time, depending on the type of solvent and the performance of the dryer, is typically selected within the range of 15 seconds to 5 minutes at a temperature of 40°C to 100°C, and preferably within the range of 30 seconds to 3 minutes at a temperature of 50°C to 80°C. It should be noted that the drying should preferably be carried out within the range not exceeding the firing temperature described later.

[0660] <Step (2): Step of exposing at least a portion of the coating formed in step (1)>

[0661] In the exposure process, a negative mask is used to irradiate the photosensitive coloring composition with active energy rays such as ultraviolet light or excimer laser, locally exposing the photosensitive coloring composition layer in accordance with the dam pattern. Exposure can be performed using ultraviolet light sources such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and carbon arc lamps. The exposure dose varies depending on the composition of the photosensitive coloring composition, and is preferably 10–400 mJ / cm². 2 about.

[0662] <Step (3): The process of developing the coating after exposure in step (2)>

[0663] In the developing process, a developing solution is used to develop the photosensitive coloring composition layer, which corresponds to the pattern of the spacer walls, after exposure, thereby forming the spacer walls. The developing method is not particularly limited; immersion or spray methods can be used. Specific examples of developing solutions include: organic developing solutions such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine; and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Furthermore, defoamers and surfactants may be added to the developing solution.

[0664] Following the developing process, a further exposure process (post-exposure process) is performed as needed. The developed spacer is exposed to active energy rays such as ultraviolet light or excimer laser. Alternatively, a localized exposure using a mask can be employed. Exposure can be performed using ultraviolet light sources such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps, or UV-FL (ultraviolet fluorescent lamps). The exposure dose varies depending on the composition of the photosensitive coloring composition, but is preferably 10 mJ / cm². 2 The above, more preferably 100 mJ / cm 2 The above is further optimized to 500 mJ / cm. 2 The above is particularly preferred, with 800 mJ / cm². 2 In addition, the preferred value is 10000 mJ / cm. 2 Below, 5000 mJ / cm is more preferred. 2 The following is a further preferred value: 2000 mJ / cm 2 Below. For example, preferably 10 to 10000 mJ / cm. 2 More preferably, it is 100–10000 mJ / cm 2 More preferably, it is 500–5000 mJ / cm². 2 The preferred value is 800–2000 mJ / cm³. 2 Setting the value above the lower limit tends to improve penetration resistance. Setting it below the upper limit balances penetration resistance with productivity gains from ensuring the irradiation time is not too long, and is therefore preferred from this perspective.

[0665] <Step (4): The process of firing the coating after development in step (3)>

[0666] The spacer wall is subjected to firing (post-baking), i.e., heat curing treatment (also called "thermal firing") after development or subsequent post-exposure. The firing (post-baking) conditions are preferably 80°C or higher, more preferably 90°C or higher, further preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 140°C or lower, particularly preferably 120°C or lower, and most preferably 100°C or lower. The above upper and lower limits can be combined arbitrarily. For example, 80–250°C is preferred, more preferably 80–200°C, even more preferably 80–180°C, even more preferably 80–140°C, particularly preferably 80–120°C, even more preferably 80–100°C, and especially preferably 90–100°C. By setting the lower limit or higher, there is a tendency for improved permeability and heat resistance. By setting the upper limit or lower, there is a tendency for reduced manufacturing costs and less impact on substrates and components with limited heat resistance, such as plastic substrates.

[0667] The preferred firing time is 5 to 120 minutes.

[0668] The substrate used to form the spacers is not particularly limited, and can be appropriately selected according to the type of organic electroluminescent element or color filter manufactured using the substrate with the spacers formed thereon. Preferred substrate materials include glass and various resin materials. Examples of resin materials include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resin; polysulfone; and polyimide. Glass and polyimide are preferred from the perspective of excellent heat resistance. Depending on the type of organic electroluminescent element or color filter being manufactured, a transparent electrode layer such as ITO or ZnO can also be pre-formed on the surface of the substrate where the spacers are to be formed. Furthermore, spacers for color filters can also be formed on a substrate containing the element.

[0669] Alternatively, depending on the requirements, the substrate can be subjected to various resin film formation treatments such as corona discharge treatment, ozone treatment, silane coupling agent, and urethane resin to improve surface properties such as adhesion.

[0670] The thickness of the spacer film in this invention is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, even more preferably 7 μm or more, particularly preferably 10 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 20 μm or less. The above-mentioned upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 100 μm, more preferably 3 to 50 μm, further preferably 5 to 50 μm, even more preferably 5 to 20 μm, particularly preferably 7 to 20 μm, and most preferably 10 to 20 μm. By setting it to the lower limit or above, there is a tendency to improve light-shielding properties. By setting it to the upper limit or below, there is a tendency to improve substrate adhesion.

[0671] The photosensitive coloring composition of the present invention is useful for the formation of spacers with a film thickness of 5 μm or more, for example, a height of 5 μm or more.

[0672] The thickness of the spacer wall was measured using a height difference / surface roughness / fine shape measuring device, a scanning white interference microscope, an ellipsometry, a reflective spectrophotometer, and an electron microscope.

[0673] [3] Organic electroluminescent elements

[0674] The organic electroluminescent element of the present invention has the spacer wall of the present invention.

[0675] Various organic light-emitting elements can be manufactured using a substrate having a spacer pattern created by the method described above. The method for forming the organic light-emitting element is not particularly limited, but it is preferable to form an organic layer such as a pixel by injecting ink into the area surrounded by the spacers on the substrate after forming the spacer pattern using the method described above, thereby manufacturing the organic light-emitting element.

[0676] Types of organic electroluminescent elements include, for example, bottom-emitting and top-emitting types.

[0677] In bottom-emitting types, for example, spacers are formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal electrode layer are stacked in the openings surrounded by the spacers.

[0678] In top-emitting types, for example, spacers are formed on a glass substrate with stacked metal electrode layers, and an electron transport layer, a light-emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the openings surrounded by the spacers.

[0679] When the spacer wall has a downward-sloping shape, the ink used for forming the organic layer is repelled at the downward-sloping portion of the spacer wall, so sometimes the area surrounded by the spacer wall is not sufficiently covered by the ink used for forming the organic layer. In contrast, by forming a good shape without a downward-sloping shape, the area surrounded by the spacer wall can be sufficiently covered by the ink used for forming the organic layer. Thus, for example, the halo problem of organic EL display elements can be eliminated.

[0680] As a solvent used in ink for forming an organic layer, water, organic solvents, and mixtures thereof can be used.

[0681] Organic solvents are not particularly limited as long as they can be removed from the film formed after ink injection. Examples of organic solvents include: toluene, xylene, anisole, mesitylene, tetrahydronaphthalene, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, and 3-phenoxytoluene.

[0682] Surfactants, antioxidants, viscosity modifiers, and UV absorbers can be added to ink.

[0683] As a method for injecting ink into a region surrounded by partition walls, inkjet printing is preferred from the perspective of easily injecting small amounts of ink into a designated area. The ink used in forming the organic layer is appropriately selected depending on the type of organic electroluminescent element being manufactured. When injecting ink by inkjet printing, the viscosity of the ink is not particularly limited as long as it can be well ejected from the inkjet head, but is preferably 4 to 20 mPa·s, more preferably 5 to 10 mPa·s. The viscosity of the ink can be adjusted by adjusting the solid content of the ink, changing the solvent, or adding viscosity modifiers.

[0684] Organic electroluminescent layers, as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent Publication No. 5734681, can also be used. Quantum dots, as described in Japanese Patent Publication No. 5653387 and Japanese Patent Publication No. 5653101, can also be used.

[0685] [4] Color filters containing luminescent nanocrystals

[0686] The color filter containing luminescent nanocrystals of the present invention is not particularly limited as long as it has the spacer wall of the present invention. Examples include color filters in which pixels are formed in the area divided by the spacer wall.

[0687] Figure 1 This is a schematic cross-sectional view of an example of a color filter equipped with the spacer wall of the present invention. (See attached image.) Figure 1 As shown, the color filter 100 includes a substrate 10, spacers 20 disposed on the substrate, red pixels 30, green pixels 40, and blue pixels 50. The red pixels 30, green pixels 40, and blue pixels 50 are arranged in a grid pattern in a repeating order. The spacers 20 are disposed between these adjacent pixels. In other words, these adjacent pixels are separated from each other by the spacers 20.

[0688] Red pixel 30 contains red luminescent nanocrystals 2, and green pixel 40 contains green luminescent nanocrystals 1. Blue pixel 50 is a pixel that transmits blue light from a light source.

[0689] These nanocrystals are nanoscale crystals that absorb excitation light and emit fluorescence or phosphorescence, for example, crystals with a maximum particle size of less than 100 nm as determined by transmission electron microscopy or scanning electron microscopy.

[0690] Luminescent nanocrystals can emit light of a different wavelength (fluorescence or phosphorescence) by absorbing light of a specified wavelength. For example, red luminescent nanocrystal 2 emits light with a peak wavelength in the range of 605 to 665 nm (red light), and green luminescent nanocrystal 1 emits light with a peak wavelength in the range of 500 to 560 nm (green light).

[0691] According to the solution of the Schrödinger wave equation in the square well potential model, the wavelength (emission color) of the light emitted by luminescent nanocrystals depends not only on the size (e.g., particle size) of the nanocrystals but also on the band gap they possess. Therefore, by changing the constituent materials and size of the luminescent nanocrystals used, the emission color can be selected. Examples of luminescent nanocrystals include quantum dots.

[0692] The method for manufacturing a color filter containing luminescent nanocrystals is not particularly limited, but examples include: preparing a substrate having spacers formed from the cured product of the present invention, and forming a layer containing luminescent nanocrystals in the region defined by the spacers. The method for forming the layer containing luminescent nanocrystals is not particularly limited; for example, it can be manufactured by selectively attaching an ink composition containing luminescent nanocrystals by inkjet printing, and then curing the ink composition by irradiation with active energy rays or heating.

[0693] [5] Image display device

[0694] The image display device of the present invention includes the spacer of the present invention.

[0695] As an image display device of the present invention, an image display device comprising an organic electroluminescent element can be cited as an example. As long as an organic electroluminescent element is included, there are no particular limitations on the model or structure of the image display device; for example, an active-drive type organic electroluminescent element can be used and assembled according to conventional methods. For example, the image display device of the present invention can be formed using the methods described in "Organic EL Display" (OHM Corporation, published August 20, 2004, authored by Shizushi Tokito, Chinatsuya Adachi, and Hideyuki Murata). For example, an organic electroluminescent element emitting white light can be combined with a color filter for image display, or organic electroluminescent elements emitting different colors such as RGB can be combined for image display.

[0696] As an image display device of the present invention, an image display device having a color filter comprising luminescent nanocrystals according to the present invention can be cited as an example.

[0697] Examples of image display devices include liquid crystal display devices and image display devices that include organic light-emitting elements. In the case of liquid crystal display devices, examples include liquid crystal display devices that include a light source equipped with blue LEDs and a liquid crystal layer equipped with electrodes that control the blue light emitted from the light source for each pixel.

[0698] On the other hand, in image display devices that include organic light-emitting elements, an example is an image display device in which a blue light-emitting organic light-emitting element is arranged at a position corresponding to each pixel of the color filter. Specifically, the method described in Japanese Patent Application Publication No. 2019-87746 can be cited as an example.

[0699] Example

[0700] The following specific embodiments illustrate the photosensitive coloring composition of the present invention. The present invention is not limited to the following embodiments unless it departs from its spirit.

[0701] [(A) Pigment]

[0702] CI Pigment Violet 29.

[0703] [(B) Dispersant]

[0704] In Examples 1 to 6 and Comparative Examples 1 to 6, one of the following dispersants was selected for formulation. The selection of dispersants is shown in Table 2.

[0705] <Dispersant-1>

[0706] Dispersant-1 is a methacrylic acid block copolymer with an amine value of 63 mgKOH / g and an acid value of less than 1 mgKOH / g. It contains the structural units shown in formulas (1), (2), (3) and (4) below, and has a weight-average molecular weight (Mw) of 8400.

[0707] The proportions of the structural units shown in Equations (1), (2), (3) and (4) in all structural units are 17.2 mol%, 9.2 mol%, 1.3 mol%, and 0.5 mol, respectively.

[0708] Dispersant-1 is equivalent to copolymer (B1).

[0709] [Chemical Formula 29]

[0710]

[0711] <Dispersant-2>

[0712] Dispersant-2 is a high molecular weight acrylic AB block copolymer, which contains A blocks with tertiary amino and quaternary ammonium salt groups on the side chain and B blocks without tertiary amino and quaternary ammonium salt groups. The amine value is 70 mg KOH / g and the acid value is less than 1 mg KOH / g.

[0713] The A block of the dispersant contains the structural units shown in formulas (1) and (2) below, and the B block contains the structural units shown in formula (3) below. The structural units shown in formulas (1), (2) and (3) below account for 17.0 mol%, 9.2 mol%, and 2.7 mol% of the total structural units of the dispersant, respectively.

[0714] Dispersant-2 is not equivalent to copolymer (B1).

[0715] [Chemical Formula 30]

[0716]

[0717] [(C) Alkali-soluble resin]

[0718] <Alkali-soluble resin-1>

[0719] (Synthesis of precursor resin)

[0720] Weigh 2-norbornene (75% toluene solution, Maruzen Petrochemical Co., Ltd., 125.5 g, 1.00 mol) and dimethyl 2,2'-azobis(2-methylpropionic acid) (V-601, Wako Pure Chemical Industries Co., Ltd., 9.2 g, 40 mmol) into a reaction vessel of appropriate size equipped with a stirrer and cooling pipe, and dissolve them in methyl ethyl ketone (MEK, 196.1 g).

[0721] The solution was purged with nitrogen for 10 minutes to remove oxygen, then stirred and heated to 80°C. The solution was maintained at 80°C, and a pre-prepared solution of maleic anhydride (98.1 g, 1.00 mol) dissolved in 119.9 g of MEK was added dropwise over 1.5 hours, with the reaction proceeding at this temperature for an additional 8 hours. The reaction mixture was then added dropwise to a large volume of methanol to precipitate the polymer. After filtration using a Nutsche filter, the solid was further washed with methanol and dried under vacuum at 70°C. The weight-average molecular weight (Mw) of the obtained precursor resin was 6900.

[0722] (Synthesis of Alkali-Soluble Resin-1)

[0723] The precursor resin (50.0 g) was weighed into a reaction vessel of appropriate size equipped with a stirrer and cooling pipe, and dissolved in MEK (90 g). 2-Hydroxyethyl methacrylate (21.2 g, 163 mmol) and triethylamine (5.0 g) were further added, and the mixture was heated at 70°C for 6 hours. Glycidyl methacrylate (11.1 g, 78 mmol) was added to the reaction mixture, and the mixture was stirred at 70°C for 4 hours. Formic acid was added to the reaction mixture for acid treatment, and then a large amount of pure water was added dropwise to precipitate the polymer. The filtered solid was dried in a vacuum dryer at 40°C for 16 hours to obtain alkali-soluble resin-1 containing the structural units shown in formulas (5), (6), (7), and (8). The weight-average molecular weight (Mw) was 7800. Furthermore, the double bond equivalent was 540 g / mol.

[0724] Alkali-soluble resin-1 is equivalent to resin (C3).

[0725] [Chemical Formula 31]

[0726]

[0727] <Alkali-soluble resin-2>

[0728] Alkali-soluble resin-2 is an alkali-soluble acrylic copolymer resin obtained by subjecting acrylic acid and glycidyl methacrylate to an equal-volume addition reaction, and further subjecting tetrahydrophthalic anhydride to an addition reaction at a molar ratio of 0.096 relative to 1 mole of the copolymer resin. The resin comprises structural units shown in formulas (9), (10), (11), and (12). The weight-average molecular weight (Mw) converted to polystyrene by GPC is 8900. Furthermore, the solid content acid value is 27 mg KOH / g.

[0729] Alkali-soluble resin-2 is equivalent to acrylic copolymer resin (C1).

[0730] [Chemical Formula 32]

[0731]

[0732] <Alkali-soluble resin-3>

[0733] Alkali-soluble resin-3 is an alkali-soluble acrylic copolymer resin obtained by subjecting acrylic acid and glycidyl methacrylate to an equal-volume addition reaction, and further subjecting tetrahydrophthalic anhydride to an addition reaction at a molar ratio of 0.39 relative to 1 mole of the copolymer resin. The resin comprises structural units shown in formulas (9), (10), (11), and (12). The weight-average molecular weight (Mw) converted to polystyrene by GPC is 9000. Furthermore, the solid content acid value is 80 mg KOH / g.

[0734] Alkali-soluble resin-3 is equivalent to acrylic copolymer resin (C1).

[0735] [(D) Photopolymerizable compounds]

[0736] <Photopolymerizable Compound-1>

[0737] DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate).

[0738] <Photopolymerizable Compound-2>

[0739] TMP-A (manufactured by Kyoei Chemical Co., Ltd., trimethylolpropane triacrylate).

[0740] [(E) Photopolymerization initiator]

[0741] Photopolymerization initiators

[0742] Use compounds having the following chemical structures. The following compounds can be prepared by the synthetic method described in International Publication No. 2009 / 131189.

[0743] [Chemical Formula 33]

[0744]

[0745] [Solvent]

[0746] <Solvent-1>

[0747] PGMEA (Propylene Glycol Monomethyl Ether Acetate).

[0748] Solvent-2

[0749] MB (3-methoxy-1-butanol).

[0750] [(F) compound]

[0751] <Fluorine-containing resins>

[0752] An acrylic copolymer resin has the following structural units: a perfluoroalkyl structural unit, an olefinic double bond structural unit, and a carboxyl structural unit. The weight-average molecular weight (Mw) is 90,000. Furthermore, the fluorine atoms constitute 20% of the total mass of the resin.

[0753] Resins containing fluorine atoms are equivalent to compound (F1).

[0754] [other]

[0755] <Chain transfer agent>

[0756] Pentaerythritol tetra(3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., trade name "KARENZ MT PE1").

[0757] <Additives>

[0758] Phosphate containing methacryloyl group (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYAMER PM-21").

[0759] [Preparation of Pigment Dispersion]

[0760] The pigments, dispersants, alkali-soluble resins, and solvents listed in Table 1 were mixed in the mass ratios specified in Table 1. The solution was dispersed for 8 hours using a paint shaker within a temperature range of 25–45°C. Zirconia beads with a diameter of 0.6 mm were used as beads, and 1.7 times the mass of the dispersion was added. After dispersion, the beads were separated from the dispersion by a filter to prepare the pigment dispersion.

[0761] It should be noted that the empty columns in Table 1 refer to columns where the ingredient was not incorporated (0 parts by mass).

[0762] [Table 1]

[0763]

[0764] [Examples 1 to 6 and Comparative Examples 1 to 6]

[0765] Using the pigment dispersion prepared above, each component was added in such a manner that the proportion of each component's solid content in the total solid content was as shown in Table 2. PGMEA was then added further, with the mixture stirred until dissolved, to prepare a photosensitive coloring composition. The performance of the obtained photosensitive coloring composition was evaluated using the method shown below. The results are shown in Table 2.

[0766] It should be noted that the empty columns in Table 2 refer to columns where the ingredient was not incorporated (0 parts by mass).

[0767] <Performance Evaluation>

[0768] (Evaluation of substrate fabrication)

[0769] A photosensitive coloring composition was applied to a glass substrate using a spin coater to achieve a thickness of 10 μm or 7 μm after heat curing. The coating was then dried in a vacuum dryer for 60 seconds. Next, it was heated and dried on a hot plate at 100°C for 120 seconds. The resulting coating was then exposed using a photomask. A Canon mirror projection exposure machine (MPA-600FA) was used with an exposure dose of 60 mJ / cm². 2 A 15-second exposure was performed. The illuminance was 500 mW / cm². 2 The slit width was 1.6 mm. The photomask used had multiple openings with various side lengths of 2 mm for the long side and 3–40 μm for the short side. Next, development was performed using a 0.033% (w / w) KOH aqueous solution sprayed at a pressure of 0.2 MPa, followed by rinsing with pure water for 9 seconds. The spray development time was adjusted between 10 and 120 seconds, set to 1.3 times the solvent removal time for the unexposed coating. Then, it was heated in an oven at 100°C for 20 minutes. Finally, a UV irradiation device (manufactured by Toshiba Lighting & Technology Co., Ltd.) equipped with a spectrophotometer (UV) and a spectrofluorescence spectrophotometer (FL) was used, with an illuminance of 0.15 mW / cm². 2 The substrate is exposed to UV light for 5 minutes to obtain a patterned substrate for evaluation.

[0770] (Evaluation of substrate adhesion)

[0771] In line pattern sections with short sides of 3–40 μm, the minimum side length (μm) at which each pattern resolution remains well is defined as the minimum adhesion, as shown in Table 2. The smaller this value, the better the substrate adhesion. It should be noted that good resolution retention means that three patterns of the same size are formed, and all patterns are formed normally.

[0772] [Table 2]

[0773]

[0774] As shown in Table 2, a comparison of the examples and comparative examples with the same pigment amount and film thickness demonstrates that, by using dispersant-1, the minimum adhesion value is smaller in each example regardless of the photosensitive coloring composition, indicating improved substrate adhesion. This can be attributed to the fact that dispersant-1 used in each example contains (B1-1) structural units, specifically ester and hydroxyl groups as polar functional groups, thus further promoting bonding with the outermost surface of the glass, i.e., adhesion, throughout the cured product.

[0775] Explanation of reference numerals in the attached figures

[0776] 1: Green luminescent nanocrystals;

[0777] 2: Red luminescent nanocrystals;

[0778] 10: Substrate;

[0779] 20: partition wall;

[0780] 30: Red pixel;

[0781] 40: Green pixels;

[0782] 50: Blue pixels;

[0783] 100: Color Filter.

Claims

1. A photosensitive coloring composition, characterized in that, Containing (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, the photosensitive coloring composition is used to form spacer walls, wherein, The content of colorant (A) is 15% by mass or less relative to the total solid content of the photosensitive coloring composition. The (B) dispersant contains a copolymer (B1) having at least the following (B1-1) and (B1-2) structural units. (B1-1) Structural Unit: The structural unit shown in the following general formula (B1-1), (B1-2) Structural unit: A structural unit having at least one of a tertiary amino group and a quaternary ammonium group. [Chemical Formula 1] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents, where n represents an integer from 1 to 10. * indicates a bond.

2. A photosensitive coloring composition, characterized in that, It contains (A) colorant, (B) dispersant, (C) alkali-soluble resin, (D) photopolymerizable compound, and (E) photopolymerization initiator, among which, The colorant (A) contains CI pigment violet 29. The (B) dispersant contains a copolymer (B1) having at least the following (B1-1) and (B1-2) structural units. (B1-1) Structural Unit: The structural unit shown in the following general formula (B1-1), (B1-2) Structural unit: A structural unit having at least one of a tertiary amino group and a quaternary ammonium group. [Chemical Formula 2] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents, where n represents an integer from 1 to 10. * indicates a bond.

3. A photosensitive coloring composition, characterized in that, It contains (A) colorant, (B) dispersant, (C) alkali-soluble resin, (D) photopolymerizable compound, and (E) photopolymerization initiator, among which, The (B) dispersant contains a copolymer (B1) having at least the following (B1-1) and (B1-2) structural units. The photosensitive coloring composition is used to form spacer walls with a height of 5 μm or more. (B1-1) Structural Unit: The structural unit shown in the following general formula (B1-1), (B1-2) Structural unit: A structural unit having at least one of a tertiary amino group and a quaternary ammonium group. [Chemical Formula 3] In equation (B1-1), R 1 R represents a hydrogen atom or a methyl group. 2 and R 3 Each of the following independently represents an alkylene group having 1 to 8 carbon atoms, optionally with substituents, where n represents an integer from 1 to 10. * indicates a bond.

4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein, The copolymer (B1) also has the following (B1-3) structural units, (B1-3) Structural Unit: The structural unit shown in the following general formula (B1-3), [Chemical Formula 4] In equation (B1-3), R 11 R represents a hydrogen atom or a methyl group. 12 Indicates ethylene or propyleneene, R 13 The symbol indicates an alkyl group that may optionally have substituents, m represents an integer from 1 to 20, and * represents a bonded bond.

5. The photosensitive coloring composition according to claim 4, wherein, The content of the (B1-1) structural unit in the copolymer (B1) is 100 mol%, and the content of the (B1-3) structural unit is 20 to 500 mol%.

6. The photosensitive coloring composition according to any one of claims 1 to 3, wherein, The (B1-2) structural unit in the copolymer (B1) comprises at least one of the structural units shown in general formula (B1-2-1) and general formula (B1-2-2). [Chemical Formula 5] In equation (B1-2-1), R 21 R represents a hydrogen atom or a methyl group. 22 and R 23 Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, Z 1 This indicates a divalent linker, and * indicates a bond. [Chemical Formula 6] In equation (B1-2-2), R 24 R represents a hydrogen atom or a methyl group. 25 ~R 27 Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, X 1 Y represents a divalent linker group. - * indicates counteracting anions, and * indicates bonding bonds.

7. The photosensitive coloring composition according to any one of claims 1 to 3, wherein, The copolymer (B1) comprises a block copolymer.

8. The photosensitive coloring composition according to any one of claims 1 to 3, wherein, The photosensitive coloring composition also contains a compound having a crosslinking group and having fluorine atoms and / or siloxane chains.

9. The photosensitive coloring composition according to any one of claims 1 to 3, wherein, The photosensitive coloring composition also contains a solvent.

10. The photosensitive coloring composition according to any one of claims 1 to 3, wherein, The photosensitive coloring composition is used for firing at temperatures below 140°C.

11. A cured product formed by curing the photosensitive coloring composition according to any one of claims 1 to 3.

12. A spacer wall comprising the solidified material according to claim 11.

13. An organic electroluminescent element having a spacer wall as described in claim 12.

14. A color filter having a spacer wall as claimed in claim 12, and further comprising luminescent nanocrystals.

15. An image display device comprising the spacer wall according to claim 12.

Images