WO2024034637A1 - 感光性着色樹脂組成物、顔料分散液、硬化物、隔壁、有機電界発光素子、カラーフィルター及び画像表示装置 - Google Patents

感光性着色樹脂組成物、顔料分散液、硬化物、隔壁、有機電界発光素子、カラーフィルター及び画像表示装置 Download PDF

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WO2024034637A1
WO2024034637A1 PCT/JP2023/029097 JP2023029097W WO2024034637A1 WO 2024034637 A1 WO2024034637 A1 WO 2024034637A1 JP 2023029097 W JP2023029097 W JP 2023029097W WO 2024034637 A1 WO2024034637 A1 WO 2024034637A1
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mass
acid
carbon atoms
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French (fr)
Japanese (ja)
Inventor
良尚 沢井
麗華 裴
佑樹 田中
賀子 宮下
宏明 石井
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to KR1020257033666A priority Critical patent/KR20250152686A/ko
Priority to CN202511485428.4A priority patent/CN121254561A/zh
Priority to CN202380047921.0A priority patent/CN119384640B/zh
Priority to JP2024540508A priority patent/JPWO2024034637A1/ja
Priority to KR1020247039376A priority patent/KR102874587B1/ko
Publication of WO2024034637A1 publication Critical patent/WO2024034637A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a photosensitive colored resin composition, a pigment dispersion, a cured product, a partition wall, an organic electroluminescent device, a color filter, and an image display device.
  • Liquid crystal displays utilize the property that the arrangement of liquid crystal molecules is switched by turning on and off a voltage to the liquid crystal.
  • many of the members constituting the cell of an LCD are formed by a method using a photosensitive composition, typified by a photolithography method.
  • the range of application of this photosensitive composition is expanding further because it is easy to form a fine structure and it is easy to process substrates for large screens.
  • Image display devices that include organic electroluminescent elements (also referred to as organic electroluminescence, organic EL) have excellent visibility and responsiveness such as contrast and viewing angle, and are designed to reduce power consumption, be thinner and lighter, and display the display itself. Because it can be made flexible, it is attracting attention as a next-generation flat panel display (FPD).
  • An organic electroluminescent device has a structure in which a light emitting layer or an organic layer including various functional layers is sandwiched between a pair of electrodes, at least one of which is translucent.
  • An image display device displays an image by driving a panel in which an organic electroluminescent element is arranged for each pixel.
  • organic electroluminescent devices Conventionally, such organic electroluminescent devices have been manufactured by forming barrier ribs (banks) on a substrate and then stacking a light-emitting layer or various functional layers within a region surrounded by the barrier ribs.
  • a vapor deposition method is mainly used in which a material is sublimated in a vacuum and deposited on a substrate to form a film.
  • wet process methods such as casting, spin coating, and inkjet printing have attracted attention.
  • the inkjet printing method can reduce unevenness in film thickness when printing on large areas, and can also improve the resolution of displays, reduce the amount of materials used, and improve yields by separating the coatings during coating. Therefore, it is suitable as a method for forming an organic layer in a large panel.
  • a method of easily forming partition walls a method of forming them by photolithography using a photosensitive composition is known. Furthermore, as a method of imparting light-shielding properties to partition walls and suppressing light leakage between pixels, a method of incorporating a coloring agent into a photosensitive composition is known.
  • Patent Document 1 describes a photosensitive colored resin composition that has high light-shielding properties and a low dielectric constant by using a specific organic black pigment and a dispersant.
  • Patent Document 2 describes a photosensitive colored resin composition used for partition walls of organic electroluminescent devices that is effective in suppressing outgas generation by using a specific organic black pigment and an alkali-soluble resin. ing.
  • a known method for preparing a photosensitive colored resin composition used for light-shielding partition wall applications is to add a pigment as a coloring agent and mix a pigment dispersion, which is dispersed using a dispersant, with other components. ing.
  • a pigment dispersion which is dispersed using a dispersant, with other components. ing.
  • sufficient dispersibility and storage stability may not be ensured depending on the type of pigment, dispersant, and dispersion resin.
  • the remaining film rate of the photosensitive colored resin composition is low in the developing process and baking process during the production of partition walls, the developer resistance and heat resistance during baking will be poor, resulting in decomposition products and by-products in the composition. uncured substances may remain or re-deposit on the anode.
  • the inventors have investigated that when a partition wall is used in an organic electroluminescent device, it may not be possible to obtain sufficient brightness due to residues and re-deposition on the anode if the device current density with respect to the applied voltage is low. It has also been found that the photosensitive colored resin compositions described in Patent Documents 1 and 2 have insufficient film remaining ratio and device current density.
  • the first object of the present invention is to provide a photosensitive colored resin composition having a high residual film rate.
  • Another object of the present invention is to provide a photosensitive colored resin composition that has a high residual film rate and has a high device current density when used for a partition wall for an organic electroluminescent device.
  • a second object of the present invention is to provide a pigment dispersion with excellent dispersibility. Furthermore, it is an object of the present invention to provide a photosensitive colored resin composition, an organic electroluminescent device, and an image display device.
  • a photosensitive colored resin composition containing (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photoinitiator,
  • the colorant (A) contains an organic pigment (A-1)
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
  • Each * represents a bond.
  • [2] The photosensitive colored resin composition of [1], wherein the resin (C1) has a structural unit represented by the following general formula (2).
  • A represents a hydrogen atom or a polybasic acid residue.
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • Each * represents a bond.
  • the organic black pigment includes a benzodifuranone-based organic black pigment.
  • the organic black pigment contains an organic black pigment that is a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.
  • Photosensitive colored resin composition is a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.
  • R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom;
  • a pigment dispersion containing (A) a colorant, (B) a dispersant, and (C) an alkali-soluble resin contains an organic pigment (A-1), A pigment dispersion, wherein the alkali-soluble resin (C) contains a resin (C1) having a structural unit represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
  • Each * represents a bond.
  • A represents a hydrogen atom or a polybasic acid residue.
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • Each * represents a bond.
  • the organic black pigment contains an organic black pigment that is a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer. ] Pigment dispersion.
  • R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom;
  • An organic electroluminescent device comprising the partition wall of [18].
  • a color filter comprising luminescent nanocrystal particles and having the partition wall of [19].
  • An image display device comprising the partition wall of [19].
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
  • Each * represents a bond.
  • a photosensitive colored resin composition with a high residual film rate can be provided.
  • a pigment dispersion liquid having excellent dispersibility can be provided.
  • an organic electroluminescent device and an image display device can be provided.
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter including the partition walls of the present invention.
  • (meth)acrylic means “acrylic and/or methacrylic", and the same applies to "(meth)acrylate” and "(meth)acryloyl”.
  • Acrylic resin means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylic acid ester having a carboxy group.
  • Total solid content means all components other than the solvent contained in the photosensitive colored resin composition or pigment dispersion, and even if the components other than the solvent are liquid at room temperature, the components are Not included in solvent, included in total solids.
  • (Co)polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer), and “acid (anhydride)” and “(anhydride)...acid” , is meant to include both acids and their anhydrides.
  • the term “monomer” refers to a so-called high-molecular substance (polymer), and includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.
  • Weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
  • amine value refers to the amine value in terms of effective solid content, and is a value expressed by the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant. The measurement method will be described later.
  • Acid value refers to the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
  • C.I means Color Index. In this specification, percentages and parts expressed by “mass” are synonymous with percentages and parts expressed by “weight.”
  • the photosensitive colored resin composition according to the first aspect of the present invention contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photoinitiator, and (A)
  • the colorant contains an organic pigment (A-1), and the alkali-soluble resin (C) contains a resin (C1) represented by formula (1).
  • the pigment dispersion according to the second aspect of the present invention contains (A) a colorant, (B) a dispersant, and (C) an alkali-soluble resin, and the (A) colorant contains an organic pigment (A-1).
  • (C) alkali-soluble resin contains resin (C1) represented by formula (1).
  • (A) colorant, (B) dispersant, (C) alkali-soluble resin, and (D) photoinitiator are the photosensitive colored resin composition according to the first aspect, and the constituent requirements of both the pigment dispersion liquid according to the second aspect.
  • the photosensitive colored resin composition of the present invention is Contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
  • the photosensitive colored resin composition of the present invention contains (A) a coloring agent.
  • a coloring agent By containing the colorant (A), it is possible to obtain appropriate light absorbing properties, particularly appropriate light blocking properties when used for forming light blocking members such as partition walls.
  • the colorant (A) of the present invention contains an organic pigment (A-1). Containing the organic pigment (A-1) tends to improve insulation properties.
  • the number of pigments contained in the coloring agent may be one type alone, or two or more types may be used. From the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness, it is preferable to use two or more types.
  • Organic pigments that can be used as the colorant are not particularly limited, and examples include organic coloring pigments and organic black pigments.
  • the organic colored pigment means an organic pigment exhibiting a color other than black, and includes, for example, a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment.
  • organic pigments it is preferable to use organic coloring pigments from the viewpoint of suppressing absorption of ultraviolet rays, having high curability, and making it easier to control the shape of the cured product.
  • organic black pigment it is preferable to use an organic black pigment from the viewpoint of having high light-shielding properties and being able to lower the pigment concentration relative to the solid content.
  • organic black pigments examples include perylene black pigments, aniline black pigments, and benzodifuranone black pigments.
  • perylene-based black pigments examples include Lumogen Black (registered trademark) FK4281, K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF).
  • aniline black pigment examples include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).
  • benzodifuranone black pigments are preferred from the viewpoints of light-shielding properties, dispersibility, developability, and luminescent properties.
  • benzodifuranone black pigments from the viewpoint of light-shielding properties, dispersibility, developability, and luminescent properties, compounds represented by the following general formula (A-1-1) (hereinafter referred to as "compounds (A-1-1)”) ), geometric isomers of compound (A-1-1), salts of compound (A-1-1), and salts of geometric isomers of compound (A-1-1). It is preferable to use an organic black pigment (hereinafter sometimes referred to as "organic black pigment represented by general formula (A-1-1)”) containing at least one member selected from the group.
  • R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • compound (A-1-1) When compound (A-1-1) is anionic, its charge can be reduced to any known suitable cation, such as a metal, organic, inorganic or metal-organic cation, in particular an alkali metal, alkaline earth metal, transition Salts compensated with metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexes are preferred. Furthermore, when the geometric isomer of compound (A-1-1) is anionic, a similar salt is preferable.
  • a metal, organic, inorganic or metal-organic cation in particular an alkali metal, alkaline earth metal, transition Salts compensated with metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexe
  • R 612 , R 614 , R 615 , R 617 , R 619 and R 620 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
  • R 613 and R 618 each independently preferably represent a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 ) (C 2 H 5 ), N(C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 - , more preferably a hydrogen atom or SO 3 H, particularly preferably is a hydrogen atom.
  • R 611 and R 616 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
  • at least one combination selected from the group consisting of R 611 and R 616 , R 612 and R 617 , R 613 and R 618 , R 614 and R 619 , and R 615 and R 620 is the same, and more preferably R 611 is the same as R 616 , R 612 is the same as R 617 , R 613 is the same as R 618 , R 614 is the same as R 619 , and R 615 is the same as R 620 . are the same.
  • alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group, a bornyl group, and a norcalyl group. , calyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.
  • alkenyl groups having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene group.
  • Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thujen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadien-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group, or camphenyl group.
  • alkynyl group having 2 to 12 carbon atoms examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl group. group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octyn-8-yl group, 1-nonyn-9-yl group, It is a 1-decyn-10-yl group or a 1-dodecyn-12-yl group.
  • the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • the organic black pigment represented by formula (A-1-1) is preferably a compound represented by the following general formula (A-1-2) (hereinafter also referred to as "compound (A-1-2)"). ), and geometric isomers of compound (A-1-2).
  • Examples of the compound (A-1-2) include the trade name Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
  • This organic black pigment is preferably used after being dispersed using a dispersant, solvent, and method described below.
  • the sulfonic acid derivative of compound (A-1-1), especially the sulfonic acid derivative of compound (A-1-2) is present during dispersion, dispersibility and storage stability may be improved.
  • the black pigment contains these sulfonic acid derivatives.
  • the chemical structure of the organic coloring pigment is not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are shown below using pigment numbers. "C.I.” in “C.I. Pigment Red 2" and the like listed below means a color index.
  • red pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200
  • C. I. It is preferable to use Pigment Red 177, 254, and 272.
  • a red pigment with low ultraviolet absorbance When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use a red pigment with low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Red 254 and 272.
  • orange pigments examples include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. From the viewpoint of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Orange 13, 43, 64, and 72. When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use an orange pigment with a low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Orange 64 and 72.
  • blue pigments examples include C.I. I. 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, 79. From the viewpoint of light-shielding properties, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned. In addition, in terms of dispersibility and light blocking properties, C. I. Pigment Blue 15:6, 16, 60 is preferably used. When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use a blue pigment with low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Blue 60.
  • the purple pigment for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
  • C.I. I. Pigment Violet 19 23, 29, more preferably C.I. I. Pigment Violet 23 may be mentioned.
  • C. I. It is preferable to use Pigment Violet 23, 29.
  • When curing the photosensitive colored resin composition with ultraviolet rays it is preferable to use a purple pigment with a low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Violet 29.
  • green pigments examples include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. .
  • C. I. Pigment Green 7 and 36 can be mentioned.
  • yellow pigments examples include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 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
  • Red pigment C. I. Pigment Red 177, 254, 272
  • Orange pigment C. I. Pigment orange 43, 64, 72
  • Blue pigment C. I. Pigment Blue 15:6,60 Purple pigment: C. I. pigment violet 23, 29
  • the combination of organic coloring pigments when two or more types of organic coloring pigments are used together is not particularly limited, but from the viewpoint of light shielding, at least one type selected from the group consisting of red pigments and orange pigments, and blue pigments and purple pigments. It is preferable to contain at least one member selected from the group consisting of:
  • the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, examples include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment.
  • colorants other than the organic pigment (A-1) may be used in combination.
  • the colorant that can be used in combination is not particularly limited, and pigments or dyes may be used.
  • the other coloring agents used in combination with the organic pigment one type may be used alone, or two or more types may be used in combination. From the viewpoint of durability, it is preferable to use pigments. Examples include inorganic pigments.
  • inorganic black pigment it is preferable to use an inorganic black pigment from the viewpoint of higher light-shielding properties.
  • inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
  • Carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics.
  • Examples of carbon black include the following carbon blacks. Made by Mitsubishi Chemical: 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, #960, #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.
  • Printex registered trademark, same hereinafter
  • Printex3OP Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex8 5, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBla ck4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170.
  • Monarch registered trademark, same hereinafter
  • Monarch280 Monarch280
  • Monarch460 Monarch460
  • Monarch800 Monarch880
  • Monarch900 Monarch1000, Monarch1100, Monarch1300, Monarch1 400, Monarch4630
  • REGAL registered trademark, same hereinafter
  • REGAL registered trademark, same hereinafter
  • REGAL99R REGAL415
  • REGAL415R REGAL250
  • REGAL250R REGAL330
  • REGAL400R REGAL550R
  • REGAL660R BLACK PEARLS480, PEARLS130
  • VULCAN registered trademark, the same applies hereinafter
  • XC72R ELFTEX (registered trademark) Trademark)-8.
  • RAVEN registered trademark, same hereinafter
  • RAVEN14 RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, R AVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 .
  • Carbon black whose surface has been acid-treated may be used.
  • carbon black described in Japanese Patent No. 3,674,086 can be suitably used.
  • carbon black coated with a resin may be used.
  • Use of resin-coated carbon black has the effect of improving adhesion to glass substrates and volume resistivity.
  • the resin-coated carbon black for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used.
  • Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.
  • the average particle diameter of the pigment is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.25 ⁇ m or less.
  • the standard for the average particle diameter is the number of pigment particles.
  • the average particle diameter of the pigment is a value determined from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is performed using a sufficiently diluted photosensitive colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if the concentration is recommended by the measuring device) , according to its concentration) and measured at 25°C.
  • dyes may also be used.
  • dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes examples include C.I. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Dispersed Red 58, C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7 is mentioned.
  • anthraquinone dyes examples include C.I. I. Bat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Dispersed Red 60, C. I. Disperse Blue 56, C. I. An example is Disperse Blue 60.
  • phthalocyanine dyes examples include C.I. I. Bat Blue 5 is an example.
  • quinoneimine dyes include C.I. I. Basic Blue 3, C. I. Basic Blue 9 is an example.
  • quinoline dyes examples include C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64 is mentioned.
  • nitro dyes examples include C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. An example is Disperse Yellow 42.
  • the photosensitive colored resin composition of the present invention contains (B) a dispersant in order to finely disperse the colorant (A) and stabilize the dispersion state.
  • a dispersant a polymer dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary Polymer dispersants having functional groups such as an amino group; a quaternary ammonium group; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine are preferred.
  • polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium groups; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are used in small amounts as dispersants. It is particularly preferred from the viewpoint of being able to disperse pigments.
  • polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ether-based dispersants.
  • examples include dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersants examples include, for example, the trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), DISPARBYK (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.). (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.).
  • One type of polymer dispersant may be used alone, or two or more types may be used in combination.
  • the dispersant (B) preferably contains one or both of a urethane polymer dispersant having a functional group and an acrylic polymer dispersant, and an acrylic polymer dispersant. It is particularly preferable to include. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and one or both of a polyester bond and a polyether bond is preferred.
  • urethane-based and acrylic-based polymer dispersants examples include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic) (all manufactured by BYK Chemie). ).
  • the amine value of the polymer dispersant having a basic functional group is not particularly limited, but is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more. , 50 mgKOH/g or more is particularly preferred. Further, it is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, even more preferably 100 mgKOH/g or less, even more preferably 90 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 140 mgKOH/g, more preferably 10 to 120 mgKOH/g, even more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and particularly preferably 50 to 80 mgKOH/g.
  • the content is equal to or more than the lower limit, the dispersibility tends to be improved.
  • the content is below the upper limit, the compatibility with the alkali-soluble resin (C) tends to improve.
  • the acrylic dispersant is preferably an AB or BAB block copolymer composed of an A block having the above functional group and a B block not having the above functional group.
  • the A block in addition to the partial structure derived from the unsaturated group-containing monomer containing the above-mentioned functional group, contains a partial structure derived from the unsaturated group-containing monomer that does not contain the above-mentioned functional group. These may be contained in the A block in either random copolymerization or block copolymerization.
  • the content of the partial structure not containing a functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 10% by mass or less, Particularly preferably, it is 0% by mass.
  • the B block is preferably composed only of partial structures derived from unsaturated group-containing monomers that do not contain the above-mentioned functional groups, and two or more types of monomers are contained in one B block. may contain a partial structure derived from a body, and these may be contained in the B block in either random copolymerization or block copolymerization mode.
  • the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below. Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods. Among these, in the anionic living polymerization method, the polymerization active species is an anion, and is represented by the following scheme, for example.
  • Ar 1 is a monovalent organic group
  • Ar 2 is a monovalent organic group different from Ar 1
  • M is a metal atom
  • s and t are each an integer of 1 or more.
  • the polymerization active species is a radical, and is shown, for example, in the scheme below.
  • Ar 1 is a monovalent organic group
  • Ar 2 is a monovalent organic group different from Ar 1
  • j and k are each an integer of 1 or more
  • R a is a hydrogen atom or 1 It is a valent organic group
  • R b is a hydrogen atom or a monovalent organic group different from R a .
  • the acrylic dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block/B block copolymer constituting the copolymer may be
  • the block ratio is also not particularly limited, and is preferably 1/99 to 80/20 (mass ratio), more preferably 5/95 to 60/40 (mass ratio). By keeping it within this range, it tends to be easier to ensure a balance between dispersibility and storage stability.
  • the amount of quaternary ammonium groups in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By keeping it within this range, it tends to be easy to ensure good dispersibility.
  • Such an acrylic dispersant may contain an amino group.
  • the amine value of the acrylic dispersant is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more. Further, it is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, even more preferably 100 mgKOH/g or less, even more preferably 90 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the content is preferably 1 to 140 mgKOH/g, more preferably 10 to 120 mgKOH/g, even more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and particularly preferably 50 to 80 mgKOH/g.
  • the content is equal to or more than the lower limit, the dispersibility tends to be improved.
  • the content is below the upper limit, the compatibility with the alkali-soluble resin (C) tends to improve.
  • the amine value of the acrylic dispersant is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
  • Amine value [mgKOH/g] (561 ⁇ V)/(W ⁇ S) [However, W: weighed amount of dispersant sample [g], V: titration amount at titration end point [mL], S: solid content concentration of dispersant sample [mass %]. ]
  • the weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more. Further, it is preferably 50,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 50,000, more preferably 3,000 to 50,000, even more preferably 4,000 to 20,000, and particularly preferably 5,000 to 15,000.
  • the acrylic dispersant preferably has a tertiary amino group and/or a quaternary ammonium group.
  • the acrylic dispersant has a quaternary ammonium group as a functional group
  • the chemical structure of the repeating unit containing the quaternary ammonium group is not particularly limited. From the viewpoint of dispersibility, it is preferable that the acrylic dispersant has a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as "repeat unit (V)").
  • R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. and two or more of R 31 to R 33 may be bonded to each other to form a cyclic structure.
  • R 34 is a hydrogen atom or a methyl group.
  • X is a divalent linking group, and Y - is a counter anion.
  • the alkyl group which may have a substituent in R 31 to R 33 of formula (V) may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 2 or less.
  • the number is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 2.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group;
  • a group is preferable, a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are even more preferable.
  • the number of carbon atoms in the optionally substituted aryl group in R 31 to R 33 of formula (V) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and more preferably 12 or less.
  • 6 to 16 is preferable, and 6 to 12 is more preferable.
  • aryl group examples include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group; phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
  • the number of carbon atoms in the optionally substituted aralkyl group in R 31 to R 33 of formula (V) is not particularly limited, but is preferably 7 or more, preferably 16 or less, more preferably 12 or less, It is more preferably 10 or less, particularly preferably 8 or less.
  • the number is preferably 7 to 16, more preferably 7 to 12, even more preferably 7 to 10, and particularly preferably 7 to 8.
  • Examples of the aralkyl group include phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, and phenylisopropyl group, with phenylmethyl group, phenylethyl group, phenylpropyl group, and phenylbutyl group being preferred, and phenylmethyl and phenylethyl group are more preferred.
  • R 31 to R 33 are each independently an alkyl group or an aralkyl group, and it is preferable that R 31 to R 33 are each independently a methyl group or a phenylmethyl group.
  • Y ⁇ in formula (V) include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , and PF ⁇ .
  • Sulfate anions and alkylsulfonate anions can also be suitably used.
  • Cl - is preferable as Y - .
  • alkylsulfonate anions are preferred.
  • repeating unit (VI) When a polymeric dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility and luminescent properties, the repeating unit represented by the following general formula (VI) (hereinafter referred to as “repeating unit (VI)”) ) is preferable.
  • R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • R 35 and R 36 may be bonded to each other to form a cyclic structure.
  • R 37 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group.
  • alkyl group which may have a substituent in R 35 and R 36 of formula (VI) those exemplified as R 31 to R 33 of formula (V) can be preferably employed.
  • aryl group which may have a substituent in R 35 and R 36 of formula (VI) those exemplified as R 31 to R 33 of formula (V) can be preferably employed.
  • aralkyl group which may have a substituent in R 35 and R 36 of formula (VI) those exemplified as R 31 to R 33 of formula (V) can be preferably employed.
  • R 35 and R 36 are each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
  • Examples of the substituent that the alkyl group, aralkyl group, or aryl group in R 31 to R 33 of formula (V) and R 35 and R 36 of formula (VI) may have include a halogen atom, an alkoxy group, Examples include benzoyl group and hydroxyl group.
  • X in formula (V) and Z in formula (VI) are, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 - group, -COOR 44 -, respectively.
  • the content ratio of the repeating unit (V) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more. , 8 mol% or more is particularly preferred. Further, it is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less.
  • the content of the repeating unit (VI) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. , 20 mol% or more is particularly preferred. Moreover, it is preferably 60 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
  • acrylic dispersants are used as repeating units represented by the following general formula (VII) (hereinafter referred to as “repeating units (VII)”). )”) is preferable.
  • R 40 is an ethylene group or a propylene group
  • R 41 is an alkyl group which may have a substituent
  • R 42 is a hydrogen atom or a methyl group.
  • n is an integer from 1 to 20.
  • the alkyl group which may have a substituent in R 41 of formula (VII) may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Further, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group;
  • a group is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable.
  • n is preferably 1 or more, and more preferably 2 or more, from the viewpoint of compatibility and dispersibility with an alkali-soluble resin component such as a solvent. Moreover, 10 or less is preferable, and 5 or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, and 2 to 5 is more preferable.
  • the content of the repeating unit (VII) in all repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more. Moreover, it is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%. When it is within the above range, it tends to be easy to achieve both compatibility with an alkali-soluble resin component such as a solvent and dispersion stability.
  • the acrylic dispersant is a repeating unit represented by the following general formula (VIII) (hereinafter referred to as a "repeat unit ( VIII).
  • R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 39 is a hydrogen atom or a methyl group.
  • the alkyl group which may have a substituent in R 38 of formula (VIII) may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more. Moreover, 10 or less is preferable, and 8 or less is more preferable.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group; , pentyl group, hexyl group, and 2-ethylhexyl group are preferable, and methyl group, ethyl group, propyl group, butyl group, and 2-ethylhexyl group are more preferable.
  • the number of carbon atoms in the aryl group which may have a substituent in R 38 of formula (VIII) is not particularly limited, but is preferably 6 or more. Moreover, it is preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, the number is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 8.
  • aryl group examples include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group; phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
  • the number of carbon atoms in the optionally substituted aralkyl group in R 38 of formula (VIII) is not particularly limited, but is preferably 7 or more, preferably 16 or less, more preferably 12 or less, and 10 or less. More preferred. For example, the number is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 10.
  • the aralkyl group include phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, and phenylisopropyl group, and phenylmethyl group, phenylethyl group, phenylpropyl group, or phenylbutyl group is mentioned.
  • a phenylmethyl group or a phenylethyl group is more preferable.
  • R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, ethyl group, butyl group, 2-ethylhexyl group or phenylmethyl group.
  • substituents that the alkyl group in R 38 may have include a halogen atom and an alkoxy group.
  • substituents that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
  • the chain alkyl group represented by R 38 includes both straight chain and branched chain alkyl groups.
  • the content of the repeating unit (VIII) in all repeating units of the dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. Further, it is preferably 80 mol% or less, more preferably 70 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, even more preferably 50 to 70 mol%.
  • the acrylic dispersant may have repeating units other than repeating units (V), repeating units (VI), repeating units (VII), and repeating units (VIII).
  • repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Examples include (meth)acrylamide monomers such as methylol acrylamide; repeating units derived from monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine.
  • the acrylic dispersant consists of an A block having a repeating unit (V) and a repeating unit (VI), and a B block not having a repeating unit (V) and a repeating unit (VI). It is preferable that it is a block copolymer having the following.
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer.
  • the B block has a repeating unit (VII), and more preferably a repeating unit (VIII).
  • the repeating unit (V) and the repeating unit (VI) may be contained in either random copolymerization or block copolymerization.
  • two or more types of repeating units (V) and repeating units (VI) may be contained in one A block, and in that case, each repeating unit may be randomly copolymerized or block It may be contained in any form of copolymerization.
  • Repeating units other than the repeating unit (V) and the repeating unit (VI) may be contained in the A block, and examples of such repeating units include the above-mentioned (meth)acrylic acid ester monomers. Examples include repeating units derived from The content of repeating units other than repeating units (V) and repeating units (VI) in A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are It is particularly preferred that it is not contained in the block.
  • Repeating units other than the repeating unit (VII) and the repeating unit (VIII) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and ⁇ -methylstyrene.
  • (meth)acrylate monomers such as (meth)acrylic acid chloride;
  • (meth)acrylamide monomers such as (meth)acrylamide and N-methylol acrylamide; vinyl acetate, acrylonitrile, allyl glycidyl ether, croton
  • Examples include repeating units derived from monomers such as acid glycidyl ether and N-methacryloylmorpholine.
  • the content ratio of repeating units other than the repeating unit (VII) and the repeating unit (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are It is particularly preferred that it is not contained in the block.
  • These acrylic dispersants may be used alone or in combination of two or more.
  • the photosensitive colored resin composition of the present invention contains (C) an alkali-soluble resin.
  • the alkali-soluble resin contains a resin (C1) having a structural unit represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
  • Each * represents a bond.
  • the resin (C1) has a high affinity with pigments, contains a methylene group in its main chain, and has flexibility that can follow the pigment, so it tends to exhibit high pigment dispersibility.
  • the resin (C1) contains many aromatic rings in the main chain, it has high developer resistance during development in photosensitive colored resin compositions, and high heat resistance during baking, resulting in a high residual film rate.
  • a high residual film rate tends to prevent decomposed products, by-products, uncured products, etc. in the composition from remaining on the electrode (anode) or re-adhering.
  • an organic electroluminescent device is formed using a barrier rib obtained by curing a photosensitive colored resin composition, the amount of residue and re-deposition on the anode is reduced, which reduces the amount of deposits on the pixel area. This tends to increase the current density when a voltage is applied to the organic electroluminescent device and improve the brightness of the light emitting device.
  • Each R 2 in formula (1) independently represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of solvent solubility, the number of carbon atoms in the alkyl group in R 2 is preferably 1 or more, preferably 3 or less, and more preferably 2 or less.
  • the alkyl group may be straight chain or branched. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group. A methyl group is preferred from the viewpoint of dispersibility.
  • (L) L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
  • L preferably has 3 or more carbon atoms, more preferably 4 carbon atoms. Moreover, 5 or less is preferable. For example, it may be 3-6, it may be 3-5, it may be 4-6, it may be 4-5.
  • L has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent, and may be further substituted with a methoxy group or an ethoxy group.
  • the polybasic acid means a polybasic acid listed in the polybasic acid residues described below.
  • the ester group of a hydroxyl group and a polybasic acid means a group in which a hydroxyl group bonded to L forms an ester with a polybasic acid.
  • the structural units of formula (1) it is preferable to have a structural unit described by the following general formula (2).
  • A represents a hydrogen atom or a polybasic acid residue.
  • R 1 represents a hydrogen atom or a methyl group.
  • Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
  • Each * represents a bond.
  • a in formula (1) represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
  • Examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more Preferred are phthalic acid, succinic acid, trimellitic acid, and pyromellitic acid.
  • trimellitic acid is preferred because the number of hydroxyl groups with high solvent affinity increases relative to the other basic acid residues.
  • R 1 ) R 1 in formula (1) represents a hydrogen atom or a methyl group. Hydrogen atoms are preferred from the viewpoint of curability.
  • Each R 2 in formula (1) independently represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of solvent solubility, the number of carbon atoms in the alkyl group in R 2 is preferably 1 or more, preferably 3 or less, and more preferably 2 or less.
  • the alkyl group may be straight chain or branched. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group. A methyl group is preferred from the viewpoint of dispersibility.
  • the partial structure represented by formula (1) contained in the resin (C1) may be one type or two or more types, for example, one where A is a hydrogen atom and one where A is a polybasic acid residue. They may be mixed.
  • Examples of the resin (C1) include structures represented by the following general formulas (C1-1) to (C1-8).
  • the resin (C1) preferably has a structure represented by formula (C1-1), formula (C1-3), formula (C1-7), or formula (C1-8).
  • the acid value of the resin (C1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g or more. Further, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, even more preferably 100 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 200 mgKOH/g, more preferably 30 to 150 mgKOH/g, even more preferably 40 to 100 mgKOH/g, and even more preferably 50 to 80 mgKOH/g.
  • the amount is at least the lower limit, development solubility tends to improve and resolution tends to improve. There is a tendency for the residual film rate to become good by setting it below the upper limit value.
  • the method for producing the resin (C1) is not particularly limited, but for example, (meth)acrylic acid is added to an epoxy resin represented by the following general formula (1-2), and then reacted with a polybasic acid and/or its anhydride. It can be obtained by letting
  • R 2 and * in formula (1-2) have the same meanings as in formula (1).
  • Examples of the epoxy resin represented by formula (1-2) include the following epoxy resins.
  • m represents an integer from 2 to 8.
  • an epoxy resin and (meth)acrylic acid can be reacted at a temperature of 50 to 150° C. in the presence of an esterification catalyst.
  • an esterification catalyst for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
  • tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine
  • quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
  • polybasic acid and/or its anhydride the above-mentioned polybasic acid or its anhydride can be mentioned.
  • the addition reaction of a polybasic acid and/or its anhydride can be performed using a known method.
  • the photosensitive colored resin composition used in the present invention may contain (C) an alkali-soluble resin other than the resin (C1).
  • an alkali-soluble resin other than the resin (C1) there is no particular limitation as long as the resin exhibits alkali solubility, and examples thereof include resins containing carboxyl groups or hydroxyl groups. More specifically, examples include epoxy (meth)acrylate resins, acrylic resins, and carboxyl group-containing epoxy resins. Examples include resins, carboxyl group-containing urethane resins, novolac resins, polyvinylphenol resins, and isocyanuric skeleton-containing resins.
  • the alkali-soluble resin (C) other than resin (C1) is (C2) Epoxy (meth)acrylate resin (C3) Isocyanuric skeleton-containing resin (C4)
  • Acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making properties. These can be used alone or in combination of two or more.
  • the (C2) epoxy (meth)acrylate resin in the present invention is an alkali-soluble resin (C) other than the resin (C1), and is composed of an epoxy compound (epoxy resin) and an ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester.
  • a compound that has two or more substituents that can further react with a hydroxyl group such as a polybasic acid and/or its anhydride, in addition to the hydroxyl group produced by the reaction with an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in its moiety.
  • the isocyanuric skeleton-containing resin (C3) described below is not included. Before reacting the polybasic acid and/or its anhydride with a hydroxyl group, a compound having two or more substituents that can react with a hydroxyl group is reacted, and then the polybasic acid and/or its anhydride is reacted. The resin obtained by this is also included in the (C2) epoxy (meth)acrylate resin.
  • Epoxy (meth)acrylate resin has a chemical structure that substantially does not have an epoxy group, and is not limited to "(meth)acrylate,” but it uses an epoxy compound (epoxy resin) as a raw material, and , "(meth)acrylate” is a typical example, so it is named this way according to common usage.
  • epoxy (meth)acrylate resin used in the present invention the following epoxy (meth)acrylate resin (C2-1) and/or epoxy (meth)acrylate resin (C2-2) (hereinafter referred to as "carboxylic (sometimes referred to as “group-containing epoxy (meth)acrylate resin”) is preferably used from the viewpoint of developability and reliability.
  • carboxylic sometimes referred to as "group-containing epoxy (meth)acrylate resin”
  • epoxy (meth)acrylate resin one having an aromatic ring in the main chain can be more preferably used from the viewpoint of outgassing.
  • the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer. Examples of the types of epoxy resins used as raw materials include cresol novolak epoxy resin, phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, trisphenolmethane epoxy resin, biphenyl novolac epoxy resin, and naphthalene.
  • Novolak-type epoxy resins epoxy resins that are reaction products of polyaddition products of dicyclopentadiene and phenol or cresol, and epihalohydrin, adamantyl group-containing epoxy resins, and fluorene-type epoxy resins can be suitably used. Those having an aromatic ring can be more preferably used.
  • epoxy resins examples include bisphenol A type epoxy resins (for example, "jER (registered trademark, the same applies hereinafter) 828", “jER1001", “jER1002", “jER1004", etc. manufactured by Mitsubishi Chemical Corporation), bisphenol A type epoxy resins, etc. Epoxy resins obtained by the reaction of alcoholic hydroxyl groups of epoxy resins with epichlorohydrin (for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point 76°C)), bisphenol F type resins (for example, manufactured by Mitsubishi Chemical Co., Ltd.) "JER807", “EP-4001”, “EP-4002", “EP-4004", etc.
  • bisphenol A type epoxy resins for example, "jER (registered trademark, the same applies hereinafter) 828", “jER1001", “jER1002", “jER1004", etc. manufactured by Mitsubishi Chemical Corporation
  • a is an average value and represents a number from 0 to 10
  • each R 111 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. group, phenyl group, naphthyl group, or biphenyl group. Note that a plurality of R 111s present in one molecule may be the same or different.
  • b1 and b2 are average values, and each independently represents a number from 0 to 10, and R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. ⁇ 10 cycloalkyl, phenyl, naphthyl, or biphenyl groups. Note that the plurality of R 121s present in one molecule may be the same or different.
  • X represents a linking group represented by the following general formula (C2 ⁇ -1) or (C2 ⁇ -2).
  • the molecular structure contains one or more adamantane structures.
  • c represents 2 or 3.
  • R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group which may have a substituent, a hydrogen atom, or a substituent. represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or a phenyl group optionally having a substituent, and * represents a bond.
  • R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
  • R 143 and R 144 are Each independently represents an alkylene group having 1 to 4 carbon atoms
  • x and y each independently represents an integer of 0 or more.
  • epoxy resin it is preferable to use an epoxy resin represented by any of the formulas (C2 ⁇ ) to (C2 ⁇ ).
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, Monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 -(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2 -(meth)acryloyl
  • a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin a known method can be used. For example, it is possible to react an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150°C in the presence of an esterification catalyst. can.
  • esterification catalyst used here for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
  • tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine
  • quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride
  • Each component of the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be selected one by one and used. , two or more types may be used in combination.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents per equivalent of epoxy group in the epoxy resin, and Preferably it is 0.7 to 1.1 equivalent.
  • polybasic acids and/or anhydrides examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, and methylhexahydrophthalic acid.
  • examples include hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • the addition reaction of a polybasic acid and/or its anhydride can be carried out using a known method.
  • the desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of carboxylic acid esters.
  • the amount of polybasic acid and/or its anhydride component added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is 10 to 150 mgKOH/g, and more preferably 20 to 150 mgKOH/g. It is preferable that the amount added be ⁇ 140 mgKOH/g.
  • the amount is equal to or more than the lower limit, the alkali developability tends to be improved. There is a tendency for curing performance to be improved by setting the amount to be less than or equal to the upper limit value.
  • polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc.
  • polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc.
  • any hydroxyl group present in the mixture of the epoxy resin and the reaction product of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and polyfunctional alcohol is removed.
  • a polybasic acid and/or its anhydride undergoes an addition reaction.
  • carboxyl group-containing epoxy (meth)acrylate resin in addition to the above-mentioned ones, examples include those described in Korean Patent Publication No. 10-2013-0022955.
  • the weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, It is even more preferably 3,000 or more, particularly preferably 4,000 or more, particularly preferably 5,000 or more. Further, it is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 1,500 to 20,000, even more preferably 1,500 to 15,000, and even more preferably 2,000 to 15,000.
  • the amount By setting the amount to be at least the lower limit, it tends to be possible to prevent the solubility in the developer from becoming too high. By setting it below the above-mentioned upper limit, there is a tendency that the solubility in the developer tends to be good.
  • the acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more. , 100 mgKOH/g or more is particularly preferred. Moreover, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, and 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
  • amount is at least the lower limit, development solubility tends to improve and resolution tends to improve.
  • the residual film rate of the photosensitive colored resin composition tends to be good.
  • the chemical structure of the epoxy (meth)acrylate resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (C2-I) Resin (hereinafter sometimes abbreviated as "(C2-I) epoxy (meth)acrylate resin”) and/or epoxy (meth)acrylate having a partial structure represented by the following general formula (C2-II) It is preferable to contain a resin (hereinafter sometimes abbreviated as "(C2-II) epoxy (meth)acrylate resin").
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group that may have a substituent
  • k represents 1 or 2
  • the benzene ring in formula (C2-I) may be further substituted with any substituent.
  • R 13 each independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represent an integer of 0 to 2
  • * represents a bond.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group that may have a substituent
  • k represents 1 or 2
  • the benzene ring in formula (C2-I) may be further substituted with any substituent.
  • R 12 represents a divalent hydrocarbon group which may have a substituent.
  • divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.
  • Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, a cyclic aliphatic group is preferable from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
  • the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
  • the divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group.
  • Examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Moreover, 12 or less is preferable, and 10 or less is more preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 12, more preferably 1 to 10, and even more preferably 2 to 10. When the amount is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate.
  • divalent cyclic aliphatic groups include hydrogen atoms removed from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, dicyclopentadiene, and dicyclopentane.
  • groups divided by two From the viewpoint of rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring is preferable.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
  • divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
  • Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • divalent aromatic heterocyclic group examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of development solubility, non-substitution is preferred.
  • the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group.
  • Examples include groups in which one or more are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, also preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
  • the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • Examples of groups connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include those represented by the following formulas (C2-I-A) to (C2-IF). Examples include groups such as In the following formulas (C2-IA) to (C2-IF), * represents a bond. From the viewpoint of rigidity of the skeleton and hydrophobicization of the membrane, a group represented by the following formula (C2-IA) is preferable.
  • k represents 1 or 2. From the viewpoint of adhesion and plate-making properties, k is preferably 1. From the viewpoint of sensitivity, k is preferably 2. Furthermore, both a partial structure in which k is 1 and a partial structure in which k is 2 may be contained in the (C2-I) epoxy (meth)acrylate.
  • the benzene ring in formula (C2-I) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of plate-making properties, it is preferable that no substitution be made.
  • the partial structure represented by formula (C2-I) is preferably a partial structure represented by the following general formula (C2-I-1) from the viewpoint of ease of synthesis.
  • R 11 , R 12 and k have the same meanings as in formula (C2-I), R x represents a hydrogen atom or a polybasic acid residue, and * represents a bond. .
  • the benzene ring in formula (C2-I-1) may be further substituted with any substituent.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
  • examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid is more preferable.
  • phthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid.
  • the benzene ring in formula (C2-I-1) may be further substituted with any substituent.
  • substituent those listed for the benzene ring in formula (C2-I) can be preferably employed.
  • the partial structure represented by formula (C2-I-1) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R x is hydrogen. There may be a mixture of atoms and those in which R x is a polybasic acid residue.
  • the number of partial structures represented by formula (C2-I) contained in one molecule of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable, and 15 or less is more preferable.
  • the above upper and lower limits can be arbitrarily combined. The number is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, most preferably 5,000 or more, and preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 1,500 to 2,000, even more preferably 1,500 to 15,000, even more preferably 2,000 to 1,500.
  • the amount is equal to or more than the lower limit, the remaining film rate of the photosensitive colored resin composition tends to be good.
  • the solubility in the developer tends to be improved.
  • the acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, and 80 mgKOH/g or more. It is even more preferable, and particularly preferably 100 mgKOH/g or more. Moreover, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is even more preferable, and 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
  • amount is at least the lower limit, development solubility tends to improve and resolution tends to improve.
  • the residual film rate of the photosensitive colored resin composition tends to be good.
  • R 13 each independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represent an integer of 0 to 2
  • * represents a bond.
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • the number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate and resolution of the photosensitive colored resin composition, an adamantane ring is preferred.
  • the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 4, even more preferably 2 to 4, and particularly preferably 3 to 4.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 4 to 40, more preferably 6 to 40, even more preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • patterning characteristics tend to be improved.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • Examples include rings. From the viewpoint of patterning properties, a fluorene ring is preferred.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are connected.
  • Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups.
  • a linear aliphatic group is preferred from the viewpoint of development solubility, while a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
  • the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
  • Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. , an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the content is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate.
  • the upper limit deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of skeleton rigidity, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
  • divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
  • Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • divalent aromatic heterocyclic group examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of development solubility, non-substitution is preferred.
  • the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group.
  • Examples include groups in which one or more are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
  • the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • Examples of groups linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include those represented by the above-mentioned formulas (C2-I-A) to (C2-IF). The following groups are mentioned. From the viewpoint of skeleton rigidity and membrane hydrophobization, a group represented by formula (C2-IC) is preferred.
  • the bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but for example, if one hydrogen atom of an aliphatic group or an aromatic ring group is Examples include an embodiment in which the aliphatic group is substituted with a hydrocarbon group, and an embodiment in which a cyclic hydrocarbon group that is a side chain includes one of the carbon atoms of the aliphatic group.
  • R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent.
  • Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups.
  • a linear aliphatic group is preferred from the viewpoint of development solubility, while a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.
  • the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
  • the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
  • the divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group.
  • Examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Moreover, 12 or less is preferable, and 10 or less is more preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, 1 to 12 is preferable, and 2 to 10 is more preferable. When the amount is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate.
  • divalent cyclic aliphatic groups include groups obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and dicyclopentadiene ring. Can be mentioned. From the viewpoint of skeleton rigidity, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
  • m and n each independently represent an integer of 0 to 2.
  • the amount is at least the lower limit, patterning becomes more appropriate and surface roughness that occurs during development tends to be less likely to occur, and when the amount is at most the upper limit, the developability tends to be good.
  • m and n are preferably 0.
  • m and n are preferably 1 or more.
  • the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-1) from the viewpoint of adhesion to the substrate.
  • R 13 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), and R ⁇ is a monovalent group which may have a substituent. represents a cyclic hydrocarbon group, p represents an integer of 1 or more, and * represents a bond.
  • the benzene ring in formula (C2-II-1) may be further substituted with any substituent.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Further, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 1 to 6 are preferred, 1 to 4 are more preferred, 1 to 3 are even more preferred, and 2 to 3 are particularly preferred.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
  • the number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
  • Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.
  • the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, preferably 2 or more, and more preferably 3 or more. Moreover, 10 or less is preferable, and 5 or less is more preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
  • the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
  • the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of development solubility, a fluorene ring is preferred.
  • substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
  • p represents an integer of 1 or more, preferably 2 or more. Moreover, 3 or less is preferable. For example, 1 to 3 are preferable, and 2 to 3 are more preferable.
  • the amount is equal to or more than the lower limit, the degree of film curing and the remaining film rate tend to be good.
  • the amount is below the upper limit, developability tends to be improved.
  • R ⁇ is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
  • the benzene ring in formula (C2-II-1) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of patterning properties, it is preferable that no substitution be made.
  • the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-2) from the viewpoint of skeleton rigidity and membrane hydrophobization.
  • R 13 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), and R ⁇ is a divalent group which may have a substituent. represents a cyclic hydrocarbon group, and * represents a bond.
  • the benzene ring in formula (C2-II-2) may be further substituted with any substituent.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Moreover, 10 or less is preferable, and 5 or less is more preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, and 2 to 5 is more preferable.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
  • the number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30.
  • Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate after development and the resolution, an adamantane ring is preferable.
  • the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Moreover, 10 or less is preferable, and 5 or less is more preferable.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
  • the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • deterioration of sensitivity and film thinning can be easily suppressed, and resolution tends to improve.
  • the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and even more preferably 10 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • fluorene rings are preferred. Since the plane forming the fluorene ring is perpendicular to the bond connecting the two benzene rings, it becomes bulkier and has a more rigid skeleton, making it difficult for developer solution to penetrate and shrinkage during baking.As a result, there is no residual film. It is estimated that the rate will increase.
  • substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
  • R ⁇ is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.
  • R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
  • the benzene ring in formula (C2-II-2) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more.
  • two benzene rings may be connected via a substituent.
  • Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH 2 -. From the viewpoint of patterning properties, it is preferable that no substitution be made. Furthermore, from the viewpoint of making film thinning less likely to occur, methyl group substitution is preferable.
  • the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-3) from the viewpoint of coating film residual rate and patterning characteristics.
  • R 13 , R 14 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), and R Z represents a hydrogen atom or a polybasic acid residue. represent.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Note that one more OH group may be removed and shared with R Z in another molecule represented by formula (C2-II-3). That is, a plurality of formulas (C2-II-3) may be connected via R Z.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
  • Examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid is more preferable.
  • They are phthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.
  • the partial structure represented by formula (C2-II-3) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R Z is hydrogen. There may be a mixture of atoms and those in which R Z is a polybasic acid residue.
  • the number of partial structures represented by the formula (C2-II) contained in one molecule of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, particularly preferably 5000 or more. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 1,000 to 10,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 8,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 7,000.
  • the amount is equal to or more than the lower limit, the remaining film rate of the photosensitive colored resin composition tends to be good.
  • the content is below the upper limit, the solubility in the developer tends to be improved.
  • the acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, and even more preferably 80 mgKOH/g or more. More preferably, 100 mgKOH/g or more is particularly preferable. Moreover, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is even more preferable, and 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
  • amount is at least the lower limit, development solubility tends to improve and resolution tends to improve.
  • the residual film rate of the photosensitive colored resin composition tends to be good.
  • the epoxy (meth)acrylate resin may be used alone or in combination of two or more.
  • an isocyanuric skeleton-containing resin having an ethylenic double bond and a carboxyl group may be used as the alkali-soluble resin (C) other than the resin (C1).
  • C3 isocyanuric skeleton-containing resin Having an isocyanuric skeleton, an ethylenic double bond, and a carboxy group improves chemical resistance and heat resistance, and reduces the amount of decomposed products during development and baking, making it easier to apply voltage in organic electric field devices. There is a tendency for the current density to become high.
  • Isocyanuric skeleton-containing resin is an alkali-soluble resin (C) other than resin (C1), and is not particularly limited as long as it has an ethylenic double bond, a carboxyl group, and an isocyanuric skeleton, but for example, the following ( Examples include resins C3-1) and (C3-2).
  • Examples of the epoxy group-containing compound having an isocyanuric skeleton include a compound represented by the following general formula (C3-1-1).
  • R 4 to R 6 each independently represent an alkylene group, and the alkylene group may be interrupted by an etheric oxygen atom.
  • the alkylene group preferably has 1 or more carbon atoms. Further, the number of carbon atoms is preferably 6 or less, more preferably 4 or less, and even more preferably 2 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, 1 to 6 are preferred, 1 to 4 are more preferred, and 1 to 2 are even more preferred.
  • the alkylene group may be linear or branched. When the amount is below the upper limit, developability tends to be good and gas barrier properties tend to improve. Examples of the alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, and n-hexylene group.
  • an alkylene group that is split by an etheric oxygen atom in the middle 1 to 10 carbon atoms of the alkylene chain, which may be a straight chain or branched with 4 to 30 carbon atoms, are replaced with oxygen atoms.
  • a group containing 2 to 9 ethoxy groups linked together and a group containing 2 to 7 propoxy groups linked together can be mentioned.
  • methylene groups, ethylene groups, and n-propylene groups are preferred, and methylene groups are more preferred.
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester compound include monocarboxylic acids such as (meth)acrylic acid, ⁇ -haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipate, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2 -(meth)acryloyloxypropyl phthalic acid, 2-
  • polybasic acids and/or anhydrides examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, and methylhexahydrophthalic acid.
  • examples include hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • the same method as for (C2) epoxy (meth)acrylate resin can be used.
  • the ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester compound include the same compounds as those described in the section of (C2) epoxy (meth)acrylate resin.
  • examples of the polybasic acid and/or its anhydride include the same compounds as those described in the section of resin (C1).
  • (C3-2) A resin obtained by reacting an epoxy group-containing (meth)acrylate compound with a compound obtained by reacting a polyisocyanate compound having an isocyanuric skeleton with an acid or an acid anhydride.
  • the resin (C3-2) include the resin described in Japanese Patent Application Publication No. 2020-75994, and intermediates thereof.
  • the weight average molecular weight (Mw) of the isocyanuric skeleton-containing resin is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, and even more preferably 4,000 or more. , 5000 or more is particularly preferred. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 10,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 8,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 7,000.
  • the amount By setting the amount to be at least the lower limit, it tends to be possible to prevent the solubility in the developer from becoming too high. By setting it below the above-mentioned upper limit, there is a tendency that the solubility in the developer tends to be good.
  • the acid value of the isocyanuric skeleton-containing resin is not particularly limited, but is preferably at least 20 mgKOH/g, more preferably at least 40 mgKOH/g, even more preferably at least 60 mgKOH/g, even more preferably at least 80 mgKOH/g, and even more preferably at least 100 mgKOH/g. g or more is particularly preferable. Moreover, 200 mgKOH/g or less is preferable, and 150 mgKOH/g or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 20 to 200 mgKOH/g is preferable, and 60 to 150 mgKOH/g is more preferable. When the amount is at least the lower limit, development solubility tends to improve and resolution tends to improve. By setting it below the upper limit, the residual film rate of the photosensitive colored resin composition tends to be good.
  • Acrylic copolymer resin may be used as the alkali-soluble resin (C4) in addition to resin (C1) from the viewpoint of compatibility with pigments, dispersants, etc.
  • acrylic copolymer resin for example, those described in Japanese Patent Application Publication No. 2014-137466 can be preferably used.
  • the acrylic copolymer resin includes, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (C4-1)”) and other copolymer resins. Examples include copolymers with possible ethylenically unsaturated monomers (hereinafter referred to as “unsaturated monomers (C4-2)"). Examples of the unsaturated monomer (C4-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid.
  • unsaturated monomer (C4-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid.
  • Examples of the unsaturated monomer (C4-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;
  • Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ]decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane, etc. ;
  • Examples include macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.
  • These unsaturated monomers (C4-2) can be used alone or in combination of two or more.
  • the copolymerization ratio of unsaturated monomer (C4-1) is preferably 5 to 50% by mass. , more preferably 10 to 40% by mass.
  • copolymers of unsaturated monomers (C4-1) and unsaturated monomers (C4-2) include Japanese Patent Application Publication No. 7-140654, Japanese Patent Application Publication No. 8-259876, Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Unexamined Japanese Patent Application No. 11-174224, Unexamined Japanese Patent Application No. 11-258415, Unexamined Japanese Patent Application No. 2000-56118, Copolymers disclosed in Japanese Patent Application Publication No. 2004-101728 can be mentioned.
  • the copolymer of unsaturated monomer (C4-1) and unsaturated monomer (C4-2) can be produced by a known method, but for example, Japanese Patent Application Publication No. 2003-222717,
  • the structure, Mw, and Mw/Mn (Mn is the number average molecular weight) can also be controlled by the methods disclosed in Japanese Patent Application Publication No. 2006-259680 and International Publication No. 2007/029871.
  • the photosensitive colored resin composition of the present invention contains (D) a photopolymerization initiator.
  • the photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization-active radicals.
  • Additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added as necessary.
  • photopolymerization initiators for example, metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Publication No.
  • metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl).
  • hexaarylbiimidazole derivatives examples include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl) ) imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'- methoxyphenyl)-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-( Examples include 4-morpholinophenyl)butan-1-one and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.
  • oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties.
  • an oxime ester compound is particularly effective in such sensitivity.
  • Oxime ester compounds are useful. Oxime ester compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. Therefore, it is possible to obtain a highly sensitive photosensitive colored resin composition in a small amount.
  • oxime ester compounds include compounds represented by the following general formula (IV).
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 21b represents an arbitrary substituent containing an aromatic ring.
  • R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
  • n represents an integer of 0 or 1.
  • the number of carbon atoms in the alkyl group in R21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, 10 The following are more preferred.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group.
  • alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group and N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
  • Examples of the aromatic ring group for R 21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive colored resin composition. Further, from the viewpoint of developability, the number is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
  • Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.
  • Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked.
  • R 21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent.
  • R 21b is an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, or an optionally substituted indolyl group can be mentioned. From the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred. From the viewpoint of electrical reliability, an optionally substituted diphenyl sulfide group is preferred.
  • the number of carbon atoms in the alkanoyl group in R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, 5 The following are particularly preferred.
  • examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.
  • substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
  • the number of carbon atoms in the aroyl group in R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, more preferably 8 or more, and preferably 20 or less, more preferably 15 or less, 10 The following are more preferred.
  • Examples of the aroyl group include a benzoyl group and a naphthoyl group.
  • substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
  • R 22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • the initiator described in Japanese Patent Application Publication No. 2016-133574 can also be suitably used in terms of reducing staining caused by colorants.
  • the photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing the sensitivity.
  • the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335.
  • a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
  • a sensitizing dye a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
  • Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benz
  • polymerization accelerator for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described below are used. .
  • aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate
  • aliphatic amines such as n-butylamine and N-methyldiethanolamine
  • mercapto compounds described below are used.
  • the polymerization accelerators may be used alone or in combination of two or more.
  • the photosensitive colored resin composition of the present invention may also contain (E) an ethylenically unsaturated compound.
  • (E) Containing an ethylenically unsaturated compound tends to improve sensitivity.
  • the ethylenically unsaturated compound (E) used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples include (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and monoester of polyhydric or monohydric alcohol.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly preferable to use.
  • the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 4 or more, even more preferably 5 or more, and preferably 8 or less, More preferably, the number is 7 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 2 to 8, more preferably 2 to 7, even more preferably 4 to 7, and particularly preferably 5 to 7.
  • the value is equal to or higher than the lower limit value, there is a tendency for high sensitivity to be obtained.
  • polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a compound, and an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyhydroxy compound acrylic esters; methacrylic esters in which these acrylates are replaced with methacrylate; Examples include itaconate esters in which acrylate is replaced with itaconate; crotonic esters in which these acrylates are replaced with cronates; and maleate esters in which these acrylates are replaced with maleates.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • acid esters include acid esters.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyhydric hydroxy compound is not necessarily a single substance, but for example, a condensate of acrylic acid, phthalic acid, and ethylene glycol, Examples include condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.
  • the polyfunctional ethylenic monomer used in the present invention includes, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylic ester.
  • Urethane (meth)acrylates such as those obtained; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; Acrylamides such as ethylene bisacrylamide; Diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate.
  • urethane (meth)acrylates examples 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 Kyoeisha Chemical Co., Ltd.), UV-1700B, UV- Examples include 7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
  • (E) ethylenically unsaturated compounds include (meth)acrylic acid alkyl esters, polyisocyanate compounds and hydroxyl group-containing (meth)acrylic esters, or polyisocyanate compounds and polyols and hydroxyl group-containing (meth)acrylic esters. It is preferable to use urethane (meth)acrylates such as those obtained by reacting the following, and it is more preferable to use a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester. These may be used alone or in combination of two or more.
  • the photosensitive colored resin composition of the present invention includes adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, etc. Additives may be appropriately blended.
  • the photosensitive colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion with the substrate.
  • an adhesion improver silane coupling agents and phosphoric acid group-containing compounds are preferred.
  • silane coupling agent various types such as epoxy type, (meth)acrylic type, and amino type may be used alone or in combination of two or more types.
  • silane coupling agent examples include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxysilanes such as 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples include isocyanate silanes such as 3-isocyanatepropyltriethoxysilane.
  • Silane coupling agents such as epoxysilanes are particularly preferred.
  • (meth)acryloyl group-containing phosphates are preferred, and those represented by the following general formula (g1), (g2) or (g3) are preferred.
  • R 51 represents a hydrogen atom or a methyl group
  • l and l' are integers of 1 to 10
  • m is 1, 2 or 3.
  • These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
  • the photosensitive colored resin composition of the present invention may contain a surfactant to improve coating properties.
  • surfactant various types of surfactants can be used, such as anionic, cationic, nonionic, and amphoteric surfactants. It is preferable to use nonionic surfactants because they are less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are more preferable from the viewpoint of coating properties. Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340.
  • surfactant manufactured by Shin-Etsu Silicone
  • F-470, F-475, F-478, F-554, F-559 manufactured by DIC
  • SH7PA manufactured by Toray Dow Corning
  • DS-401 manufactured by Daikin
  • L-77 manufactured by Nippon Unicar
  • FC4430 manufactured by 3M.
  • One type of surfactant may be used, or two or more types may be used in combination.
  • Pigment derivative The photosensitive colored resin composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
  • pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, and diketopyrrolopyrrole. and dioxazine derivatives, with phthalocyanine derivatives and quinophthalone derivatives being preferred.
  • substituents on pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, and amide groups directly on the pigment skeleton, or, for example, alkyl Examples include those bonded via a group, an aryl group, or a heterocyclic group, and preferably a sulfonic acid group.
  • a single pigment skeleton may be substituted with a plurality of substituents, or may be substituted with a plurality of types of substituents.
  • pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.
  • the photosensitive colored resin composition of the present invention may contain a mercapto compound as a polymerization accelerator and to improve adhesion to the substrate.
  • Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate nate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol
  • the photosensitive colored resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. Since the inclusion of a polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film, it is thought that the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred.
  • Hydroquinone monomethyl ether and methylhydroquinone are preferred from the viewpoint of particularly excellent safety to the human body.
  • the polymerization inhibitors may be used alone or in combination of two or more.
  • a polymerization inhibitor may be contained in the resin, and it may be used as the polymerization inhibitor of the present invention, or in addition to the polymerization inhibitor in the resin, The same or different polymerization inhibitor may be added during production of the photosensitive colored resin composition.
  • the photosensitive colored resin composition contains a polymerization inhibitor
  • its content is not particularly limited, but is preferably 0.0005% by mass or more, more preferably 0.0005% by mass or more, based on the total solid content of the photosensitive colored resin composition. .001% by mass or more, more preferably 0.01% by mass or more, and preferably 0.3% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less. .
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.0005% to 0.3% by weight, more preferably 0.001% to 0.2% by weight, and even more preferably 0.01% to 0.1% by weight.
  • the shape of the cured product can be controlled by setting it above the lower limit value.
  • necessary sensitivity can be maintained by setting it below the upper limit value.
  • the photosensitive colored resin composition of the present invention preferably contains a solvent. By including a solvent, the colorant can be dispersed or dissolved in the solvent, and application becomes easier.
  • the photosensitive colored resin composition of the present invention includes, for example, (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and various other materials used as necessary. The materials are used dissolved or dispersed in a solvent. Organic solvents are preferred from the viewpoint of dispersibility and coating properties.
  • an organic solvent with a boiling point of 100 to 300°C, more preferably 120 to 280°C.
  • the boiling point here means the boiling point at a pressure of 1013.25 hPa, and the same applies to all boiling points below.
  • organic solvents examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether.
  • propylene glycol-t-butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl - Glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
  • Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate linear or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxyprop
  • organic solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2.
  • Solvesso #150 Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cellosolve” is a registered trademark. The same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all may also be used (trade name).
  • These organic solvents may be used alone or in combination of two or more.
  • an organic solvent with a boiling point of 100 to 240°C, more preferably 120 to 200°C, even more preferably 120 to 170°C. .
  • glycol alkyl ether acetates are preferred from the standpoint of good balance in coating properties, surface tension, etc., and relatively high solubility of the constituent components in the composition.
  • One type of glycol alkyl ether acetate may be used alone, or two or more types may be used in combination.
  • glycol alkyl ether acetates may be used alone, other organic solvents may also be used in combination.
  • As the organic solvent used in combination glycol monoalkyl ethers are preferred. Propylene glycol monomethyl ether is preferred from the viewpoint of solubility of the components in the composition.
  • Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, which tends to reduce the storage stability such as increasing the viscosity of the photosensitive colored resin composition obtained later.
  • the proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
  • the photosensitive colored resin composition will be difficult to dry, but the pigment will not be uniformly dispersed in the composition.
  • a high boiling point solvent may be used in combination, since this has the effect of preventing the state from being destroyed by rapid drying. For example, it has the effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of colorants and the like at the tip of the slit nozzle.
  • diethylene glycol mono-n-butyl ether diethylene glycol mono-n-butyl ether acetate
  • diethylene glycol monoethyl ether acetate diethylene glycol monoethyl ether acetate
  • the content of the high boiling point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass.
  • the amount By setting the amount to be equal to or more than the lower limit, it tends to be possible to suppress the precipitation and solidification of the coloring agent and the like at the tip of the slit nozzle, thereby causing foreign matter defects.
  • it By setting it below the above upper limit, it is possible to suppress an increase in the drying time of the composition and tend to suppress problems such as tact failure in the vacuum drying process and pin marks during prebaking.
  • the high boiling point solvent may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, there is no need to separately contain a high boiling point solvent.
  • Preferred high-boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin. .
  • the content ratio of the colorant (A) in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more based on the total solid content of the photosensitive colored resin composition. It is preferably 15% by mass or more, and more preferably 15% by mass or more. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 15 to 30% by weight, even more preferably 15 to 25% by weight, and particularly preferably 15 to 20% by weight.
  • light-shielding properties can be ensured by setting the amount to be equal to or more than the lower limit value. By setting it below the above upper limit, the amount of dispersant can be reduced and surface roughness tends to be suppressed.
  • the content of the organic pigment (A-1) in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, and 10% by mass based on the total solid content of the photosensitive colored resin composition.
  • the content is more preferably 15% by mass or more, and even more preferably 15% by mass or more.
  • it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 15 to 30% by weight, even more preferably 15 to 25% by weight, and particularly preferably 15 to 20% by weight.
  • There is a tendency that light-shielding properties can be ensured by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit value, the residual film rate tends to increase.
  • the content ratio of the organic black pigment in the photosensitive colored resin composition is not particularly limited, but is based on the total solid content of the photosensitive colored resin composition.
  • the content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 15 to 30% by weight, even more preferably 15 to 25% by weight, and particularly preferably 15 to 20% by weight.
  • There is a tendency that light-shielding properties can be ensured by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit value, the residual film rate tends to increase.
  • the content thereof is not particularly limited, but is 1% by mass in the total solid content of the photosensitive colored resin composition.
  • the content is preferably at least 5% by mass, more preferably at least 10% by mass. Further, it is preferably 30% by mass or less, more preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, and even more preferably 10 to 20% by weight.
  • the amount is equal to or more than the lower limit, the light blocking property tends to be enhanced while suppressing the loss of ultraviolet light necessary for curing. By setting it below the upper limit value, the residual film rate tends to increase.
  • the content ratio of the dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, based on the total solid content of the photosensitive colored resin composition.
  • the content is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 7% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, even more preferably 3 to 10% by weight, and particularly preferably 3 to 7% by weight.
  • sufficient dispersibility can be easily obtained by setting the amount to be equal to or more than the lower limit value.
  • outgassing can be reduced by setting it below the upper limit value.
  • the content ratio of the dispersant (B) to 100 parts by mass of the colorant (A) is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and 50 parts by mass or more.
  • the amount is preferably at most 30 parts by mass, more preferably at most 30 parts by mass.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 50 parts by weight, more preferably 10 to 50 parts by weight, and even more preferably 15 to 30 parts by weight. There is a tendency that sufficient dispersibility can be easily obtained by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit value, the residual film rate tends to increase.
  • the content ratio of the alkali-soluble resin (C) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more based on the total solid content of the photosensitive colored resin composition. , even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less. It is not more than 55% by mass, particularly preferably not more than 55% by mass.
  • the above upper and lower limits can be arbitrarily combined.
  • the amount is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, even more preferably 20 to 60% by weight, even more preferably 30 to 60% by weight, even more preferably 30 to 55% by weight, and even more preferably 40 to 55% by weight. % by weight is particularly preferred.
  • the amount By setting the amount to be equal to or higher than the lower limit, it tends to be possible to suppress a decrease in the solubility of an unexposed area in a developer and to suppress development defects.
  • the upper limit value By setting it below the upper limit value, appropriate sensitivity can be maintained, dissolution of the exposed area by the developer can be suppressed, and the taper angle tends to be low.
  • the content ratio of the resin (C1) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, based on the total solid content of the photosensitive colored resin composition.
  • the content is preferably 20% by mass or less, more preferably 17% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20% by weight, more preferably 3 to 17% by weight, even more preferably 3 to 15% by weight, and particularly preferably 5 to 10% by weight.
  • dispersion stability can be improved by setting the above lower limit value or more. When the amount is below the upper limit, the solubility in the developer tends to be good.
  • the content ratio of the resin (C1) is not particularly limited, but in the alkali-soluble resin (C), it is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. Further, it is preferably 100% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, even more preferably 40% by mass or less, particularly preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 100% by weight, more preferably 5 to 80% by weight, even more preferably 10 to 60% by weight, even more preferably 10 to 40% by weight, and particularly preferably 10 to 20% by weight.
  • the amount By setting the amount to be equal to or higher than the lower limit, it tends to be possible to suppress a decrease in the solubility of an unexposed area in a developer and to suppress development defects.
  • it By setting it below the above-mentioned upper limit, it is possible to maintain appropriate sensitivity, suppress dissolution of the exposed area by the developer, and tend to suppress deterioration of sharpness and adhesion of the pattern.
  • the content ratio of (C2) epoxy (meth)acrylate resin is not particularly limited, but the photosensitive colored resin of the present invention Preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, especially It is preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably 55% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, even more preferably 15 to 60% by weight, even more preferably 20 to 60% by weight, even more preferably 30 to 55% by weight, and even more preferably 40 to 60% by weight. Particularly preferred is 55% by weight.
  • the content ratio of the (C2) epoxy (meth)acrylate resin contained in the alkali-soluble resin (C) is not particularly limited, but Preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less. be.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 20 to 100% by weight, more preferably 30 to 90% by weight, even more preferably 40 to 80% by weight.
  • the content ratio of the (C3) isocyanuric skeleton-containing resin contained in the (C) alkali-soluble resin is not particularly limited, but is preferably 20% by mass or more. , more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, even more preferably 40 to 70% by weight.
  • the amount is equal to or more than the lower limit, the light emitting characteristics tend to be improved. There is a tendency for developability to be improved by setting it below the upper limit value.
  • the content ratio of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass based on the total solid content of the photosensitive colored resin composition of the present invention. Above, more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less. It is less than 6% by mass, particularly preferably less than 6% by mass. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass.
  • a decrease in sensitivity can be suppressed by setting the value to be equal to or more than the lower limit value. By setting it below the upper limit, it is possible to suppress a decrease in the solubility of an unexposed area in a developer, and tend to suppress development defects.
  • the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass based on the total solid content of the photosensitive colored resin composition of the present invention. or more, and preferably 10% by mass or less, more preferably 5% by mass or less. For example, it is preferably 0.05 to 10% by weight, more preferably 0.05 to 5% by weight.
  • the polymerization accelerator is preferably used in a proportion of 0.1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the photopolymerization initiator (D).
  • the content of the sensitizing dye is not particularly limited, but from the viewpoint of sensitivity, it is preferably 20% by mass based on the total solid content in the photosensitive colored resin composition. % or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.
  • the content of (E) the ethylenically unsaturated compound is not particularly limited, but the total content of the photosensitive colored resin composition of the present invention is Based on the solid content, it is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and preferably 30% by mass or less, more preferably is 25% by mass or less, more preferably 20% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, even more preferably 10 to 25% by weight, and particularly preferably 15 to 20% by weight.
  • the above lower limit or more it is possible to maintain appropriate sensitivity, suppress dissolution of the exposed area by the developer, and tend to suppress deterioration of sharpness and adhesion of the pattern.
  • the upper limit value there is a tendency that the permeability of the developer into the exposed area is suppressed from increasing and it becomes easy to obtain a good image.
  • the content ratio of (C) alkali-soluble resin to 100 parts by mass of (E) ethylenically unsaturated compound is not particularly limited, but may be 100 parts by mass. It is preferably at least 200 parts by mass, more preferably at least 250 parts by mass, even more preferably at least 300 parts by mass, and particularly preferably at least 350 parts by mass. Moreover, it is preferably 700 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 100 to 700 parts by weight, more preferably 200 to 700 parts by weight, even more preferably 250 to 500 parts by weight, even more preferably 300 to 450 parts by weight, and particularly preferably 350 to 400 parts by weight.
  • it is preferably 100 to 700 parts by weight, more preferably 200 to 700 parts by weight, even more preferably 250 to 500 parts by weight, even more preferably 300 to 450 parts by weight, and particularly preferably 350 to 400 parts by weight.
  • an adhesion improver When using an adhesion improver, its content is not particularly limited, but it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass based on the total solid content of the photosensitive colored resin composition. , more preferably 0.4 to 2% by mass. There is a tendency that the effect of improving adhesion can be sufficiently obtained by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit, it tends to be possible to suppress decreases in sensitivity and defects caused by residue remaining after development.
  • the content is not particularly limited, but it is preferably 0.001 to 10% by mass, more preferably 0.005 to 1% by mass, based on the total solid content of the photosensitive colored resin composition. , more preferably 0.01 to 0.5% by weight, particularly preferably 0.03 to 0.3% by weight.
  • the amount is equal to or more than the lower limit, the coating film tends to exhibit smoothness and uniformity. By setting it below the above-mentioned upper limit, smoothness and uniformity of the coating film are likely to be exhibited, and deterioration of other properties tends to be suppressed.
  • the photosensitive colored resin composition of the present invention has a total solid content of preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and , preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the content is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and even more preferably 15 to 25% by weight.
  • the optical density (OD) of the photosensitive colored resin composition of the present invention per 1 ⁇ m of coating film thickness is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, and 0.7 or more. is more preferably 0.9 or more, further preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.2 to 4.0, more preferably 0.5 to 4.0, even more preferably 0.5 to 3.0, even more preferably 0.5 to 2.0, and even more preferably 0.7 to 4.0. 2.0 is particularly preferred, and 0.9 to 1.5 is particularly preferred.
  • the optical density (OD) per 1 ⁇ m of the film thickness of the coating film may be measured using a coating film cured from the photosensitive colored resin composition of the present invention, and is 0.5 to 0.00000 ⁇ m after curing by heating at 230°C for 20 minutes. It can be measured using a coating film of about 1.5 ⁇ m.
  • the optical density refers to the transmission optical density where the spectral sensitivity characteristic of the light receiving section is indicated by ISO Visual density in the ISO 5-3 standard.
  • an A light source defined by CIE (Commission Internationale de l'Eclairage) is used.
  • CIE Commission Internationale de l'Eclairage
  • An example of a measuring instrument that can be used to measure transmission optical density is X-Rite 361T (V) manufactured by Sakata Inx Engineering Co., Ltd.
  • the components constituting the pigment dispersion of the present invention and their composition will be explained.
  • the pigment dispersion of the present invention contains (A) a colorant, (B) a dispersant, and (C) an alkali-soluble resin, and in particular, the colorant (A) contains an organic pigment (A-1). , (C) alkali-soluble resin contains resin (C1). Moreover, it is preferable that a solvent is included.
  • the constituent components of the pigment dispersion of the present invention those listed as the same items in the photosensitive colored resin composition of the present invention can be preferably employed.
  • the resin (C1) Since the resin (C1) has a high affinity with pigments and also contains a methylene group in its main chain and has flexibility that can follow the pigment, the pigment dispersion of the present invention tends to exhibit high pigment dispersibility. be. Furthermore, the photosensitive colored resin composition using the pigment dispersion of the present invention tends to have a high residual film rate. This is because, as described above, the resin (C1) contains many aromatic rings in its main chain, so it tends to have high developer resistance during development and high heat resistance during baking. Furthermore, when an organic electroluminescent device is formed using partition walls obtained from a photosensitive colored resin composition, the current density when voltage is applied tends to be high, as described above.
  • the content of the colorant (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass based on the total solid content in the pigment dispersion. More preferably, the content is 40% by weight or more, particularly preferably 50% by weight or more, particularly preferably 55% by weight or more. Further, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • a photosensitive colored resin composition can be produced with an appropriate solid content concentration, and by setting it to below the above upper limit, the dispersibility tends to improve.
  • the combination of upper and lower limits is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. Particularly preferred, and most preferably 55 to 65% by weight.
  • the content of the organic pigment (A-1) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more based on the total solid content in the pigment dispersion. It is at least 40% by weight, even more preferably at least 40% by weight, even more preferably at least 50% by weight, particularly preferably at least 55% by weight. Further, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • the combination of upper and lower limits is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. Particularly preferred, and most preferably 55 to 65% by weight.
  • the content of the organic black pigment is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, based on the total solid content in the pigment dispersion. It is even more preferably 40% by weight or more, particularly preferably 50% by weight or more, particularly preferably 55% by weight or more. Further, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • the combination of upper and lower limits is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. Particularly preferred, and most preferably 55 to 65% by weight.
  • the content of the dispersant (B) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass based on the total solid content in the pigment dispersion. That's all. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. Setting the value above the lower limit tends to improve dispersibility, and setting the value below the upper limit prevents excess dispersant from being reduced, improving the developability of the resulting photosensitive colored resin composition. tends to be good.
  • the combination of upper and lower limits is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and even more preferably 8 to 15% by mass. Particularly preferred.
  • the content of the acrylic dispersant is preferably 2% by mass or more, more preferably 2% by mass or more based on the total solid content in the pigment dispersion. Preferably it is 5% by mass or more, more preferably 8% by mass or more. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the value is at least the above lower limit, the dispersibility tends to be good and the pattern adhesion during development of the cured product tends to be good. Developability tends to be good.
  • the combination of upper and lower limits is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and even more preferably 10 to 15% by mass. Particularly preferred.
  • the content of the alkali-soluble resin (C) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass based on the total solid content in the pigment dispersion. % or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. Setting the value above the lower limit tends to improve dispersibility, and setting the value below the upper limit allows the amount of colorant in the resulting photosensitive colored resin composition to be optimized, resulting in sufficient light-shielding properties. tends to be secured.
  • the combination of upper and lower limits is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, even more preferably 20 to 35% by mass, and even more preferably 25 to 35% by mass. Particularly preferred.
  • the content of the resin (C1) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, based on the total solid content in the pigment dispersion. It is even more preferably 20% by mass or more, particularly preferably 25% by mass or more. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
  • the combination of upper and lower limits is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, even more preferably 20 to 35% by mass, and even more preferably 25 to 35% by mass. Particularly preferred.
  • the pigment dispersion of the present invention is prepared using the above-mentioned organic solvent so that its solid content concentration is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.
  • the viscosity of the pigment dispersion is preferably 1 MPa ⁇ s or more, more preferably 3 MPa ⁇ s or more, and even more preferably 5 MPa ⁇ s or more. Further, the pressure is preferably 15 MPa ⁇ s or less, and more preferably 10 MPa ⁇ s or less. The viscosity can be measured using, for example, a rotational viscometer.
  • the pigment dispersion of the present invention is produced according to a conventional method.
  • the colorant is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the colorant (A) is made into fine particles by the dispersion treatment, the coating properties of the photosensitive colored resin composition tend to improve and the surface roughness tends to decrease.
  • the dispersion treatment is performed using a system that uses part or all of (A) a colorant, (B) a dispersant, and a solvent, and (C) an alkali-soluble resin, or a system that uses (A) a colorant, (B) a dispersant, It is preferable to use a system in which a part or all of the alkali-soluble resin (C), a solvent, and (C) are used in combination. In particular, it is preferable to use a polymer dispersant as the dispersant (B) because it suppresses thickening of the obtained pigment dispersion and photosensitive colored resin composition over time, that is, it has excellent dispersion stability.
  • the (A) colorant, (B) dispersant, and solvent that can be used in the pigment dispersion those described as those that can be used in the photosensitive colored resin composition can be preferably employed.
  • a dispersion treatment When a dispersion treatment is performed on a liquid containing all components to be blended into a photosensitive colored resin composition, highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymeric dispersant.
  • a polymeric dispersant When dispersing the colorant (A) with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used.
  • the temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate.
  • a guideline for dispersion is to control the gloss of the pigment dispersion so that the 20 degree specular gloss (JIS Z8741) of the photosensitive colored resin composition is in the range of 50 to 300.
  • the dispersion treatment is often insufficient and rough pigment (colorant) particles remain, which may affect developability, adhesion, resolution, surface roughness, etc. may be insufficient.
  • the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed and a large number of ultrafine particles will be produced, which tends to impair the dispersion stability.
  • the dispersed particle diameter of the pigment dispersed in the pigment dispersion is preferably 0.03 to 0.3 ⁇ m, and can be measured by a dynamic light scattering method.
  • the pigment dispersion obtained by the above dispersion treatment and other components contained in the photosensitive colored resin composition are mixed to form a uniform solution or dispersion.
  • fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive colored resin composition using a filter or the like.
  • the cured product of the present invention can be obtained by curing the photosensitive colored resin composition of the present invention.
  • the cured product obtained by curing the photosensitive colored resin composition of the present invention can be suitably used as a black matrix, an insulating film, and a partition wall, and can be more suitably used as a partition wall.
  • the film thickness of the cured product is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and even more preferably 0.9 ⁇ m or more. Moreover, it is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the thickness is preferably 0.5 to 15 ⁇ m, more preferably 0.7 to 10 ⁇ m, and even more preferably 0.9 to 5 ⁇ m.
  • the optical density (OD) per 1 ⁇ m of the cured product of the present invention is preferably 0.2 or more, more preferably 0.5 or more, even more preferably 0.7 or more, and 0.9 or more from the viewpoint of light shielding properties. Particularly preferred. Further, it is preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less.
  • optical density (OD) is a value measured by a method described later.
  • the material of the support for forming the cured product is not particularly limited as long as it has appropriate strength.
  • Substrates are mainly used, and materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. , thermosetting resin sheets such as unsaturated polyester resins, poly(meth)acrylic resins, and various glasses. From the viewpoint of heat resistance, glass and heat-resistant resin are preferred. Further, a transparent electrode such as ITO or IZO, or a metal electrode such as silver, gold, platinum, aluminum, or magnesium may be formed on the surface of the substrate. In addition to the above-mentioned substrates, it is also possible to form on a TFT array.
  • the support may be subjected to, for example, corona discharge treatment, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary, in order to improve surface properties such as adhesion.
  • the thickness of the support is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 7 mm. Further, when performing a thin film formation treatment of various resins, the film thickness is preferably in the range of 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m.
  • a photosensitive colored resin composition is supplied in the form of a film or pattern by a method such as coating onto the support on which the cured product is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as photolithography that involves exposure and development. Thereafter, a cured product is formed on the substrate by performing additional exposure or heat curing treatment if necessary.
  • the photosensitive colored resin composition of the present invention is preferably supplied onto a support in a state in which it is dissolved or dispersed in a solvent.
  • a method for supplying it conventionally known methods such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, and a spray coating method can be used.
  • it may be supplied in a pattern by, for example, an inkjet method or a printing method.
  • the die coating method the amount of coating liquid used is significantly reduced, there is no influence of mist etc. that adheres when using the spin coating method, and the generation of foreign matter is suppressed, from a comprehensive perspective. preferable.
  • the amount of coating varies depending on the application, it is applied so that the dry film thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 9 ⁇ m, particularly preferably 1 to 7 ⁇ m. It is important that the dry film thickness or the height of the finally formed cured product be uniform over the entire support. By reducing the variation, the light-shielding property within the support becomes uniform, and when used as a partition wall, the light-emitting layer can be made uniform, and display defects during light emission can be suppressed.
  • the photosensitive colored resin composition of the present invention When the photosensitive colored resin composition of the present invention is used to collectively form cured products with different heights by photolithography, the heights of the finally formed cured products will be different.
  • Drying method The drying after supplying the photosensitive colored resin composition onto the support is preferably carried out by a drying method using a hot plate, an IR oven, or a convection oven.
  • a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be combined.
  • Drying conditions can be selected as appropriate depending on the type of solvent component, the performance of the dryer used, etc.
  • the drying time is preferably selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130°C, more preferably at a temperature of 50 to 110°C, depending on the type of solvent component, the performance of the dryer used, etc.
  • the duration is selected from 30 seconds to 3 minutes.
  • Exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating it with an ultraviolet or visible light source through this mask pattern.
  • the exposure mask may be placed close to the coating film of the photosensitive colored resin composition, or the exposure mask may be placed at a position away from the coating film of the photosensitive colored resin composition.
  • a method of projecting exposure light through an exposure mask may also be used.
  • a scanning exposure method using laser light without using a mask pattern may also be used.
  • exposure may be carried out in an oxygen-free atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Good too.
  • a light-shielding area (light transmittance 0%) and an opening with the highest average light transmittance (completely transparent opening) are formed as multiple openings. ) is used.
  • An exposure mask having an opening (intermediate transmission opening) with a small average light transmittance is used.
  • the difference in film remaining ratio is caused by the difference in average light transmittance between the intermediate transmission aperture and the complete transmission aperture, that is, the difference in exposure amount.
  • a method is known in which the intermediate transmission opening is fabricated using a matrix-like light-shielding pattern having minute polygonal light-shielding units.
  • a method is known in which the absorber is manufactured by controlling the light transmittance using a film of a chromium-based, molybdenum-based, tungsten-based, or silicone-based material, for example.
  • the light source used for exposure is not particularly limited.
  • Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When using irradiation with light of a specific wavelength, an optical filter can also be used.
  • the optical filter may be, for example, a thin film type that can control the light transmittance at the exposure wavelength, and the material in this case may be, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, and Al.
  • a Cr compound Cr oxide, nitride, oxynitride, fluoride, etc.
  • MoSi Si, W, and Al.
  • the exposure amount is not particularly limited, but is preferably 1 mJ/cm 2 or more, more preferably 5 mJ/cm 2 or more, even more preferably 10 mJ/cm 2 or more, and preferably 300 mJ/cm 2 or less, more preferably is 200 mJ/cm 2 or less, more preferably 150 mJ/cm 2 or less.
  • an image pattern can be formed on the support by development using an aqueous solution of an alkaline compound or an organic solvent.
  • the aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
  • alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus.
  • Inorganic alkaline compounds such as acid potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or Organics such as trimethylamine, mono-, di- or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
  • Examples include alkaline compounds. These alkaline compounds may be used alone or in combination of two or more.
  • surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids
  • alkylbenzene sulfonic acids examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Further, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
  • the conditions for the development treatment are not particularly limited, and the development temperature is preferably 10 to 50°C, more preferably 15 to 45°C, and still more preferably 20 to 40°C.
  • the development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
  • thermosetting treatment also referred to as baking
  • the heat curing treatment conditions are such that the temperature is preferably 100 to 280°C, more preferably 150 to 250°C, and the time is 5 to 60 minutes.
  • the photosensitive colored resin composition of the present invention can be suitably used to form partition walls, particularly partition walls for partitioning organic layers of an organic electroluminescent device.
  • the organic layer used in the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on the hole injection layer, as described in Japanese Patent Application Publication No. 2016-165396. Examples include the organic layer used.
  • the size, shape, etc. are appropriately adjusted depending on the specifications of the organic electroluminescent device to which it is applied, but the film thickness of the partition formed from the photosensitive colored resin composition of the present invention is , the optical density (OD) per ⁇ m is similar to that of the cured film.
  • the organic electroluminescent device of the present invention includes a cured product formed from the photosensitive colored resin composition of the present invention, for example, a partition wall.
  • various organic electroluminescent devices are manufactured using a substrate provided with a barrier rib pattern manufactured by the method described above.
  • the method for forming an organic electroluminescent device is not particularly limited, but preferably, after forming a barrier rib pattern on a substrate by the method described above, the functional material is sublimated in a vacuum to form an area surrounded by the barrier ribs on the substrate.
  • An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an inkjet printing method.
  • Types of organic electroluminescent devices include bottom emission type and top emission type.
  • a partition wall is formed on a glass substrate laminated with a transparent electrode, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the partition wall. Ru.
  • a partition is formed on a glass substrate with a metal electrode layer laminated as a reflective layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are formed in the opening surrounded by the partition. It is made by laminating layers.
  • the anode is mounted on a support, but is not limited thereto.
  • Examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent No. 5734681.
  • quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
  • each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency.
  • the thickness of each layer is not particularly limited, but from the viewpoint of luminous efficiency and brightness, it is preferably 1 to 500 nm.
  • the organic electroluminescent element may be formed with RGB colors separated for each opening, or two or more colors may be stacked in one opening.
  • the organic electroluminescent device may include a sealing layer from the viewpoint of improving reliability.
  • the sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and reducing luminous efficiency.
  • the organic electroluminescent device may include a low-reflection film at the interface with air from the viewpoint of improving light extraction efficiency. By arranging a low-reflection film at the interface between air and the element, it is expected that the gap in refractive index will be reduced and reflection at the interface will be suppressed. For example, a moth-eye structure or a super multilayer film technique can be applied to such a low reflection film.
  • an organic electroluminescent device When using an organic electroluminescent device as a pixel in an image display device, it is necessary to prevent light from the light emitting layer of one pixel from leaking to other pixels, and in addition, if the electrodes are made of metal, it is necessary to prevent the light from the light emitting layer of one pixel from leaking to other pixels. Since it is necessary to prevent image quality from deteriorating due to reflection of light, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent device. In an organic electroluminescent device, it is necessary to provide electrodes on the upper and lower surfaces of the partition walls, so from the viewpoint of insulation, the partition walls preferably have high resistance and low dielectric constant. Therefore, when using a coloring agent to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment that has high resistance and low dielectric constant.
  • the color filter containing the luminescent nanocrystal particles according to the present invention is not particularly limited as long as it is provided with the barrier ribs of the present invention, and examples thereof include those in which pixels are formed in regions partitioned by the barrier ribs.
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter including partition walls of the present invention.
  • the color filter 100 includes a substrate 10, a partition wall 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50.
  • the red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a grid pattern so as to be repeated in this order.
  • the partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are separated by the partition wall 20.
  • the red pixel 30 contains red light-emitting nanocrystal particles 2
  • the green pixel 40 contains green light-emitting nanocrystal particles 1.
  • the blue pixel 50 is a pixel that transmits blue light from a light source.
  • nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have a maximum particle diameter of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope. It is a crystalline substance.
  • Luminescent nanocrystal particles are particles that can emit light (fluorescence or phosphorescence) at a wavelength different from the absorbed wavelength by absorbing light at a predetermined wavelength; for example, red luminescent nanocrystal particles 2 emits light (red light) having an emission peak wavelength in the range of 605 to 665 nm, and green-emitting nanocrystal particles 1 emit light (green light) having an emission peak wavelength in the range of 500 to 560 nm. ).
  • the wavelength of light emitted by a luminescent nanocrystal particle depends on the size of the luminescent nanocrystal particle (for example, particle diameter). It also depends on the energy gap that the crystal grains have. Therefore, the color of the emitted light can be selected by changing the constituent material and size of the luminescent nanocrystal particles used. Examples of the luminescent nanocrystal particles include quantum dots and the like.
  • the method for producing a color filter containing luminescent nanocrystal particles is not particularly limited, but it may be necessary to prepare a substrate having partition walls formed from the cured product of the present invention, and to contain luminescent nanocrystal particles in regions partitioned by the partition walls.
  • Examples include a method of forming a layer.
  • the method for forming a layer containing luminescent nanocrystal particles is not particularly limited, but for example, an ink composition containing luminescent nanocrystal particles is selectively deposited by an inkjet method, and the ink composition is formed by irradiation with active energy rays or heating. It can be manufactured by a method of curing an object.
  • Examples of the image display device of the present invention include an organic EL display device having partition walls and organic electroluminescent elements containing the cured product of the present invention.
  • the organic EL display device includes the above-mentioned organic electroluminescent device, there are no particular restrictions on the type or structure of the image display device, and for example, the organic EL display device can be assembled according to a conventional method using an active drive type organic electroluminescent device. can. For example, it can be formed by the method described in "Organic EL Display” (Ohmsha, published August 20, 2004, written by Seiji Tokito, Chinaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent device that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent devices that emit light of different colors, such as RGB.
  • the alkali-soluble resin-I thus obtained has a weight average molecular weight Mw of 2456 and an acid value of 64 mgKOH/g as measured by GPC, and corresponds to resin (C1) and has a structure represented by formula (C1-1). Applicable.
  • EPICLON HP7200HH manufactured by DIC Corporation polyglycidyl ether of dicyclopentadiene/phenol polymer, weight average molecular weight 1000, epoxy equivalent weight 270
  • EPICLON HP7200HH manufactured by DIC Corporation polyglycidyl ether of dicyclopentadiene/phenol polymer, weight average molecular weight 1000, epoxy equivalent weight 270
  • 155 parts by mass 41 parts by mass of acrylic acid, 0.1 part by mass of p-methoxyphenol, triphenylphosphine 2.5 parts by mass and 270 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and heated and stirred at 100°C until the acid value became 3.0 mgKOH/g or less. It took 9 hours for the acid value to reach the target (acid value 2.9 mgKOH/g).
  • alkali-soluble resin-II has a weight average molecular weight Mw of 3500 and an acid value of 60 mgKOH/g, and does not correspond to resin (C1).
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic dianhydride
  • THPA tetrahydrophthalic anhydride
  • Alkali-soluble resin-VI > "KBR-201" manufactured by KISCO.
  • Alkali-soluble resin-VI corresponds to (C2) epoxy (meth)acrylate resin.
  • Alkali-soluble resin-VII was obtained having a weight average molecular weight (Mw) of 2800 in terms of polystyrene and a weight average molecular weight (Mw) of 145 mgKOH/g measured by GPC.
  • Alkali-soluble resin-VII corresponds to (C3) isocyanuric skeleton-containing resin.
  • alkali-soluble resin-I has a weight average molecular weight Mw of 1668 and an acid value of 96.3 mgKOH/g as measured by GPC, and corresponds to resin (C1) and is represented by formula (C1-1). Applies to structure.
  • ⁇ Dispersant-I> A block copolymer consisting of an A block containing a repeating unit having a solvent-philic group and a B block containing a repeating unit having a tertiary amino group.
  • ⁇ Dispersant-II> A block copolymer consisting of an A block containing a repeating unit having a solvent-philic group and a B block containing a repeating unit having a tertiary amino group and a quaternary ammonium group.
  • Viscosity evaluation> Immediately after preparing the pigment dispersion using a RE-85L viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23°C, 20rpm), after preparing the pigment dispersion, leave it at room temperature (24°C) for one day. , and after standing for 3 days, the viscosity of the pigment dispersion was measured and determined as follows. From the viewpoint of applicability and stability over time of the photosensitive colored resin composition, it is preferable that the viscosity of the pigment dispersion is low. A: Viscosity is 10 mPa ⁇ s or less B: Viscosity is greater than 10 mPa ⁇ s C: Solidifies without being able to disperse
  • a spinner was used on a substrate on which an indium tin oxide (ITO) film was formed on the surface of a glass substrate with a film thickness of 0.7 mm, and each example A photosensitive colored resin composition of a comparative example was applied. Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Subsequently, it was heated and dried for 100 seconds on a hot plate heated to 100° C. to obtain a coated film substrate. The film thickness of the heat-dried coating film was measured by the method described below, and the film thickness T1 ( ⁇ m) was determined. The obtained coated substrate was exposed to light using a photomask.
  • ITO indium tin oxide
  • a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc.
  • exposure was performed for 20 seconds so that the exposure amount was 80 mJ/cm 2 .
  • the illuminance was 500 mW/cm 2 and the slit width was 1.6 mm.
  • a mask having a grid-like opening (having a 50 ⁇ m square-shaped underside and having a plurality of the above-mentioned covering portions through an exposed portion of 50 ⁇ m) was used.
  • the water pressure was 0 at 24°C.
  • the developing solution was flushed with pure water to stop the development, and the film was washed with water washing spray for 10 seconds.
  • the shower development time was set to be 1.6 times the time for dissolving and removing the unexposed areas of the coating film.
  • the photosensitive colored resin composition is washed away in the portion corresponding to the square light-shielding portion, so that the ITO substrate is exposed and a hole portion is formed. This substrate was heated and cured (baked) at 230° C. for 30 minutes in an oven to obtain a patterned substrate for patternability measurement. At this time, the film thickness T2 ( ⁇ m) was measured.
  • the film thickness of the coating film at each step (after drying, after baking) on the patterned substrate was measured using a non-contact surface/layer cross-sectional shape measuring system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd.
  • VertScan the ratio of the film thickness after firing (T2) to the film thickness after drying (T1) was calculated as the residual film ratio.
  • Remaining film rate (%) (T2/T1) x 100 (%)
  • the calculated residual film rate was determined as follows. A has the highest residual film rate and is good, and if the residual film rate is 75% or more, there is a tendency that there is no problem in practical use.
  • Remaining film rate 80% or more B: Remaining film rate less than 80% but 75% or more
  • C Remaining film rate less than 75% Note that the residual film rate depends on the exposure sensitivity of the resist, its solubility in the developer, and the time of baking. Thermal decomposability is involved, and the higher the residual film rate, the better.
  • optical density per unit film thickness (unit OD value)> The optical density per unit film thickness was measured according to the following procedure.
  • the photosensitive colored resin compositions of each example and comparative example were applied onto a glass substrate using a spinner so that the thickness would be 1.5 ⁇ m after heat curing (baking). Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Subsequently, it was heated and dried for 100 seconds on a hot plate heated to 100°C. The obtained coating film was exposed to light without using an exposure mask.
  • a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used as the irradiation light source, and exposure was performed for 20 seconds so that the exposure amount was 80 mJ/cm 2 .
  • the illuminance was 500 mW/ cm2 .
  • the resist-coated substrate 1 was obtained by heating and curing in an oven at 230° C. for 30 minutes.
  • the optical density (OD value) of the obtained resist-coated substrate 1 was measured using an X-Rite 361T(V) transmission densitometer (color temperature of illumination light source: approximately 2850K (equivalent to CIE standard light source A), spectral sensitivity of light receiving part).
  • the film thickness was measured using VertScan (R) 2.0, a non-contact surface/layer cross-sectional shape measurement system manufactured by Ryoka System Co., Ltd., and the optical density ( The optical density (unit OD value) per unit film thickness (1 ⁇ m) was calculated from the OD value) and the film thickness.
  • the OD value is a numerical value indicating the light-shielding ability, and the larger the value, the higher the light-shielding ability.
  • ⁇ Preparation of patterned substrate for organic electroluminescent device> Each example was prepared using a spinner on a substrate on which an anode was formed by depositing an indium tin oxide (ITO) transparent conductive film to a thickness of 70 nm on glass using ordinary photolithography technology and hydrochloric acid etching. - A photosensitive colored resin composition of a comparative example was applied. Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Subsequently, it was heated and dried for 100 seconds on a hot plate heated to 100°C. The obtained coated substrate was exposed to light using a photomask.
  • ITO indium tin oxide
  • the photomask is a mask having a grid-like opening (having a rectangular covering part of 40 ⁇ m in length x 80 ⁇ m in width, and having a plurality of said covering parts through an exposed part of 20 ⁇ m in the long axis and short axis directions). It was used.
  • the water pressure was 0 at 24°C.
  • the developing solution was flushed with pure water to stop the development, and the film was washed with water washing spray for 10 seconds.
  • the shower development time was set to be 1.6 times the time for dissolving and removing the unexposed areas of the coating film.
  • An organic electroluminescent device was fabricated by sequentially stacking 8-hydroxyquinolinolato-lithium as an electron injection layer to a thickness of 1 nm and aluminum as a cathode to a thickness of 80 nm using a vacuum evaporation method. Next, a desiccant was applied to the recessed part of the sealing glass having a recessed part in the center, and a UV curing resin was applied to the frame portion around the recessed part. The concave portion of the sealing glass is arranged so as to cover all the organic electroluminescent elements on the electrode substrate, the sealing glass is attached to the electrode substrate, and the UV curing resin is cured by irradiating UV to seal the hollow structure. By doing this, a device for evaluating organic electroluminescent elements was fabricated.
  • Examples 1 to 4 using alkali-soluble resin-I were observed to have low viscosity and excellent dispersibility.
  • Comparative Examples 1, 3, and 4 could not be dispersed and solidified, and Comparative Example 2 was dispersible but had a high viscosity and poor dispersibility.
  • the viscosity of Examples 3 to 5 remains stable even 3 days after the preparation of the pigment dispersion, but the viscosity of Comparative Example 5 gradually increases immediately after the preparation of the pigment dispersion. was observed.
  • resin (C1) has a high affinity with pigments because it contains many aromatic rings in its main chain, and also has a flexibility that can follow the surface shape of pigments because it also contains methylene groups in its main chain. It is considered to have a high effect on pigment dispersibility.
  • Alkali-soluble resin-I and alkali-soluble resin-VIII correspond to resin (C1) and are considered to have high pigment dispersibility. Furthermore, it is thought that the pigment dispersibility and viscosity stability were improved because the alkali-soluble resin-VIII had more hydroxyl groups with higher solvent affinity than the alkali-soluble resin-I.
  • alkali-soluble resin-II has a low content of aromatic rings in its main chain, it has a bulky dicyclopentane skeleton, so it is considered to have a low pigment dispersibility effect.
  • alkali-soluble resins III and IV contain many aromatic rings in their main chains, their main chains are rigid and have poor flexibility, and are disadvantageous in that they follow the surface shape of pigments, so they have poor pigment dispersibility effects. considered to be low.
  • Table 5 shows the evaluation results of organic electroluminescent devices produced using the adjusted photosensitive colored resin compositions of Examples 6, 8, and 10 and Comparative Examples 6 and 7.
  • Examples 6, 8, and 10 in Table 5 tend to have high current densities during light emission. This is because Alkali Soluble Resin-I and Alkali Soluble Resin-VIII contain many aromatic rings in their main chains, which improves developer resistance during development. It is assumed that this is because the accumulation of decomposed products is reduced. In addition, the alkali-soluble resin-VII has an isocyanuric skeleton with high heat resistance, and it is thought that the accumulation of thermal decomposition products in the pixels during firing is reduced, resulting in a higher current density value. On the other hand, in Comparative Examples 6 and 7, the current density tends to be low. It is presumed that this is because the number of aromatic rings contained in the main chain is small and developer resistance is reduced, which increases the amount of decomposed products deposited in the pixel portion of the organic electroluminescent device during development.
  • Green-emitting nanocrystal particles 1 Green-emitting nanocrystal particles 2 Red-emitting nanocrystal particles 10 Substrate 20 Partition wall 30 Red pixel 40 Green pixel 50 Blue pixel 100 Color filter

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