WO2022264934A1 - Composition de résine photosensible, produit durci, procédé de production de produit durci, et dispositif d'affichage - Google Patents

Composition de résine photosensible, produit durci, procédé de production de produit durci, et dispositif d'affichage Download PDF

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Publication number
WO2022264934A1
WO2022264934A1 PCT/JP2022/023438 JP2022023438W WO2022264934A1 WO 2022264934 A1 WO2022264934 A1 WO 2022264934A1 JP 2022023438 W JP2022023438 W JP 2022023438W WO 2022264934 A1 WO2022264934 A1 WO 2022264934A1
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resin
group
compound
carbon atoms
structural unit
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PCT/JP2022/023438
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English (en)
Japanese (ja)
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谷垣勇剛
佐伯昭典
日比野千香
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東レ株式会社
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Priority to JP2022538120A priority Critical patent/JPWO2022264934A1/ja
Publication of WO2022264934A1 publication Critical patent/WO2022264934A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • 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 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 radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product, a method for producing the cured product, and a display device.
  • the display device it particularly relates to an organic electroluminescent (hereinafter “organic EL”) display, a quantum dot display, or a micro light emitting diode (hereinafter “micro LED”) display.
  • organic EL organic electroluminescent
  • quantum dot display a quantum dot display
  • micro LED micro light emitting diode
  • the pixel division layer of organic EL displays In order to improve the light emission characteristics and reliability of organic EL displays, the pixel division layer of organic EL displays, the thin film transistor (hereinafter referred to as "TFT") flattening layer or TFT protective layer, or the interlayer insulating layer or gate in TFT array formation
  • TFT thin film transistor
  • a highly heat-resistant photosensitive composition is used for the insulating layer.
  • the photosensitive composition is required to suppress development residue on the anode surface of the opening. From the viewpoint of improving the light emission characteristics of the organic EL display, the durability of the organic EL display can be improved by making the light emitting element highly reliable.
  • the photosensitive composition is also required to have properties capable of improving the reliability of the light-emitting element and enabling low-voltage driving.
  • a film of a light-emitting material by vapor deposition through a vapor deposition mask, and then form a film of the second electrode by vapor deposition. It is also common to form a thick region (hereinafter referred to as a “thick film portion”) in a portion of the pixel dividing layer as a support for a vapor deposition mask when depositing a light-emitting material by vapor deposition.
  • a thick film portion can be formed by a two-layer film forming process in which the pixel dividing layer is formed, and then the photosensitive composition is formed again on the upper layer and patterned.
  • the organic EL display has a self-luminous element, visibility and contrast decrease due to the reflection of external light such as sunlight in the outdoors. Therefore, as a technique for blocking external light and reducing external light reflection, it is common to incorporate a colorant into the photosensitive composition forming the pixel dividing layer to improve light blocking properties.
  • the photosensitive composition examples include a negative photosensitive composition containing an amide-imide resin (see Patent Document 1), and a negative photosensitive composition containing a first resin such as polyimide and a second resin such as a cardo-based resin. Examples thereof include photosensitive compositions (see Patent Document 2).
  • the development residue on the surface of the anode (first electrode) in the opening of the pixel dividing layer described above reduces the alkali solubility of the components in the coating film due to the heat reaction during prebaking in the coating film forming process of the photosensitive composition. may occur as a dominant factor.
  • the opening corresponds to the unexposed area, the decrease in the alkali solubility of the coating film during prebaking causes significant deterioration of development residue.
  • the development residue on the anode surface of the opening not only increases the drive voltage required to obtain a desired current density, but also causes dark spots originating from the development residue, Outgassing from the development residue is a factor that lowers the reliability of the light-emitting element.
  • the thick film portion and the thin film portion may be formed into desired portions by pattern exposure through a halftone photomask.
  • halftone characteristics the characteristics of batch formation by film thickness
  • the extent to which the improvement in the alkali solubility of the coating film in the exposed area varies within the plane of the substrate affects the variation in the opening pattern dimensions.
  • the alkali solubility of the coating film in the exposed area is excessive, the size of the opening pattern tends to vary greatly.
  • the variation in opening pattern dimensions tends to increase.
  • the extent to which the decrease in alkali solubility due to photocuring of the coating film in the exposed area varies within the surface of the substrate determines the variation in the size of the opening pattern. influence.
  • the photo-curing of the exposed portion is excessive, the photo-curing over the pattern dimension of the photomask tends to cause large variations.
  • the photocuring of the exposed portion is insufficient, side etching of the deep portion of the coating film during alkali development tends to cause large variations.
  • the photosensitive composition is required to have material properties that combine post-development residue suppression, excellent halftone properties, and suppression of variations in opening pattern dimensions after development.
  • material properties capable of providing a cured product capable of improving the reliability of light-emitting elements in an organic EL display and driving the light-emitting elements at a low voltage.
  • all of the photosensitive compositions described in the above documents are insufficient in any of the above properties.
  • the photosensitive resin composition of the first aspect of the present invention is a photosensitive resin composition containing (A) an alkali-soluble resin and (C) a photosensitive agent,
  • the (A) alkali-soluble resin contains at least the following (AX) resin,
  • the photosensitive resin composition further contains one or more resins selected from the group consisting of the following (A1) resin, (A2) resin and (A3) resin.
  • (AX) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • (A1) Resin A resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure and having no ethylenically unsaturated double bond group.
  • (A2) Resin A resin having an ethylenically unsaturated double bond group.
  • (A3) Resin Resin having a phenolic hydroxyl group.
  • a display device has at least a substrate, a first electrode, a second electrode and a pixel division layer, Furthermore, a display device having an organic EL layer containing a light-emitting layer and/or a light extraction layer containing a light-emitting layer, the pixel division layer is formed on the first electrode so as to partially overlap the first electrode; an organic EL layer including the light emitting layer and/or a light extraction layer including the light emitting layer is formed on the first electrode and between the first electrode and the second electrode;
  • the pixel division layer has at least the following (X-DL) resin, Further, the display device has one or more resins selected from the group consisting of the following (I-DL) resin, (II-DL) resin and (III-DL) resin.
  • (X-DL) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • (I-DL) resin A resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure.
  • (II-DL) resin a resin having a structural unit represented by general formula (24).
  • (III-DL) resin one or more resins selected from the group consisting of phenolic resins, polyhydroxystyrenes, phenolic group-modified epoxy resins and phenolic group-modified acrylic resins.
  • R 67 to R 69 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a is 0 or 1; * 1 represents the bonding point in the resin.
  • the photosensitive resin composition of the first aspect of the present invention it is possible to provide a photosensitive resin composition that suppresses residue after development, has excellent halftone characteristics, and suppresses variations in opening pattern dimensions after development. is.
  • the photosensitive resin composition of the first aspect of the present invention it is possible to provide a cured product capable of improving the reliability of the light-emitting element in an organic EL display and lowering the driving voltage of the light-emitting element.
  • the display device According to the display device according to the second aspect of the present invention, it is possible to provide a display device that achieves both improved reliability of the light-emitting element and low-voltage driving of the light-emitting element.
  • FIG. 1 is a schematic cross-sectional view illustrating the manufacturing process of steps 1 to 7 in an organic EL display using a cured product of the photosensitive resin composition of the first embodiment of the present invention.
  • FIG. 2 is a schematic diagram of the arrangement and dimensions of a light-transmitting portion, a light-shielding portion, and a semi-light-transmitting portion in a halftone photomask used for evaluation of pattern dimension variation.
  • FIG. 3 is a schematic diagram illustrating the arrangement and dimensions of a light-transmitting portion, a light-shielding portion, and a semi-light-transmitting portion in a halftone photomask used for halftone characteristic evaluation.
  • FIG. 4 is a schematic plan view illustrating the manufacturing process of steps 1 to 4 for the substrate of the organic EL display used for evaluating the light emission characteristics.
  • the photosensitive resin composition which is the first aspect of the present invention, will be described below.
  • a display device which is a second aspect of the present invention will also be described.
  • the photosensitive resin composition of the present invention it is the description relating to the photosensitive resin composition which is the first aspect of the present invention.
  • the display device of the present invention it relates to the display device of the second aspect of the present invention and the display device provided with the cured product obtained by curing the photosensitive resin composition of the first aspect of the present invention. It is described.
  • the photosensitive resin composition of the first aspect of the present invention is a photosensitive resin composition containing (A) an alkali-soluble resin and (C) a photosensitive agent,
  • the (A) alkali-soluble resin contains at least the following (AX) resin,
  • the photosensitive resin composition further contains one or more resins selected from the group consisting of the following (A1) resin, (A2) resin and (A3) resin.
  • (AX) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • (A1) Resin A resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure and having no ethylenically unsaturated double bond group.
  • (A2) Resin A resin having an ethylenically unsaturated double bond group.
  • (A3) Resin A resin having a phenolic hydroxyl group.
  • the photosensitive resin composition of the first aspect of the present invention contains (A) an alkali-soluble resin, (A) the alkali-soluble resin contains at least (AX) resin, and further the following (A1) resin, ( It contains one or more resins selected from the group consisting of A2) resins and (A3) resins.
  • A1 Resin A resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure and having no ethylenically unsaturated double bond group.
  • (A2) Resin A resin having an ethylenically unsaturated double bond group.
  • (A3) Resin Resin having a phenolic hydroxyl group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • the alkali-soluble resin contains one or more resins selected from the group consisting of (A1) resin, (A2) resin and (A3) resin, thereby suppressing residue after development and improving halftone characteristics. effect becomes remarkable. In addition, the effect of improving the reliability of the light-emitting element in the organic EL display becomes remarkable.
  • the resin does not have an ethylenically unsaturated double bond group in the resin main chain, the resin side chain and the end of the resin, and has an imide structure, an amide structure, an oxazole structure and a siloxane structure in the structural unit of the resin.
  • the imide structure also includes the polyimide precursor structure described below.
  • the oxazole structure also includes the polybenzoxazole precursor structure described below.
  • (A2) Resin refers to a resin having an ethylenically unsaturated double bond group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • the (A3) resin is a resin having a phenolic hydroxyl group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin, and is different from the resins (A1) and (A2). say.
  • (A1) resin, (A2) resin and (A3) resin are classified into any one of them according to the following rules when each has a structure or group that constitutes a different resin.
  • the structural unit of the resin has one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure, and has an ethylenically unsaturated double bond group. If the resin does not have a phenolic hydroxyl group, it is classified as (A1) resin.
  • a resin having one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure in the structural unit of the resin has an ethylenically unsaturated double bond group and a phenol If it does not have a reactive hydroxyl group, it is classified as (A2) resin.
  • A2 resin a resin having an ethylenically unsaturated double bond group does not have a phenolic hydroxyl group
  • it is classified as (A3) resin when a resin having an ethylenically unsaturated double bond group has a phenolic hydroxyl group.
  • the resin has a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure, and a siloxane structure, has an ethylenically unsaturated double bond group, and further has a phenolic hydroxyl group.
  • the resins having such properties are classified as (A2) resins. If the resin has a structural unit containing a cyclic structure having at least three nitrogen atoms, it is classified as an (AX) resin regardless of other structures.
  • the resin has a structural unit containing a cyclic structure having at least three nitrogen atoms, it is not included in (A1) resin, (A2) resin and (A3) resin, and is classified as (AX) resin.
  • the (A) alkali-soluble resin preferably contains the (A1) resin and/or the (A3) resin.
  • (A1) resin and/or (A3) resin By containing (A1) resin and/or (A3) resin in (A) alkali-soluble resin, the effect of suppressing residue after development, improving halftone characteristics, and suppressing variation in opening pattern size after development is remarkable. becomes. In addition, the effect of improving the reliability of the light-emitting element in the organic EL display and driving the light-emitting element at a low voltage becomes remarkable.
  • (A) alkali-soluble resin more preferably contains (A1) resin, more preferably contains (A1) resin and (A3) resin, and contains (A1) resin having a phenolic hydroxyl group is most preferred.
  • the size of the opening pattern tends to vary greatly after development.
  • the (A3) resin having a phenolic hydroxyl group By containing the (A3) resin having a phenolic hydroxyl group, the phenolic hydroxyl group moderately promotes alkali dissolution, making it difficult for the exposed area to become excessively soluble in alkali and suppressing variations in the size of the opening pattern after development. Conceivable.
  • the mild acidity of the phenolic hydroxyl group causes gradual film reduction in the halftone exposed area during development, which is presumed to improve the halftone workability.
  • the size of the opening pattern tends to vary due to photocuring caused by radicals generated during pattern exposure.
  • the (A3) resin having a phenolic hydroxyl group side etching of the deep portion of the film during alkali development in the exposed portion is suppressed by the moderate alkali dissolution promoting action of the phenolic hydroxyl group, and the opening pattern size after development is reduced. It is considered that the variation is suppressed.
  • the phenolic hydroxyl group controls excessive photocuring in the exposed area, thereby making the gradient of the degree of photocuring relative to the amount of exposure gentle.
  • the mild acidity of the phenolic hydroxyl group causes gradual film reduction in the halftone-exposed areas during development, thereby improving the halftone workability.
  • the (A1) resin having a structural unit containing one or more types of structures selected from the group consisting of imide structure, amide structure, oxazole structure, and siloxane structure, which are rigid skeletons, steric hindrance due to the rigid skeleton Excessive photocuring in the exposed area is controlled by inhibition of molecular motion.
  • the (A1) resin is the following (A1-1) resin, (A1-2) resin, (A1-3) resin, (A1-4) resin, (A1-5) resin and (A1-6) resin It is preferable to contain one or more resins selected from the group consisting of. As a result, the effects of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development become remarkable. In addition, the effect of improving the reliability of the light-emitting element in the organic EL display and lowering the driving voltage of the light-emitting element becomes remarkable.
  • A1-3 Resin: Polybenzoxazole.
  • A1-4 Resin: Polybenzoxazole precursor.
  • A1-6 Resin: Polysiloxane.
  • (A1) resin is one or more selected from the group consisting of (A1-1) resin, (A1-2) resin, (A1-3) resin, (A1-4) resin and (A1-5) resin It is more preferable to contain a resin, and it is even more preferable to contain (A1-1) resin and/or (A1-5) resin.
  • the resin may be either a single resin or a copolymer.
  • (A3) resin is selected from the group consisting of (A3-1) phenolic resin, (A3-2) polyhydroxystyrene, (A3-3) phenol group-modified epoxy resin and (A3-4) phenol group-modified acrylic resin It preferably contains one or more resins. As a result, the effects of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development become remarkable. In addition, the effect of low-voltage driving of the light-emitting elements in the organic EL display becomes remarkable. (A3) resin more preferably contains (A3-1) resin and/or (A3-3) resin, and more preferably contains (A3-1) resin. (A3) The resin may be either a single resin or a copolymer.
  • (A3) resin is composed of (A3-1 ) resin, (A3-2) resin, (A3-3) resin and (A3-4) one or more resins selected from the group consisting of resins, and containing resins corresponding to the following (A3b) resins It is also preferable to (A3b) Resin: Among (A3) resins, a resin having a phenolic hydroxyl group and an ethylenically unsaturated double bond group.
  • the resin has a phenolic hydroxyl group in at least one of a resin main chain, a resin side chain and a resin terminal, and A resin having at least one ethylenically unsaturated double bond group, which is different from the resin (A1).
  • the ethylenically unsaturated double bond group possessed by the resin is preferably a radically polymerizable group from the viewpoint of improving sensitivity during exposure, and is a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and a carbon More preferably, it is one or more groups selected from the group consisting of 2 to 5 alkynyl groups.
  • the photoreactive group is preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, more preferably a (meth)acryloyl group.
  • alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms examples include vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl-2-butenyl group, 3-methyl -2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is preferred, and vinyl group or allyl group is more preferred.
  • the double bond equivalent of the resin is preferably 500 g/mol or more, more preferably 700 g/mol or more, and even more preferably 1,000 g/mol or more, from the viewpoint of improving halftone characteristics.
  • the double bond equivalent is preferably 3,000 g/mol or less, more preferably 2,000 g/mol or less, more preferably 1,500 g, from the viewpoints of improving sensitivity during exposure and suppressing variations in opening pattern dimensions after development. /mol or less is more preferable.
  • (A3) resin is (A3-1)
  • One or more resins selected from the group consisting of resins, (A3-2) resins, (A3-3) resins and (A3-4) resins, containing resins corresponding to the following (A3a) resins is also preferred.
  • (A3a) Resin Among (A3) resins, a resin having a phenolic hydroxyl group and not having an ethylenically unsaturated double bond group.
  • (A3a) that the resin does not have an ethylenically unsaturated double bond group means that it does not have an ethylenically unsaturated double bond group that is a radically polymerizable group.
  • the resin does not have an ethylenically unsaturated double bond group in the resin main chain, the resin side chain and the resin terminal, and at least the resin main chain, the resin side chain and the resin terminal One of them is a resin having a phenolic hydroxyl group, which is different from the resins (A1) and (A2).
  • the alkali-soluble resin contains the above-described (A3b) resin, from the viewpoint of improving sensitivity during exposure, suppressing residue after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development
  • the alkali-soluble resin preferably further contains the above-described (A3a) resin.
  • the alkali-soluble resin preferably contains the (A2) resin.
  • the (A) alkali-soluble resin contains the (A2) resin, the effects of improving sensitivity during exposure, suppressing residue after development, and improving halftone characteristics become remarkable. In addition, the effect of improving the reliability of the light-emitting element in the organic EL display becomes remarkable.
  • Alkali-soluble resin more preferably contains (A1) resin and/or (A3) resin, and further contains (A2) resin.
  • Alkali-soluble resin more preferably contains (A1) resin and (A2) resin, and more preferably contains (A1) resin, (A3) resin and (A2) resin.
  • Alkali-soluble resin contains (A1) resin and/or (A3) resin and further contains (A2) resin, thereby improving sensitivity during exposure, suppressing residue after development, and improving halftone characteristics. , and the effect of suppressing the variation in opening pattern size after development becomes remarkable. In addition, the effect of improving the reliability of the light-emitting element in the organic EL display and driving the light-emitting element at a low voltage becomes remarkable.
  • the ethylenically unsaturated double bond group possessed by the resin is preferably a radically polymerizable group from the viewpoint of improving sensitivity during exposure, and is a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and a carbon More preferably, it is one or more groups selected from the group consisting of 2 to 5 alkynyl groups.
  • the photoreactive group is preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, more preferably a (meth)acryloyl group.
  • alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms examples include vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl-2-butenyl group, 3-methyl -2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is preferred, and vinyl group or allyl group is more preferred.
  • (A2) resin is the following (A2-a) resin, (A2-b) resin, (A2-c) resin, (A2-d) resin, (A2-e) resin, (A2-f) resin, It is preferable to contain one or more resins selected from the group consisting of (A2-1) resin, (A2-2) resin and (A2-3) resin.
  • (A2-a) Resin Ethylenically unsaturated double bond group-containing polyimide.
  • Resin a polybenzoxazole precursor containing an ethylenically unsaturated double bond group.
  • A2-e Resin: Ethylenically unsaturated double bond group-containing polyamideimide.
  • A2-f Resin: Ethylenically unsaturated double bond group-containing polysiloxane.
  • A2-1 Resin: a resin containing a polycyclic side chain.
  • A2-2 Resin: acid-modified epoxy resin.
  • (A2) resin is , (A2-a) resin, (A2-b) resin, (A2-c) resin, (A2-d) resin, (A2-e) resin and (A2-f) one type selected from the group consisting of resin It is more preferable to contain the above resins, selected from the group consisting of (A2-a) resin, (A2-b) resin, (A2-c) resin, (A2-d) resin and (A2-e) resin It is more preferable to contain one or more resins, and it is particularly preferable to contain (A2-a) resin and/or (A2-e) resin.
  • (A2) resin is composed of (A2-1) resin, (A2-2) resin and (A2- 3) It is more preferable to contain one or more resins selected from the group consisting of resins, and it is even more preferable to contain (A2-1) resin and/or (A2-2) resin.
  • (A2) resin includes (A2-a) resin, (A2-b) resin, (A2-c) resin, (A2-d) resin, (A2-e) resin, and (A2-f) containing one or more resins selected from the group consisting of resins, and further containing one or more resins selected from the group consisting of (A2-1) resin, (A2-2) resin, and (A2-3) resin Containing is also preferable.
  • the resin may be either a single resin or a copolymer.
  • (A) resin contains at least the following (AX) resin.
  • (AX) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • Alkali-soluble resin refers to a resin having an alkali-soluble group, which will be described later. Alkali-soluble resin has solubility in an alkaline developer by having an alkali-soluble group.
  • the alkali-soluble resin is added with (C) a photosensitizer, which will be described later, to impart positive or negative photosensitivity to the composition, and by developing with an alkaline developer, a positive or negative pattern can be formed.
  • a resin having a high solubility is preferred.
  • the (A) alkali-soluble resin contains at least the (AX) resin
  • the effects of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development become remarkable.
  • the effect of improving the reliability of the light-emitting element in the organic EL display and driving the light-emitting element at a low voltage becomes remarkable.
  • (AX) resin refers to a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms in the structural unit of the resin (hereinafter, "cyclic structural unit of (AX) resin").
  • the cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure, more preferably an isocyanuric acid structure.
  • the (AX) resin a resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure (hereinafter referred to as "specific (AX) resin") is preferable.
  • the (AX) resin has a structural unit containing an isocyanuric acid structure and/or a triazine structure, and contains one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure. It preferably has a structural unit.
  • (AX) Resin more preferably has a structural unit containing an isocyanuric acid structure.
  • the alkali-soluble resin contains (A1) resin and/or (A3) resin, and (AX) resin contains an isocyanuric acid structure and/or It preferably has a structural unit containing a triazine structure and also has a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure.
  • the (AX) resin more preferably has a structural unit containing an isocyanuric acid structure.
  • the (A) alkali-soluble resin contains (A1) resin and/or (A3) resin, and (AX) resin contains isocyanuric acid structure and/or triazine Having a structural unit containing a structure, and the structural unit containing an isocyanuric acid structure and/or a triazine structure has one or more structures selected from the group consisting of an aliphatic structure, an alicyclic structure and an aromatic structure It preferably has at least two organic groups.
  • the fatty structure is preferably an aliphatic structure having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.
  • the alicyclic structure is preferably an alicyclic structure having 4 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 20 carbon atoms, and even more preferably a cycloalkylene group having 4 to 10 carbon atoms.
  • the aromatic structure is preferably an aromatic structure having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 30 carbon atoms, and even more preferably an arylene group having 6 to 15 carbon atoms.
  • the (AX) resin has a structural unit containing an isocyanuric acid structure and/or a triazine structure, and the following (AX-1) resin, (AX -2) One or more resins selected from the group consisting of resins, (AX-3) resins, (AX-4) resins, (AX-5) resins and (AX-6) resins (hereinafter referred to as "particularly suitable (AX) is sometimes referred to as "resin").
  • the alkali-soluble resin contains (A1) resin and/or (A3) resin, and (AX) resin contains an isocyanuric acid structure and/or Having a structural unit containing a triazine structure, and the following (AX-1) resin, (AX-2) resin, (AX-3) resin, (AX-4) resin, (AX-5) resin and ( AX-6) It is preferable to contain one or more resins selected from the group consisting of resins.
  • the (AX) resin more preferably has a structural unit containing an isocyanuric acid structure.
  • (AX-1) Resin Nitrogen ring-containing polyimide.
  • AX-2 Resin: Nitrogen ring-containing polyimide precursor.
  • AX-3) Resin: Nitrogen ring-containing polybenzoxazole.
  • AX-4) Resin: Nitrogen ring-containing polybenzoxazole precursor.
  • AX-5 Resin: Nitrogen ring-containing polyamideimide.
  • AX-6 Resin: Nitrogen ring-containing polysiloxane.
  • (AX) resin is a group consisting of (AX-1) resin, (AX-2) resin, (AX-3) resin, (AX-4) resin, (AX-5) resin and (AX-6) resin
  • (AX) resin is one or more selected from the group consisting of (AX-1) resin, (AX-2) resin, (AX-3) resin, (AX-4) resin and (AX-5) resin It is more preferable to contain a resin, and it is even more preferable to contain (AX-1) resin and/or (AX-5) resin.
  • the (AX) resin may be either a single resin or a copolymer.
  • nitrogen ring refers to a "(AX) resin cyclic structural unit", that is, a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • (AX-1) resin, (AX-2) resin, (AX-3) resin, (AX-4) resin, (AX-5) resin and (AX-6) resin have isocyanuric acid as the nitrogen ring. structure and/or triazine structure.
  • the alkali-soluble resin preferably contains the following (AXb) resin.
  • (AXb) resin Among (AX) resins, a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and further having an ethylenically unsaturated double bond group.
  • the (A) alkali-soluble resin contains the (AXb) resin
  • the (AXb) resin has a cyclic structural unit of the (AX) resin in the structural unit of the resin, and at least one of the main chain of the resin, the side chain of the resin and the end of the resin is ethylenically unsaturated. Refers to a resin having a double bond group.
  • the ethylenically unsaturated double bond group possessed by the (AXb) resin is preferably a radically polymerizable group from the viewpoint of improving sensitivity during exposure, such as a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and a carbon More preferably, it is one or more groups selected from the group consisting of 2 to 5 alkynyl groups.
  • the photoreactive group is preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, more preferably a (meth)acryloyl group.
  • an alkenyl group having 2 to 5 carbon atoms or an alkynyl group having 2 to 5 carbon atoms is a vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl-2-butenyl group, 3- A methyl-2-butenyl group, a 2,3-dimethyl-2-butenyl group, an ethynyl group or a 2-propargyl group is preferable, and a vinyl group or an allyl group is more preferable.
  • the alkali-soluble resin preferably contains the following (AXa) resin.
  • (AXa) resin Among (AX) resins, a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and having no ethylenically unsaturated double bond group.
  • (AXa) resins a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and having no ethylenically unsaturated double bond group.
  • the fact that the (AXa) resin does not have an ethylenically unsaturated double bond group means that it does not have an ethylenically unsaturated double bond group, which is a radically polymerizable group.
  • the (A) alkali-soluble resin contains the (AXa) resin, the effects of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development become remarkable.
  • the (AXa) resin has a cyclic structural unit of the (AX) resin in the structural unit of the resin, and an ethylenically unsaturated double bond group on the main chain of the resin, the side chain of the resin and the end of the resin. It refers to a resin that does not have
  • the alkali-soluble resin preferably contains the (AXb) resin and the (AXa) resin.
  • Alkali-soluble resin containing (AXa) resin and (AXb) resin improves sensitivity during exposure, suppresses residue after development, improves halftone characteristics, and suppresses variation in opening pattern dimensions after development. The effect is remarkable.
  • the (A1) resin, (A2) resin, (A3) resin and (AX) resin each have an acidic group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • the (A1) resin, (A2) resin, (A3) resin and (AX) resin preferably have at least one of a structural unit having an acidic group and a terminal structure having an acidic group.
  • the acidic group includes a carboxy group, a carboxylic anhydride group, a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, 1,1-bis A (trifluoromethyl)methylol group, a sulfonic acid group or a mercapto group is preferred.
  • Phenolic hydroxyl group, hydroxyimide group, hydroxyamide group, silanol group or 1,1-bis(trifluoromethyl)methylol group is more preferred from the viewpoint of improving halftone characteristics and suppressing variation in opening pattern dimensions after development. More preferred is a hydroxy group or a silanol group, and particularly preferred is a phenolic hydroxy group.
  • a carboxy group or a carboxylic anhydride group is preferred from the viewpoint of suppressing residue after development.
  • the acid equivalent of the (AX) resin is preferably 200 g/mol or more, more preferably 250 g/mol or more, and even more preferably 300 g/mol or more, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the acid equivalent is preferably 600 g/mol or less, more preferably 500 g/mol or less, and even more preferably 450 g/mol or less, from the viewpoint of suppressing residue after development.
  • the acid equivalent of the resin is preferably 200 g/mol or more, more preferably 250 g/mol or more, and even more preferably 300 g/mol or more, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the acid equivalent is preferably 600 g/mol or less, more preferably 500 g/mol or less, and even more preferably 450 g/mol or less, from the viewpoint of suppressing residue after development.
  • the acid equivalent of the resin is preferably 300 g/mol or more, more preferably 350 g/mol or more, and even more preferably 400 g/mol or more, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the acid equivalent is preferably 700 g/mol or less, more preferably 600 g/mol or less, and even more preferably 550 g/mol or less, from the viewpoint of suppressing residue after development.
  • the resin has a phenolic hydroxyl group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • the resin preferably has at least one of a structural unit having a phenolic hydroxyl group and a terminal structure having a phenolic hydroxyl group. Moreover, it may have other acidic groups. Other acidic groups are preferably a carboxy group, a carboxylic anhydride group, a hydroxyimide group, a hydroxyamide group, a silanol group, a 1,1-bis(trifluoromethyl)methylol group, a sulfonic acid group or a mercapto group.
  • a hydroxyimide group, a hydroxyamide group, a silanol group or a 1,1-bis(trifluoromethyl)methylol group is preferred from the viewpoint of improving tone characteristics.
  • a carboxy group or a carboxylic anhydride group is preferred from the viewpoint of suppressing residue after development.
  • the acid equivalent of the resin is preferably 70 g/mol or more, more preferably 80 g/mol or more, and even more preferably 90 g/mol or more, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the acid equivalent is preferably 450 g/mol or less, more preferably 350 g/mol or less, and even more preferably 300 g/mol or less, from the viewpoint of suppressing residue after development.
  • the alkali-soluble resin preferably contains, as the (AX) resin, one or more resins selected from the group consisting of the following (AX1) resin, (AX2) resin and (AX3) resin.
  • (AX1) resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure; and having no ethylenically unsaturated double bond groups.
  • (AX2) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and further having an ethylenically unsaturated double bond group.
  • (AX3) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and further having a phenolic hydroxyl group.
  • (A1-1) resin, (A1-2) resin, (A1-3) resin, (A1-4) resin, (A1-5) resin and (A1-6) resin have at least 3 nitrogen atoms resins are classified as (AX) resins when they have a structural unit containing a cyclic structure with Such resins are respectively the following (AX1-1) resins, (AX1-2) resins, (AX1-3) resins, (AX1-4) resins, (AX1-5) resins and (AX1-6) resins It is assumed that (AX1-1) Resin: Nitrogen ring-containing polyimide having no ethylenically unsaturated double bond group.
  • (AX1-2) Resin A nitrogen ring-containing polyimide precursor having no ethylenically unsaturated double bond group.
  • (AX1-3) Resin Nitrogen ring-containing polybenzoxazole having no ethylenically unsaturated double bond group.
  • (AX1-4) Resin A nitrogen ring-containing polybenzoxazole precursor having no ethylenically unsaturated double bond group.
  • the above-mentioned (A2-a) resin (A2-b) resin, (A2-c) resin, (A2-d) resin, (A2-e) resin and (A2-f) resin has at least three nitrogen atoms resins are classified as (AX) resins when they have a structural unit containing a cyclic structure having Such resins are respectively referred to as (AX2-a) resins (AX2-b) resins, (AX2-c) resins, (AX2-d) resins, (AX2-e) resins and (AX2-f) resins below. shall be (AX2-a) Resin: Ethylenically unsaturated double bond group-containing polyimide having a nitrogen ring.
  • (AX2-b) resin a polyimide precursor containing an ethylenically unsaturated double bond group having a nitrogen ring.
  • (AX2-c) Resin Polybenzoxazole containing an ethylenically unsaturated double bond group having a nitrogen ring.
  • (AX2-d) Resin A polybenzoxazole precursor containing an ethylenically unsaturated double bond group having a nitrogen ring.
  • (A2-1) resin, (A2-2) resin and (A2-3) resin have a structural unit containing a cyclic structure having at least three nitrogen atoms
  • those resins are (AX) It is classified as a resin.
  • Such resins are referred to below as (AX2-1) resin, (AX2-2) resin, and (AX2-3) resin, respectively.
  • (AX2-1) Resin a resin containing a polycyclic side chain having a nitrogen ring.
  • (A3-1) resin, (A3-2) resin, (A3-3) resin and (A3-4) resin have a structural unit containing a cyclic structure having at least three nitrogen atoms
  • Resins are classified as (AX) resins.
  • Such resins are referred to below as (AX3-1) resins, (AX3-2) resins, (AX3-3) resins and (AX3-4) resins, respectively.
  • (AX) resins when the (A3a) resin and (A3b) resin described above have a structural unit containing a cyclic structure having at least three nitrogen atoms, these resins are classified as (AX) resins. Such resins are referred to below as (AX3a) and (AX3b) resins, respectively.
  • (AX3a) Resin Among (AX3) resins, a resin having a nitrogen ring and a phenolic hydroxyl group and not having an ethylenically unsaturated double bond group.
  • (AX3b) Resin Among (AX3) resins, a resin having a nitrogen ring, a phenolic hydroxyl group and an ethylenically unsaturated double bond group.
  • polyimide precursors examples include polyamic acids, polyamic acid esters, polyamic acid amides, or polyisoimides obtained by reacting tetracarboxylic acids or corresponding tetracarboxylic dianhydrides with diamines or diisocyanate compounds.
  • Polyimides include, for example, resins obtained by dehydrating and ring-closing a polyimide precursor by heating or reacting with a catalyst.
  • Polyimides and polyimide precursors may be copolymers with polyamides obtained by further using dicarboxylic acids or corresponding dicarboxylic acid activated diesters in reactions for synthesizing resins.
  • the polyimide preferably has a structural unit represented by the general formula (1) from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • the content ratio of the structural unit represented by general formula (1) in the total structural units in the polyimide is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%.
  • the polyimide precursor preferably has a structural unit represented by the general formula (3) from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • the content ratio of the structural unit represented by general formula (3) in the total structural units in the polyimide precursor is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%.
  • R 1 and R 9 each independently represent a tetravalent to decavalent organic group.
  • R 2 and R 10 each independently represent a divalent to decavalent organic group.
  • R 3 , R 4 and R 13 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by general formula (6) or general formula (7).
  • R 11 represents a substituent represented by general formula (6) or general formula (7).
  • R12 represents a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group.
  • R 3 or R 4 represents a phenolic hydroxyl group
  • R 1 or R 2 bonded to the phenolic hydroxyl group represents an aromatic structure.
  • R 12 or R 13 represents a phenolic hydroxyl group
  • R 9 or R 10 bonding with the phenolic hydroxyl group represents an aromatic structure.
  • R 1 and R 9 each independently represent an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or a A 4- to 10-valent organic group having an aromatic structure of 6-30 is preferred.
  • R 2 and R 10 are each independently divalent to decavalent having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 6 to 30 carbon atoms. is preferred.
  • q is preferably an integer of 1-8.
  • v is preferably an integer of 1-8.
  • R 1 and R 9 each independently represent a tetracarboxylic acid residue or a tetracarboxylic acid derivative residue.
  • R 2 and R 10 each independently represent a diamine residue or a diamine derivative residue.
  • Tetracarboxylic acid derivatives include tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid activated diesters.
  • Diamine derivatives include diisocyanate compounds or trimethylsilylated diamines.
  • the aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.
  • R 25 to R 27 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 carbon atoms. represents an aryl group of -15.
  • R 25 to R 27 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or 6 to 10 aryl groups are preferred.
  • the alkyl groups, acyl groups, and aryl groups described above may have heteroatoms and may be unsubstituted or substituted.
  • R 11 in the structural unit represented by general formula (3) is a substituent represented by general formula (6) and R 25 is a hydrogen atom
  • R 11 in the structural unit represented by general formula (3) is a substituent represented by general formula (6)
  • R 25 is an alkyl group having 1 to 10 carbon atoms and an acyl group having 2 to 6 carbon atoms.
  • an aryl group having 6 to 15 carbon atoms is referred to as an amic acid ester structural unit.
  • a case where R 11 in the structural unit represented by general formula (3) is a substituent represented by general formula (7) is called an amic acid amide structural unit.
  • the polyimide precursor preferably has an amic acid ester structural unit and/or an amic acid amide structural unit from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • a polyimide precursor having an amic acid ester structural unit and/or an amic acid amide structural unit part of the carboxy groups, which are tetracarboxylic acid residues and/or tetracarboxylic acid derivative residues, are esterified and/or amide Examples include resins obtained by converting
  • the polyimide precursor may have an imide ring-closed structural unit in which a part of the amic acid structural unit, the amic acid ester structural unit, and the amic acid amide structural unit is imide ring-closed.
  • the total content ratio of amic acid ester structural units and amic acid amide structural units in the total content ratio of amic acid structural units, amic acid ester structural units, amic acid amide structural units, and imide ring-closing structural units is From the viewpoint of suppressing the variation in opening pattern dimensions in , it is preferably 10 mol % or more, more preferably 30 mol % or more, and even more preferably 50 mol % or more.
  • the total content of the amic acid ester structural unit and the amic acid amide structural unit is preferably 100 mol % or less, more preferably 90 mol % or more, and even more preferably 80 mol % or more, from the viewpoint of suppressing residue after development.
  • (A1-3) resin, (AX1-3) resin, (A2-c) resin and (AX2-c) resin, which are polybenzoxazoles, will be collectively described.
  • the polybenzoxazole precursors (A1-4) resin, (AX1-4) resin, (A2-d) resin and (AX2-d) resin will be collectively described.
  • polybenzoxazole precursors include polyhydroxyamides obtained by reacting a dicarboxylic acid or a corresponding dicarboxylic acid active diester with a diamine such as a bisaminophenol compound.
  • polybenzoxazole include resins obtained by dehydrating and ring-closing a polybenzoxazole precursor by heating or reacting with a catalyst.
  • Polybenzoxazole and polybenzoxazole precursors may be copolymers with polyamide obtained by further using a diamine or diisocyanate compound in the reaction for synthesizing the resin.
  • the polybenzoxazole preferably has a structural unit represented by the general formula (2) from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • the content ratio of the structural unit represented by general formula (2) in the total structural units in the polybenzoxazole is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%.
  • the polybenzoxazole precursor preferably has a structural unit represented by general formula (4) from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • the content ratio of the structural unit represented by the general formula (4) in the total structural units in the polybenzoxazole precursor is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and further 70 to 100 mol%. preferable.
  • R 5 and R 14 each independently represent a divalent to decavalent organic group.
  • R 6 and R 15 each independently represent a 4- to 10-valent organic group having an aromatic structure.
  • R 7 , R 8 and R 16 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the general formula (6) or general formula (7) described above.
  • R 17 represents a phenolic hydroxyl group.
  • R 18 represents a sulfonic acid group, a mercapto group, or a substituent represented by general formula (6) or general formula (7) described above.
  • R7 represents a phenolic hydroxyl group
  • R5 bonding to the phenolic hydroxyl group represents an aromatic structure.
  • R 16 represents a phenolic hydroxyl group
  • R 14 bonding to the phenolic hydroxyl group represents an aromatic structure.
  • R 5 and R 14 each independently represent an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or 6 carbon atoms. Bi- to decavalent organic radicals with ⁇ 30 aromatic structures are preferred.
  • R 6 and R 15 are each independently preferably a tetravalent to decavalent organic group having an aromatic structure with 6 to 30 carbon atoms. s is preferably an integer of 1-6.
  • R5 and R14 each independently represent a dicarboxylic acid residue or a dicarboxylic acid derivative residue.
  • R6 and R15 each independently represent a bisaminophenol compound residue or a bisaminophenol compound derivative residue.
  • Dicarboxylic acid derivatives include dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, and diformyl compounds.
  • the aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.
  • polyamideimide ⁇ (A) alkali-soluble resin; polyamideimide>
  • the (A1-5) resin, (AX1-5) resin, (A2-e) resin and (AX2-e) resin, which are polyamideimides, will be collectively described below.
  • Polyamideimides include, for example, resins obtained by reacting tricarboxylic acids or corresponding tricarboxylic acid anhydrides with diamines or diisocyanate compounds. A resin obtained by further dehydrating and ring-closing the obtained resin by heating or by a reaction using a catalyst is also included.
  • Polyamideimide may be a copolymer with polyamide obtained by further using a dicarboxylic acid or a corresponding dicarboxylic acid activated diester in the reaction for synthesizing the resin.
  • the polyamideimide preferably has a structural unit represented by general formula (5).
  • the content ratio of the structural unit represented by general formula (5) to the total structural units in the polyamideimide is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%.
  • R 19 represents a trivalent to decavalent organic group.
  • R 20 represents a divalent to decavalent organic group.
  • R 21 and R 22 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (6) or general formula (7).
  • m represents an integer of 0 to 7;
  • n represents an integer of 0 to 8;
  • R 21 or R 22 represents a phenolic hydroxyl group, R 19 or R 20 bonding with the phenolic hydroxyl group represents an aromatic structure.
  • R 19 is a trivalent to decavalent organic compound having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 6 to 30 carbon atoms. groups are preferred.
  • R 20 is preferably a divalent to decavalent organic group having an aliphatic structure of 2 to 20 carbon atoms, an alicyclic structure of 4 to 20 carbon atoms or an aromatic structure of 6 to 30 carbon atoms.
  • n is preferably an integer of 1-8.
  • R 19 represents a tricarboxylic acid residue or a tricarboxylic acid derivative residue.
  • R20 represents a diamine residue or a diamine derivative residue.
  • Tricarboxylic acid derivatives include tricarboxylic acid anhydrides, tricarboxylic acid chlorides or tricarboxylic acid active esters.
  • Diamine derivatives include diisocyanate compounds or trimethylsilylated diamines.
  • the aliphatic structures, alicyclic structures, and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.
  • Polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and polyamideimides improve sensitivity during exposure, improve halftone characteristics, and suppress variations in opening pattern dimensions after development. From the viewpoint of, it is preferable to have a structural unit having a fluorine atom.
  • exposure means irradiation with actinic rays (radiation), and examples thereof include irradiation with visible light, ultraviolet rays, electron beams, X-rays, and the like.
  • exposure refers to irradiation with actinic rays (radiation).
  • polyimide-based resins among all the structural units of each resin, structural units derived from carboxylic acids or structural units derived from carboxylic acid derivatives and/or structural units derived from amines or structural units derived from amine derivatives
  • the total content ratio of structural units having fluorine atoms in all structural units of the resin is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and even more preferably 50 to 100 mol%.
  • the polyimide resin has an acidic group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • These resins preferably have an acidic group in a structural unit derived from a carboxylic acid or a structural unit derived from a diamine, or have a terminal structure having an acidic group.
  • a resin obtained by reacting a part of the hydroxy group of each resin with a polyfunctional carboxylic acid dianhydride is also preferable, and among the main chain of each resin, the side chain of the resin and the end of the resin A resin in which an acidic group is introduced into at least one by a reaction using a catalyst is also preferable.
  • A2 resin (A2-a) resin, (A2-b) resin, (A2-c) resin, (A2-d) resin and (A2-e) resin (hereinafter referred to as "polyimide-based (A2) resin") and (AX2) resin (AX2-a) resin, (AX2-b) resin, (AX2-c) resin, (AX2-d) resin and (AX2-e) resin (hereinafter referred to as "polyimide-based (AX2) resin”) has an ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A2) resins and (AX2) resins include (A1-1) resin, (A1-2) resin, (A1-3) resin, (A1-4) resin and (A1-5) resin (hereinafter , "polyimide-based (A1) resin") and (AX1-1) resin, (AX1-2) resin, (AX1-3) resin, (AX1-4) resin and (AX1-5) resin (hereinafter, " Among the polyimide-based (AX1) resins, resins obtained by reacting some of the acidic groups of each resin with a compound having an ethylenically unsaturated double bond group are preferred.
  • a resin in which an ethylenically unsaturated double bond group is introduced into at least one of the side chains of each resin and the end of the resin by a reaction using a catalyst.
  • an electrophilic compound having an ethylenically unsaturated double bond group is preferred.
  • the electrophilic compound is preferably an isocyanate compound, an epoxy compound, an alcohol compound, an aldehyde compound, a ketone compound or a carboxylic acid anhydride, and more preferably an isocyanate compound, an epoxy compound or an alcohol compound, from the viewpoint of reactivity and compound usability. preferable.
  • the double bond equivalent of the polyimide-based (A2) resin and the polyimide-based (AX2) resin described above is preferably 500 g/mol or more, more preferably 700 g/mol or more, more preferably 1,000 g, from the viewpoint of improving halftone characteristics. /mol or more is more preferable.
  • the double bond equivalent is preferably 3,000 g/mol or less, more preferably 2,000 g/mol or less, more preferably 1,500 g/mol, from the viewpoint of improving sensitivity during exposure and suppressing variations in opening pattern dimensions after development. mol or less is more preferable.
  • These resins include, in the reaction for synthesizing the polyimide-based resin described in the section of (A1) resin, a tetracarboxylic acid containing a cyclic structure having at least three nitrogen atoms or a corresponding tetracarboxylic dianhydride; nitrogen dicarboxylic acids or corresponding dicarboxylic acid activated diesters containing cyclic structures having at least 3 atoms; tricarboxylic acids or corresponding tricarboxylic anhydrides containing cyclic structures having at least 3 nitrogen atoms; cyclic structures having at least 3 nitrogen atoms.
  • a resin obtained by using a diamine, diisocyanate compound, triamine or triisocyanate compound containing a cyclic structure having at least three nitrogen atoms is more preferable.
  • At least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • a cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • an electrophilic compound or a nucleophilic compound is preferred.
  • electrophilic compounds isocyanate compounds, epoxy compounds, alcohol compounds, aldehyde compounds, ketone compounds, carboxylic acid anhydrides, (meth)acryloyl compounds, vinyl compounds, allyl compounds or alkoxysilane compounds are preferred, and isocyanate compounds and epoxy compounds. or alcohol compounds are more preferred.
  • the nucleophilic compound is preferably an alcohol compound, an amine compound, a thiol compound or a carboxylic acid compound, more preferably an alcohol compound or an amine compound.
  • an isocyanuric acid compound having a hydrogen atom bonded to a nitrogen atom derived from isocyanuric acid or an oxygen atom derived from cyanuric acid (an oxygen atom bonded to a triazine structure) having a hydrogen atom bonded to Cyanuric acid compounds are preferred.
  • the isocyanuric acid compound and the cyanuric acid compound may have a substituent.
  • the polyimide-based (AX) resin preferably has a structural unit containing an isocyanuric acid structure and/or a triazine structure from the viewpoint of suppressing residue after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development. , an isocyanuric acid structure and/or a triazine structure. Further, the polyimide-based (AX) resin preferably contains (AX-1) resin and/or (AX-5) resin.
  • polyimide-based (AX) resin among all the structural units of each resin, when structural units derived from all amines or structural units derived from all amine derivatives contain an isocyanuric acid structure and/or a triazine structure, all amines
  • the total content of structural units containing an isocyanuric acid structure and/or a triazine structure in the total structural units derived from and all amine derivatives is preferably 10 to 100 mol%, and 30 to 100 mol%. More preferably, 50 to 100 mol % is even more preferable.
  • the polyimide-based (AX) resin has a structural unit containing an isocyanuric acid structure and/or a triazine structure, and the structural unit containing the isocyanuric acid structure and/or the triazine structure has an aliphatic structure, an alicyclic structure and an aromatic structure. It preferably has at least two, more preferably at least three, organic groups having one or more structures selected from the group consisting of structures.
  • the aliphatic structure is preferably an aliphatic structure having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.
  • the alicyclic structure is preferably an alicyclic structure having 4 to 20 carbon atoms, more preferably a cycloalkylene group having 4 to 20 carbon atoms, and even more preferably a cycloalkylene group having 4 to 10 carbon atoms.
  • the aromatic structure is preferably an aromatic structure having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 30 carbon atoms, and even more preferably an arylene group having 6 to 15 carbon atoms.
  • the polyimide-based (AX) resin has a structural unit represented by the general formula (21) as a structural unit derived from a diamine, a diisocyanate compound, a triamine or a triisocyanate containing an isocyanuric acid structure and/or a triazine structure and/or general It preferably has a structural unit represented by formula (22), and more preferably has a structural unit represented by general formula (21).
  • W 48 to W 50 each independently represent a direct bond or an oxygen atom.
  • Y 45 to Y 50 each independently represent a direct bond or an aliphatic structure having 1 to 20 carbon atoms.
  • Z 45 to Z 50 each independently represent a direct bond, an alicyclic structure having 4 to 20 carbon atoms or an aromatic structure having 6 to 30 carbon atoms.
  • R 47 and R 50 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a bonding point.
  • * 1 to * 4 each independently represent a point of attachment.
  • the "bonding point” means a point of bonding with another structure.
  • the above-mentioned aliphatic structure, alicyclic structure and aromatic structure may have heteroatoms and may be unsubstituted or substituted.
  • at least one of Y 45 to Y 50 preferably has an aliphatic structure with 1 to 20 carbon atoms.
  • At least one of Z 45 to Z 50 is preferably an alicyclic structure having 4 to 20 carbon atoms or an aromatic structure having 6 to 30 carbon atoms.
  • Y 45 to Y 50 are each independently preferably a direct bond or an aliphatic structure having 1 to 10 carbon atoms, more preferably a direct bond or an alkylene group having 1 to 10 carbon atoms.
  • Z 45 to Z 50 are each independently preferably a direct bond, an alicyclic structure having 4 to 10 carbon atoms or an aromatic structure having 6 to 15 carbon atoms, and a direct bond or cycloalkylene having 4 to 10 carbon atoms. or an arylene group having 6 to 15 carbon atoms is more preferred.
  • Examples of diamines, diisocyanate compounds, triamines, or triisocyanate compounds containing an isocyanuric acid structure and/or triazine structure include 1,3-bis(4-aminophenyl)isocyanuric acid, 1,3-bis[4-[2-( 4-aminophenyl)]ethynylphenyl]isocyanuric acid, 1,3,5-tris(4-aminophenyl)isocyanuric acid, 1,3,5-tris(4-amino-2-methylphenyl)isocyanuric acid, 1, 3,5-tris[4-[2-(4-aminophenyl)]ethynylphenyl]isocyanuric acid, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-bis(4- Aminophenoxy)-6-hydroxy-1,3,5-triazine or 2,4,6-tris(4-aminophenoxy)-1,3,
  • the polyimide-based (AX) resin contains an isocyanuric acid structure and/or a triazine structure, and further contains an alicyclic structure, from the viewpoint of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development.
  • (AX) resin specific structural unit a structural unit derived from a diamine, diisocyanate compound, triamine or triisocyanate compound containing an isocyanuric acid structure and/or triazine structure and having an alicyclic structure
  • (AX) resin specific structural unit a structural unit derived from a diamine, diisocyanate compound, triamine or triisocyanate compound containing an isocyanuric acid structure and/or triazine structure and having an alicyclic structure.
  • the diamine, diisocyanate compound, triamine or triisocyanate compound containing an isocyanuric acid structure and/or triazine structure and further having an alicyclic structure includes an isocyanuric acid-modified form of isophorone diisocyanate (isocyanuric acid-type triisocyanate) and isocyanurate of isophorone diisocyanate.
  • a compound obtained by converting an acid-modified form into a triamine (triamine form of isocyanuric acid-type triisocyanate), a condensate of isophorone diisocyanate and cyanuric acid (triazine-type triisocyanate having a urethane bond), or a condensate of isophorone diisocyanate and cyanuric acid
  • triamine form of isocyanuric acid-type triisocyanate a condensate of isophorone diisocyanate and cyanuric acid
  • a compound converted to triamine (a triamine form of triazine-type triisocyanate having a urethane bond) is preferred.
  • the polyimide and polyimide precursor described above preferably have a structural unit derived from a tetracarboxylic acid having an alicyclic structure or a corresponding tetracarboxylic dianhydride.
  • the above-mentioned polybenzoxazole and polybenzoxazole precursor preferably have a structural unit derived from a dicarboxylic acid having an alicyclic structure or a corresponding dicarboxylic acid active diester.
  • the polyamideimide described above preferably has a structural unit derived from a tricarboxylic acid having an alicyclic structure or a corresponding tricarboxylic acid anhydride.
  • the total content ratio of the structural units is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and even more preferably 50 to 100 mol%.
  • the dicarboxylic acid having an alicyclic structure or the corresponding dicarboxylic acid active diester which accounts for the total number of structural units derived from all carboxylic acids and all structural units derived from all carboxylic acid derivatives
  • the total content ratio of the derived structural units is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, even more preferably 50 to 100 mol%.
  • the content ratio of structural units derived from a tricarboxylic acid having an alicyclic structure or a corresponding tricarboxylic acid anhydride to the total of structural units derived from all carboxylic acids and structural units derived from all carboxylic acid derivatives is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, even more preferably 50 to 100 mol %.
  • Polyamideimide having a structural unit derived from a tricarboxylic acid or a corresponding tricarboxylic acid anhydride having a specific structural unit and alicyclic structure of the (AX) resin described above, for example, "UNIDIC” (registered trademark) EMG-793 , V-8000, V-8002, V-8004 or V-8005 or "LUXYDIR” (registered trademark) V-8000BM, EMG-1015, ELG-1302, EQG-1170 (any of the above (manufactured by DIC Corporation).
  • the polyimide-based (AX) resin should have a side chain structure and/or a terminal structure containing an isocyanuric acid structure and/or a triazine structure from the viewpoint of suppressing post-development residue and post-development variation in opening pattern dimensions. is preferred.
  • resins having these side chain structures and terminal structures an isocyanuric acid compound and/or a triazine compound is added to a polyimide-based (AX) resin having a side chain structure containing a reactive group or a terminal structure containing a reactive group. Resins obtained by reaction are preferred.
  • the side chain structure containing a reactive group a side chain structure having an ethylenically unsaturated double bond group is preferred.
  • a terminal structure containing a reactive group a terminal structure having a maleimide group is preferred.
  • the isocyanuric acid structure and/or the triazine structure more preferably have a hydrogen atom bonded to the nitrogen atom of the isocyanuric acid structure and/or a hydrogen atom bonded to the oxygen atom of the triazine structure.
  • Resins having these side chain structures and terminal structures include isocyanuric acid compounds having at least two hydrogen atoms bonded to nitrogen atoms or triazine compounds having at least two hydrogen atoms bonded to oxygen atoms in the reaction described above. Resins obtained by reaction are preferred.
  • the structural unit possessed by the polyimide-based resin from the viewpoint of improving the reliability of the light-emitting element in the organic EL display, it has an aromatic group such as a structural unit derived from an aromatic carboxylic acid or a structural unit derived from an aromatic diamine. Structural units are also preferred. Further, from the viewpoint of low tapering of the pattern shape, a structural unit having a silyl group or a siloxane bond, such as a structural unit derived from siliconediamine, or a structural unit having an oxyalkylene skeleton, such as a structural unit derived from oxyalkylenediamine, is also preferable. . In addition, it is also preferable to have a structure in which the ends of the resin are blocked with a terminal blocking agent such as monoamine or dicarboxylic acid anhydride.
  • a terminal blocking agent such as monoamine or dicarboxylic acid anhydride.
  • the weight average molecular weight (hereinafter, "Mw") of the polyimide-based resin is measured by gel permeation chromatography (hereinafter, "GPC") from the viewpoint of improving the reliability of the light-emitting element in the organic EL display, in terms of polystyrene.
  • Mw is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more.
  • Mw is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, and particularly 20,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape. preferable.
  • the Mw of the (AX-5) resin is measured by GPC from the viewpoint of suppressing residue after development, improving the reliability of the light emitting element in the organic EL display, and driving the light emitting element at a low voltage, in terms of polystyrene conversion measured by GPC.
  • 500 or more is preferable, 1,000 or more is more preferable, and 2,000 or more is still more preferable.
  • Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and even more preferably 10,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape. More preferably, 5,000 or less is particularly preferable.
  • a polyimide resin can be synthesized by a known method. Tetracarboxylic acids, tricarboxylic acids, dicarboxylic acids and their derivatives and diamines, bisaminophenol compounds, monoamines and their derivatives used in the synthesis of each resin include, for example, International Publication No. 2017/057281 or International Publication No. Compounds described in 2017/159876 can be mentioned.
  • polysiloxane ⁇ (A) Alkali-soluble resin; polysiloxane>
  • the (A1-6) resin, (AX1-6) resin, (A2-f) resin and (AX2-f) resin, which are polysiloxanes, will be collectively described below.
  • Examples of polysiloxane include resins obtained by hydrolyzing at least one compound selected from the group consisting of trifunctional organosilane, tetrafunctional organosilane, difunctional organosilane and monofunctional organosilane, followed by dehydration condensation. mentioned.
  • Polysiloxane is a trifunctional organosilane unit represented by the general formula (8) and/or the general formula ( It preferably has a tetrafunctional organosilane unit represented by 9).
  • R 29 represents a hydrogen atom or an organic group.
  • * 1 to * 3 each independently represent a bonding point in the resin.
  • R 29 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or 4 carbon atoms.
  • Halogenated cycloalkyl groups of ⁇ 10 or halogenated aryl groups of 6-15 carbon atoms are preferred.
  • alkyl group, cycloalkyl group, aryl group, halogenated alkyl group, halogenated cycloalkyl group and halogenated aryl group described above may have heteroatoms and may be unsubstituted or substituted. I do not care.
  • the content ratio of the trifunctional organosilane unit represented by the general formula (8) in the polysiloxane is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, more preferably 70 to 100 mol% in terms of Si atom mol. preferable.
  • the trifunctional organosilane unit is preferably an organosilane unit having an epoxy group.
  • the content ratio of the tetrafunctional organosilane unit represented by the general formula (9) in the polysiloxane is preferably 1 mol % or more, more preferably 5 mol % or more in terms of Si atomic mol ratio, from the viewpoint of suppressing residue after development. , more preferably 10 mol % or more.
  • the content ratio of the tetrafunctional organosilane unit represented by the general formula (9) is preferably 40 mol % or less, more preferably 30 mol % or less, and 20 mol in Si atomic mol ratio from the viewpoint of reducing the taper of the pattern shape. % or less is more preferable.
  • Polysiloxane has an acidic group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the terminal of the resin.
  • the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
  • a resin having an organosilane unit having an acidic group is preferable as the polysiloxane.
  • a resin obtained by reacting a part of the hydroxy group or the like of the resin with a polyfunctional carboxylic acid dianhydride is also preferable, and at least one of the resin main chain, the resin side chain and the end of the resin Also preferred are resins into which acidic groups have been introduced by reaction using a catalyst.
  • (A2) resin (A2-f) resin and (AX2) resin (AX2-f) resin have an ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A2-f) resin and (AX2-f) resin a resin having an organosilane unit having an ethylenically unsaturated double bond group is preferred. Also preferred is a resin obtained by reacting a part of the acidic group of the resin with a compound having an ethylenically unsaturated double bond group.
  • the double bond equivalent of the (A2-f) resin and the (AX2-f) resin is preferably 500 g/mol or more, more preferably 700 g/mol or more, and 1,000 g/mol or more. More preferred.
  • the double bond equivalent is preferably 3,000 g/mol or less, more preferably 2,000 g/mol or less, more preferably 1,500 g/mol, from the viewpoint of improving sensitivity during exposure and suppressing variations in opening pattern dimensions after development. mol or less is more preferable.
  • the (AX1-6) resins and (AX2-f) resins described above are included in the (AX) resins. These resins are preferably resins obtained by using an organosilane containing a cyclic structure having at least three nitrogen atoms in the reaction for synthesizing the polysiloxane described above. In addition, at least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms. Resins into which three cyclic structures are introduced are also preferred. A cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • Organosilanes containing an isocyanuric acid structure and/or a triazine structure include 1,3,5-tris(3-trimethoxysilylpropyl)isocyanuric acid and 1,3,5-tris(3-triethoxysilylpropyl)isocyanuric acid.
  • 2,4,6-tris[(3-trimethoxysilylpropyl)amino]-1,3,5-triazine, 2,4,6-tris[(3-triethoxysilylpropyl)amino]-1,3 ,5-triazine, 2,4-diamino-6-(2-triethoxysilylethyl)amino-1,3,5-triazine or 2,4-diamino-6-(2-triethoxysilylethoxy)-1, 3,5-triazines are preferred.
  • each organosilane unit can be in either regular or random arrangement. Regular arrangements include, for example, alternating copolymerization, periodic copolymerization, block copolymerization, or graft copolymerization. Irregular sequences include, for example, random copolymerization. Also, each organosilane unit may be arranged two-dimensionally or three-dimensionally. A two-dimensional arrangement includes, for example, a linear arrangement. Examples of three-dimensional arrays include ladder-like, cage-like, and mesh-like arrangements.
  • the Mw of polysiloxane is preferably 500 or more, more preferably 1,000 or more, in terms of polystyrene measured by GPC. On the other hand, Mw is preferably 50,000 or less, more preferably 10,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • Polysiloxane can be synthesized by a known method.
  • Organosilanes include, for example, compounds described in WO2017/057281 or WO2017/159876.
  • polycyclic side chain-containing resin ⁇ (A) Alkali-soluble resin; polycyclic side chain-containing resin>
  • the polycyclic side chain-containing resins (A2-1) and (AX2-1) are collectively described below.
  • Examples of polycyclic side chain-containing resins include resins obtained by the following (1-a2-1) to (6-a2-1). If necessary, the polyfunctional alcohol compound may be further reacted in any reaction step.
  • (1-a2-1) A resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound and a polyfunctional carboxylic acid dianhydride with an epoxy compound.
  • (2-a2-1) A resin obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional phenol compound and an epoxy compound.
  • (3-a2-1) A resin obtained by reacting a compound obtained by reacting a polyfunctional alcohol compound containing a cyclic skeleton and a polyfunctional carboxylic acid dianhydride with an epoxy compound.
  • (4-a2-1) A resin obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional alcohol compound containing a cyclic skeleton with an epoxy compound.
  • (5-a2-1) A resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound and a polyfunctional carboxylic acid compound with an epoxy compound.
  • (6-a2-1) A resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound and a carboxylic acid compound with a polyfunctional carboxylic acid dianhydride.
  • a polycyclic side chain-containing resin has a structure in which a main chain and a bulky side chain having a cyclic skeleton are connected by one atom in the structural unit of the resin.
  • a structural unit represented by general formula (41) it is preferable to have a structural unit represented by general formula (41).
  • X 41 and X 42 each independently represent a direct bond or a substituent represented by general formula (42) or general formula (43).
  • Y 41 represents a tri- or tetravalent organic group which is a carboxylic acid residue or a carboxylic acid derivative residue.
  • W1 represents an organic group having at least two aromatic groups.
  • R 101 and R 102 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 103 and R 104 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or represents an organic group having an ethylenically unsaturated double bond group.
  • R 105 and R 106 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an organic group having an ethylenically unsaturated double bond group. show. * 1 and * 2 each independently represent a bonding point with W1 in general formula (41) or a bonding point with a carbon atom. * 3 and * 4 each independently represent a bonding point with an oxygen atom in general formula (41).
  • Y 41 is a tri- to tetravalent organic compound having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms or an aromatic structure having 6 to 30 carbon atoms. groups are preferred.
  • W 1 is preferably a substituent represented by any one of the general formulas (44) to (49) from the viewpoint of suppressing the variation in the size of the opening pattern after development and improving the reliability of the light emitting device.
  • R 103 and R 104 are each independently preferably a hydrogen atom or an organic group having an ethylenically unsaturated double bond group.
  • the organic group having an ethylenically unsaturated double bond group in R 103 to R 106 is a (meth)acryloyl group or a substituent represented by general formula (50).
  • the alkyl groups, aliphatic structures, alicyclic structures and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.
  • X 43 to X 52 each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
  • Y 43 and Y 53 each independently represent a direct bond, a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
  • R 107 to R 117 each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 118 to R 124 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a, b, c and d each independently represent an integer of 0 to 4; e and f each independently represent an integer of 0 to 5; g, h and i each independently represent an integer of 0 to 4; j and k each independently represents an integer of 0 to 3; l is 0 when Y 43 is a direct bond, an oxygen atom or a sulfur atom. l is 1 when Y 43 is a nitrogen atom. l is 2 when Y 43 is a carbon atom. m is 0 when Y 53 is a direct bond, an oxygen atom or a sulfur atom. m is 1 when Y 53 is a nitrogen atom; m is 2 when Y 53 is a carbon atom.
  • * 1 to * 6 each independently represent a bonding point with X 41 in the general formula (47) or a bonding point with an oxygen atom.
  • * 7 to * 12 each independently represent a bonding point with X42 in the general formula (47) or a bonding point with an oxygen atom.
  • X 43 to X 52 are each independently preferably a monocyclic or condensed polycyclic hydrocarbon ring having 6 to 15 carbon atoms.
  • Y 43 and Y 53 are each independently preferably a direct bond or an oxygen atom.
  • the alkyl group, cycloalkyl group, aryl group and monocyclic or condensed polycyclic aromatic hydrocarbon ring described above may have a heteroatom and may be unsubstituted or substituted. No.
  • X 54 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms.
  • R 125 represents a vinyl group, an allyl group, a crotonyl group, a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group.
  • R 126 represents a carboxylic acid derivative residue having a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carboxy group.
  • the alkylene group, cycloalkylene group and arylene group described above may have a heteroatom and may be unsubstituted or substituted.
  • the polycyclic side chain-containing resin is a structural unit having a condensed polycyclic structure or a condensed polycyclic structure, from the viewpoint of improving halftone characteristics, suppressing variations in opening pattern dimensions after development, and improving the reliability of light-emitting elements in organic EL displays. It preferably has a structural unit having a polycyclic heterocyclic structure.
  • a fluorene skeleton, a xanthene skeleton or an isoindolinone skeleton is preferred.
  • the polycyclic side chain-containing resin has an acidic group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
  • the polycyclic side chain-containing resin preferably has at least one of a structural unit derived from a polyfunctional carboxylic acid compound, a structural unit derived from a polyfunctional carboxylic acid dianhydride, and a terminal structure having an acidic group.
  • a resin obtained by reacting a part of the hydroxy group or the like of the resin with a polyfunctional carboxylic acid dianhydride is also preferable, and at least one of the resin main chain, the resin side chain and the end of the resin
  • resins into which acidic groups have been introduced by reaction using a catalyst.
  • (A2) resin (A2-1) resin and (AX2) resin (AX2-1) resin have an ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A2-1) resin and (AX2-1) resin are structural units derived from an epoxy compound having an ethylenically unsaturated double bond group, and structures derived from a carboxylic acid compound having an ethylenically unsaturated double bond group. It is preferred to have at least one of a terminal structure having a unit and an ethylenically unsaturated double bond group.
  • a resin obtained by reacting a part of the acidic group of the resin with a compound having an ethylenically unsaturated double bond group is also preferred.
  • the double bond equivalent weights of (A2-1) resin and (AX2-1) resin are preferably 300 g/mol or more, more preferably 400 g/mol or more, and even more preferably 500 g/mol or more. .
  • the double bond equivalent is preferably 1,500 g/mol or less, more preferably 1,000 g/mol or less, and 700 g/mol or less, from the viewpoint of improving sensitivity during exposure and suppressing variations in opening pattern dimensions after development. is more preferred.
  • the (AX2-1) resin described above is included in the (AX) resin.
  • AX2-1) As the resin in the reaction for synthesizing the polycyclic side chain-containing resin described above, a polyfunctional phenol compound containing a cyclic structure having at least three nitrogen atoms, a polyfunctional alcohol compound containing a cyclic skeleton, a polyfunctional epoxy A resin obtained by using a compound, a polyfunctional carboxylic acid compound, a polyfunctional carboxylic acid dianhydride, an epoxy compound, a carboxylic acid compound, or the like is preferable.
  • At least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • the cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • ⁇ Other structural units, terminal blockers and molecular weights> As the structural unit possessed by the polycyclic side chain-containing resin, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display, a structural unit derived from an aromatic polyfunctional carboxylic acid compound or an aromatic polyfunctional carboxylic acid dianhydride is used. Structural units having aromatic groups, such as derived structural units, are also preferred. In addition, it is also preferable to have a structure in which the ends of the resin are blocked with a terminal blocking agent such as monocarboxylic acid, dicarboxylic acid anhydride or tricarboxylic acid anhydride.
  • a terminal blocking agent such as monocarboxylic acid, dicarboxylic acid anhydride or tricarboxylic acid anhydride.
  • the Mw of the polycyclic side chain-containing resin is preferably 500 or more, more preferably 1,000 or more, in terms of polystyrene measured by GPC.
  • Mw is preferably 50,000 or less, more preferably 10,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • a polycyclic side chain-containing resin can be synthesized by a known method. Phenolic compounds, alcohol compounds, epoxy compounds, carboxylic anhydrides and carboxylic acid compounds include, for example, compounds described in International Publication No. 2017/057281 or International Publication No. 2017/159876.
  • Polycyclic side chain-containing resins include, for example, "ADEKA ARKLS” (registered trademark) WR-101 or WR-301 (both of which are manufactured by ADEKA Corporation) or "OGSOL” (registered trademark) CR-1030 ( manufactured by Osaka Gas Chemicals Co., Ltd.).
  • Acid-modified epoxy resins include, for example, resins obtained in the following (1-a2-2) to (2-a2-2). If necessary, the polyfunctional alcohol compound may be further reacted in any reaction step.
  • (1-a2-2) A resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound and a polyfunctional carboxylic acid compound with an epoxy compound.
  • (2-a2-2) A resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound and a carboxylic acid compound with a polyfunctional carboxylic acid dianhydride.
  • Acid-modified epoxy resin has a cyclic skeleton in the structural unit of the resin. Further, from the viewpoint of suppressing variations in opening pattern dimensions after development, one or more structural units selected from the group consisting of structural units represented by any of general formulas (61), (62) and (63) are added. It is preferable to have
  • X 61 and X 62 each independently represent an aliphatic structure having 1 to 6 carbon atoms.
  • X 63 represents an alkylene group having 1 to 6 carbon atoms.
  • W2 represents an organic group having at least one aromatic group.
  • R 141 and R 142 each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • R 143 represents a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 144 to R 146 each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or the general formula (69) represents a substituent group.
  • R 147 represents a hydrogen atom or a substituent represented by general formula (70).
  • R 148 and R 149 each independently represent an organic group having an ethylenically unsaturated double bond group.
  • a and b each independently represent an integer of 0 to 10;
  • c represents an integer of 0 to 14;
  • d represents an integer of 0 to 3;
  • e and f each independently represent an integer of 0 to 4;
  • W 2 is a substituent represented by any one of the general formulas (64) to (68), from the viewpoint of suppressing variations in the size of the opening pattern after development and improving the reliability of the light-emitting element. is preferred.
  • the organic group having an ethylenically unsaturated double bond group in R 148 and R 149 is a (meth)acryloyl group or general formula (72) or general formula (73)
  • the indicated substituents are preferred.
  • the above-described aliphatic structures, alkylene groups, alkyl groups, cycloalkyl groups and aryl groups may have heteroatoms and may be unsubstituted or substituted.
  • X 64 represents an aliphatic structure having 1 to 6 carbon atoms.
  • X 65 and X 66 each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
  • Y65 represents a direct bond, a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
  • R 150 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • R 151 to R 159 each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or the general formula (69) represents a substituent group.
  • R 160 to R 162 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • R 163 to R 169 each independently represent an organic group having an ethylenically unsaturated double bond group.
  • i and j each independently represent an integer of 0 to 3; k is 0 when Y 65 is a direct bond, an oxygen atom or a sulfur atom. k is 1 when Y 65 is a nitrogen atom. k is 2 when Y 65 is a carbon atom.
  • * 1 to * 5 each independently represent a bonding point with X 61 in the general formula (61) described above.
  • * 6 to * 10 each independently represent a bonding point in general formula (61) described above.
  • X 65 and X 66 are each independently preferably a monocyclic or condensed polycyclic hydrocarbon ring having 6 to 15 carbon atoms.
  • Y 65 is preferably a direct bond or an oxygen atom.
  • the organic group having an ethylenically unsaturated double bond group for R 163 to R 169 is preferably a (meth)acryloyl group or a substituent represented by general formula (72) or (73).
  • the above-mentioned aliphatic structures, alkyl groups, cycloalkyl groups, aryl groups and monocyclic or condensed polycyclic aromatic hydrocarbon rings may have heteroatoms and may be unsubstituted or substituted. It doesn't matter if there is.
  • R170 and R172 each independently represent a substituent represented by general formula (72) or general formula (73).
  • R 171 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or represented by general formula (69) or general formula (71) represents a substituent.
  • a represents an integer of 0 to 4;
  • R 173 and R 174 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 175 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms or a substituent represented by general formula (69).
  • b represents an integer of 0 to 5;
  • X 67 and X 68 are each independently a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or 6 carbon atoms. represents an arylene group of ⁇ 15.
  • R 176 and R 177 each independently represent a vinyl group, allyl group, crotonyl group, styryl group, cinnamoyl group, maleimide group or (meth)acryloyl group.
  • R 178 and R 179 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituent represented by general formula (74).
  • X 69 is an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, a cycloalkenylene group having 4 to 10 carbon atoms, or a carbon represents an arylene group of numbers 6 to 15;
  • X 69 is preferably a carboxylic anhydride residue.
  • alkyl group, cycloalkyl group, aryl group, alkylene group, alkenylene group, cycloalkylene group, cycloalkenylene group and arylene group described above may have heteroatoms and may be unsubstituted or substituted. I don't mind.
  • the acid-modified epoxy resin has a structural unit having a condensed polycyclic structure, a condensed polycyclic It is preferable to have a structural unit having a heterocyclic structure, a structural unit having a structure in which an aromatic ring skeleton and an alicyclic skeleton are directly connected, or a structural unit having a structure in which at least two aromatic ring skeletons are directly connected.
  • a condensed polycyclic structure or condensed polycyclic heterocyclic structure a naphthalene skeleton, a fluorene skeleton or a xanthene skeleton is preferable.
  • a tricyclo[5.2.1.0 2,6 ]decane skeleton is preferred.
  • a biphenyl skeleton is preferable as the structure in which at least two aromatic ring skeletons are directly linked.
  • W 2 is a substituent represented by any one of general formulas (65) to (67) and Y 65 is a direct bond or an oxygen atom, a structure having a naphthalene skeleton unit, a structural unit having a biphenyl skeleton, a structural unit having a fluorene skeleton, or a structural unit having a xanthene skeleton.
  • the general formula (62) described above has a structural unit having a structure in which an aromatic ring skeleton and a tricyclo[5.2.1.0 2,6 ]decane skeleton are directly linked.
  • the acid-modified epoxy resin has an acidic group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • Examples of the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
  • the acid-modified epoxy resin preferably has at least one of a structural unit derived from a polyfunctional carboxylic acid compound, a structural unit derived from a polyfunctional carboxylic acid dianhydride, and a terminal structure having an acidic group.
  • a method of producing an acid-modified epoxy resin for example, a method of introducing an acidic group into a resin having no acidic group can also be mentioned.
  • a method of reacting a portion of the hydroxy group of the resin with a polyfunctional carboxylic acid dianhydride examples include a method of introducing an acidic group to at least one of the terminals by a reaction using a catalyst.
  • (A2) resin (A2-2) resin and (AX2) resin (AX2-2) resin have an ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A2-2) resin and (AX2-2) resin are a structural unit derived from an epoxy compound having an ethylenically unsaturated double bond group, and a structure derived from a carboxylic acid compound having an ethylenically unsaturated double bond group. It is preferred to have at least one of a terminal structure having a unit and an ethylenically unsaturated double bond group.
  • a resin obtained by reacting a part of the acidic group of the resin with a compound having an ethylenically unsaturated double bond group is also preferred.
  • the double bond equivalent weights of (A2-2) resin and (AX2-2) resin are preferably 300 g/mol or more, more preferably 400 g/mol or more, and even more preferably 500 g/mol or more. .
  • the double bond equivalent is preferably 1,500 g/mol or less, more preferably 1,000 g/mol or less, and 700 g/mol or less, from the viewpoint of improving sensitivity during exposure and suppressing variations in opening pattern dimensions after development. is more preferred.
  • the (AX2-2) resin described above is included in the (AX) resin.
  • the (AX2-2) resin includes a polyfunctional epoxy compound containing a cyclic structure having at least three nitrogen atoms, a polyfunctional carboxylic acid compound, and a polyfunctional carboxylic acid dianhydride in the reaction for synthesizing the acid-modified epoxy resin described above.
  • an epoxy compound, a carboxylic acid compound, or the like is preferable.
  • At least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • a cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • the structural unit possessed by the acid-modified epoxy resin is a structural unit derived from an aromatic polyfunctional carboxylic acid compound or derived from an aromatic polyfunctional carboxylic acid dianhydride, from the viewpoint of improving the reliability of a light-emitting element in an organic EL display.
  • Structural units having aromatic groups, such as structural units, are also preferred.
  • the Mw of the acid-modified epoxy resin is preferably 500 or more, more preferably 1,000 or more in terms of polystyrene measured by GPC, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display.
  • Mw is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • An acid-modified epoxy resin can be synthesized by a known method. Examples of epoxy compounds, carboxylic acid anhydrides and carboxylic acid compounds include compounds described in International Publication No. 2017/057281 or International Publication No. 2017/159876.
  • Acid-modified epoxy resins include, for example, "KAYARAD” (registered trademark) PCR-1222H, CCR-1171H, TCR-1348H, ZAR-1494H, ZFR-1401H, ZCR-1798H, ZXR-1807H, and ZCR-6002H or ZCR-8001H (both manufactured by Nippon Kayaku Co., Ltd.).
  • acrylic resin ⁇ (A) alkali-soluble resin; acrylic resin>
  • the acrylic resins (A2-3) and (AX2-3) are collectively described below.
  • acrylic resins include resins obtained by radical copolymerization of one or more monomers selected from the group consisting of (meth)acrylic acid derivatives, (meth)acrylic acid ester derivatives, styrene derivatives and other copolymerization components. is mentioned.
  • the acrylic resin preferably has a structural unit represented by general formula (81) and/or a structural unit represented by general formula (82), from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • X 81 represents a direct bond or an alkylene group having 1 to 10 carbon atoms.
  • X 82 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms.
  • R 201 to R 206 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 207 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or 4 to 4 carbon atoms. It represents a halogenated cycloalkyl group of 10 or a halogenated aryl group of 6 to 15 carbon atoms.
  • R 208 represents a vinyl group, allyl group, crotonyl group, styryl group, cinnamoyl group, maleimide group or (meth)acryloyl group.
  • R 209 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituent represented by general formula (83).
  • X 83 is an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, a cycloalkenylene group having 4 to 10 carbon atoms, or a carbon represents an arylene group of numbers 6 to 15;
  • X 83 is preferably a carboxylic anhydride residue.
  • it is preferred that X 81 is a direct bond and R 207 is a hydrogen atom.
  • alkyl group, cycloalkyl group, aryl group, halogenated alkyl group, halogenated cycloalkyl group, halogenated aryl group, alkylene group, alkenylene group, cycloalkylene group, cycloalkenylene group and arylene group have a heteroatom. It may be either unsubstituted or substituted.
  • the acrylic resin has an acidic group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
  • the acrylic resin preferably has a structural unit derived from a (meth)acrylic acid derivative or a terminal structure having an acidic group.
  • a resin obtained by reacting a part of the hydroxy group or the like of the resin with a polyfunctional carboxylic acid dianhydride is also preferable, and at least one of the resin main chain, the resin side chain and the end of the resin. Also preferred are resins into which acidic groups have been introduced by reaction using a catalyst.
  • (A2) resin (A2-3) resin and (AX2) resin (AX2-3) resin have an ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A2-3) resin and (AX2-3) resin a resin obtained by reacting a part of the acidic group of the resin with an epoxy compound having an ethylenically unsaturated double bond group is preferable. .
  • a resin obtained by reacting an epoxy group or the like of the resin with a carboxylic acid compound or the like having an ethylenically unsaturated double bond group is also preferable.
  • the double bond equivalent weights of (A2-3) resin and (AX2-3) resin are preferably 500 g/mol or more, more preferably 700 g/mol or more, and 1,000 g/mol or more. More preferred.
  • the double bond equivalent is preferably 4,000 g/mol or less, more preferably 3,000 g/mol or less, more preferably 2,000 g/mol, from the viewpoint of improving sensitivity during exposure and suppressing variations in opening pattern dimensions after development. mol or less is more preferable, and 1,500 g/mol or less is particularly preferable.
  • the (AX2-3) resins described above are included in the (AX) resins.
  • (AX2-3) resins include (meth)acrylic acid derivatives, (meth)acrylic acid ester derivatives, styrene derivatives or Resins obtained by using other copolymer components are preferred.
  • at least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • a cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • the structural units possessed by acrylic resins include aromatic groups such as structural units derived from aromatic (meth)acrylic acid ester derivatives or structural units derived from styrene derivatives. Also preferred are structural units having an alicyclic group, such as structural units derived from alicyclic (meth)acrylic acid ester derivatives.
  • the Mw of the acrylic resin is preferably 1,000 or more, more preferably 3,000 or more in terms of polystyrene measured by GPC, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display.
  • Mw is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • An acrylic resin can be synthesized by a known method. Examples of (meth)acrylic acid derivatives, (meth)acrylic acid ester derivatives, styrene derivatives and other copolymerization components include compounds described in International Publication No. 2017/057281 or International Publication No. 2017/159876. .
  • phenol resin ⁇ (A) Alkali-soluble resin; phenolic resin>
  • (A3-1) resin and (AX3-1) resin which are phenolic resins, will be collectively described.
  • phenol resins include resins obtained by reacting a phenol compound or the like with one or more compounds selected from the group consisting of aldehyde compounds, ketone compounds, alkoxymethyl compounds and methylol compounds.
  • the phenolic resin preferably contains a novolac resin and/or a resole resin.
  • a novolac resin is a resin obtained by reacting in the presence of an acid catalyst.
  • a resole resin is a resin obtained by reacting in the presence of a base catalyst.
  • the phenol resin preferably has a structural unit represented by the general formula (36) from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • the content ratio of the structural unit represented by general formula (36) in the total structural units of the phenol resin is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%.
  • X 38 represents an aliphatic structure having 1 to 6 carbon atoms.
  • R 94 is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. It represents an oxy group, an acyl group having 1 to 10 carbon atoms, a carboxy group, an amino group or a group forming a ring.
  • the rings joined by a ring-forming group represent monocyclic or condensed polycyclic hydrocarbon rings.
  • R 95 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a represents an integer of 1 to 4;
  • b represents an integer of 0 to 3;
  • ⁇ represents an integer of 0 to 4;
  • the aliphatic structures, alkyl groups, aryl groups, alkenyl groups, alkoxy groups, acyl groups, ring-forming groups and alkylene groups described above may have heteroatoms and may be unsubstituted or substituted. I don't mind.
  • Examples of the condensed polycyclic hydrocarbon ring formed by a ring-forming group include naphthalene ring, anthracene ring, pyrene ring, indane ring, indene ring, tetrahydronaphthalene ring, fluorene ring, xanthene ring and isoindolinone ring. preferable.
  • the phenolic resin has a phenolic hydroxyl group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the terminal of the resin.
  • the phenolic resin is preferably a resin obtained by reacting a phenolic compound with one or more compounds selected from the group consisting of aldehyde compounds, alkoxymethyl compounds and methylol compounds.
  • a resin in which a phenolic hydroxyl group is introduced into at least one of the main chain of the resin, the side chain of the resin and the terminal of the resin by a reaction using a catalyst.
  • it may have a carboxy group and/or a carboxylic acid anhydride group.
  • Examples thereof include a resin obtained by reacting a phenolic hydroxyl group of a resin with a carboxylic anhydride or a resin obtained by reacting a phenolic compound having a carboxyl group and/or a carboxylic anhydride group as a phenolic compound.
  • the phenol resin preferably contains the following (A3b-1) resin and/or (AX3b-1) resin.
  • (A3b-1) resins are (A3b) resins having at least one ethylenically unsaturated double bond group.
  • (AX3b-1) resins are (AX3b) resins having cyclic structural units of (AX) resins and at least one ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A3b-1) Resin Ethylenically unsaturated double bond group-containing phenolic resin.
  • (AX3b-1) Resin A phenolic resin containing an ethylenically unsaturated double bond group having a nitrogen ring.
  • (A3b-1) resin and (AX3b-1) resin a resin obtained by reacting a part of the acidic group of the resin with an epoxy compound having an ethylenically unsaturated double bond group is preferable. . Also preferred is a resin in which an ethylenically unsaturated double bond group is introduced into at least one of the side chain of the resin and the end of the resin by a reaction using a catalyst.
  • the alkali-soluble resin contains (A3b-1) resin and / or (AX3b-1) resin
  • (A) alkali-soluble resin further contains the following (A3a-1) resin and / or ( It is preferable to contain AX3a-1) resin.
  • (A3a-1) resin and (AX3a-1) resin do not have ethylenically unsaturated double bond groups. That is, the (A3a-1) resin and the (AX3a-1) resin do not have an ethylenically unsaturated double bond group that is a radically polymerizable group.
  • (A3a-1) Resin Phenolic resin having no ethylenically unsaturated double bond group.
  • (AX3a-1) Resin nitrogen ring-containing phenolic resin having no ethylenically unsaturated double bond group.
  • the (AX3-1) resin, (AX3a-1) resin, and (AX3b-1) resin described above are included in the (AX) resin.
  • These resins are obtained by using a phenol compound, an aldehyde compound, a ketone compound, an alkoxymethyl compound, a methylol compound, or the like containing a cyclic structure having at least three nitrogen atoms in the reaction for synthesizing the phenol resin described above.
  • a resin obtained by using a phenol compound, an alkoxymethyl compound, or a methylol compound containing a cyclic structure having at least three nitrogen atoms is more preferable.
  • At least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • the cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • Phenolic compounds containing an isocyanuric acid structure and/or triazine structure include 1,3-bis(4-hydroxyphenyl)isocyanuric acid, 1,3,5-tris(4-hydroxyphenyl)isocyanuric acid, 2,4-bis (4-hydroxyphenoxy)-6-hydroxy-1,3,5-triazine, 2,4,6-tris(4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(4 -hydroxyphenyl)amino-1,3,5-triazine, 1,3,5,7-tetrakis[(2-hydroxyphenyl)methyl]glycoluril are preferred.
  • Alkoxymethyl compounds or methylol compounds containing an isocyanuric acid structure and/or a triazine structure include 2,4,6-tris[N,N-bis(methoxymethyl)amino]-1,3,5-triazine, 2,4 ,6-tris[N,N-bis(butoxymethyl)amino]-1,3,5-triazine, 2,4,6-tris[N,N-bis(hydroxymethyl)amino]-1,3,5 -triazine, 2,4,6-tris[N-(methoxymethyl)amino]-1,3,5-triazine, 2,4-bis[N,N-bis(methoxymethyl)amino]-6-phenyl- 1,3,5-triazine, 1,3,5,7-tetrakis(methoxymethyl)glycoluril, or 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidone are preferred.
  • a structure having an aromatic group such as a structural unit derived from an aromatic aldehyde compound or a structural unit derived from an aromatic ketone compound.
  • Units are also preferred, such as a structural unit derived from an alicyclic aldehyde compound, a structural unit derived from an alicyclic ketone compound, a structural unit derived from an alicyclic alkoxymethyl compound, or a structural unit derived from an alicyclic methylol compound.
  • Structural units having an alicyclic group of are also preferred.
  • the Mw of the phenol resin is preferably 500 or more, more preferably 1,000 or more in terms of polystyrene measured by GPC, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display.
  • Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 10,000 or less, and even more preferably 5,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape. More preferably, 3,000 or less is particularly preferable.
  • a phenol resin can be synthesized by a known method. Phenol compounds, aldehyde compounds, ketone compounds, alkoxymethyl compounds and methylol compounds include, for example, compounds described in International Publication No. 2017/159876.
  • polyhydroxystyrene ⁇ (A) Alkali-soluble resin; polyhydroxystyrene>
  • the polyhydroxystyrene (A3-2) resin and (AX3-2) resin are collectively described below.
  • Examples of polyhydroxystyrene include resins obtained by radical copolymerization of hydroxystyrene derivatives and the like with styrene derivatives and/or other copolymerization components.
  • Other copolymerization components include (meth)acrylic acid derivatives and (meth)acrylic acid ester derivatives.
  • Polyhydroxystyrene preferably has a structural unit represented by general formula (91) and/or a structural unit represented by general formula (92), from the viewpoint of suppressing variations in opening pattern dimensions after development.
  • the content ratio of the structural unit represented by the general formula (91) and the structural unit represented by the general formula (92) in the total structural units of the polyhydroxystyrene is preferably 50 to 100 mol%, and 60 to 100 mol%. More preferably, 70 to 100 mol % is even more preferable.
  • X 121 represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms.
  • R 221 to R 226 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 227 and R 228 are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • the rings joined by a ring-forming group represent monocyclic or condensed polycyclic hydrocarbon rings.
  • a and b each independently represent an integer of 1 to 5;
  • c and d each independently represent an integer of 0 to 4;
  • the alkyl group, aryl group, alkenyl group, alkoxy group, acyl group, ring-forming group, alkylene group, cycloalkylene group and arylene group described above may have heteroatoms and may be unsubstituted or substituted. It doesn't matter which one.
  • Examples of the condensed polycyclic hydrocarbon ring formed by a ring-forming group include naphthalene ring, anthracene ring, pyrene ring, indane ring, indene ring, tetrahydronaphthalene ring, fluorene ring, xanthene ring and isoindolinone ring. preferable.
  • Polyhydroxystyrene has a phenolic hydroxyl group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the terminal of the resin.
  • the polyhydroxystyrene is preferably a resin obtained by radical copolymerization of a copolymer component containing at least a hydroxystyrene derivative. Further, in a resin obtained by radical copolymerization of a copolymer component containing a (meth)acrylic acid ester having a reactive group such as an epoxy group, the epoxy group possessed by the resin and a phenol compound having a carboxy group, etc.
  • a resin obtained by reacting with is also preferable, and a resin obtained by introducing a phenolic hydroxyl group into at least one of the resin main chain, the resin side chain and the terminal of the resin by reaction using a catalyst is also preferable.
  • it may have a carboxy group and/or a carboxylic acid anhydride group.
  • a resin obtained by reacting a phenolic hydroxyl group of a resin with a carboxylic anhydride, or a resin obtained by reacting a copolymer component having a carboxy group and/or a carboxylic anhydride group as another copolymer component. are mentioned.
  • Polyhydroxystyrene preferably contains the following (A3b-2) resin and/or (AX3b-2) resin.
  • (A3b-2) resins are (A3b) resins having at least one ethylenically unsaturated double bond group.
  • (AX3b-2) resins are (AX3b) resins having cyclic structural units of (AX) resins and at least one ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A3b-2) resin and (AX3b-2) resin a resin obtained by reacting a part of the acidic group of the resin with an epoxy compound having an ethylenically unsaturated double bond group is preferable. .
  • a resin obtained by reacting an epoxy group or the like of the resin with a carboxylic acid compound or the like having an ethylenically unsaturated double bond group is also preferable.
  • the alkali-soluble resin contains (A3b-2) resin and / or (AX3b-2) resin
  • (A) alkali-soluble resin further contains the following (A3a-2) resin and / or ( It is preferable to contain AX3a-2) resin.
  • (A3a-2) and (AX3a-2) resins do not have ethylenically unsaturated double bond groups. That is, the (A3a-2) resin and the (AX3a-2) resin do not have an ethylenically unsaturated double bond group that is a radically polymerizable group.
  • (A3a-2) Resin polyhydroxystyrene having no ethylenically unsaturated double bond group.
  • the (AX3-2) resin, (AX3a-2) resin, and (AX3b-2) resin described above are included in the (AX) resin.
  • These resins are preferably resins obtained by using a hydroxystyrene derivative, a styrene derivative, or other copolymer components containing a cyclic structure having at least three nitrogen atoms in the reaction for synthesizing polyhydroxystyrene described above. .
  • At least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • the cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • a structural unit having an aromatic group such as a structural unit derived from an aromatic (meth)acrylic acid ester derivative is also preferable, from the viewpoint of improving the reliability of a light-emitting element in an organic EL display.
  • a structural unit having an alicyclic group such as a structural unit derived from an alicyclic (meth)acrylate derivative is also preferred.
  • the Mw of polyhydroxystyrene is preferably 500 or more, more preferably 1,000 or more, in terms of polystyrene measured by GPC, from the viewpoint of improving the reliability of light-emitting elements in organic EL displays. On the other hand, Mw is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • Polyhydroxystyrene can be synthesized by a known method. Hydroxystyrene derivatives, styrene derivatives and other copolymerization components include, for example, compounds described in International Publication No. 2017/159876.
  • the (A3-3) resin and (AX3-3) resin which are phenol group-modified epoxy resins, will be collectively described.
  • the phenol group-modified epoxy resin include resins obtained by the following (1-a3-3) to (2-a3-3). If necessary, the polyfunctional alcohol compound may be further reacted in any of the reaction steps.
  • a phenol group-modified epoxy resin has a cyclic skeleton in the structural unit of the resin.
  • (1-a3-3) A resin obtained by reacting a polyfunctional epoxy compound with a phenol compound having an epoxy-reactive group.
  • (2-a3-3) A resin obtained by further reacting the above resin (1-a3-3) with a polyfunctional carboxylic acid dianhydride or a polyfunctional carboxylic acid compound.
  • the phenol group-modified epoxy resin has a phenolic hydroxyl group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • a resin obtained by reacting a polyfunctional epoxy compound or the like with a phenol compound having a carboxy group is preferable.
  • it may have a carboxy group and/or a carboxylic acid anhydride group. Examples thereof include resins obtained by reacting hydroxy groups of resins with carboxylic anhydrides.
  • the phenol group-modified epoxy resin preferably contains the following (A3b-3) resin and/or (AX3b-3) resin.
  • (A3b-3) resins are (A3b) resins having at least one ethylenically unsaturated double bond group.
  • (AX3b-3) resins are (AX3b) resins having cyclic structural units of (AX) resins and at least one ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • (A3b-3) Resin phenol group-modified epoxy resin containing an ethylenically unsaturated double bond group.
  • (AX3b-3) Resin A phenol group-modified epoxy resin containing an ethylenically unsaturated double bond group having a nitrogen ring.
  • the alkali-soluble resin contains (A3b-3) resin and / or (AX3b-3) resin
  • (A) alkali-soluble resin further contains the following (A3a-3) resin and / or ( It preferably contains AX3a-3) resin.
  • (A3a-3) and (AX3a-3) resins do not have ethylenically unsaturated double bond groups. That is, the (A3a-3) resin and the (AX3a-3) resin do not have an ethylenically unsaturated double bond group that is a radically polymerizable group.
  • (A3a-3) Resin A phenol group-modified epoxy resin having no ethylenically unsaturated double bond group.
  • (AX3a-3) Resin nitrogen ring-containing phenol group-modified epoxy resin having no ethylenically unsaturated double bond group.
  • the (AX3-3) resin, (AX3a-3) resin and (AX3b-3) resin described above are included in the (AX) resin.
  • These resins include a polyfunctional epoxy compound containing a cyclic structure having at least three nitrogen atoms, a phenol compound having an epoxy-reactive group, a polyfunctional carboxylic A resin obtained by using an anhydride or a polyfunctional carboxylic acid compound is preferable.
  • at least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • the cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • a structural unit derived from an aromatic polyfunctional carboxylic acid compound or derived from an aromatic polyfunctional carboxylic acid dianhydride As the structural unit possessed by the phenol group-modified epoxy resin, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display, a structural unit derived from an aromatic polyfunctional carboxylic acid compound or derived from an aromatic polyfunctional carboxylic acid dianhydride.
  • a structural unit having an aromatic group such as a structural unit having a
  • the Mw of the phenol group-modified epoxy resin is preferably 500 or more, more preferably 1,000 or more in terms of polystyrene measured by GPC, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display.
  • Mw is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • a phenol group-modified epoxy resin can be synthesized by a known method.
  • the (A3-4) resin and (AX3-4) resin which are phenol group-modified acrylic resins, will be collectively described.
  • the phenol group-modified acrylic resin include resins obtained by the following (1-a3-4) to (2-a3-4).
  • (1-a3-4) obtained by radical copolymerization of one or more monomers selected from the group consisting of (meth)acrylic acid derivatives, (meth)acrylate derivatives, styrene derivatives, and other copolymerization components;
  • (2-a3-4) A resin obtained by further reacting the above resin (1-a3-4) with a polyfunctional carboxylic acid dianhydride or a polyfunctional carboxylic acid compound.
  • the phenol group-modified acrylic resin has a phenolic hydroxyl group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin.
  • the phenol group-modified acrylic resin in a resin obtained by radical copolymerization of a copolymer component containing a (meth)acrylic acid ester having a reactive group such as an epoxy group, an epoxy group possessed by the resin and a carboxy group
  • it may have a carboxy group and/or a carboxylic acid anhydride group. Examples thereof include resins obtained by reacting hydroxy groups of resins with carboxylic anhydrides.
  • the phenol group-modified acrylic resin preferably contains the following (A3b-4) resin and/or (AX3b-4) resin.
  • (A3b-4) resins are (A3b) resins having at least one ethylenically unsaturated double bond group.
  • (AX3b-4) resins are (AX3b) resins having cyclic structural units of (AX) resins and at least one ethylenically unsaturated double bond group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • the alkali-soluble resin contains (A3b-4) resin and / or (AX3b-4) resin
  • (A) alkali-soluble resin further contains the following (A3a-4) resin and / or ( It preferably contains AX3a-4) resin.
  • (A3a-4) and (AX3a-4) resins do not have ethylenically unsaturated double bond groups. That is, the (A3a-4) resin and the (AX3a-4) resin do not have an ethylenically unsaturated double bond group that is a radically polymerizable group.
  • the (AX3-4) resin, (AX3a-4) resin and (AX3b-4) resin described above are included in the (AX) resin.
  • these resins include phenol compounds containing a cyclic structure having at least three nitrogen atoms, (meth)acrylic acid derivatives, (meth)acrylic acid ester derivatives, and styrene derivatives in the reaction for synthesizing the phenol group-modified acrylic resin described above.
  • other copolymer components a phenol compound having an addition-reactive group, a polyfunctional carboxylic acid dianhydride, a polyfunctional carboxylic acid compound, or the like is preferably used.
  • At least one of the main chain of the resin, the side chain of the resin and the end of the resin is reacted with a compound having a cyclic structure having at least three nitrogen atoms by a reaction using a catalyst to remove at least nitrogen atoms.
  • Resins into which three cyclic structures are introduced are also preferred.
  • the cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • structural units possessed by phenol group-modified acrylic resins include structural units derived from aromatic (meth)acrylic acid ester derivatives, structural units derived from styrene derivatives, and the like.
  • a structural unit having an aromatic group is also preferred, and a structural unit having an alicyclic group such as a structural unit derived from an alicyclic (meth)acrylic acid ester derivative is also preferred.
  • the Mw of the phenol group-modified acrylic resin is preferably 1,000 or more, more preferably 3,000 or more, in terms of polystyrene measured by GPC, from the viewpoint of improving the reliability of light-emitting elements in organic EL displays.
  • Mw is preferably 50,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing residue after development and reducing the taper of the pattern shape.
  • a phenol group-modified acrylic resin can be synthesized by a known method.
  • the total content of the (AX) resin in the total 100% by mass of the (A) alkali-soluble resin is to suppress residue after development, improve halftone characteristics, and open after development. From the viewpoint of suppressing variations in pattern dimensions, improving the reliability of light-emitting elements in organic EL displays, and driving light-emitting elements at low voltage, it is preferably 5% by mass or more, more preferably 15% by mass or more, and 25% by mass. % or more is more preferable.
  • the total content of the (AX) resin is preferably 95% by mass or less, more preferably 85% by mass or less, even more preferably 75% by mass or less, and 65% by mass or less, from the viewpoint of reducing the taper of the pattern shape. is even more preferable, and 55% by mass or less is particularly preferable.
  • the total content ratio of (A1) resin and (AX1) resin in the total 100% by mass of (A) alkali-soluble resin is to suppress residue after development and improve halftone characteristics.
  • the amount is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 25% by mass or more.
  • the total content of the (A1) resin and the (AX1) resin is preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 75% by mass or less, from the viewpoint of reducing the taper of the pattern shape. , 65 mass % or less is even more preferable, and 55 mass % or less is particularly preferable.
  • the total content ratio of the (A2) resin and the (AX2) resin in the total 100% by mass of the (A) alkali-soluble resin is improved sensitivity during exposure and opening after development From the viewpoint of suppressing variations in pattern dimensions, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more.
  • the total content of the (A2) resin and the (AX2) resin is preferably 65% by mass or less, more preferably 55% by mass or less, more preferably 45% by mass, from the viewpoint of improving the halftone characteristics and reducing the taper of the pattern shape. % or less is more preferable.
  • the total content ratio of (A3) resin and (AX3) resin in the total 100% by mass of (A) alkali-soluble resin is improved halftone characteristics and opening pattern after development
  • the content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more.
  • the total content of the (A3) resin and the (AX3) resin is preferably 85% by mass or less, more preferably 75% by mass or less, more preferably 65% by mass, from the viewpoint of suppressing residue after development and improving halftone properties. The following is more preferable, 55% by mass or less is even more preferable, and 45% by mass or less is particularly preferable.
  • the content ratio of the (A) alkali-soluble resin in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is determined from the viewpoint of improving the halftone characteristics and suppressing the variation in opening pattern size after development and the organic EL display. From the viewpoint of improving the reliability of the light-emitting element in , the content is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. On the other hand, the content ratio of (A) the alkali-soluble resin is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 55% by mass or less, from the viewpoint of improving sensitivity during exposure and suppressing residue after development. . In addition, in this invention, solid content means all the components except the solvent in the photosensitive resin composition.
  • the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin and (B) a radically polymerizable compound described later
  • the content of (A) the alkali-soluble resin is (A) the alkali-soluble resin and (B)
  • the total amount of the radically polymerizable compound is 100 parts by mass, it is preferably 25 parts by mass or more, more preferably 35 parts by mass or more, and even more preferably 45 parts by mass or more.
  • the content of (A) the alkali-soluble resin is preferably 85 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (B) a radically polymerizable compound (hereinafter referred to as "(B) compound").
  • (B) A compound refers to a compound having at least two ethylenically unsaturated double bond groups.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • the photosensitive resin composition of the present invention has negative photosensitivity
  • the radicals generated from the (C1) photopolymerization initiator described later degrade the (B) compound.
  • a negative pattern can be formed by the progress of radical polymerization and the insolubilization of the exposed portion of the film to an alkaline developer.
  • photocuring at the time of exposure is accelerated, and the effect of improving the sensitivity at the time of exposure becomes remarkable.
  • the photosensitive resin composition of the present invention has positive photosensitivity
  • radical polymerization of the compound (B) proceeds during exposure or heat curing after development in the unexposed area during pattern exposure, and the composition By improving the degree of cross-linking of the film obtained from, the effect of pattern shape control after heat curing becomes remarkable.
  • the ethylenically unsaturated double bond group of the compound (B) preferably has a (meth)acryloyl group from the viewpoint of facilitating radical polymerization.
  • the (B) compound is one or more selected from the group consisting of (B1) a radically polymerizable compound containing a hydrophobic skeleton, (B2) a radically polymerizable compound containing a flexible skeleton, and (B3) a radically polymerizable compound containing a cyclic skeleton, which will be described later. It is preferable to contain a compound of (B1) a radically polymerizable compound containing a hydrophobic skeleton, (B2) a radically polymerizable compound containing a flexible skeleton, and (B3) a radically polymerizable compound containing a cyclic skeleton, which will be described later. It is preferable to contain a compound of
  • the double bond equivalent of the compound (B) is preferably 80 g/mol or more, more preferably 90 g/mol or more, from the viewpoint of improving halftone characteristics.
  • the double bond equivalent is preferably 800 g/mol or less, more preferably 600 g/mol or less, from the viewpoint of improving sensitivity during exposure.
  • the content of the (B) compound is, when the total of the (A) alkali-soluble resin and (B) compound is 100 parts by mass, From the viewpoint of improving sensitivity during exposure and suppressing residue after development, the amount is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more.
  • the content of the compound (B) is preferably 75 parts by mass or less, more preferably 65 parts by mass or less, and 55 parts by mass from the viewpoint of improving the halftone characteristics and improving the reliability of the light-emitting element in the organic EL display. More preferred are:
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (B1) a hydrophobic skeleton-containing radically polymerizable compound (hereinafter referred to as "(B1) compound").
  • (B1) compound means a compound having the following (I-b1) structure and (II-b1) structure and having at least two (II-b1) structures.
  • (I-b1) structure a structure containing one or more structures selected from the group consisting of a fluorene structure, an indane structure, a condensed polycyclic alicyclic structure, an indolinone structure and an isoindolinone structure.
  • (II-b1) structure at least two organic groups having ethylenically unsaturated double bond groups.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • the ethylenically unsaturated double bond group preferably has a (meth)acryloyl group.
  • the above-mentioned (I-b1) structure is represented by any one of general formulas (141) to (147) from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • a structure is preferred.
  • X 201 to X 208 each independently represent a monocyclic or condensed polycyclic hydrocarbon ring.
  • X 210 to X 214 each independently represent an aliphatic structure having 1 to 6 carbon atoms.
  • Y 201 and Y 209 each independently represent a direct bond, a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
  • R 301 to R 309 each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 310 to R 316 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • R 317 and R 318 each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • a, b, c, d, e, f and g each independently represents an integer of 0 to 4;
  • h and i each independently represent an integer of 0 to 3;
  • j is 0 when Y 201 is a direct bond, an oxygen atom or a sulfur atom.
  • j is 1 when Y 201 is a nitrogen atom; j is 2 when Y 201 is a carbon atom; k is 0 when Y 209 is a direct bond, an oxygen atom or a sulfur atom. k is 1 when Y 209 is a nitrogen atom. k is 2 when Y 209 is a carbon atom. l and m each independently represent an integer of 0 to 14; n represents an integer of 0 to 2; * 1 to * 15 each independently represent a point of attachment to the structure (II-b1) described above.
  • X 201 to X 208 are each independently preferably a monocyclic or condensed polycyclic hydrocarbon ring having 6 to 15 carbon atoms.
  • Y 201 and Y 209 are each independently preferably a direct bond or an oxygen atom.
  • the above-mentioned aliphatic structures, alkyl groups, cycloalkyl groups, aryl groups and monocyclic or condensed polycyclic aromatic hydrocarbon rings may have heteroatoms and may be unsubstituted or substituted. It doesn't matter if there is.
  • the (B1) compound has the (I-b1) structure, the (II-b1) structure and the It is more preferable to have the following (III-b1) structure or (IV-b1) structure.
  • (III-b1) Structure alkylenecarbonyl group, oxyalkylenecarbonyl group or aminoalkylenecarbonyl group.
  • (IV-b1) structure an alkylene group containing a hydroxy group or an oxyalkylene group containing a hydroxy group.
  • the total number of (III-b1) structures or (IV-b1) structures possessed by the (B1) compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. On the other hand, the total number of (III-b1) structures or (IV-b1) structures is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.
  • the (B1) compound preferably has the (III-b1) structure.
  • the (III-b1) structure is preferably a structure derived from a lactone compound or a structure derived from a lactam compound.
  • * 1 to * 15 are each independently the above ( It represents the point of attachment to the II-b1) structure, the point of attachment to the above-described (III-b1) structure, or the attachment point to the above-described (IV-b1) structure.
  • the compound (B1) has a structure represented by general formula (157) described later, it has the structure (III-b1) described above.
  • the (B1) compound has a structure represented by the general formula (156) described later, and X 231 represents an alkylene group having 1 to 10 carbon atoms containing a hydroxy group
  • the above (IV-b1) structure have
  • * 1 and * 2 each independently represent a point of attachment to structure (I-b1) described above.
  • * 3 and * 4 each independently represent a point of attachment to the (II-b1) structure described above.
  • * 1 and * 2 are each independently preferably a bonding point with the oxygen atom in general formulas (141) to (147) described above.
  • the double bond equivalent of the (B1) compound is preferably 150 g/mol or more, more preferably 190 g/mol or more, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the double bond equivalent is preferably 600 g/mol or less, more preferably 400 g/mol or less, from the viewpoint of suppressing residue after development.
  • the content of the (B1) compound is, when the total of (A) the alkali-soluble resin and (B) the compound is 100 parts by mass, From the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development, it is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.
  • the content of the (B1) compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of suppressing residue after development.
  • the photosensitive resin composition of the first aspect of the present invention further contains (B2) a flexible skeleton-containing radically polymerizable compound (hereinafter referred to as "(B2) compound"), and (B2) compound is the following ( It has I-b2) structure, (II-b2) structure and (III-b2) structure, and preferably has at least two (II-b2) structures.
  • (I-b2) structure a structure derived from a compound having at least two hydroxy groups.
  • (II-b2) structure an organic group having an ethylenically unsaturated double bond group.
  • (III-b2) structure an alkylene group, an oxyalkylene group, an alkylene group containing a hydroxy group, an oxyalkylene group containing a hydroxy group, an alkylenecarbonyl group, an oxyalkylenecarbonyl group, or an aminoalkylenecarbonyl group.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • the ethylenically unsaturated double bond group preferably has a (meth)acryloyl group.
  • the (I-b2) structure is more preferably the following (I-b2x) structure from the viewpoint of improving sensitivity during exposure, suppressing residue after development, and suppressing variation in opening pattern dimensions after development.
  • (I-b2x) structure a structure containing one or more types of structures selected from the group consisting of structures derived from aliphatic polyfunctional alcohols, alicyclic structures and heteroalicyclic structures.
  • the (B2) compound has the above-mentioned (I-b2x) structure represented by general formulas (151) to (154). It is preferable that it is a structure represented by either.
  • X 221 to X 228 each independently represent an aliphatic structure having 1 to 6 carbon atoms.
  • R 321 to R 325 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms.
  • a and b each independently represents an integer of 0 to 5;
  • * 1 to * 16 each independently represent a bonding point with the above-described (II-b2) structure or a bonding point with the above-described (III-b2) structure.
  • the above-described aliphatic structures, alkyl groups and cycloalkyl groups may have heteroatoms and may be unsubstituted or substituted.
  • the compound (B2) contains a compound having the above-described (I-b2x) structure
  • the compound (B2) further includes the above-described (I-b2 ) as the structure, it preferably contains a compound having a structure represented by general formula (155).
  • X 229 and X 230 each independently represent an aliphatic structure having 1 to 6 carbon atoms.
  • Y 229 represents a direct bond, a nitrogen atom, or an oxygen atom.
  • R 326 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms.
  • a is 0 when Y 229 is a direct bond or an oxygen atom.
  • a is 1 when Y 229 is a nitrogen atom; * 1 and * 2 each independently represent a point of attachment to the (III-b2) structure described above.
  • the aliphatic structures described above may have heteroatoms and may be unsubstituted or substituted.
  • the (B2) compound more preferably has the following (III-b2x) structure from the viewpoint of improving sensitivity during exposure, suppressing residue after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development.
  • (III-b2x) structure alkylenecarbonyl group, oxyalkylenecarbonyl group or aminoalkylenecarbonyl group.
  • the total number of (III-b2) structures and (III-x) structures possessed by the (B2) compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the total number of (III-b2) structures and (III-b2x) structures is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • As the alkylene group, the oxyalkylene group, the alkylene group containing a hydroxy group, and the oxyalkylene group containing a hydroxy group a structure derived from an epoxy compound or a structure derived from an alkylene glycol is preferable.
  • the (B2) compound preferably has the (III-b2x) structure.
  • the (III-b2x) structure is preferably a structure derived from a lactone compound or a structure derived from a lactam compound.
  • the above-mentioned (III-b2) structure has general formula (156) and general formula ( 157), preferably one or more structures selected from the group consisting of structures represented by any one of 157).
  • X 231 and X 232 each independently represent an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms including a hydroxy group.
  • Y 231 and Y 232 each independently represent a direct bond, a nitrogen atom or an oxygen atom.
  • R 327 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms.
  • a and b each independently represents an integer of 1 to 4; c is 0 when Y 232 is a direct bond or an oxygen atom. c is 1 when Y 232 is a nitrogen atom.
  • * 1 and * 2 each independently represent the point of attachment to the (I-b2) structure described above.
  • * 3 and * 4 each independently represent the point of attachment to the (II-b2) structure described above.
  • * 1 and * 2 are each independently preferably a bonding point with an oxygen atom in general formulas (151) to (154).
  • the alkylene group, alkyl group and cycloalkyl group described above may have a heteroatom and may be unsubstituted or substituted.
  • the compound (B2) has the structure represented by the general formula (157), it has the structure (III-b2x) described above.
  • the number of ethylenically unsaturated double bond groups possessed by the compound (B2) is preferably 2 or more, and 3 or more, from the viewpoints of improving sensitivity during exposure, suppressing residue after development, and suppressing variation in opening pattern dimensions after development. is more preferred, and 4 or more is even more preferred.
  • the number of ethylenically unsaturated double bond groups is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less, from the viewpoint of improving halftone characteristics and reducing the taper of the pattern shape.
  • the double bond equivalent is preferably 100 g/mol or more, more preferably 120 g/mol or more, from the viewpoint of improving the halftone characteristics and reducing the taper of the pattern shape.
  • the double bond equivalent is preferably 600 g/mol or less, more preferably 400 g/mol or less, from the viewpoints of improving sensitivity during exposure, suppressing residue after development, and suppressing variation in opening pattern dimensions after development.
  • the (B2) compound is a compound having at least three (II-b2) structures and 2 It is more preferred to contain compounds with two (II-b2) structures.
  • the content of the (B2) compound is, when the total of (A) the alkali-soluble resin and (B) the compound is 100 parts by mass, It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, from the viewpoints of improving sensitivity during exposure, suppressing residue after development, and suppressing variations in opening pattern dimensions after development.
  • the content of the (B2) compound is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, from the viewpoint of improving the halftone characteristics and reducing the taper of the pattern shape.
  • the photosensitive resin composition of the first aspect of the present invention further contains (B3) a cyclic skeleton-containing radically polymerizable compound (hereinafter referred to as "(B3) compound"), and (B3) compound is the following ( It has an I-b3) structure and an (II-b3) structure, and preferably has at least two (II-b3) structures.
  • (I-b3) structure a structure containing an alicyclic structure and/or a heteroalicyclic structure.
  • (II-b3) structure an organic group having an ethylenically unsaturated double bond group.
  • the (B3) compound is a compound different from the (B1) compound and the (B2) compound.
  • a compound corresponding to both the (B1) compound and the (B2) compound is included in the (B1) compound.
  • the ethylenically unsaturated double bond group is preferably a radically polymerizable group.
  • the ethylenically unsaturated double bond group preferably has a (meth)acryloyl group.
  • the (B3) compound has a cyclic structure in which the above-mentioned (I-b3) structure has at least two nitrogen atoms, from the viewpoint of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development. It is preferable that it is a structure containing.
  • the cyclic structure having at least two nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
  • the double bond equivalent of the (B3) compound is preferably 150 g/mol or more, more preferably 190 g/mol or more, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the double bond equivalent is preferably 600 g/mol or less, more preferably 400 g/mol or less, from the viewpoint of suppressing residue after development.
  • the content of the (B3) compound is, when the total of (A) the alkali-soluble resin and (B) compound is 100 parts by mass, From the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development, it is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. On the other hand, the content of the (B3) compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of suppressing residue after development.
  • the photosensitive resin composition of the first aspect of the present invention contains (C) a photosensitive agent.
  • C) Photosensitizer refers to a compound that imparts positive or negative photosensitivity to a composition by bond cleavage, reaction, or structural change upon exposure to generate another compound.
  • the photosensitizer comprises (C1) a photopolymerization initiator (hereinafter “(C1) compound”), (C2) a photoacid generator and (C3) a naphthoquinonediazide compound (hereinafter “(C3) compound”) from It is preferable to contain one or more compounds selected from the group consisting of:
  • a (C1) compound When imparting negative photosensitivity to the composition, it preferably contains a (C1) compound, and further preferably contains a (C2) photoacid generator and/or a (C3) compound.
  • When imparting positive photosensitivity to the composition it preferably contains a (C3) compound, and further preferably contains a (C1) compound and/or a (C2) photoacid generator.
  • the content ratio of the (C) photosensitive agent in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is preferably 0.3% by mass or more, preferably 1.0%, from the viewpoint of improving sensitivity during exposure. % by mass or more is more preferable, and 2.0% by mass or more is even more preferable.
  • the content ratio of (C) the photosensitive agent is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of suppressing residue after development.
  • the (C) photosensitive agent preferably contains the (C1) compound.
  • the compound (C1) is, as described above, a photopolymerization initiator, that is, a compound that cleaves bonds and/or reacts with exposure to generate radicals. During exposure, even if the amount of radicals generated from the compound (C1) is very small, radical polymerization of the compound (B) and the like proceeds in a chain reaction, so negative pattern formation is possible with a low exposure amount of light. , and the effect of improving the sensitivity at the time of exposure becomes remarkable.
  • (C1) compounds include benzyl ketal-based compounds, ⁇ -hydroxyketone-based compounds, ⁇ -aminoketone-based compounds, acylphosphine oxide-based compounds, biimidazole-based compounds, oxime ester-based compounds, acridine-based compounds, titanocene-based compounds, and benzophenone. Acetophenone-based compounds, aromatic ketoester-based compounds, or benzoic acid ester-based compounds are preferred. From the viewpoint of improving sensitivity during exposure, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine oxide compounds, biimidazole compounds, or oxime ester compounds are more preferable, improving sensitivity during exposure and halftone properties. From the viewpoint of improvement and suppression of residue after development, oxime ester compounds are more preferable.
  • the content ratio of the (C1) compound in the total solid content of the photosensitive resin composition of the present invention excluding the solvent is preferably 0.3% by mass or more, and 1.0% by mass, from the viewpoint of improving sensitivity during exposure. % or more is more preferable, and 2.0% by mass or more is even more preferable.
  • the content of the compound (C1) is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of suppressing residue after development.
  • the content of the (C1) compound is 100 parts by mass of the total of (A) the alkali-soluble resin and (B) the compound.
  • WHEREIN 1 mass part or more is preferable, 3 mass parts or more are more preferable, 5 mass parts or more are still more preferable.
  • the content of the compound (C1) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the (C1) compound preferably contains (C1-1) an oxime ester compound (hereinafter, “(C1-1) compound”).
  • the (C1-1) compound refers to a compound having an oxime ester structure as a skeleton that cleaves bonds and/or reacts with exposure to generate radicals.
  • the (C1) compound contains the (C1-1) compound from the viewpoint of improving sensitivity during exposure, improving halftone characteristics, and suppressing residue after development. Furthermore, it is preferable to contain the above-mentioned (B) compound. Since the compound (C1-1) has a high absorbance to light during exposure, it is suitable for highly efficient radical generation, and the reaction rate of the radical polymerization of the compound (B) is significantly improved.
  • the (C1-1) compound preferably has a condensed polycyclic structure, a condensed polycyclic heterocyclic structure or a diphenylsulfide structure.
  • (C1-1) compound is a structure in which at least one oxime ester structure is bonded to a condensed polycyclic structure, a condensed polycyclic heterocyclic structure or a diphenyl sulfide structure ( ⁇ -oxime structure) or at least one oxime ester It preferably has a structure in which a carbonyl structure is bonded (that is, a structure in which an oxime ester structure is bonded via a carbonyl structure; a ⁇ -oxime structure), and more preferably a structure in which at least one oxime ester structure is bonded.
  • the condensed polycyclic structure is preferably a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, an indene structure, an indane structure, a benzoindene structure or a benzoindane structure, and more preferably a fluorene structure, a benzofluorene structure or a dibenzofluorene structure.
  • the condensed polycyclic heterocyclic structure is preferably a carbazole structure, a dibenzofuran structure, a dibenzothiophene structure, a benzocarbazole structure, an indole structure, an indoline structure, a benzoindole structure, a benzoindoline structure, a phenothiazine structure or a phenothiazine oxide structure, and a carbazole structure, A benzocarbazole structure, an indole structure or a benzoindole structure is more preferred.
  • the (C1-1) compound has a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, a benzocarbazole structure, an indole structure, or It preferably has a benzoindole structure.
  • the photosensitive agent contains (C1) compound, (C1) compound contains (C1-1) compound, and (C1-1)
  • the compound has one or more structures selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, a furylcarbonyl structure, at least two oxime ester structures and at least two oxime ester carbonyl structures. is preferred.
  • (C1-1) a compound selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, a furylcarbonyl structure, at least two oxime ester structures and at least two oxime ester carbonyl structures;
  • the compound (C1-1) comprises a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, a furylcarbonyl structure and at least two oxime ester structures. It preferably has one or more structures selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, and a dibenzofluorene skeleton.
  • the compound (C1-1) has one or more structures selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, and a dibenzofluorene skeleton, the compound (C1-1) has photobleaching properties.
  • the effects of improving the time sensitivity, improving the halftone characteristics, and suppressing variations in opening pattern dimensions after development are remarkable.
  • Photobleaching means that bond cleavage and/or reaction due to exposure reduces absorbance at wavelengths in the ultraviolet region (for example, 400 nm or less) and/or absorbance at wavelengths in visible light (380 to 780 nm). say.
  • the compound (C1-1) preferably has a diphenylsulfide structure, an indole structure or a benzoindole structure, and a condensed polycyclic structure or a condensed polycyclic heterocyclic structure. It is also preferred to have a structure in which an oxime ester carbonyl structure is bonded to .
  • the compound (C1-1) preferably has a group substituted with a halogen atom from the viewpoint of improving sensitivity during exposure, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development. group is more preferred.
  • the above-mentioned (A) alkali-soluble resin has a structural unit having a halogen atom, the improved compatibility between the resin and the photopolymerization initiator leads to improved sensitivity during exposure, improved halftone characteristics, and improved aperture pattern dimensions after development. The effect of suppressing variation becomes remarkable.
  • the polyimide-based resin described above preferably has the structural unit having the fluorine atom described above.
  • Groups substituted with halogen atoms include trifluoromethyl group, trifluoropropyl group, trichloropropyl group, tetrafluoropropyl group, fluorocyclopentyl group, fluorophenyl group, pentafluorophenyl group, trifluoropropoxy group, tetrafluoropropoxy groups or pentafluorophenoxy groups are preferred.
  • the compound (C1-1) contains a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and a It preferably has one or more groups selected from the group consisting of 5 alkynyl groups. Among them, it preferably has a structure in which at least one alkenyl group having 1 to 5 carbon atoms is bonded to a condensed polycyclic structure, a condensed polycyclic heterocyclic structure or a diphenylsulfide structure.
  • the photoreactive group is preferably a radically polymerizable group, more preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, and still more preferably a (meth)acryloyl group.
  • the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms is preferably a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • the (C1-1) compound having a condensed polycyclic structure, a condensed polycyclic heterocyclic structure or a diphenyl sulfide structure has the general formula ( 17) It preferably contains one or more compounds selected from the group consisting of compounds represented by any one of (18) and (19), and contains a compound represented by general formula (18). is more preferred.
  • Y 1 and Y 2 are each independently a carbon atom in general formulas (17) and (18).
  • Y 1 and Y 2 each independently represent a nitrogen atom, an oxygen atom or a sulfur atom in general formulas (17) and (18).
  • X 1 , X 2 , X 4 , X 5 and X 6 are each independently a direct bond, a C 1-10 alkylene group, a C 4-10 It represents a cycloalkylene group or an arylene group having 6 to 15 carbon atoms.
  • Y 1 and Y 2 each independently represent a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
  • R 451 to R 456 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a carbon represents a hydroxyalkyl group of numbers 1-10;
  • R 457 to R 459 each independently represent a substituent represented by any one of general formulas (37) to (40) or a nitro group.
  • R 460 to R 467 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms or a ring having 4 to 10 carbon atoms represents a group that forms R 468 and R 469 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 10 carbon atoms or acyl group having 2 to 15 carbon atoms.
  • R 471 to R 473 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms.
  • R 474 to R 476 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a represents an integer of 0 to 3;
  • c represents an integer of 0 to 5;
  • b and d each independently represent 0 or 1;
  • e and f each independently represent an integer of 0 to 2;
  • g and h are each independently 2 when Y 1 and Y 2 are each independently a carbon atom;
  • g and h are each independently 1 when Y 1 and Y 2 are each independently a nitrogen atom;
  • g and h are each independently 0 when Y 1 and Y 2 are each independently an oxygen atom or a sulfur atom;
  • j, k, and l each independently represent 0 or 1;
  • m, n and o each independently represent an integer of 1 to 10;
  • R 477 to R 480 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. , represents an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or a group forming a ring.
  • Examples of the ring formed by multiple R 477 to R 480 include benzene ring, naphthalene ring, anthracene ring, cyclopentane ring and cyclohexane ring.
  • a benzene ring or a naphthalene ring is preferable as the ring formed by a plurality of R 477 to R 480 .
  • the content ratio of the (C1-1) compound in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is 0.3% by mass or more from the viewpoint of improving sensitivity during exposure and improving halftone characteristics. is preferred, 1.0% by mass or more is more preferred, and 2.0% by mass or more is even more preferred.
  • the content of the (C1-1) compound is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of suppressing residue after development.
  • the photosensitive resin composition of the present invention contains the (B) compound
  • the content of the (C1-1) compound is 100 parts by mass of the total of (A) the alkali-soluble resin and (B) the compound.
  • WHEREIN 1 mass part or more is preferable, 3 mass parts or more are more preferable, 5 mass parts or more are still more preferable.
  • the content of the (C1-1) compound is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the photosensitive agent may contain (C2) a photoacid generator.
  • C2) Photoacid generator refers to a compound that cleaves bonds and/or reacts with exposure to light to generate an acid. At the time of exposure, even if the amount of acid generated from the photoacid generator (C2) is small, the cationic polymerization of the cationic polymerizable compound and/or the crosslinking of the resin with the (G) crosslinking agent described below will form a chain. Since it progresses exponentially, it is suitable for forming a negative pattern with a low exposure dose, and the effect of improving the sensitivity during exposure is remarkable.
  • the photosensitive agent preferably contains the above-described (C1) compound and (C2) photoacid generator.
  • the (C) photosensitive agent contains a (C3) compound and (C2) a photoacid generator, which will be described later, an acid can be generated from the (C2) photoacid generator during exposure after alkali development and before thermal curing. .
  • the generated acid can promote crosslinking between the resin and the (C) crosslinking agent described later during the subsequent heat curing, so that the effect of improving the heat resistance of the cured product and improving the chemical resistance of the cured product becomes remarkable.
  • Photoacid generators include, for example, ionic compounds and nonionic compounds.
  • ionic compound a triorganosulfonium salt compound is preferred.
  • Preferred nonionic compounds are halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, sulfonimide compounds, phosphate ester compounds and sulfonebenzotriazole compounds.
  • the photosensitive agent preferably contains (C3) a naphthoquinonediazide compound (hereinafter, "(C3) compound”).
  • the compound (C3) refers to a compound that undergoes a structural change upon exposure to generate indenecarboxylic acid and/or sulfoindenecarboxylic acid.
  • the exposed portion of the film obtained from the composition is made soluble in an alkaline developer by the acidic compound in which the (C3) compound is structurally changed, so that a positive pattern can be formed.
  • the solubility of the exposed portion in an alkaline developer is selectively improved, and the effect of improving the resolution after development becomes remarkable.
  • the (C) photosensitive agent contains the above-described (C1) compound and (C3) compound, whereby development The effect of suppressing pattern shape change and reducing the taper of the pattern shape becomes remarkable.
  • the (C3) compound is preferably a 5-naphthoquinonediazidesulfonic acid ester or a 4-naphthoquinonediazidesulfonic acid ester of a compound having a phenolic hydroxyl group.
  • a method for producing the compound (C3) for example, a method of esterifying a compound having a phenolic hydroxyl group and naphthoquinonediazide sulfonic acid, or a method of esterifying a compound having a phenolic hydroxyl group and naphthoquinonediazide sulfonic acid chloride. and the like.
  • the naphthoquinonediazidesulfonic acid chloride 5-naphthoquinonediazidesulfonic acid chloride or 4-naphthoquinonediazidesulfonic acid chloride is preferred.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (D) a colorant.
  • the colorant preferably contains (Da) a black agent.
  • the colorant refers to a compound that colors the composition by absorbing light with a visible wavelength (380 to 780 nm).
  • a coloring agent By including (D) a coloring agent, the light transmitted through the cured product obtained from the composition or the light reflected from the cured product obtained from the composition can be colored in a desired color.
  • a light-shielding property can be imparted to a cured product obtained from the composition.
  • Colorant is preferably (D1) pigment or (D2) dye.
  • a black agent is preferable as the (D) coloring agent.
  • the blackening agent is a compound that blackens the composition by absorbing visible light.
  • a cured product obtained from a composition containing a black agent is suitable for applications requiring high contrast due to suppression of external light reflection, prevention of light leakage from adjacent pixels, prevention of TFT malfunction, etc. It is particularly preferably used as a pixel dividing layer, a TFT flattening layer, a TFT protective layer, an interlayer insulating layer or a gate insulating layer of an organic EL display. It is also preferably used as a black matrix or black column spacer.
  • the photosensitive resin composition of the first aspect of the present invention contains (Da) the black agent and the above-described (AX) resin, so that the effect of suppressing residue after development and suppressing variation in opening pattern size after development is achieved. becomes conspicuous. In addition, the effect of improving the reliability of the light-emitting element in the organic EL display and driving the light-emitting element at a low voltage becomes remarkable. This is probably because the interaction between the (AX) resin and the (Da) black agent improves the solubility of the (Da) black agent in the alkaline developer on the substrate surface. In addition, it is presumed that side etching of the deep portion of the film during alkali development was suppressed by the action of the (AX) resin described above.
  • the photosensitive resin composition may contain (Da) a black agent and may further contain (Db) a colorant other than black. (Db) By including a colorant other than black, the cured product obtained from the composition can be colored to desired color coordinates.
  • (D2) Dye refers to a compound that chemically adsorbs to the surface structure of an object to color it, and is generally soluble in solvents.
  • D2 Dyes include, for example, anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, threne dyes, perinone dyes, perylene dyes, triarylmethane dyes and xanthene dyes.
  • (D) Black in colorants refers to those that include "BLACK” in the Color Index Generic Name (hereinafter "C.I. number”).
  • C.I. number When a material not assigned a number is included, it means that the cured product is black.
  • the black color in the case of a cured product refers to the transmittance per 1.0 ⁇ m film thickness at a wavelength of 550 nm in the transmission spectrum of the cured product of the composition containing the (D) colorant, based on the Lambert-Beer formula, When the film thickness is converted within the range of 0.1 to 1.5 ⁇ m so that the transmittance at a wavelength of 550 nm is 10%, the transmittance at a wavelength of 450 to 650 nm in the converted transmission spectrum is 25% or less.
  • the transmission spectrum of the cured product can be obtained based on the method described in paragraph [0285] of WO2019/087985.
  • the content ratio of the (D) colorant in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is 5 from the viewpoint of improving the light-shielding property and improving the reliability of the light-emitting element in the organic EL display. % by mass or more is preferable, 20% by mass or more is more preferable, and 30% by mass or more is even more preferable.
  • the content ratio of (D) the colorant is preferably 70% by mass or less, more preferably 50% by mass or less, from the viewpoint of improving the sensitivity during exposure and improving the reliability of the light-emitting element in the organic EL display.
  • the preferred content ratio of (Da) the black agent is the same as the preferred content ratio of (D) the colorant described above.
  • the black agent preferably contains (D1a) a black pigment.
  • a black pigment refers to a pigment that blackens a composition by absorbing light having a wavelength of visible light.
  • a pigment is a compound that physically adsorbs or interacts with the surface of an object to color it, and is generally insoluble in solvents and the like.
  • D1a By containing a black pigment, the effect of improving the light-shielding property of the film obtained from the composition and improving the reliability of the light-emitting element in the organic EL display becomes remarkable.
  • a black pigment contains (D1a-1) an organic black pigment and/or (D1a-2) an inorganic black pigment, which will be described later, it may further contain (D1b) a pigment other than black.
  • D1b By including a pigment other than black, the film obtained from the composition can be colored to desired color coordinates.
  • the non-black pigment is preferably one or more pigments selected from the group consisting of blue pigments, red pigments, yellow pigments, purple pigments, orange pigments and green pigments, which will be described later.
  • the preferred content ratio of (D1a) black pigment is the same as the preferred content ratio of (D) colorant described above.
  • (D1a) black pigment includes (D1a-1) organic black pigment (hereinafter "(D1a-1) compound”), (D1a-2) inorganic black pigment (hereinafter "(D1a-2) compound”) and ( D1a-3)
  • One or more pigments selected from the group consisting of two or more color pigment mixtures hereinafter referred to as "(D1a-3) compounds" are preferred.
  • the (D1a-1) compound and/or the (D1a-3) compound are more preferable, and the (D1a-1) compound is even more preferable, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display.
  • Examples of (D1a-1) compounds include (D1a-1a) benzofuranone black pigment, (D1a-1b) perylene black pigment, (D1a-1c) azo black pigment, anthraquinone black pigment, and aniline black pigment. , azomethine black pigments or carbon black.
  • (D1a-2) compounds include, for example, graphite or silver-tin alloys or fine particles containing metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitrides.
  • the (D1a-3) compound is a pigment mixture that exhibits a pseudo-black color by containing two or more pigments in combination. Due to the mixing of two or more pigments, the resulting film from the composition can be toned to the desired color coordinates.
  • the photosensitive resin composition of the first aspect of the present invention further contains (D1a-1) compound and/or (D1a-3) compound,
  • (D1a-1) compound contains one or more pigments selected from the group consisting of (D1a-1a) benzofuranone black pigment, (D1a-1b) perylene black pigment and (D1a-1c) azo black pigment
  • (D1a-3) Compound preferably contains two or more pigments selected from the group consisting of red, orange, yellow, green, blue and purple pigments.
  • the photosensitive resin composition of the first aspect of the present invention contains the above-described (AX) resin as the (D1a) black pigment, even when it contains these pigments with high light-shielding properties, so that the above-described (AX) resin and the (D1a) black pigment improves the solubility of the (D1a) black pigment on the substrate surface in an alkaline developer, which is preferable. In addition, side etching of the deep portion of the film during alkali development is suppressed by the action of the (AX) resin described above, which is preferable.
  • the (D1a-3) compound preferably contains two or more pigments selected from the group consisting of red, orange, yellow, green, blue and purple pigments.
  • the (D1a-3) compound includes (I-d1) a blue pigment, a red pigment, and a yellow pigment from the viewpoint of improving sensitivity during exposure, improving halftone characteristics, and improving the reliability of light-emitting elements in organic EL displays.
  • (II-d1) a colored pigment mixture containing a blue pigment, a red pigment and an orange pigment
  • (III-d1) a colored pigment mixture containing a blue pigment, a purple pigment and an orange pigment
  • (IV-d1) a purple pigment and a yellow pigment.
  • the blue pigment is C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6 or C.I. I. Pigment Blue 60 is preferred, and C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179 or C.I. I. Pigment Red 190 is preferred, and as a yellow pigment, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I.
  • Pigment Yellow 192 or C.I. I. Pigment Yellow 194 is preferred, and C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 29 or C.I. I. Pigment Violet 37 is preferred, and C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 64 or C.I. I. Pigment Orange 72 is preferred (all values are C.I. numbers).
  • the total content ratio of (D1a-1) compound, (D1a-2) compound and (D1a-3) compound is the same as the preferred content ratio of (D) colorant described above. is.
  • (D1a-1a) compound, (D1a-1b) compound and (D1a-1c) compound> (D1a-1) compound is one or more pigments selected from the group consisting of (D1a-1a) benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments and (D1a-1c) azo-based black pigments (hereinafter , “Specific (D1a-1) organic black pigment”), and more preferably (D1a-1a) benzofuranone-based black pigment.
  • the specific (D1a-1) organic black pigment has excellent light-shielding properties per unit content ratio of the pigment in the composition compared to general organic pigments, and transmits wavelengths in the ultraviolet region (e.g., 400 nm or less). Since the ratio is high, the effects of improving sensitivity during exposure, suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development are remarkable. In addition, the effect of low-voltage driving of the light-emitting elements in the organic EL display becomes remarkable. In addition, since it is excellent in insulating properties and low dielectric properties compared to general organic pigments and inorganic pigments, the effect of improving the reliability of light-emitting elements in organic EL displays is remarkable.
  • the (D1a-1) compound suitable for combination with the above-described (AX) resin includes a pigment having high light-shielding properties in visible light wavelengths and a pigment having an ultraviolet (D1a-1a) Benzofuranone-based black pigments are particularly preferred from the viewpoint of high transmittance in the wavelength range.
  • the photosensitive resin composition of the first aspect of the present invention preferably contains a (D1a-1) compound, and the (D1a-1) compound preferably contains (D1a-1a) a benzofuranone-based black pigment.
  • the benzofuranone-based black pigment preferably has a benzofuran-2(3H)-one structure or a benzofuran-3(2H)-one structure, and is represented by either general formula (161) or general formula (162) It is more preferred to have compounds represented by, geometric isomers thereof, salts thereof or salts of geometric isomers thereof.
  • R 341 to R 344 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 345 to R 348 may be directly bonded to each other or form a ring with an oxygen atom bridge, sulfur atom bridge, NH bridge or NR 353 bridge.
  • R 349 to R 352 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • a, b, c and d each independently represent an integer of 0 to 4;
  • the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group and aryl group described above may have heteroatoms and may be unsubstituted or substituted.
  • (D1a-1b) perylene-based black pigments compounds having a perylene structure and represented by any one of general formulas (164) to (166) or salts thereof are preferable.
  • X 241 and X 242 each independently represent a direct bond or an alkylene group having 1 to 10 carbon atoms.
  • Y 241 and Y 242 each independently represent a direct bond or an arylene group having 6 to 15 carbon atoms.
  • R 361 and R 362 each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms.
  • a plurality of R 367 to R 369 may be directly bonded to each other or may form a ring with oxygen atom bridge, sulfur atom bridge, NH bridge or NR 370 bridge.
  • a and b each independently represents an integer of 0 to 5;
  • c, d, e, and f each independently represents an integer of 0-4.
  • g, h, and i each independently represent an integer from 0 to 8;
  • R 361 and R 362 are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a and b are 1.
  • R 361 and R 362 are preferably hydroxy groups, and a and b are 1.
  • R 361 and R 362 are each independently a hydroxy group, An alkoxy group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms is preferable, and a and b each independently represent an integer of 0 to 5.
  • the alkylene group, arylene group, alkyl group, alkoxy group and acyl group described above may have a heteroatom and may be unsubstituted or substituted.
  • a compound having an azo group in the molecule and represented by general formula (168) or a salt thereof is preferable.
  • X 251 represents an arylene group having 6 to 15 carbon atoms.
  • Y 251 represents an arylene group having 6 to 15 carbon atoms.
  • R 381 to R 383 may be directly bonded to each other or may form a ring with an oxygen atom bridge, a sulfur atom bridge, an NH bridge, or an NR 390 bridge.
  • R 384 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a nitro group.
  • R 385 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acylamino group having 2 to 10 carbon atoms or a nitro group.
  • R 386 to R 389 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the arylene group, alkyl group, alkoxy group and acylamino group described above may have a heteroatom and may be unsubstituted or substituted.
  • (D1a-1a) Benzofuranone-based black pigments include, for example, "IRGAPHOR” (registered trademark) BLACK S0100CF (manufactured by BASF), the black pigment described in International Publication No. 2010/081624, or the black pigment described in International Publication No. 2010/081756. of black pigments.
  • Examples of (D1a-1b) perylene-based black pigments include C.I. I. Pigment Black 31 or C.I. I. Pigment Black 32 (all numerical values are C.I. numbers).
  • PALIOGEN registered trademark
  • BLACK S0084, K0084, L0086, K0086, K0087, K0088, EH0788, FK4280, or FK4281 can be mentioned.
  • (D1a-1c) azo black pigments include, for example, "CHROMOFINE” (registered trademark) BLACK A1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.), black pigments described in JP-A-01-170601, Alternatively, black pigments described in JP-A-02-034664 may be used.
  • the total content ratio of the specific (D1a-1) organic black pigment is the same as the preferred content ratio of the (D) colorant described above.
  • the (D1a-1) compound preferably further contains a (DC) coating layer.
  • the (DC) coating layer refers to a layer that coats the pigment surface and is formed by treatment such as surface treatment with a silane coupling agent, surface treatment with a silicate, surface treatment with a metal alkoxide, or coating treatment with a resin. .
  • the acid resistance, alkali resistance, solvent resistance, dispersion stability or heat resistance of the (D1a-1) compound can be improved, and the residue after development can be suppressed, the halftone characteristics can be improved, and the organic
  • the effect of improving the reliability of the light-emitting element in the EL display becomes remarkable.
  • the above-mentioned (D1a-1) compound contains (D1a-1a) a benzofuranone-based black pigment
  • the inclusion of the (DC) coating layer suppresses residue after development caused by the pigment, and The effect of suppressing variations in opening pattern dimensions is remarkable.
  • the average coverage of the (DC) coating layer with respect to the (D1a-1) compound is preferably 50 to 100%, from the viewpoint of suppressing residue after development and improving the reliability of the light emitting element in the organic EL display, and 70 to 70%. 100% is more preferred, and 90-100% is even more preferred.
  • the average coverage of the (DC) coating layer with respect to the (D1a-1) compound can be determined based on the method described in paragraph [0349] of WO 2019/087985.
  • the (DC) coating layer is a (DC-1) silica coating layer (hereinafter referred to as "(DC-1) coating layer") from the viewpoint of suppressing residue after development and improving the reliability of light-emitting elements in organic EL displays. ), (DC-2) metal oxide coating layer (hereinafter “(DC-2) coating layer”) and (DC-3) metal hydroxide coating layer (hereinafter “(DC-3) coating layer”) It preferably contains one selected from the group consisting of (DC-1) more preferably contains a coating layer.
  • (DC-1) Silica in the coating layer includes, for example, silicon dioxide or a hydrous product thereof.
  • the metal oxide in the coating layer includes not only the metal oxide itself but also, for example, a hydrate of the metal oxide.
  • metal oxides include alumina (Al 2 O 3 ) and alumina hydrate (Al 2 O 3 ⁇ nH 2 O).
  • DC-3 Examples of the metal hydroxide in the coating layer include aluminum hydroxide (Al(OH) 3 ).
  • the content of the (DC-1) coating layer is, when the (D1a-1) compound is 100 parts by mass, from the viewpoint of suppressing residue after development and light emission in an organic EL display From the viewpoint of improving the reliability of the device, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more.
  • the content of the (DC-1) coating layer is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of suppressing residue after development.
  • the total content of the (DC-2) coating layer and (DC-3) coating layer is, when the (D1a-1) compound is 100 parts by mass, the development From the viewpoint of suppressing subsequent residue and improving the reliability of light-emitting elements in organic EL displays, the amount is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more.
  • the total content of the (DC-2) coating layer and (DC-3) coating layer is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of suppressing residue after development.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (E) a dispersant.
  • the dispersant refers to a compound having a surface affinity group that interacts with the surface of the pigment (D1) described above and a dispersion stabilizing structure that improves dispersion stability.
  • the dispersion stabilizing structure includes, for example, an ionic substituent or a polar substituent that stabilizes dispersion by electrostatic repulsion, or a polymer chain that stabilizes dispersion by steric hindrance.
  • D1 When the number average particle size of the pigment is 500 nm or less, the increase in the surface area reduces the dispersion stability and tends to cause aggregation of the particles.
  • the dispersant has at least one structure selected from the group consisting of a basic group, an acidic group, a salt structure of a basic group, and a salt structure of an acidic group, from the viewpoint of suppressing residue after development. is preferred, and it is more preferred to have a basic group and/or a salt structure of the basic group.
  • a dispersant having only a basic group, a dispersant having a basic group and an acidic group, and a dispersant having a structure in which a basic group is salted with an acid A dispersant having a structure in which an agent or an acid group is salted with a base is preferred, and a dispersant having only a basic group or a dispersant having both a basic group and an acid group is more preferred.
  • a dispersing agent having only acidic groups or a dispersing agent having neither basic groups nor acidic groups may be contained.
  • the basic group possessed by the dispersant is preferably a group having a tertiary amino group or a nitrogen-containing ring skeleton such as a pyrrolidine skeleton, a pyrrole skeleton, an imidazole skeleton, or a piperidine skeleton.
  • the acidic group possessed by the dispersant is preferably a carboxy group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group.
  • the structure in which the basic group of the dispersant is salt-formed with an acid is preferably a quaternary ammonium salt structure or a structure in which the nitrogen-containing ring skeleton described above is salt-formed.
  • the counter anion in the salt structure of the basic group is preferably a carboxylate anion, a sulfonate anion, a phenoxy anion, a sulfate anion, a nitrate anion, a phosphate anion, or a halogen anion, more preferably a carboxylate anion.
  • dispersants having a polymer chain include acrylic resin-based dispersants, polyoxyalkylene ether-based dispersants, polyester-based dispersants, polyurethane-based dispersants, polyol-based dispersants, polyalkyleneamine-based dispersants, and polyethyleneimine. A system dispersant or a polyallylamine system dispersant is preferred.
  • the dispersant preferably contains (E1) a pigment dispersant having a basic group (hereinafter referred to as "(E1) compound"), and the (E1) compound is represented by general formulas (26) and (27) , (28) and (29), and a polyoxyalkylene structure.
  • the (E1) compound has a structure represented by the general formula (26) and a polyoxyalkylene structure from the viewpoint of suppressing viscosity increase during storage of the pigment dispersion, improving flatness of the cured product, and suppressing residue after development. is more preferred.
  • (E1) a pigment dispersant having a basic group has a structure represented by the general formula (29), and Having a polyoxyalkylene structure is also more preferred.
  • R 56 to R 59 each independently represent an alkyl group having 1 to 6 carbon atoms.
  • n represents an integer of 1-9.
  • * 1 to * 6 each independently represent a bonding point with a polyoxyalkylene structure.
  • X 56 and X 57 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Y 56 to Y 59 each independently represent an alkylene group having 1 to 6 carbon atoms.
  • a and b each independently represents an integer of 1 to 100;
  • c and d each independently represent an integer of 0 to 100; * 7 represents a point of attachment to a carbon or nitrogen atom.
  • a and b are each independently an integer of 5-60, more preferably an integer of 10-40.
  • c and d are each independently preferably an integer of 0-20, more preferably an integer of 0-10.
  • the amine value of the (E) dispersant (including the (E1) compound) is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, from the viewpoint of suppressing residue after development. On the other hand, the amine value is preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less, from the viewpoint of suppressing residue after development.
  • the term "amine value" as used herein refers to the mass of potassium hydroxide equivalent to the acid reacting with 1 g of the (E) dispersant, and the unit is mgKOH/g.
  • the acid value of the (E) dispersant is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, from the viewpoint of suppressing residue after development.
  • the acid value is preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less, from the viewpoint of suppressing residue after development.
  • the acid value as used herein refers to the mass of potassium hydroxide that reacts with 1 g of the (E) dispersant, and the unit is mgKOH/g.
  • the content of (E) dispersant is 100 parts by mass of (D1) pigment , the amount is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, from the viewpoint of suppressing residue after development.
  • the content of (E) the dispersant is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, from the viewpoint of suppressing residue after development.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains the following (F0) compound and/or (FB) compound.
  • (F0) compound a compound having an acidic group containing a phosphorus atom and/or a salt of an acidic group containing a phosphorus atom (hereinafter, "(F0) compound”).
  • (FB) compound a compound having a betaine structure containing a phosphorus atom (hereinafter, "(FB) compound”).
  • the (F0) compound, the (FB) compound, the (FC1) compound described later, and the (FT) compound described later may be collectively referred to as the "(F) compound" hereinafter.
  • the (F0) compound preferably has the following (I-f0) structure.
  • (I-f0) structure from the group consisting of an oxyalkylene group to which a monovalent to divalent aliphatic group having 4 to 30 carbon atoms, an alkylaryl group having 10 to 30 carbon atoms and an aryl group having 6 to 15 carbon atoms are bonded One or more groups selected.
  • the (FB) compound preferably has the following (I-fb) structure.
  • (I-fb) structure a monovalent to divalent aliphatic group having 1 to 6 carbon atoms and having an ammonium cation structure.
  • (F0) compounds and/or (FB) compounds preferably contain two or more types of compounds, and preferably contain two or more types of (F0) compounds and two or more types of (FB) compounds. It is particularly preferred to contain the (F0) compound and the (FB) compound.
  • the photosensitive resin composition of the first aspect of the present invention contains a (F0) compound and/or (FB) compound, the (F0) compound includes the following (F1) compound, and (FB)
  • the compound preferably contains the following (FB1) compound.
  • (F1) compound one or more compounds selected from the group consisting of phosphoric acid compounds, phosphonic acid compounds, phosphinic acid compounds and salts thereof (hereinafter, "(F1) compounds”).
  • (FB1) compound one or more compounds selected from the group consisting of betaine phosphate compounds, betaine phosphonate compounds and betaine phosphinate compounds (hereinafter, "(FB1) compound”).
  • the (F1) compound preferably has the following (I-f1) structure and/or (II-f1) structure.
  • (I-f1) structure one type selected from the group consisting of a monovalent aliphatic group having 4 to 30 carbon atoms, a divalent aliphatic group having 6 to 30 carbon atoms and an alkylaryl group having 10 to 30 carbon atoms above basis.
  • (II-f1) structure an oxyalkylene group bonded to a monovalent aliphatic group having 4 to 30 carbon atoms, an oxyalkylene group bonded to an alkylaryl group having 10 to 30 carbon atoms, and an aryl group having 6 to 15 carbon atoms one or more groups selected from the group consisting of oxyalkylene groups having 4 to 15 carbon atoms to which is bonded.
  • the (FB1) compound preferably has the following (I-fb1) structure.
  • (I-fb1) structure a monovalent to divalent aliphatic group having 1 to 6 carbon atoms and having an ammonium cation structure.
  • the (F1) compound and/or the (FB1) compound preferably contain two or more compounds, and preferably contain two or more (F1) compounds and two or more (FB1) compounds. It is particularly preferred to contain the (F1) compound and the (FB1) compound.
  • the (F1) compound has the following (I-f1) structure and/or (II-f1) structure as a substituent bonded to the phosphorus atom and/or a substituent bonded to the oxygen atom on the PO bond: is preferred.
  • (I-f1) structure the following (I-f1x) structure is preferable.
  • (I-f1x) structure one type selected from the group consisting of a monovalent aliphatic group having 6 to 12 carbon atoms, a divalent aliphatic group having 6 to 12 carbon atoms and an alkylaryl group having 14 to 26 carbon atoms above basis.
  • the monovalent aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group.
  • the divalent aliphatic group is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the (I-f1) structure is preferably a linear structure and/or a branched structure.
  • (II-f1) structure the following (II-f1x) structure is preferable.
  • (II-f1x) structure an oxyalkylene group to which a monovalent aliphatic group having 6 to 12 carbon atoms is bonded, an oxyalkylene group to which an alkylaryl group having 14 to 26 carbon atoms is bonded, and an aryl group having 6 to 10 carbon atoms one or more groups selected from the group consisting of oxyalkylene groups having 6 to 12 carbon atoms to which is bonded.
  • the monovalent aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group.
  • the (II-f1) structure is preferably a linear structure and/or a branched structure.
  • Salts of an acidic group containing a phosphorus atom in the compound include salts of an acidic group containing a phosphorus atom and a compound having a cationic structure.
  • the salt of the phosphoric acid compound, the salt of the phosphonic acid compound, or the salt of the phosphinic acid compound in the compound (F1) includes salt.
  • Compounds having a cationic structure include compounds having one or more structures selected from the group consisting of metal atom cations, ammonium cations, phosphonium cations, and sulfonium cations, and compounds having an ammonium cation are preferred.
  • the ammonium cation is preferably a primary ammonium cation, a secondary ammonium cation, a tertiary ammonium cation, or a quaternary ammonium cation, more preferably a quaternary ammonium cation.
  • the ammonium cation preferably has at least one aliphatic group having 1 to 30 carbon atoms, more preferably has an aliphatic group having 1 to 15 carbon atoms, and has an aliphatic group having 1 to 10 carbon atoms. is more preferred, and having an aliphatic group having 1 to 6 carbon atoms is particularly preferred.
  • the aliphatic group is preferably a monovalent or divalent linear and/or branched aliphatic group, preferably a group selected from the group consisting of linear alkyl groups, alkenyl groups, and alkynyl groups. Alkyl groups with a chain structure are more preferred.
  • the (F1) compound preferably contains one or more compounds selected from the group consisting of compounds represented by any of general formulas (11), (12) and (13) and salts thereof. It is also preferable to contain two or more compounds selected from the group consisting of compounds represented by any of formulas (11), (12) and (13) and salts thereof.
  • the (F1) compound is represented by at least general formula (12) from the viewpoints of suppressing residue after development and improving halftone characteristics, improving the reliability of light-emitting elements in organic EL displays, and driving light-emitting elements at low voltage. and/or salts thereof.
  • Z 11 to Z 13 each independently represent a direct bond, a divalent aliphatic group having 6 to 30 carbon atoms, or a group represented by general formula (14).
  • Z 14 to Z 16 each independently represent a direct bond, a divalent aliphatic group having 6 to 30 carbon atoms or a group represented by general formula (15).
  • Z 11 in general formula (11) is a direct bond
  • the corresponding R 31 represents a monovalent aliphatic group having 4 to 30 carbon atoms or an alkylaryl group having 10 to 30 carbon atoms.
  • Z 12 and corresponding R 32 , and Z 13 and corresponding R 33 have the same relationship as Z 11 and corresponding R 31 in general formula (11).
  • Z 14 in general formula (11) is a direct bond
  • the corresponding R 34 is a hydrogen atom, a monovalent aliphatic group having 4 to 30 carbon atoms, an alkylaryl group having 10 to 30 carbon atoms, or a photoreactive group.
  • Z 15 and corresponding R 35 and Z 16 and corresponding R 36 in general formulas (12) and (13) are the same as Z 14 and corresponding R 34 in general formula (11).
  • Z 11 and Z 14 in general formula (11) is a divalent aliphatic group having 6 to 30 carbon atoms
  • the corresponding R 31 and/or R 34 are each independently a hydrogen atom , represents a hydroxy group or a monovalent organic group having 1 to 15 carbon atoms.
  • Z 12 and Z 15 and corresponding R 32 and R 35 and Z 13 and Z 16 and corresponding R 33 and R 36 also Z 11 in general formula (11) and Z 14 and the corresponding R 31 and R 34 relationships.
  • Z 11 in general formula (11) is a group represented by general formula (14)
  • the corresponding R 31 is a monovalent aliphatic group having 4 to 30 carbon atoms, alkylaryl having 10 to 30 carbon atoms, group or an aryl group having 6 to 15 carbon atoms.
  • Z 12 and corresponding R 32 and Z 13 and corresponding R 33 in general formulas (12) and (13) are the same as Z 11 and corresponding R 31 in general formula (11).
  • Z 14 in general formula (11) is a group represented by general formula (15)
  • the corresponding R 34 is a hydrogen atom, a monovalent aliphatic group having 4 to 30 carbon atoms, or 10 to 30 carbon atoms.
  • the photoreactive group, the alkenyl group having 2 to 5 carbon atoms, and the alkynyl group having 2 to 5 carbon atoms are preferably radically polymerizable groups.
  • the heat-reactive group an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, or a blocked isocyanate group is preferred.
  • Y 11 and Y 12 each independently represent an alkylene group having 1 to 15 carbon atoms.
  • R 37 and R 38 each independently represent an alkyl group having 1 to 6 carbon atoms.
  • m and n each independently represent an integer of 1 to 15;
  • p and q each independently represent an integer of 0 to 4;
  • * 1 represents the bonding point with the oxygen atom in general formula (11), the bonding point with the phosphorus atom in general formula (12), or the bonding point with the phosphorus atom in general formula (13).
  • * 2 represents the bonding point with R 31 in general formula (11), the bonding point with R 32 in general formula (12), or the bonding point with R 33 in general formula (13).
  • * 3 represents a bonding point with an oxygen atom in general formula (11), a bonding point with an oxygen atom in general formula (12), or a bonding point with a phosphorus atom in general formula (13).
  • * 4 represents the bonding point with R34 in general formula (11), the bonding point with R35 in general formula (12), or the bonding point with R36 in general formula (13).
  • the photosensitive resin composition of the first aspect of the present invention contains propylene glycol monoalkyl ether acetate as a solvent having an acetate bond described later, and the compound (F1) is represented by the general formulas (11) to ( In 13), when Z 11 to Z 13 are a direct bond or a group represented by general formula (14), the monovalent aliphatic groups having 4 to 30 carbon atoms in R 31 to R 33 are each independently is a monovalent aliphatic group having 6 to 12 carbon atoms, and in the general formulas (11) to (13) described above, when Z 14 to Z 16 are direct bonds, R 34 to R 36 are hydrogen atoms; is preferred.
  • Such (F1) compounds are hereinafter referred to as "specific (F1) compounds".
  • the (F1) compound is a monovalent aliphatic group having 6 to 12 carbon atoms as the structure (I-f1) described above and/or a monovalent aliphatic group having 6 to 12 carbon atoms as the structure (II-f1) described above.
  • the aliphatic group of has an attached oxyalkylene group, such compounds are also referred to hereinafter as "specific (F1) compounds”.
  • the solubility of the (F1) compound in propylene glycol monoalkyl ether acetate can be significantly improved.
  • the effects of suppressing residues after development and improving halftone characteristics become remarkable.
  • the effect of improving the reliability of the light-emitting element in the organic EL display and lowering the driving voltage of the light-emitting element becomes remarkable.
  • propylene glycol monoalkyl ether acetate propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate are preferable, and propylene glycol monomethyl ether acetate is more preferable.
  • the (F1) compound has the above (I-f1) structure and/or ( In addition to the II-f1) structure, it is also preferred to have the following (III-f1) structure.
  • (III-f1) structure one or more groups selected from the group consisting of a photoreactive group, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms.
  • the photoreactive group is preferably a radically polymerizable group, more preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, and still more preferably a (meth)acryloyl group.
  • the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms is preferably a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • the photosensitive resin composition of the first aspect of the present invention contains the above-described (F1) compound and / or (FB1) compound, and is different from the (F1) compound, the above-described photoreactive group, carbon
  • the (FB1) compound preferably has the following (I-fb1) structure as a substituent bonded to the phosphorus atom and/or a substituent bonded to the oxygen atom on the PO bond.
  • the monovalent to divalent aliphatic group having 1 to 6 carbon atoms is preferably a divalent aliphatic group having 1 to 4 carbon atoms.
  • the monovalent aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group.
  • the divalent aliphatic group is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the monovalent to divalent aliphatic group having 1 to 6 carbon atoms preferably has a linear structure and/or a branched structure.
  • a monovalent to divalent aliphatic group having 1 to 6 carbon atoms may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group or a hydroxy group as a substituent. .
  • the ammonium cation structure is preferably an ammonium cation, a monoalkylammonium cation, a dialkylammonium cation or a trialkylquaternary ammonium cation, more preferably a trialkylquaternary ammonium cation.
  • the (I-fb1) structure is more preferably a structure derived from a nitrogen-containing aliphatic alcohol compound having 1 to 6 carbon atoms and having at least one hydroxy group and at least one ammonium group or amino group.
  • Such compounds are preferably ethanolamine, propanolamine, butanolamine, pentanolamine, serine, threonine, thiocine or choline, more preferably ethanolamine, serine or choline.
  • the photosensitive resin composition of the first aspect of the present invention contains at least propylene glycol monoalkyl ether acetate as a solvent having an acetate bond, which will be described later, and diethylene glycol dialkyl ether and diethylene glycol dialkyl ether as a solvent having at least three ether bonds, which will be described later.
  • the (FB1) compound when containing one or more solvents selected from the group consisting of propylene glycol monoalkyl ether, alkyl lactate, alkyl hydroxyacetate and hydroxyalkyl acetate as a solvent having an alcoholic hydroxyl group (hereinafter referred to as "a specific solvent When it contains”), the (FB1) compound preferably has a trialkyl quaternary ammonium cation structure in the (I-fb1) structure described above.
  • the trialkyl quaternary ammonium cation structure preferably has three alkyl groups of 1 to 6 carbon atoms, more preferably three alkyl groups of 1 to 4 carbon atoms.
  • Such (FB1) compounds are hereinafter referred to as "specific (FB1) compounds”.
  • the (FB1) compound containing the specific (FB1) compound can significantly improve the solubility of the (FB1) compound in the solvent.
  • the effects of suppressing residues after development and improving halftone characteristics become remarkable.
  • the effect of improving the reliability of the light-emitting element in the organic EL display and lowering the driving voltage of the light-emitting element becomes remarkable.
  • propylene glycol monoalkyl ether acetate propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate are preferable, and propylene glycol monomethyl ether acetate is more preferable.
  • diethylene glycol dialkyl ether diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether are preferred, and diethylene glycol ethyl methyl ether is more preferred.
  • Propylene glycol monoalkyl ether, alkyl lactate, alkyl hydroxyacetate or hydroxyalkyl acetate include propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate and 2-hydroxy acetate. Methyl and 2-hydroxyethyl acetate are preferred, more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl hydroxyacetate or 2-hydroxyethyl acetate.
  • the (FB1) compound has substituents and/or Alternatively, it is preferable to have the following (II-fb1) structure in addition to the (I-fb1) structure as a substituent bonded to the oxygen atom on the PO bond.
  • (II-fb1) structure a fatty acid ester structure derived from a fatty acid compound having 6 to 30 carbon atoms and/or an aliphatic ether structure derived from an aliphatic alcohol having 6 to 30 carbon atoms.
  • the (II-fb1) structure preferably has a mono- to divalent aliphatic group with 6 to 30 carbon atoms, more preferably a mono- to divalent aliphatic group with 10 to 20 carbon atoms.
  • the monovalent aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group.
  • the divalent aliphatic group is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the monovalent to divalent aliphatic group having 6 to 30 carbon atoms preferably has a linear structure and/or a branched structure.
  • the (FB1) compound has the above-mentioned (II-fb1) structure, so that the solubility of the (FB1) compound in the solvent is further specifically improved. can.
  • the (FB1) compound has the (I-fb1) structure from the viewpoint of suppressing residue after development and improving halftone characteristics, improving the reliability of light-emitting elements in organic EL displays, and driving light-emitting elements at low voltage. Furthermore, it preferably contains a compound having the following (IV-fb1) structure or (V-fb1) structure (hereinafter, “betaine-type phospholipid (FB1) compound”).
  • (IV-fb1) structure an ester structure derived from an aliphatic polyfunctional alcohol compound having 2 to 6 carbon atoms and having at least 3 hydroxy groups.
  • (V-fb1) structure an ester structure derived from a C15-20 nitrogen-containing aliphatic alcohol compound having at least two hydroxy groups and at least one amino group or at least one alkylamide group.
  • the (FB1) compound contains a betaine-type phospholipid (FB1) compound, so that the solubility of the (FB1) compound in the solvent is further specifically enhanced. can be improved to
  • the (FB1) compound particularly preferably contains a glycerophospholipid and/or a sphingolipid as a betaine-type phospholipid (FB1) compound.
  • (FB1) compounds of betaine-type phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingomyelin, hydrogenated phosphatidylcholine, hydrogenated phosphatidylethanolamine, hydrogenated phosphatidylserine, hydrogenated sphingomyelin, lysophosphatidylcholine, and lysophosphatidylethanolamine.
  • lysophosphatidylserine lysosphingomyelin
  • lecithin hydrogenated lecithin
  • lysolecithin cephalin
  • cephalin hydrogenated cephalin
  • lysocephalin plasmalogen
  • platelet-activating factor and (trimethylammonio) ethylphosphonate ceramide It is particularly preferable to contain the above compounds.
  • the (FB1) compound has, in addition to the (I-fb1) structure, Furthermore, it is also preferable to have the following (III-fb1) structure.
  • (III-fb1) structure one or more groups selected from the group consisting of a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms.
  • the (FB1) compound contains two or more types of (FB1) compounds, and is selected from the group consisting of the above-described (II-fb1) structure, the above-described (IV-fb1) structure and the above-described (V-fb1) structure. It is also preferred to include a compound having one or more types of structures as described above, and further including a compound having the (III-fb1) structure.
  • the photoreactive group is preferably a radically polymerizable group, more preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, and still more preferably a (meth)acryloyl group.
  • the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms is preferably a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • the total content ratio of the (F1) compound and (FB1) compound in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is from the viewpoint of suppressing residue after development and the light emitting element in the organic EL display. From the viewpoint of reliability improvement and low-voltage driving of the light-emitting element, it is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, further preferably 0.15% by mass or more, and 0.25% by mass or more. is particularly preferred. On the other hand, the total content ratio of the (F1) compound and the (FB1) compound is 1.
  • the photosensitive resin composition of the present invention contains the (B) compound
  • the total content of the (F1) compound and the (FB1) compound is the total content of the (A) alkali-soluble resin and (B) compound is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0.30 parts by mass or more, and particularly preferably 0.50 parts by mass or more.
  • the total content of the (F1) compound and the (FB1) compound is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, further preferably 2.0 parts by mass or less, and 1.5 Part by mass or less is particularly preferred.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (FC1) a non-betaine phospholipid (hereinafter referred to as "(FC1) compound").
  • (FC1) compound a non-betaine phospholipid
  • the (FC1) compound preferably contains two or more kinds of compounds, including the (F1) compound and/or the (FB1) compound, and particularly preferably containing the (FC1) compound.
  • the (FC1) compound has at least the following (I-fc1) structure and (II-fc1) structure.
  • I-fc1) structure one or more structures selected from the group consisting of an acid group containing a phosphorus atom, an anion structure containing a phosphorus atom, and a salt of an acid group containing a phosphorus atom.
  • II-fc1) structure a fatty acid ester structure derived from a fatty acid compound having 6 to 30 carbon atoms and/or an aliphatic ether structure derived from an aliphatic alcohol having 6 to 30 carbon atoms.
  • the (FC1) compound When the (I-fc1) structure is an acidic group containing a phosphorus atom and/or an anionic structure containing a phosphorus atom, the (FC1) compound preferably does not have an ammonium cation structure.
  • the above-mentioned anion structure containing a phosphorus atom is preferably an anion structure derived from an acidic group containing a phosphorus atom.
  • the (FC1) compound may have the (I-fc1) structure and (II-fc1) structure as a substituent bonded to the phosphorus atom and/or a substituent bonded to the oxygen atom on the PO bond. preferable.
  • the (I-fc1) structure is preferably a phosphate group, a phosphonate group or a phosphinate group and/or a phosphate anion, a phosphonate anion or a phosphinate anion.
  • the (II-fc1) structure preferably has a mono- to divalent aliphatic group with 6 to 30 carbon atoms, more preferably a mono- to divalent aliphatic group with 10 to 20 carbon atoms.
  • the monovalent aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group.
  • the divalent aliphatic group is preferably an alkylene group, an alkenylene group or an alkynylene group.
  • the monovalent to divalent aliphatic group having 6 to 30 carbon atoms preferably has a linear structure and/or a branched structure.
  • FC1 compounds from the group consisting of phosphatidic acid, phosphatidylglycerol, lysophosphatidic acid, lysophosphatidylglycerol, phosphatidylinositol, lysophosphatidylinositol, diphosphatidylglycerol, cardiolipin, sphingosine-1-phosphate and phosphatidyl-cytidine monophosphate It is particularly preferable to contain one or more selected compounds.
  • the total content ratio of the (F1) compound, the (FB1) compound and the (FC1) compound is the preferred content ratio of the (F1) compound and the (FB1) compound described above.
  • the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin and (B) a compound
  • the total content of the (F1) compound, (FB1) compound and (FC1) compound is
  • the preferred contents of the (F1) compound and (FB1) compound are as follows.
  • the photosensitive resin composition of the first aspect of the present invention may further contain an ester compound of an acidic group containing a phosphorus atom (hereinafter referred to as "(FT) compound") having a (FT) reactive group. preferable.
  • (FT) compound By containing the (FT) compound, the effect of improving the halftone characteristics and suppressing pattern peeling after development becomes remarkable.
  • the (FT) compound preferably contains two or more kinds of compounds, and particularly preferably contains the (F1) compound and/or the (FB1) compound, and further contains the (FT) compound.
  • the (FT) compound preferably has a radically polymerizable group, and at least one group selected from the group consisting of a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms.
  • (FT) The number of one or more groups selected from the group consisting of a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms, which the compound has (X), and (FT ) one or more selected from the group consisting of a monovalent to divalent aliphatic group, a monovalent to divalent alicyclic group, a monovalent to divalent aromatic group, and an oxyalkylene group to which a substituent is attached, which the compound has
  • the number of groups is (Y)
  • (X) and (Y) preferably satisfy all of the following general formulas (FT- ⁇ ) to (FT- ⁇ ).
  • X+Y 3 (FT- ⁇ ). 1 ⁇ X ⁇ 3 (FT- ⁇ ). 0 ⁇ Y ⁇ 2 (FT ⁇ ).
  • X is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.
  • Y is preferably an integer of 0 to 2, more preferably 0 or 1.
  • the substituent preferably has a radically polymerizable group, photoreaction It is more preferable to have one or more groups selected from the group consisting of a sexual group, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms. Further, the substituent is one selected from the group consisting of a monovalent to divalent aliphatic group, a monovalent to divalent alicyclic group, a monovalent to divalent aromatic group and an oxyalkylene group to which a substituent is bonded. It is also preferred to have more than one type of group.
  • the photosensitive resin composition of the first aspect of the present invention further includes the following (FT1) compound, the compound having the (III-f1) structure described above as the (F1) compound, and the (FB1) compound described above as the (III- It is preferable to contain one or more compounds selected from the group consisting of compounds having the fb1) structure.
  • (FT1) compound an acidic group containing a phosphorus atom, having at least three groups selected from the group consisting of a photoreactive group, an alkenyl group having 2 to 5 carbon atoms and an alkynyl group having 2 to 5 carbon atoms. ester compound.
  • the photoreactive group is preferably a radically polymerizable group, more preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, and still more preferably a (meth)acryloyl group.
  • the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms is preferably a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • a radical polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • the (FT) compound is a phosphate triester compound having one or more groups selected from the group consisting of the photoreactive group, the alkenyl group having 2 to 5 carbon atoms and the alkynyl group having 2 to 5 carbon atoms, It preferably contains one or more compounds selected from the group consisting of phosphite triester compounds, phosphonate diester compounds, hypophosphite diester compounds and phosphinic acid monoester compounds.
  • the total content of the (F1) compound, the (FB1) compound and the (FT) compound is the preferred content of the (F1) compound and the (FB1) compound described above.
  • the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin and (B) a compound
  • the total content of the (F1) compound, (FB1) compound and (FT) compound is
  • the preferred contents of the (F1) compound and (FB1) compound are as follows.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (G) a cross-linking agent.
  • G) A cross-linking agent refers to a compound having a cross-linkable group capable of bonding with a resin or a compound having a cationic polymerizable group.
  • the cross-linking reaction with a resin by a cross-linkable group and the cationic polymerization by a cationic polymerizable group can be promoted by acid and/or heat, and are suitable for improving the heat resistance of the cured product and improving the chemical resistance of the cured product. is.
  • the cross-linking agent is preferably a compound having at least two groups selected from the group consisting of alkoxyalkyl groups, hydroxyalkyl groups, epoxy groups, oxetanyl groups, vinyl groups and allyl groups (however, the above-mentioned except for the (B) compound).
  • alkoxyalkyl group an alkoxymethyl group is preferable, and a methoxymethyl group is more preferable.
  • a methylol group is preferred as the hydroxyalkyl group.
  • the photosensitive resin composition of the first aspect of the present invention preferably contains (G1) a hydrophobic skeleton-containing epoxy cross-linking agent (hereinafter referred to as "(G1) compound").
  • (G1) compound means a compound having the following (I-g1) structure and (II-g1) structure and having at least two (II-g1) structures.
  • (I-g1) structure consisting of a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, a structure in which an aromatic ring skeleton and an alicyclic skeleton are directly linked, and a structure in which at least two aromatic ring skeletons are directly linked
  • (II-g1) structure an organic group having an epoxy group.
  • the (G1) compound has the above-described (I-g1) structure, which is a fluorene structure, an indane structure, an indolinone structure, an isoindolinone structure, and a xanthene structure, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development. structure, tricyclo[5.2.1.0 2,6 ]decane structure and binaphthyl structure.
  • the epoxy group equivalent of the (G1) compound is preferably 150 g/mol or more, more preferably 170 g/mol or more, and even more preferably 190 g/mol or more, from the viewpoint of suppressing residue after development.
  • the epoxy group equivalent is preferably 800 g/mol or less, more preferably 600 g/mol or less, and even more preferably 500 g/mol or less, from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development.
  • the content ratio of the (G1) compound in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is 0.3 mass from the viewpoint of improving halftone characteristics and suppressing variations in opening pattern dimensions after development. % or more is preferred, 1.0 mass % or more is more preferred, and 2.0 mass % or more is even more preferred.
  • the content of the (G1) compound is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of suppressing residue after development.
  • the content of the (G1) compound is 100 parts by mass of the total of the (A) alkali-soluble resin and (B) compound.
  • WHEREIN 1 mass part or more is preferable, 3 mass parts or more are more preferable, 5 mass parts or more are still more preferable.
  • the content of the (G1) compound is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the photosensitive resin composition of the first aspect of the present invention further contains the following (G2) compound and/or (G3) compound, wherein the crosslinkable group is an alkoxyalkyl group, a hydroxyalkyl group, an epoxy group, It preferably contains one or more groups selected from the group consisting of an oxetanyl group, a vinyl group and an allyl group.
  • the alkoxyalkyl group an alkoxymethyl group is preferable, and a methoxymethyl group is more preferable.
  • a preferred hydroxyalkyl group is a methylol group.
  • (G2) Compound a compound having at least two phenolic hydroxyl groups and at least two crosslinkable groups.
  • the number of crosslinkable groups possessed by the compound (G2) or the compound (G3) is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the number of crosslinkable groups is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
  • the (G2) compound preferably has at least two of the following (I-g2) structures.
  • the (G2) compound more preferably has at least two (I-g2x) structures below.
  • (I-g2) Structure A structure in which a phenolic hydroxyl group and a crosslinkable group are bonded to one aromatic structure.
  • (I-g2x) structure A structure in which a phenolic hydroxyl group and at least two crosslinkable groups are bonded to one aromatic structure.
  • the total number of (I-g2) structures and (I-g2x) structures possessed by the (G2) compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the total number of (I-g2) structures and (I-g2x) structures is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
  • the (G2) compound preferably has a hydrophobic skeleton such as an aromatic structure.
  • the hydrophobic skeleton consists of a fluorene structure, an indane structure, a condensed polycyclic alicyclic structure, a structure in which at least two aromatic ring skeletons are linked by an aliphatic group, and a structure in which at least two aromatic ring skeletons are directly linked. Structures containing one or more structures selected from the group are preferred.
  • the number of phenolic hydroxyl groups possessed by the (G2) compound is preferably 2 or more, more preferably 3 or more, from the viewpoints of suppressing residue after development, improving halftone characteristics, and driving a light-emitting element in an organic EL display at a low voltage. , more preferably four or more.
  • the number of phenolic hydroxyl groups is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
  • the (G3) compound preferably has the following (I-g3) structure. Further, the (G3) compound more preferably has the following (I-g3x) structure.
  • (I-g3) Structure A structure in which a crosslinkable group is bonded to a cyclic skeleton having at least two nitrogen atoms.
  • (I-g3x) structure A structure in which at least two crosslinkable groups are bonded to a cyclic skeleton having at least two nitrogen atoms.
  • the number of crosslinkable groups in the (I-g3x) structure of the (G3) compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the number of crosslinkable groups is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
  • the cyclic skeleton having at least two nitrogen atoms possessed by the (G3) compound includes an isocyanuric acid structure and a triazine structure.
  • One or more selected structures are more preferred, and an isocyanuric acid structure and/or a triazine structure are even more preferred.
  • (G2) compound preferably contains one or more compounds selected from the group consisting of compounds represented by any one of general formulas (181), (182), (183) and (184).
  • Y 311 represents a direct bond, a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom.
  • R 411 to R 423 each independently represent a halogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 424 to R 430 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • R 431 to R 440 each independently represents an alkoxyalkyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms having an epoxy group, or a carbon having an epoxy group. It represents an alkoxyalkyl group having 2 to 10 carbon atoms, an oxetanyl group-containing alkyl group having 1 to 8 carbon atoms, an oxetanyl group-containing alkoxyalkyl group having 2 to 12 carbon atoms, a vinyl group or an allyl group.
  • a and b each independently represent an integer of 0 to 4; c and d each independently represent an integer of 0 to 2; e, f, g, h, i, j, k and l each independently represent an integer of 0 to 3; m represents an integer of 0 to 4; n is 0 when Y 311 is a direct bond, an oxygen atom, or a sulfur atom. When Y 311 is nitrogen, n is 1. n is 2 when Y 311 is a carbon atom. o, p, ⁇ and ⁇ each independently represent an integer of 1 to 3, 2 ⁇ o+ ⁇ 4, and 2 ⁇ p+ ⁇ 4.
  • q, r, ⁇ and ⁇ each independently represent an integer of 1 to 4, 2 ⁇ q+ ⁇ 5 and 2 ⁇ r+ ⁇ 5.
  • s, t, u, ⁇ , ⁇ , and ⁇ each independently represent an integer of 1 to 4, 2 ⁇ s+ ⁇ 5, 2 ⁇ t+ ⁇ 5, and 2 ⁇ u+ ⁇ 5.
  • v, w, x, ⁇ , ⁇ and ⁇ each independently represent an integer of 1 to 4, 2 ⁇ v+ ⁇ 5, 2 ⁇ w+ ⁇ 5, and 2 ⁇ x+ ⁇ 5.
  • Y 311 is preferably a direct bond or an oxygen atom.
  • the alkyl group, cycloalkyl group, aryl group, alkoxyalkyl group and hydroxyalkyl group described above may have heteroatoms and may be unsubstituted or substituted.
  • (G3) compound preferably contains one or more compounds selected from the group consisting of compounds represented by any of general formulas (171), (172) and (173).
  • Y 264 to Y 266 each independently represent a direct bond, an oxygen atom or a nitrogen atom.
  • R 261 to R 270 are each independently a group represented by any one of general formulas (174) to (178), a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 4 to 10 carbon atoms group, an aryl group having 6 to 15 carbon atoms or a hydroxy group.
  • X 271 represents an alkylene group having 1 to 6 carbon atoms.
  • X 272 to X 274 and X 276 each independently represent a direct bond or an alkylene group having 1 to 10 carbon atoms.
  • X 275 represents a direct bond, an alkylene group having 1 to 6 carbon atoms, or an arylene group having 6 to 15 carbon atoms.
  • Y 272 represents a direct bond or an alkylene group having 1 to 10 carbon atoms.
  • Z 272 and Z 273 each represent a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms.
  • R 271 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R 272 and R 273 each independently represent a group represented by general formula (179) or general formula (180).
  • R 274 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 275 and R 276 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxy group.
  • a, b and c are 1 when Y 264 to Y 266 are each independently a direct bond or an oxygen atom;
  • a, b and c are 2 when Y 264 to Y 266 are each independently a nitrogen atom;
  • d represents 0 or 1;
  • e represents 0 or 1;
  • f represents an integer of 1 to 4;
  • Y 272 represents an alkylene group having 1 to 10 carbon atoms.
  • the alkyl group, cycloalkyl group, aryl group, alkylene group, cycloalkylene group and arylene group described above may have a heteroatom and may be unsubstituted or substituted.
  • the total content ratio of the (G2) compound and (G3) compound in the total solid content of the photosensitive resin composition of the present invention, excluding the solvent, is from the viewpoint of suppressing residue after development and improving halftone characteristics and organic EL From the viewpoint of low-voltage driving of light-emitting elements in displays, the content is preferably 0.3% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more.
  • the total content of the (G2) compound and the (G3) compound is preferably 25% by mass or less, more preferably 20% by mass or less, from the viewpoint of suppressing residue after development and improving sensitivity during exposure. % or less by mass is more preferable.
  • the total content of the (G2) compound and the (G3) compound is the total content of the (A) alkali-soluble resin and (B) compound is 100 parts by mass, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more.
  • the total content of the (G2) compound and the (G3) compound is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the photosensitive resin composition of the first aspect of the present invention further contains (H) a dissolution accelerator (hereinafter referred to as "(H) compound").
  • H a dissolution accelerator
  • a compound means a compound having an acidic group and/or a hydrophilic group that is soluble in an alkaline developer. Examples of the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
  • Hydrophilic groups include hydroxy groups and oxyalkylene groups.
  • the compound (H) preferably contains one or more compounds selected from the group consisting of polyfunctional carboxylic acid compounds, polyfunctional phenol compounds, hydroxyimide compounds, and compounds having a hydroxy group and an oxyalkylene group.
  • (H) compounds include monovalent to divalent aliphatic groups having 1 to 10 carbon atoms; aryl groups having 6 to 15 carbon atoms; arylalkyl groups having 7 to 25 carbon atoms; and alkylaryl groups having 7 to 25 carbon atoms. and an aryl group having 6 to 15 carbon atoms to which at least two arylalkyl groups having 7 to 25 carbon atoms are bonded; and an oxyalkylene group to which an oxyalkylene group is bonded.
  • the arylalkyl group having 7 to 25 carbon atoms an alkenyl group having 2 to 5 carbon atoms having an aryl group having 6 to 15 carbon atoms is preferable.
  • the oxyalkylene group possessed by the compound (H) is preferably an oxyalkylene group having 1 to 6 carbon atoms, more preferably an oxyethylene group or an oxypropylene group, and still more preferably an oxyethylene group.
  • the number of repeating oxyalkylene groups in the compound (H) is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more.
  • the number of oxyalkylene groups is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less.
  • the content ratio of the (H) compound in the total solid content of the photosensitive resin composition of the present invention excluding the solvent is preferably 0.2% by mass or more, and preferably 0.3% by mass, from the viewpoint of suppressing residue after development. % or more is more preferable, and 1.0% by mass or more is even more preferable.
  • the content ratio of the (H) compound is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of suppressing pattern peeling after development.
  • the content of the (H) compound is 100 parts by mass of the total of the (A) alkali-soluble resin and the (B) compound.
  • WHEREIN 0.5 mass % or more is preferable, 1 mass part or more is more preferable, 3 mass parts or more is further more preferable.
  • the content of the (H) compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (I) inorganic particles.
  • Inorganic particles refer to particles containing an element selected from the group consisting of metal elements, metalloid elements, and semiconductor elements.
  • Inorganic particles include, for example, particles containing 90% by mass or more of a compound selected from the group consisting of metal compounds, metalloid compounds, and semiconductor compounds in the mass excluding water.
  • Metal compounds, metalloid compounds, or semiconductor compounds include, for example, halides, oxides, nitrides, hydroxides, carbonates, sulfates, nitrates, or metasilicates of the above elements.
  • the photosensitive composition of the present invention further contains (I) inorganic particles, and (I) the inorganic particles are Si, Al, Ti, V, Zn, Zr, Nb, Sn, Li, Cr, Mn, Fe , Co, Ni, Cu, Sr, Ag, Ba, La, Ce, Ta, W, or Re as an element of the main component, silicon, aluminum, titanium, vanadium, chromium, iron, cobalt, copper, It more preferably contains zinc, zirconium, niobium, tin, or cerium as the main component element, and further preferably contains silicon as the main component element.
  • the element that is the main component in the inorganic particles refers to the element that is contained most abundantly among the constituent elements selected from the group consisting of metal elements, metalloid elements, and semiconductor elements that constitute the (I) inorganic particles.
  • the main component is determined based on the mass of any one of the above elements alone. By including these elements as the elements of the main component, outgassing from the pixel division layer or the like is suppressed, so that the effect of improving the reliability of the light emitting element becomes remarkable.
  • the inorganic particles include silica particles, alumina particles, titania particles, vanadium oxide particles, chromium oxide particles, iron oxide particles, cobalt oxide particles, zinc oxide particles, zirconium oxide particles, niobium oxide particles, tin oxide particles, or Cerium oxide particles are preferred, and silica particles are more preferred.
  • the inorganic particles have a group consisting of a radically polymerizable group, a thermally reactive group, a silanol group, an alkoxysilyl group, an alkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, a phenylsilyl group, and a diphenylsilyl group on the surface.
  • the crosslinked structure of the radically polymerizable group or the thermally reactive group allows the exposed area in the case of a positive photosensitive composition to be formed. It is presumed that the above-mentioned effect becomes remarkable by suppressing excessive alkali dissolution in the case of a negative photosensitive composition or by suppressing side etching in the deep part of the film during alkali development in the exposed area in the case of a negative photosensitive composition.
  • the cured product of the photosensitive composition since a crosslinked structure obtained by radically polymerizing a radically polymerizable group such as a (meth)acryloyl group is introduced, the cured product of the photosensitive composition has a remarkable effect of improving the heat resistance due to the improvement of the crosslinking density. As a result, outgassing from the pixel division layer or the like is suppressed, so it is presumed that the effect of improving the reliability of the light-emitting element becomes remarkable.
  • the radically polymerizable group an ethylenically unsaturated double bond group is preferred.
  • the radically polymerizable group one or more groups selected from the group consisting of a photoreactive group, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms are more preferable.
  • the photoreactive group is preferably a styryl group, a cinnamoyl group, a maleimide group, or a (meth)acryloyl group, more preferably a (meth)acryloyl group.
  • the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms includes vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl-2-butenyl group, 3 -methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is preferred, and vinyl group or allyl group is more preferred.
  • the heat-reactive group an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, or a blocked isocyanate group is preferred.
  • the content ratio of the inorganic particles (I) in the total solid content of the photosensitive composition of the present invention, excluding the solvent, is from the viewpoint of improving the halftone characteristics and suppressing the variation in opening pattern dimensions after development, and from the viewpoint of the light emitting device. From the viewpoint of improving reliability, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. On the other hand, the content ratio of (I) the inorganic particles is preferably 50% by mass or less, more preferably 40% by mass or less, from the viewpoint of improving the reliability of the light-emitting device.
  • the photosensitive resin composition of the first aspect of the present invention preferably further contains (I) inorganic particles, and (I) inorganic particles preferably contain (I1) silica particles.
  • the cured product of the photosensitive composition is remarkably improved in heat resistance due to the introduction of a robust structure of (I1) silica particles, and outgassing from the pixel dividing layer and the like. is suppressed.
  • deterioration of the light-emitting element is suppressed, so that the effect of improving the reliability of the light-emitting element becomes remarkable.
  • reflection and scattering of external light incident on the surface of the cured product are reduced, the effect of suppressing external light reflection becomes remarkable.
  • Silica particles refer to inorganic particles containing silicon as the main component element.
  • Silica particles include, for example, particles having a pure silicon dioxide content of 90% by mass or more in the mass excluding water, particles made of silicon dioxide (anhydrous silicic acid), silicon dioxide hydrate (hydrous silicic acid or white carbon), particles of quartz glass, or particles of orthosilicic acid, metasilicic acid, and metadisilicic acid.
  • As the silica particles it is preferable to add a silica particle dispersion using an organic solvent and/or water as a dispersion medium to the composition.
  • the structure of these particles is not particularly limited, and they may have internal voids.
  • the silicon dioxide contained in the surface treatment agent or coating layer of the organic pigment and inorganic pigment is not included in the silica particles, regardless of the primary particle diameter or aspect ratio.
  • Aggregation form of silica particles is not particularly limited. Aggregated forms controlled by the manufacturing method of silica particles include, for example, beaded silica particles, chain-like silica particles, associative silica particles, and marimo-like silica particles. These aggregated silica particles are regarded as secondary particles or tertiary particles composed of a plurality of primary particles.
  • the silica particles preferably have a primary particle size and an average primary particle size of 5 to 50 nm.
  • the primary particle size and average primary particle size of silica particles are preferably 5 nm or more from the viewpoints of improving halftone characteristics, suppressing variations in opening pattern dimensions after development, and improving the reliability of light-emitting elements. 7 nm or more is more preferable, and 10 nm or more is even more preferable.
  • the primary particle size and average primary particle size of the silica particles are preferably 50 nm or less, more preferably 40 nm or less, and even more preferably 30 nm or less, from the viewpoint of suppressing external light reflection and improving the reliability of the light emitting device.
  • the primary particle diameter of silica particles refers to the major axis diameter of primary particles of silica particles.
  • the preferred range of the average primary particle size of (I1) the silica particles in the silica particle dispersion is as the primary particle size of the (I1) silica particles and the preferred range of the average primary particle size.
  • the aspect ratio and average aspect ratio of the silica particles are preferably 1.00 or more, more preferably 1.05 or more, and even more preferably 1.10 or more.
  • the aspect ratio and average aspect ratio of (I1) silica particles are preferably 1.50 or less, more preferably 1.40 or less, still more preferably 1.30 or less, and particularly preferably 1.20 or less.
  • the aspect ratio of silica particles refers to a value obtained by dividing the major axis diameter by the minor axis diameter of the primary particle diameter of silica particles and rounding off to the third decimal place.
  • Silica particles with an aspect ratio of 1.00 to less than 1.05 are considered spherical silica particles.
  • the primary particle size and aspect ratio of the silica particles are measured by thinly cutting the cured product as a measurement sample, and using a TEM for a cross section that has been polished by ion milling to increase smoothness. An image of a point located in the range of 0.2 to 0.8 ⁇ m in the depth direction was observed at a magnification of 50,000 times using image analysis type particle size distribution measurement software (Mac-View; manufactured by MOUNTECH). can be measured.
  • the average primary particle diameter of silica particles can be calculated as an average value obtained by measuring 30 primary particles of (I1) silica particles by imaging and analyzing a cross section of a measurement sample.
  • the average primary particle size of (I1) silica particles in the silica particle dispersion can be obtained by measuring the particle size distribution by a dynamic light scattering method.
  • the photosensitive composition of the present invention contains (I1) silica particles having a primary particle size or an average primary particle size of 5 to 50 nm, and (I1) silica particles having a primary particle size or an average primary particle size of less than 5 nm, And/or it may contain (I1) silica particles having a primary particle size or an average primary particle size of more than 50 nm.
  • the photosensitive composition of the present invention also contains (I1) silica particles having an aspect ratio or average aspect ratio of 1.00 to 1.50, and (I1) having an aspect ratio or average aspect ratio exceeding 1.50. It may contain silica particles.
  • the silica particles preferably contain sodium element from the viewpoint of improving the reliability of the light emitting device.
  • Existence forms of elemental sodium include, for example, ions (Na + ) and salts with silanol groups (Si—ONa).
  • the content of sodium element in the silica particles is preferably 1 ppm or more, more preferably 5 ppm or more, still more preferably 10 ppm or more, and particularly preferably 50 ppm or more.
  • it is preferably 100 ppm or more, more preferably 300 ppm or more, and even more preferably 500 ppm or more.
  • (I1) the content of sodium element in the silica particles is preferably 10,000 ppm or less, more preferably 7,000 ppm or less, even more preferably 5,000 ppm or less, and even more preferably 3,000 ppm or less. 000 ppm or less is particularly preferred.
  • Silica particles containing elemental sodium are obtained by reacting sodium silicate, which is a strong alkali as a silicon source, with a mineral acid, which is a strong acid, under alkaline conditions.
  • the preferred content ratio of (I1) silica particles is the same as the preferred content ratio of (I) inorganic particles described above.
  • the photosensitive resin composition of the first aspect of the present invention contains one or more components selected from the group consisting of a component containing a halogen element, a component containing a sulfur element, and a component containing a phosphorus element, and the following ( It is preferable to satisfy one or more of the conditions 1) to (3).
  • the content of halogen elements in the photosensitive resin composition is 0.01 to 100 ppm.
  • the sulfur element content in the photosensitive resin composition is 0.01 to 100 ppm.
  • the content of phosphorus element in the photosensitive resin composition is 0.01 to 100 ppm.
  • the photosensitive resin composition of the first aspect of the present invention more preferably satisfies the condition (1) and/or the condition (2), and more preferably satisfies the condition (2).
  • the photosensitive resin composition of the first aspect of the present invention preferably satisfies two or more conditions selected from the group consisting of conditions (1) to (3). It is more preferable to satisfy the condition of 2), and it is further preferable to satisfy all of the conditions of (1) to (3).
  • Halogen elements include chlorine, bromine, iodine, and fluorine.
  • the halogen element preferably contains one or more elements selected from the group consisting of chlorine element, bromine element and iodine element, more preferably contains chlorine element and/or bromine element, and further contains chlorine element. preferable.
  • the content of the halogen element in the photosensitive resin composition is preferably 0.01 ppm or more, more preferably 0.03 ppm or more, and 0.05 ppm or more. is more preferred, 0.07 ppm or more is even more preferred, and 0.1 ppm or more is particularly preferred.
  • the halogen element content is preferably 700 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less.
  • it is preferably 100 ppm or less, more preferably 70 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and particularly preferably 10 ppm or less. Furthermore, from the viewpoint of low-voltage driving of the light-emitting element, it is preferably 7 ppm or less, more preferably 5 ppm or less, even more preferably 3 ppm or less, and particularly preferably 1 ppm or less.
  • the content of sulfur element in the photosensitive resin composition is preferably 0.01 ppm or more, more preferably 0.03 ppm or more, and 0.05 ppm or more. is more preferred, 0.07 ppm or more is even more preferred, and 0.1 ppm or more is particularly preferred.
  • the sulfur element content is preferably 700 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less.
  • it is preferably 100 ppm or less, more preferably 70 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and particularly preferably 10 ppm or less.
  • it is preferably 7 ppm or less, more preferably 5 ppm or less, even more preferably 3 ppm or less, and particularly preferably 1 ppm or less.
  • the content of phosphorus element in the photosensitive resin composition is preferably 0.01 ppm or more, more preferably 0.03 ppm or more, and 0.05 ppm or more. is more preferred, 0.07 ppm or more is even more preferred, and 0.1 ppm or more is particularly preferred.
  • the phosphorus element content is preferably 700 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less.
  • it is preferably 100 ppm or less, more preferably 70 ppm or less, even more preferably 50 ppm or less, even more preferably 30 ppm or less, and particularly preferably 10 ppm or less. Furthermore, from the viewpoint of low-voltage driving of the light-emitting element, it is preferably 7 ppm or less, more preferably 5 ppm or less, even more preferably 3 ppm or less, and particularly preferably 1 ppm or less.
  • the photosensitive resin composition contains one or more components selected from the group consisting of a component containing a halogen element, a component containing a sulfur element, and a component containing a phosphorus element, and the halogen element accounts for the photosensitive resin composition.
  • sulfur element, and phosphorus element the content of one or more elements selected from the group consisting of elements is set to a specific range, the effect of improving the reliability of the light emitting element in the organic EL display and driving the light emitting element at a low voltage. becomes conspicuous.
  • the surface of the first electrode is modified by these elements by adding a trace amount of a component containing these elements to the photosensitive resin composition.
  • these elements contained in the pixel division layer transition after forming the pixel division layer, so that the surface of the first electrode is modified by these elements. Therefore, it is presumed that the adjustment of the work function difference between the first electrodes will significantly reduce the voltage driving of the light emitting elements in the organic EL display.
  • the polarization structure and charge balance in the pixel division layer in an organic EL display can be controlled.
  • the component containing a halogen element, the component containing a sulfur element, and the component containing a phosphorus element contained in the photosensitive resin composition are preferably simple substances, ions, compounds, or compound ions. That is, the photosensitive resin composition contains an elemental halogen element, an ion of a halogen element, a compound containing a halogen element, a compound ion containing a halogen element, an elemental sulfur element, an ion of a sulfur element, a compound containing a sulfur element, and an elemental sulfur.
  • a compound ion containing an elemental element of phosphorus, an ion of elemental phosphorus, a compound containing elemental phosphorus, or a compound ion containing elemental phosphorus.
  • the content of halogen elements in the photosensitive resin composition is the total amount of halogen elements that are simple substances, ions, compounds, or compound ions.
  • the content of elemental sulfur in the photosensitive resin composition is the total amount of elemental sulfur, which is an element, an ion, a compound, or a compound ion.
  • the content of elemental phosphorus in the photosensitive resin composition is the total amount of elemental elemental phosphorus, ion, compound, or compound ion.
  • the photosensitive resin composition contains a halogen element ion, a halogen element-containing compound ion, a sulfur element ion, a sulfur element-containing compound ion, a phosphorus element ion, or a phosphorus element-containing compound ion, a counter cation
  • it may contain a counter anion.
  • counter cations include metal element ions, ammonium ions, primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, and quaternary ammonium ions, with quaternary ammonium ions being preferred.
  • metal element ions include alkali metal ions, alkaline earth metal ions, main element metal ions, and transition metal ions.
  • the metal element is preferably Li, Be, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or Zn.
  • Primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, and quaternary ammonium ions each have 1 to 4 aliphatic, alicyclic, or aromatic groups.
  • Counter anions include hydroxide ions, carboxylate ions, hyponitrite ions, nitrite ions, nitrate ions, or phenoxy ions.
  • the photosensitive resin composition of the first aspect of the present invention further contains an ink repellent agent.
  • An ink-repellent agent refers to a compound having a water-repellent structure and/or an oil-repellent structure. Since the liquid repellency of the film can be improved by containing the ink repellent agent, the contact angle of the film to pure water and/or the contact angle of the film to organic solvent can be increased.
  • the ink repellent agent is selected from the group consisting of at least two photoreactive groups, at least two alkenyl groups having 2 to 5 carbon atoms, at least two alkynyl groups having 2 to 5 carbon atoms and at least two thermally reactive groups.
  • the photoreactive group is preferably a radically polymerizable group, more preferably a styryl group, a cinnamoyl group, a maleimide group or a (meth)acryloyl group, and still more preferably a (meth)acryloyl group.
  • the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms is preferably a radically polymerizable group such as vinyl group, allyl group, 2-methyl-2-propenyl group, crotonyl group, 2-methyl -2-butenyl group, 3-methyl-2-butenyl group, 2,3-dimethyl-2-butenyl group, ethynyl group or 2-propargyl group is more preferable, and vinyl group or allyl group is further preferable.
  • Preferred thermally reactive groups are alkoxymethyl groups, methylol groups, epoxy groups, oxetanyl groups and blocked isocyanate groups.
  • the ink repellent agent also preferably has a polymer chain, and the side chain of the repeating unit of the polymer chain has a water-repellent structure, an oil-repellent structure, at least two photoreactive groups, and at least two alkenyl groups having 2 to 5 carbon atoms. It is also preferred to have one or more groups selected from the group consisting of groups, at least two alkynyl groups having 2 to 5 carbon atoms, and at least two thermally reactive groups.
  • examples of ink repellent agents having polymer chains include acrylic resin ink repellent agents, polyoxyalkylene ether ink repellent agents, polyester ink repellent agents, polyurethane ink repellent agents, polyol ink repellent agents, and polyethyleneimine ink repellent agents. Ink agents or polyallylamine-based ink repellent agents may be mentioned.
  • the photosensitive resin composition of the first aspect of the present invention further contains one or more additives selected from the group consisting of sensitizers, chain transfer agents, polymerization inhibitors, silane coupling agents and surfactants. Containing is also preferable.
  • sensitizers compounds having a fluorene skeleton, benzofluorene skeleton, fluorenone skeleton or thioxanthone skeleton are preferred.
  • chain transfer agent the effect of improving the sensitivity at the time of exposure becomes remarkable.
  • a compound having at least two mercapto groups is preferred as the chain transfer agent.
  • a polymerization inhibitor By containing a polymerization inhibitor, the effect of improving the resolution after development becomes remarkable.
  • a polymerization inhibitor a hindered phenol compound, a hindered amine compound or a benzimidazole compound is preferred.
  • the silane coupling agent By containing the silane coupling agent, the effect of improving the adhesion between the cured product and the underlying substrate becomes remarkable.
  • Preferred silane coupling agents are trifunctional organosilanes, tetrafunctional organosilanes, and silicate compounds.
  • a surfactant By containing a surfactant, the effect of improving the film thickness uniformity of the coating film becomes remarkable.
  • a fluororesin-based surfactant a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant is preferable.
  • the content ratio of the surfactant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, of the entire photosensitive resin composition.
  • the surfactant content is preferably 1% by mass or less, more preferably 0.5% by mass or less.
  • the photosensitive resin composition of the first aspect of the present invention further contains a solvent.
  • a solvent By containing a solvent, a film obtained from the composition can be formed on a substrate with a desired uniform thickness.
  • the solvent is preferably a compound having an alcoholic hydroxyl group, a compound having a carbonyl group, a compound having an ester bond, or a compound having at least three ether bonds.
  • a compound having a boiling point of 110° C. or higher under atmospheric pressure is preferable from the viewpoint of improving the uniformity of the film thickness of the coating film.
  • the content ratio of the solvent in the photosensitive resin composition of the present invention can be appropriately adjusted according to the coating method and the like. For example, when forming a coating film by spin coating, it is generally 50 to 95 mass % of the total photosensitive resin composition.
  • the solvent contains a solvent having a carbonyl group or a solvent having an ester bond
  • (D1) Due to the improved dispersion stability of the pigment, the effect of suppressing residue after development becomes remarkable.
  • the carbonyl group is preferably an alkylcarbonyl group, a dialkylcarbonyl group, a formyl group, a carboxyl group, an amide group, an imide group, a urea bond or a urethane bond.
  • the ester bond is preferably a carboxylate bond, a carbonate bond or a formate bond, and more preferably a carboxylate bond.
  • an acetate bond, a propionate bond or a butyrate bond is more preferable, and an acetate bond is even more preferable.
  • Preferred solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, or butylene glycol monoalkyl ether acetate, and particularly preferred solvents include propylene glycol monoalkyl ether acetate.
  • the total content ratio of the solvent having a carbonyl group or the solvent having an ester bond in the solvent is from the viewpoint of suppressing residue after development and improving resolution after development. , preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass.
  • the content ratio of propylene glycol monoalkyl ether acetate in the solvent is preferably 30 to 100% by mass, 50 to 100% by mass is more preferable, and 70 to 100% by mass is even more preferable.
  • the content ratio of propylene glycol monoalkyl ether acetate in the solvent is preferably 30% by mass or more, and 40% by mass or more. % by mass or more is more preferable, and 50% by mass or more is even more preferable.
  • the content of propylene glycol monoalkyl ether acetate is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the total content ratio of the diethylene glycol dialkyl ether and/or the solvent having an alcoholic hydroxyl group in the solvent is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. On the other hand, the total content of these solvents is preferably 50% by mass or less, more preferably 40% by mass or less.
  • a solvent having an alcoholic hydroxyl group and an ether bond and/or an ester bond is preferred.
  • the ester bond is preferably a carboxylate bond, a carbonate bond, or a formate bond, and more preferably a carboxylate bond.
  • solvent having an alcoholic hydroxyl group and an ether bond and/or a carboxylate ester bond one or more solvents selected from the group consisting of propylene glycol monoalkyl ether, alkyl lactate, alkyl hydroxyacetate and hydroxyalkyl acetate are preferred. .
  • ⁇ Method for producing the photosensitive resin composition of the present invention A representative method for producing the photosensitive resin composition of the present invention will be described.
  • (D) When the colorant contains (Da) a black agent and (Da) the black agent contains (D1a) a black pigment,
  • (A) the solution of the alkali-soluble resin is optionally added with (E) a dispersant.
  • a dispersing machine is used to disperse (D1a) a black pigment in the resulting mixed solution to prepare a pigment dispersion.
  • an alkali-soluble resin, (C) a photosensitive agent, other additives and an optional solvent are added to this pigment dispersion, and the mixture is stirred for 20 minutes to 3 hours to form a uniform solution.
  • a bead mill is preferable from the viewpoint of suppressing residue after development.
  • Beads used in the bead mill include, for example, titania beads, zirconia beads, and zircon beads.
  • the bead diameter is preferably 0.01 to 6 mm, more preferably 0.015 to 5 mm, even more preferably 0.03 to 3 mm.
  • the cured product of the present invention is obtained by curing the above photosensitive resin composition.
  • the term “curing” refers to, for example, the formation of a crosslinked structure in the components constituting the composition due to a reaction and the loss of fluidity of the composition, or the state thereof.
  • the reaction is not particularly limited and may be by heating, irradiation with energy rays or the like, but is preferably by heating. Curing by heating is referred to as heat curing. Heating conditions will be described later.
  • the optical density at the wavelength of visible light (380 to 780 nm) per 1 ⁇ m of film thickness is 1.0 to 5.0 from the viewpoint of suppressing external light reflection and preventing light leakage from adjacent pixels. preferable.
  • the optical density per 1 ⁇ m film thickness can be adjusted by adjusting the composition and content ratio of the colorant (D) described above.
  • After forming the photosensitive resin composition of the present invention into a desired pattern shape it is cured to obtain a cured product having a desired pattern shape. This is called a hardening pattern.
  • the taper angle of the inclined side in the cross section of the cured pattern is preferably 20 to 45° from the viewpoint of preventing disconnection of the electrode and improving the reliability of the light emitting device.
  • the thickness of the region with the largest thickness (thick film portion) and the region with the smallest thickness (thin film portion) ) is preferably 1.0 to 5 ⁇ m from the viewpoint of improving the reliability of the light emitting device.
  • the contact angle of the thick film portion with respect to pure water in the cured product including the cured pattern having the stepped shape is defined as (CAw FT )°
  • the contact angle difference ( ⁇ CAw FT-HT )° between (CAw FT )° and (CAw HT )° can be obtained by inkjet coating.
  • the angle is preferably 20° or more, more preferably 40° or more.
  • the contact angle difference ( ⁇ CAw FT-HT )° with respect to pure water is preferably 90° or less, more preferably 70° or less.
  • the contact angle of the thick film portion of the cured product containing the pattern having the stepped shape with respect to propylene glycol monomethyl ether acetate is (CAp FT )°. and when the contact angle of the thin film portion with respect to propylene glycol monomethyl ether acetate is (CAp HT )°, the contact angle difference between (CAp FT )° and (CAp HT )° is ( ⁇ CAp FT-HT )°. is preferably 10° or more, more preferably 30° or more, from the viewpoint of preventing color mixing between inks when forming an organic EL layer by inkjet coating.
  • the contact angle difference ( ⁇ CAp FT-HT )° with respect to propylene glycol monomethyl ether acetate is preferably 70° or less, more preferably 50° or less.
  • a display device comprising the cured product of the present invention and a display device according to the second aspect of the present invention will be described below.
  • Examples of the display device of the present invention include organic EL displays, quantum dot displays, micro LED displays, LED displays, liquid crystal displays, plasma displays and field emission displays.
  • An organic EL display, a quantum dot display or a micro LED display is preferred, and an organic EL display is more preferred.
  • the photosensitive resin composition of the present invention is capable of improving sensitivity during exposure, excellent halftone properties, and suppressing variations in opening pattern dimensions after development. In addition, it is possible to improve the reliability of the light-emitting element in the organic EL display and to drive the light-emitting element at a low voltage. Therefore, the cured product obtained by curing the photosensitive resin composition of the present invention is particularly preferably used as a pixel dividing layer, a TFT flattening layer, a TFT protective layer, an interlayer insulating layer or a gate insulating layer of an organic EL display. It is also preferably used as a black matrix or black column spacer. The cured product is particularly suitable for use in organic EL displays.
  • the durability of the organic EL display can be improved due to the high reliability of the light-emitting elements, and high brightness and power saving can be achieved by driving the light-emitting elements at a low voltage.
  • the photosensitive resin composition of the present invention is particularly suitable for use in forming pixel dividing layers in organic EL displays. Furthermore, since it has excellent halftone characteristics, it is particularly suitable for use in collectively forming the stepped shape of the pixel division layer in an organic EL display.
  • the photosensitive resin composition of the first aspect of the present invention is preferably used for collectively forming the stepped shape of the pixel dividing layer in the organic EL display.
  • an organic EL display comprising a cured product obtained by curing the photosensitive resin composition of the present invention has a polarizing film such as a linear polarizing plate, a quarter-wave plate or a circular polarizing plate on the light extraction side of the light emitting element. Even without it, it is possible to suppress reflection of external light. Therefore, it is particularly suitable for a flexible organic EL display having a structure in which a cured product is laminated on a flexible substrate and which does not have a polarizing film.
  • the flexible substrate a polyimide substrate, a polyethylene terephthalate substrate, a cycloolefin polymer substrate, a polycarbonate substrate or a cellulose triacetate substrate is preferable.
  • the flexible organic EL display preferably has a curved display portion, an outwardly bendable display portion, or an inwardly bendable display portion.
  • the display device is preferably a display device having organic layers including a substrate, a first electrode, a second electrode, a pixel dividing layer, and a light-emitting layer. It is preferable that the pixel division layer is the cured product of the present invention. Moreover, the display device comprising the cured product of the present invention is preferably an organic EL display.
  • An organic EL display has at least a substrate, a first electrode, a second electrode, a pixel division layer and a luminescent layer, the pixel division layer and the luminescent layer are formed on the first electrode, and the luminescent layer is formed on the first electrode and the second electrode. It is preferred to have a laminated structure formed between the electrodes.
  • a display device has at least a substrate, a first electrode, a second electrode, and a pixel division layer, and further includes an organic EL layer including a light-emitting layer and/or a light extraction layer including a light-emitting layer.
  • the display device includes one or more resins selected from the group consisting of I-DL) resin, (II-DL) resin and (III-DL) resin.
  • (X-DL) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • (I-DL) resin A resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure.
  • (II-DL) resin A resin having a structural unit represented by general formula (24) described below.
  • (III-DL) resin one or more resins selected from the group consisting of phenolic resins, polyhydroxystyrenes, phenolic group-modified epoxy resins and phenolic group-modified acrylic resins.
  • a glass substrate is preferable from the viewpoint of improving impact resistance.
  • substrates include oxides containing one or more metals selected from indium, tin, zinc, aluminum, and gallium, metals (molybdenum, silver, copper, aluminum, chromium, titanium, etc.) on a glass plate, Alternatively, a substrate on which electrodes and/or wirings made of CNT (Carbon Nano Tube) are formed.
  • a flexible substrate such as a polyimide substrate is preferable from the viewpoint of improving bendability.
  • a display device has a substrate, a first electrode and a second electrode in this order.
  • a transparent electrode for one of the first electrode and the second electrode and a non-transparent electrode for the other By using a transparent electrode for one of the first electrode and the second electrode and a non-transparent electrode for the other, light emitted from the light-emitting layer, which will be described later, can be extracted to one side.
  • the transparent electrode and the non-transparent electrode must have excellent electrical properties, can efficiently inject holes when used as an anode, and can efficiently inject electrons when used as a cathode. Composite characteristics are required.
  • a transparent conductive oxide film layer containing one or more metals selected from the group consisting of indium, tin, zinc, aluminum and gallium is provided as the outermost layer of the first electrode on the light emitting layer side. It preferably has a transparent conductive oxide film layer containing at least indium, more preferably has an amorphous transparent conductive oxide film layer containing at least indium.
  • a layer made of indium tin oxide (ITO) or indium zinc oxide (IZO) is preferable from the viewpoint of low-voltage driving of light emission characteristics by adjusting the work function difference, and ITO.
  • a layer consisting of is more preferable.
  • the first electrode has a single-layer structure or a multi-layer structure.
  • the first electrode is a transparent electrode, preferably a transparent conductive oxide film layer containing indium.
  • the first electrode is a transparent electrode or a non-transparent electrode, and preferably has a transparent conductive oxide film layer containing at least indium as the outermost layer on the light emitting layer side of the first electrode.
  • the second electrode is a single-layer transparent electrode, a multi-layer transparent electrode, a single-layer non-transparent electrode, or a multi-layer non-transparent electrode. If the display device is of bottom emission type, the first electrode is a transparent electrode and the second electrode is a non-transparent electrode.
  • the first electrode is a non-transparent electrode and the second electrode is a transparent electrode.
  • the above-described first electrode has a multilayer structure including at least a transparent conductive oxide film layer and a non-transparent conductive metal layer, and at least an indium and the non-transparent conductive metal layer preferably has an alloy layer containing at least silver ⁇ Pixel dividing layer>
  • a display device according to a second aspect of the present invention has a pixel division layer, and the pixel division layer is formed on the above-described first electrode so as to partially overlap the first electrode. That is, the pixel division layer is formed between the first electrode and the second electrode.
  • the pixel division layer As the pixel division layer, a cured product obtained by curing the photosensitive resin composition described above is preferable.
  • the first electrode and the second electrode in an arbitrary pixel can be insulated, and a short circuit between the first electrode and the second electrode can be prevented. It is possible to suppress the pixel non-lighting caused by this.
  • the first electrode of an arbitrary pixel can be insulated from the first electrode of a pixel adjacent to that pixel, thereby suppressing non-lighting of the pixel due to a short circuit between the first electrodes.
  • the pixel division layer described above has at least the following (X-DL) resin.
  • (X-DL) resin a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms.
  • the (X-DL) resin is preferably a resin having an isocyanuric acid structure and/or a triazine structure in its structural unit, more preferably a resin having an isocyanuric acid structure in its structural unit.
  • the (X-DL) resin is preferably a resin having one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure in the structural unit of the resin.
  • a resin having one or more structures selected from the group consisting of a structure, an amide structure and an oxazole structure is more preferable.
  • the (X-DL) resin is preferably a resin having a structure derived from the (AX) resin described above.
  • the (X-DL) resin preferably has a structural unit represented by the general formula (21) and/or a structural unit represented by the general formula (22) described above, and is represented by the general formula (21) It is more preferable to have a structural unit. Further, the (X-DL) resin is a structural unit represented by any of the above general formulas (1), (2), (3), (4), (5), (8) and (9) It preferably has one or more structures selected from the group consisting of, and more preferably has a structural unit represented by general formula (1) and/or a structural unit represented by general formula (5).
  • the (X-DL) resin is preferably a resin having a structure derived from the specific (AX) resin described above, and is a resin having a structure derived from the particularly suitable (AX) resin described above. is more preferred.
  • the effects of improving the reliability of the light-emitting element in the display device and driving the light-emitting element at a low voltage are remarkable. It is presumed that the presence of these resins in the pixel division layer modifies the surface of the conductive oxide film layer corresponding to the opening of the pixel division layer, thereby improving the light emission characteristics. In addition, when forming the opening of the pixel division layer, it is considered that there is a synergistic effect due to the suppression of residue in the opening by these resins. In addition, it is presumed that low outgassing due to heat resistance of the cyclic structure having at least three nitrogen atoms, which is abundantly contained in these resins, is effective in improving reliability.
  • the above-mentioned pixel division layer is further selected from the group consisting of the following (I-DL) resin, (II-DL) resin and (III-DL) resin. or more resin.
  • (I-DL) resin A resin having a structural unit containing one or more structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure.
  • (II-DL) resin a resin having a structural unit represented by general formula (24).
  • III-DL) resin one or more resins selected from the group consisting of phenolic resins, polyhydroxystyrenes, phenolic group-modified epoxy resins and phenolic group-modified acrylic resins.
  • R 67 to R 69 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • a is 0 or 1; * 1 represents the bonding point in the resin.
  • the (I-DL) resin is preferably a resin having one or more structures selected from the group consisting of an imide structure, an amide structure and an oxazole structure in the structural unit of the resin. Further, the (I-DL) resin is preferably a resin having a structure derived from the above-described (A1) resin and/or a structure derived from the above-described (A2) resin.
  • the (I-DL) resin consists of a structural unit represented by any one of the above general formulas (1), (2), (3), (4), (5), (8) and (9). It preferably has one or more structural units selected from the group, and more preferably has a structural unit represented by general formula (1) and/or a structural unit represented by general formula (5).
  • the (III-DL) resin has a phenolic hydroxyl group as an alkali-soluble group in at least one of the main chain of the resin, the side chain of the resin and the end of the resin, and contains an aromatic ring skeleton in the structural unit of the resin.
  • the (III-DL) resin is one selected from the group consisting of the structure derived from the resin (A3) described above, the structure derived from the resin (A1) described above, and the structure derived from the resin (A2) described above. It is preferable that the resin has more than one type.
  • the (III-DL) resin preferably has one or more structural units selected from the group consisting of structural units represented by any of the general formulas (36), (91) and (92) described above, It is more preferable to have a structural unit represented by general formula (36).
  • part of the phenolic hydroxyl groups contained in the resin preferably react with other resins or compounds to form a crosslinked structure.
  • the (II-DL) resin is preferably a resin having a structure derived from the above-described (A2) resin and/or a structure derived from the above-described (A3) resin.
  • (II-DL) resins are represented by general formulas (1), (2), (3), (4), (5), (8), (9), (41), (61), (62) ), (63), (81) and (82). It is more preferable to have one or more structural units selected from the group consisting of structural units represented by any one of (3), (4), (5), (8) and (9), and the general formula ( It is more preferable to have one or more structural units selected from the group consisting of structural units represented by any one of 1), (2), (3), (4) and (5).
  • the above-mentioned pixel division layer has (I-DL) resin and/or (III-DL) resin, it is preferable that it further has (II-DL) resin.
  • the pixel division layer contains the (I-DL) resin and/or the (III-DL) resin and further contains the (II-DL) resin, thereby improving the reliability of the light emitting element in the display device and reducing the light emitting element.
  • the effect of voltage driving becomes remarkable.
  • the display device of the present invention further includes (IV -DL) phosphate ester structure-containing compound, phosphonic acid structure-containing compound, phosphonate structure-containing compound, phosphite ester structure-containing compound, phosphinic acid structure-containing compound, phosphinate structure-containing compound, hypophosphite structure containing compound, betaine phosphate structure-containing compound, betaine phosphonate structure-containing compound, betaine phosphonate ester structure-containing compound, betaine phosphonate ester structure-containing compound, betaine phosphite ester structure-containing compound, betaine phosphinate structure-containing compound, betaine phosphinate structure-containing compound and It is preferable to contain one or more compounds selected from the group consisting of compounds having a hypophosphite betaine ester structure-containing compound (hereinafter, “(IV-DL) compound having a phosphate structure”).
  • the compound having a phosphate structure contains one or more compounds selected from the group consisting of phosphonic acid structure-containing compounds, phosphonate ester structure-containing compounds, and phosphite structure-containing compounds. It is more preferable to contain a phosphonic acid structure-containing compound and/or a phosphonic acid ester structure-containing compound.
  • the compound having a phosphate structure is preferably a compound having a structure derived from the (F0) compound and/or a compound having a structure derived from the (FB) compound described above. It is more preferably a compound having a structure derived from F1) compound and/or a compound having a structure derived from (FB1) compound.
  • the pixel division layer described above preferably further contains (D) a colorant, and more preferably contains (Da) a black agent.
  • the pixel dividing layer contains (Da) a black agent, the effect of improving the contrast of the display device and improving the reliability of the light-emitting element in the display device by improving the light-shielding property becomes remarkable.
  • the pixel division layer described above preferably further contains (D1a) a black pigment.
  • the (D1a) black pigment more preferably contains the above-described specific (D1a-1) organic black pigment, and more preferably (D1a-1a) a benzofuranone-based black pigment.
  • the pixel division layer described above is a compound having a structure represented by either general formula (161) or general formula (162), geometric isomers thereof, salts thereof, salts of geometric isomers thereof; (164), compounds having a structure represented by any of (165) and (166), salts thereof; compounds having a structure represented by general formula (168), and salts thereof, selected from the group consisting of It is also preferred to contain one or more compounds that are More preferably, the pixel division layer described above contains a compound having a structure represented by either general formula (161) or general formula (162).
  • the pixel division layer described above further includes general formulas (141), (142), ( 143), (144), (145), (146) and (147).
  • the compound having the structure in the pixel dividing layer is preferably a compound having a structure derived from the compound (B1).
  • the above-described pixel division layer further includes a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, having an indene structure, an indane structure, a benzoindene structure, a benzoindane structure, a carbazole structure, a dibenzofuran structure, a dibenzothiophene structure, a benzocarbazole structure, an indole structure, an indoline structure, a benzoindole structure, a benzoindoline structure or a diphenylsulfide structure; It preferably contains a compound having a structure in which an imino group is bonded to the structure of and/or a structure in which a carbonyl group is bonded.
  • the pixel dividing layer described above contains a compound having a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, a benzocarbazole structure, an indole structure, or a benzoindole structure.
  • the compound having the structure in the pixel dividing layer is preferably a compound having a structure derived from the (C1-1) compound.
  • the above-described pixel division layer further contains inorganic particles.
  • the inorganic particles in the pixel division layer the inorganic particles (I) described above are preferable.
  • the silica particles in the pixel division layer are preferably silica particles (I1) described above.
  • the primary particle size and average primary particle size of the silica particles in the pixel division layer are preferably 5 to 50 nm. From the viewpoint of improving the reliability of the light-emitting element, the primary particle size and average primary particle size of the silica particles in the pixel dividing layer are preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more. On the other hand, the primary particle size and average primary particle size of the silica particles in the pixel dividing layer are preferably 50 nm or less, more preferably 40 nm or less, and even more preferably 30 nm or less, from the viewpoint of suppressing external light reflection and improving the reliability of the light emitting device.
  • the primary particle diameter of silica particles refers to the major axis diameter of primary particles of silica particles.
  • the primary particle diameter of the silica particles in the pixel division layer is measured by using a thinly cut pixel division layer as a measurement sample, and polishing the surface of the pixel division layer by ion milling to improve smoothness.
  • Image analysis type particle size distribution measurement software Mac-View; manufactured by MOUNTECH
  • Mac-View is used to capture an image of a point located in the range of 0.2 to 0.8 ⁇ m in the depth direction from the observation at a magnification of 50,000 times.
  • the average primary particle diameter of the silica particles in the pixel division layer can be calculated as an average value obtained by imaging and analyzing the cross section of the measurement sample and measuring 30 primary particles of the silica particles in the pixel division layer.
  • TEM-EDX it is possible to determine the elements constituting the particles, and to identify the silica particles in the pixel division layer.
  • the display device of the second aspect of the present invention further has an organic EL layer containing a light-emitting layer and/or a light extraction layer containing a light-emitting layer, and an organic EL layer containing a light-emitting layer and/or a light-emitting layer containing a light
  • the extraction layer is formed on the above-described first electrode and between the above-described first electrode and second electrode. With such a structure, a region corresponding to a luminescent pixel portion can be formed.
  • the light-emitting layer in the organic EL layer including the light-emitting layer is a layer that emits light with a visible light wavelength (380 to 780 nm).
  • the light-emitting layer preferably contains a host material having a charge transport function of electrons and holes and a dopant (guest) material having a light-emitting function.
  • the dopant material is preferably dispersed uniformly in the host material at a concentration of about 0.1 to 1%.
  • the light-emitting layer is preferably dense and amorphous.
  • the organic EL layer including the light-emitting layer preferably further has a hole-transporting layer and/or an electron-transporting layer, and the organic EL layer is preferably formed so as to have a laminated structure of the light-emitting layer and these layers.
  • Examples of the structure of the organic EL layer including the light-emitting layer include (1) hole transport layer/light-emitting layer, (2) hole transport layer/light-emitting layer/electron transport layer, or (3) light-emitting layer/electron transport layer. are mentioned.
  • Various studies have been made on the structure of the organic EL layer including the light-emitting layer in order to comprehensively improve the injection and transport of holes and electrons, the light-emitting efficiency in the light-emitting layer, and the like.
  • the hole-transporting layer has a specific general formula: and an organic thin film EL device characterized by containing the bistriphenylamine styryl derivative shown.
  • the display device of the present invention can be manufactured as an organic EL display, which is a display device, by having a laminated structure using an organic EL layer including a light-emitting layer.
  • the display device of the present invention can be manufactured as a quantum dot display or a micro LED display, which is a display device, by having a laminated structure using a light extraction layer including a light emitting layer.
  • the light-emitting layer in the light extraction layer including the light-emitting layer is a layer that emits light of visible light wavelength (380 to 780 nm) by a mechanism different from that of the light-emitting layer in the organic EL layer including the light-emitting layer.
  • a light-outcoupling layer including a light-emitting layer refers to a layer for extracting light emitted from the light-emitting layer to the outside from the light-outcoupling side of the display device.
  • As the light extraction layer a single layer or multiple layers of organic and/or inorganic layers are preferred.
  • a quantum dot display in which the light extraction layer including the light emitting layer includes quantum dots is also preferable.
  • a quantum dot display is a display device having on a substrate a light extraction layer comprising a first electrode, a second electrode, a pixel dividing layer, and a light emitting layer, the pixel dividing layer being a first electrode on top of the first electrode.
  • a light-outcoupling layer formed to overlap with a part of the electrode and including a light-emitting layer has a configuration formed on the first electrode and between the first electrode and the second electrode, and includes a light-emitting layer.
  • the display device has a structure in which a layer contains quantum dots.
  • a layer containing self-luminous quantum dots is arranged as a light extraction layer containing a light-emitting layer.
  • Examples of the structure of the layer containing self-luminous quantum dots include hole transport layer/quantum dot layer/electron transport layer.
  • a micro LED display having a structure in which a light extraction layer including a light emitting layer includes an inorganic semiconductor is also preferable.
  • a micro LED display is a display device having on a substrate a light extraction layer comprising a first electrode, a second electrode, a pixel dividing layer, and a light emitting layer, the pixel dividing layer being a first electrode over the first electrode.
  • a light-outcoupling layer formed to overlap with a part of the electrode and including a light-emitting layer has a configuration formed on the first electrode and between the first electrode and the second electrode, and includes a light-emitting layer.
  • the display device has a structure in which a layer contains an inorganic semiconductor.
  • an inorganic LED layer which is an inorganic semiconductor, is arranged as a light extraction layer including a light emitting layer. Examples of inorganic LED layers include PN junction LED layers.
  • a display device having a laminated structure using both an organic EL layer including a light-emitting layer and a light extraction layer including a light-emitting layer is also preferable.
  • the following display devices (1) and (2) are listed.
  • An organic EL layer including a light-emitting layer and a light extraction layer including a light-emitting layer are provided on the first electrode, and the organic EL layer including the light-emitting layer and the light-emitting layer are provided.
  • a display in which both light extraction layers containing layers are light sources.
  • An organic EL layer including a light-emitting layer is provided as a light source on the first electrode, and light emitted from the organic EL layer including the light-emitting layer is emitted from the light-emitting layer provided on the organic EL layer including the light-emitting layer.
  • an organic EL layer including a light-emitting layer and a light extraction layer including a light-emitting layer are formed in this order on the first electrode.
  • the display device of the present invention has a structure in which both an organic EL layer including a light-emitting layer and a light-outcoupling layer including a light-emitting layer are provided. Also preferred is a display device having a For example, the following display devices (3) to (5) are listed.
  • An organic EL layer including a light-emitting layer is provided on the first electrode, and a light-outcoupling layer including a light-emitting layer (e.g., a layer containing quantum dots ) is provided, and both light 1 emitted from an organic EL layer including a light-emitting layer and light 2 obtained by color-converting light from a backlight such as an LED by a light-outcoupling layer including a light-emitting layer are used as light sources.
  • a light-outcoupling layer including a light-emitting layer e.g., a layer containing quantum dots
  • An organic EL layer including a light-emitting layer is provided on the first electrode, and a light-outcoupling layer including a light-emitting layer (e.g., a layer containing quantum dots) is provided on the light-outcoupling side rather than between the first electrode and the second electrode. ) is provided, and light emitted from an organic EL layer including a light-emitting layer is color-converted by a light-outcoupling layer including a light-emitting layer.
  • a light-outcoupling layer including a light-emitting layer e.g., a layer containing quantum dots
  • An organic EL layer including a light-emitting layer is provided on the first electrode, and a light-outcoupling layer including a light-emitting layer (e.g., a layer containing quantum dots ) is provided, and both light 1 from the organic EL layer including the light emitting layer and light 2 obtained by color-converting the light emitted from the organic EL layer including the light emitting layer by the light extraction layer including the light emitting layer are used as the light source. display device.
  • a light-outcoupling layer including a light-emitting layer e.g., a layer containing quantum dots
  • the display device of the present invention preferably further has a color filter containing quantum dots from the viewpoint of improving emission luminance and emission color purity.
  • the light emitting element overlapping the color filter containing quantum dots and positioned below the color filter containing quantum dots is an organic EL light emitting element that emits blue light.
  • an organic EL light-emitting element that emits white light an LED element that emits blue light, or an LED element that emits white light.
  • the display device of the present invention preferably has a pixel portion including a plurality of pixels.
  • the pixel portion is a portion of the opening of the pixel dividing layer, on which the organic EL layer including the light-emitting layer and/or the light extraction layer including the light-emitting layer is formed. preferably.
  • the region corresponding to the pixel portion corresponds to the region where the organic EL layer including the light-emitting layer and/or the light extraction layer including the light-emitting layer is in contact with the above-described first electrode portion.
  • the pixel portion preferably overlaps the openings of the color filter layer and the black matrix layer.
  • the display device of the present invention comprises, on the same substrate, a first electrode, a second electrode, a pixel dividing layer, an organic EL layer including a light-emitting layer, and/or a light extraction layer including a light-emitting layer, a sealing layer, and a color filter layer. , and a black matrix layer.
  • step 1 a thin film transistor (hereinafter referred to as "TFT") 2 is formed on a glass substrate 1, a film of a photosensitive material for a TFT flattening film is formed, patterned by photolithography, and then thermally cured. to form a cured product 3 for flattening the TFT.
  • TFT thin film transistor
  • step 2 a film of silver-palladium-copper alloy (hereinafter referred to as "APC”) is formed by sputtering on the upper layer of the TFT 2 and the cured product 3 for flattening the TFT, and patterned by etching using a photoresist.
  • APC silver-palladium-copper alloy
  • ITO indium tin oxide
  • Step 3 the photosensitive resin composition of the present invention is applied on the upper layer of the reflective electrode 4 and prebaked to form a prebaked film 5a.
  • step 4 the prebaked film 5a is irradiated with actinic rays 7 through a mask 6 having a desired pattern.
  • step 5 the exposed pre-baked film 5a is developed and patterned, and then subjected to bleaching exposure and middle baking if necessary. Further, the patterned pre-baked film 5a is thermally cured to form a cured pattern 5b having a desired pattern as a light-shielding pixel dividing layer.
  • an organic EL layer 8 is formed by depositing an EL light-emitting material on the reflective electrode 4 between the cured patterns 5b by vapor deposition through a mask. Further, a magnesium-silver alloy (hereinafter referred to as “MgAg”) is deposited on the organic EL layer 8 by vapor deposition, patterned by etching using a photoresist, and a transparent electrode 9 is formed as a second electrode.
  • MgAg magnesium-silver alloy
  • step 7 a film of a photosensitive material for a flattening film is formed on the entire upper layer of the transparent electrode 9, patterned by photolithography, and then thermally cured to form a cured product 10 for flattening, Thereafter, a cover glass 11 is bonded to the cured product 10 to obtain an organic EL display having the cured product of the photosensitive resin composition of the present invention as a light-shielding pixel dividing layer.
  • the method for producing a cured product using the photosensitive resin composition of the present invention preferably comprises the following steps (1) to (4). (1) forming a coating film of the photosensitive resin composition of the present invention on a substrate; (2) a step of irradiating the coating film of the photosensitive resin composition with actinic rays through a photomask; (3) developing with an alkaline solution to form a pattern of the photosensitive resin composition; and (4) A step of heating the pattern to obtain a cured pattern of the photosensitive resin composition.
  • the photomask includes a light-transmitting portion and a light-shielding portion, and a semi-light-transmitting portion in which the transmittance between the light-transmitting portion and the light-shielding portion is lower than the value of the light-transmitting portion and the transmittance is higher than the value of the light-shielding portion.
  • the method for producing a cured product of the present invention has (1) a step of forming a coating film of a photosensitive resin composition on a substrate.
  • Examples of the method of forming a film of the photosensitive resin composition include a method of applying the photosensitive resin composition onto the substrate, and a method of applying the photosensitive resin composition onto the substrate in a pattern. .
  • Substrates include, for example, oxides containing one or more metals selected from indium, tin, zinc, aluminum, and gallium, metals (molybdenum, silver, copper, aluminum, chromium, or titanium) or a substrate on which CNT (Carbon Nano Tube) is formed.
  • oxides containing one or more metals selected from indium, tin, zinc, aluminum and gallium include indium tin oxide (ITO).
  • ⁇ Method of applying a photosensitive resin composition on a substrate examples include spin coating, curtain flow coating, spray coating and slit coating.
  • the coating film thickness varies depending on the coating method, solid content concentration and viscosity of the photosensitive resin composition, etc., but the film thickness after coating and pre-baking is usually preferably 0.1 to 30 ⁇ m.
  • pre-bake the resulting coating film After coating the photosensitive resin composition on the substrate, it is preferable to pre-bake the resulting coating film.
  • An oven, a hot plate, an infrared ray, a flash annealing device, a laser annealing device, or the like can be used for prebaking.
  • the prebake temperature is preferably 50 to 150°C.
  • the prebake time is preferably 30 seconds to 10 minutes.
  • prebaking may be performed in two or more stages such as prebaking at 80° C. for 2 minutes and then prebaking at 120° C. for 2 minutes.
  • Method of patterning a coating film formed on a substrate examples include a method of direct patterning by photolithography and a method of patterning by etching. From the viewpoint of reducing the number of steps and shortening the process time, a method of directly patterning by photolithography is preferred.
  • the method for producing a cured product of the present invention has (2) a step of irradiating the coating film of the photosensitive resin composition described above with actinic rays through a photomask.
  • Examples of the method of irradiating actinic rays through a photomask include patterning exposure using an exposure machine such as a stepper, scanner, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA). be done.
  • the photomask is a photomask having a pattern including a light-transmitting portion and a light-shielding portion. It is preferable to use a halftone photomask having a semi-transparent portion that is higher than the value of the light-shielding portion.
  • a pattern having a step shape can be formed after development.
  • a portion formed from an exposed portion irradiated with actinic radiation through the light transmitting portion corresponds to the thick film portion, and the semi-transmitting portion.
  • the portion formed from the halftone portion irradiated with the actinic radiation through the portion corresponds to the thin film portion.
  • the exposure wavelength of actinic rays is preferably 150 nm or longer, more preferably 300 nm or longer. On the other hand, the exposure wavelength is preferably 450 nm or less, more preferably 420 nm or less.
  • Actinic rays include j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) of a mercury lamp, or a mixed line of i-line, h-line and g-line. is particularly preferred.
  • a XeF (wavelength: 351 nm) laser, a XeCl (wavelength: 308 nm) laser, a KrF (wavelength: 248 nm) laser, an ArF (wavelength: 193 nm) laser, or the like may be used as the actinic radiation.
  • the exposure dose of actinic rays is preferably 100 J/m 2 (10 mJ/cm 2 ) to 30,000 J/m 2 (3,000 mJ/cm 2 ) or less in terms of i-line illuminance.
  • Post-exposure baking may be performed on the exposed film. By performing post-exposure baking, it is possible to improve the resolution after development or expand the allowable range of development conditions.
  • the method for producing a cured product of the present invention includes (3) a step of developing with an alkaline solution to form a pattern of the photosensitive resin composition described above.
  • Examples of the method of developing with an alkaline solution after irradiating with actinic rays through a photomask include a method of developing with an automatic developing machine.
  • Examples of the developing method include puddle development, spray development and dip development.
  • the photosensitive resin composition has negative photosensitivity, it is possible to form a pattern in which the unexposed areas are removed with a developer.
  • the photosensitive resin composition has positive photosensitivity, it is possible to form a pattern in which the exposed portion is removed with a developer.
  • An alkaline solution is preferable as the developer.
  • an aqueous solution or an organic solution of a compound exhibiting alkalinity is preferable, and an aqueous solution is more preferable.
  • alkaline compounds include diethanolamine, trimethylamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide.
  • An organic solvent may be used as the developer.
  • the developer may be a mixed solution containing both a good solvent and a poor solvent for the photosensitive resin composition.
  • the alkali concentration of the alkali solution is preferably 0.01 to 5% by mass.
  • the development time is preferably 30 seconds to 10 minutes. After development, it is preferable to wash the obtained pattern with a rinsing liquid.
  • a rinsing liquid water is preferable when an alkaline aqueous solution is used as the developer.
  • an alcohol aqueous solution, an ester aqueous solution, an acidic compound aqueous solution, or an organic solvent may be used.
  • post-development exposure may be performed. By performing exposure after development, it is possible to improve the resolution after heat curing, control the pattern shape after heat curing, and form a pattern having a stepped shape after heat curing.
  • middle baking may be performed after development. By performing middle baking, it is possible to improve the resolution after heat curing and to control the pattern shape after heat curing.
  • the method for producing a cured product of the present invention includes (4) a step of heating and curing the pattern of the photosensitive resin composition described above to obtain a cured pattern of the photosensitive resin composition (hereinafter, “(4) step”).
  • heat curing methods include heating using an oven, hot plate, infrared rays, flash annealing equipment, or laser annealing equipment. By thermally curing, the heat resistance of the cured product can be improved, and a low tapered pattern can be formed.
  • the thermosetting temperature is preferably 150 to 500°C.
  • the heat curing time is preferably 5 to 300 minutes.
  • the heat curing may be performed in two or more steps such as heat curing at 150° C. for 30 minutes and then heat curing at 250° C. for 30 minutes.
  • the treatment atmosphere is, for example, an air, oxygen, nitrogen, helium, neon, argon, krypton or xenon atmosphere, a gas atmosphere containing 1 to 10,000 ppm (0.0001 to 1% by mass) of oxygen, or under vacuum. mentioned.
  • ADP (E1) a dispersant having a basic group having a tertiary amino group, a structure represented by the general formula (26), a structure represented by the general formula (29), and a polyoxyalkylene structure (amine value: 20 mg KOH / g (solid content concentration: 100% by mass))
  • APC Argentum-Palladium-Cupper (silver-palladium-copper alloy)
  • BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
  • BAPF 9,9-bis(3-amino-4-hydroxyphenyl)fluorene
  • BGPF 9,9-bis(4-glycide Xyphenyl)fluorene
  • BnMA benzyl methacrylate
  • Bk-A1103 compound represented by the general formula (168); "CHROMOFINE"
  • MEK-ST-L Silica particle dispersion using methyl ethyl ketone as a dispersion solvent (manufactured by Nissan Chemical Industries, Ltd.)
  • MeTMS methyltrimethoxysilane
  • MgAg Magnesium-Argentum (magnesium-silver alloy)
  • MOI 2-methacryloxyethyl isocyanate
  • MOP 4-methoxyphenol NA: 5-norbornene-2,3-dicarboxylic anhydride
  • NC-3500 epoxy having a structural unit containing a biphenyl skeleton, a benzene skeleton, and two epoxy groups Resin (manufactured by Nippon Kayaku Co., Ltd.)
  • ODB-HBT a mixture of dicarboxylic acid derivatives obtained by reacting bis(4-carboxyphenyl) ether with 1-hydroxy-1,2,3-benzotriazole
  • ODPA oxydiphthalic dianhydride P.
  • Synthesis Examples 1, 2 and 4 to 11 were each synthesized by the method described in Synthesis Example 1 of paragraph [0544] of WO 2017/057281.
  • (PIP-1) and (PIP-2) of Synthesis Examples 13 and 14 were synthesized by the method described in Synthesis Example 15 of paragraph [0548] of WO 2017/057281, respectively.
  • (PB-1) of Synthesis Example 15 was synthesized by the method described in Synthesis Example 12 of paragraph [0546] of WO 2017/057281.
  • (AC-1) of Synthesis Example 25 was synthesized by the method described in Synthesis Example 20 of paragraph [0739] of WO 2017/159876.
  • (PR-1) and (PR-2) of Synthesis Examples 26 and 27 were synthesized by the method described in Synthesis Example 21 of paragraph [0740] of WO 2017/159876, respectively.
  • (PHS-1) of Synthesis Example 28 was synthesized by the method described in Synthesis Example 23 of paragraph [0742] of WO 2017/159876.
  • (PBP-1) of Synthesis Example 16 was synthesized by the method described in Synthesis Example 9 of paragraph [0161] of WO 2017/057143.
  • Synthesis Example 25 an ethylenically unsaturated double bond group was introduced based on the method described in Synthesis Example 20 of paragraph [0739] of WO2017/159876.
  • NC-3500 having an epoxy group was reacted with an unsaturated carboxylic acid, and all epoxy groups derived from NC-3500 were subjected to ring-opening addition.
  • synthesizing (AC-1) in Synthesis Example 25 GMA having an epoxy group was reacted, and all the epoxy groups of GMA were subjected to ring-opening addition.
  • Polyamideimides (PAI-4) and (PAI-5) were commercially available EMG-1015 and EQG-1170, respectively.
  • Commercially available ZCR-1569H was used as the acid-modified epoxy resin (AE-1).
  • TMS-ICA 1,3,5-tris(3-trimethoxysilylpropyl)isocyanuric acid
  • TMS-TAZ 2,4,6-tris[(3-trimethoxysilylpropyl)amino]-1,3,5-triazine
  • HA hydroxy group-containing diamine having the structure shown below used in Synthesis Examples 13 and 14 was prepared according to the synthesis method described in Synthesis Example 1 in paragraphs [0374] to [0376] of WO 2016/056451. Based on this, it was synthesized by a known method.
  • Diamines or triamines (BA-ICA), (TA-ICA), and (BAH-ICA) having an isocyanuric acid structure used in Synthesis Examples 4, 6, 7, 12, and 14 are described in International Publication No. 2020/196764. It was synthesized by a known method based on the synthesis method described in paragraphs [0131] to [0133].
  • the diamine (BAE-ICA) and (BAHE-ICA) having an isocyanuric acid structure used in Synthesis Examples 5 and 8 are synthesized according to paragraphs [0136] to [0138] of WO 2020/196764. Based on, it was synthesized by a known method. The structures of these diamines and triamines are shown below.
  • the diamine (BA-TAZ) having a triazine structure used in Synthesis Example 10 was synthesized by a known method. The structure of this diamine is shown below.
  • IPTA-ICA The triamine (IPTA-ICA) having an isocyanuric acid structure used in Synthesis Example 9 was synthesized from a commercially available triisocyanate compound (IPTC-ICA) by a known method. The structures of these triamine and triisocyanate compounds are shown below.
  • the surface-coated benzofuranone-based black pigment (Bk-CBF1) used in Preparation Example 6 is based on the synthesis method described in Coating Example 1 in paragraphs [0503] to [0505] of WO 2019/087985. , synthesized by a known method.
  • the surface-coated perylene-based black pigment (Bk-CPR1) used in Preparation Example 7 was synthesized according to Example 18 in paragraphs [0186] to [0188] and [0191] of WO 2018/038083. Based on the method, it was synthesized by a known method.
  • polyalkyleneamine-polyoxyalkylene ether-based dispersant (ADP) used in Preparation Examples 1 to 7 has a structure represented by the general formula (26), a structure represented by the general formula (29), and (E1) is a pigment dispersant having a basic group having a polyoxyalkylene structure.
  • ADP used in Preparation Examples 1 to 7 was synthesized by a known method based on the method described in Synthesis Example 2 in paragraphs [0138] to [0141] of JP-A-2020-070352.
  • Synthesis Example 29 Synthesis of Silica Particle (SP-1) Dispersion
  • 104.5 g of MEK as a solvent 142.5 g of MEK-ST-40 as a silica particle dispersion containing sodium element
  • 142.5 g of MEK-ST-40 142.5 g of MEK-ST-40 as a polymerization inhibitor 0.01 g of MOP was weighed, added and mixed, and after stirring for 10 minutes, the liquid temperature was raised to 50°C.
  • a solution of 3.0 g of KBM-503 dissolved in 50.0 g of MEK was added dropwise over 10 minutes. After completion of dropping, the mixture was stirred at 50° C. for 2 hours to dehydrate and condense the surface modifier.
  • silica particle (SP-1) After the reaction, the reaction solution was cooled to room temperature to obtain a silica particle (SP-1) dispersion.
  • the obtained silica particles (SP-1) have a surface modification group containing a methacryloyl group as a radically polymerizable group.
  • Table 2-2 summarizes the composition and properties of the silica particle dispersion obtained in Synthesis Example 15 and the commercially available silica particle dispersion as the silica particles.
  • silica particle (SP-2) dispersion MEK-ST-40, which is a commercially available silica particle dispersion, was used.
  • silica particle (SP-3) dispersion MEK-ST-L, which is a commercially available silica particle dispersion, was used.
  • ITO/Ag substrate a glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as “ITO/Ag substrate”) on which a 10 nm film of ITO was formed by sputtering was processed using a desktop optical surface treatment apparatus (PL16-110; manufactured by Sen Special Light Source Co., Ltd.). was used after UV-O3 cleaning treatment for 100 seconds.
  • a Tempax glass substrate manufactured by AGC Techno Glass was used without pretreatment.
  • a post-development film of a photosensitive resin composition was prepared by the method described in Example 1 below. Using an FPD/LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolution pattern of the developed film was observed. As an index of the development residue, the presence or absence of the residue in the pattern corresponding to the opening was observed in the line and space pattern of 20 ⁇ m. A + , A, B + , B, C + and C, where the residual area was 20% or less, were evaluated as follows. The smaller the existing area of the residue, the better. A + and A, which have an existing area of the residue of 3% or less, are particularly excellent.
  • Residue existing area is 3% or less
  • B + Residue existing area is more than 3% and 6% or less
  • C + Residue existing area exceeds 10% and 15% or less
  • FIG. 3 shows a schematic diagram of the arrangement and dimensions of the light-transmitting portion, the light-shielding portion, and the semi-light-transmitting portion of the halftone photomask used for the pattern dimension variation evaluation.
  • the halftone photomask has a transparent portion T, a light shielding portion S, and a semi-transparent portion H.
  • FIG. The light-transmitting portion T has a line shape
  • the light-shielding portion S has a rectangular shape.
  • the light-transmitting portion T is adjacent to the semi-light-transmitting portion H, the light-shielding portion T is adjacent to the semi-light-transmitting portion H, and the light-shielding portion S is surrounded by the adjacent semi-light-transmitting portion H.
  • the light shielding portions S having a width of 30 ⁇ m and a length of 60 ⁇ m are arranged at a pitch of 90 ⁇ m in the width direction and a pitch of 150 ⁇ m in the length direction.
  • a semi-transparent portion H having a width of 20 ⁇ m adjacent to the light-shielding portion S is arranged on both sides of the light-transmitting portion.
  • Adjacent semi-transparent portions H having a width of 30 ⁇ m are arranged on both sides of the transparent portion.
  • the resolution pattern of the developed film having a step shape was observed.
  • the transmittance (%T HT )% of the halftone photomask is 20% or 25% of the transmittance (%T FT ) of the light-transmitting portion.
  • the portion of the film after development corresponding to the 30% was observed.
  • the opening dimension (CD DEV ) ⁇ m of the opening pattern of the film after development corresponding to the light shielding portion with a width of 30 ⁇ m in the halftone photomask was measured.
  • the exposure amount of the semi-transparent portion which is the halftone exposure portion, was such that the film thickness of the thin film portion formed from the semi-transparent portion after development was 2.0 ⁇ m.
  • the opening dimension (CD DEV ) ⁇ m of the opening pattern at four points within the plane of the same substrate was measured.
  • the standard deviation ⁇ of the aperture dimension (CD DEV ) ⁇ m of the aperture pattern at four points was calculated.
  • a + , A, B + , B, C + and C with a standard deviation ⁇ of 0.75 or less were evaluated as follows. A smaller standard deviation ⁇ is better, and A + and A with a standard deviation ⁇ of 0.30 or less are particularly excellent.
  • the halftone photomask has a light-transmitting portion, a light-shielding portion, and a semi-light-transmitting portion between the light-transmitting portion and the light-shielding portion.
  • a photomask was used having a point with a transmittance (% T FT ) of 20%, 25%, 30%, 35%, 40% or 50%.
  • the translucent part and the semi-translucent part are adjacent to each other, and the semi-translucent part and the light-shielding part are adjacent to each other.
  • FIG. 2 shows an example of the arrangement and dimensions of the light-transmitting portion, the light-shielding portion, and the semi-light-transmitting portion.
  • the light shielding portions S with a width of 10 ⁇ m are arranged at a pitch of 45 ⁇ m in the width direction.
  • a semi-transparent portion H having a width of 10 ⁇ m adjacent to the light-shielding portion S is arranged on both sides of the light-transmitting portion.
  • the film thickness (T FT ) ⁇ m after development of the thick film portion formed from the light-transmitting portion was measured.
  • the film thickness (T HT ) ⁇ m after development was measured at locations with different transmittances on the halftone photomask, and the thin film portion remaining after development was measured.
  • the minimum film thickness (T HT/min ) ⁇ m was obtained.
  • the maximum step thickness ((T FT ) ⁇ (T HT/min )) ⁇ m was calculated.
  • a + , A, B + , B, C + and C having a maximum step thickness of 0.4 ⁇ m or more were evaluated as follows. The larger the maximum step thickness, the better. A + and A, which have a maximum step thickness of 2.0 ⁇ m or more, are particularly excellent.
  • a + Maximum step thickness is 2.5 ⁇ m or more
  • C + Maximum step thickness is 0.7 ⁇ m or more and less than 1.0 ⁇ m
  • D The maximum step thickness is 0.1 ⁇ m or more and less than 0.4 ⁇ m
  • the maximum step thickness is less than 0.1 ⁇ m, or no film remains after development and cannot be measured.
  • FIG. 4 shows a schematic diagram of the substrate used.
  • an amorphous ITO film having a thickness of 10 nm is formed as a transparent conductive oxide film layer on the APC layer by sputtering, patterned by etching, and a reflective electrode composed of a lamination of the APC layer and the ITO layer is formed as the first electrode 48 . did.
  • an auxiliary electrode 49 was also formed at the same time to take out the second electrode (FIG. 4 (step 1)).
  • the resulting substrate was ultrasonically cleaned for 10 minutes using "Semico Clean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water.
  • the photosensitive resin composition was applied onto this substrate by the method described in Example 1 and prebaked to prepare a prebaked film.
  • the pre-baked film was subjected to patterning exposure through a photomask having a predetermined pattern, developed and rinsed, and then heated to be thermally cured.
  • the pixel division layer 50 having a width of 70 ⁇ m and a length of 260 ⁇ m is arranged at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction, and each opening exposes the first electrode. , was formed only in the effective area of the substrate (FIG. 4 (step 2)). It should be noted that this opening will eventually become the light-emitting pixel of the organic EL display.
  • the effective area of the substrate is 16 mm square, and the thickness of the pixel division layer 50 is about 1.0 ⁇ m.
  • an organic EL display was manufactured using the substrate on which the first electrode 48, the auxiliary electrode 49 and the pixel dividing layer 50 were formed.
  • an organic EL layer 51 including a light-emitting layer was formed in the opening of the pixel dividing layer 50 by a vacuum deposition method (FIG. 4 (step 3)).
  • the degree of vacuum during vapor deposition was 1 ⁇ 10 ⁇ 3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition.
  • the compound (HT-1) was vapor-deposited to a thickness of 10 nm as a hole injection layer, and the compound (HT-2) was vapor-deposited to a thickness of 50 nm as a hole transport layer.
  • a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were vapor-deposited to a thickness of 40 nm so that the doping concentration was 10%.
  • the compound (ET-1) and the compound (LiQ) were stacked at a volume ratio of 1:1 to a thickness of 40 nm.
  • the structures of the compounds (HT-1), (HT-2), (GH-1), (GD-1), (ET-1) and (LiQ) used in the organic EL layer are represented by the following chemical formulas. show.
  • the film thickness referred to above is a value displayed by a crystal oscillation type film thickness monitor.
  • the organic EL display manufactured by the above-described method was driven to emit light by changing the voltage sequentially from the low voltage side until the current density reached 30 mA/cm 2 .
  • the voltage value and current density were plotted when the voltage value was changed sequentially from the low voltage side, and the drive voltage at which the current density was 10 mA/cm 2 was obtained as an index of the current density-voltage characteristics.
  • a + , A, B + , B, C + and C with drive voltages of 4.5 V or less were determined as follows and passed. The smaller the drive voltage, the better, and A + and A, which have a drive voltage of 3.5 V or less, are particularly excellent.
  • E Drive voltage exceeds 5.5 V or cannot be measured.
  • the organic EL display manufactured by the method described above was made to emit light by direct-current driving at 10 mA/cm 2 , and was observed for light emission defects such as non-light-emitting areas and luminance unevenness. Further, as a durability test, the organic EL display was held at 80° C. for 500 hours. After the durability test, the organic EL display was driven to emit light at 10 mA/cm 2 by direct-current driving to observe whether there was any change in the light emission characteristics. The light-emitting region area after the test was measured. A + , A, B + , B, C + and C, which had a light-emitting region area of 80% or more, were evaluated as follows.
  • D Emission area of 60% or more and less than 80%
  • E Emission area of less than 60%.
  • each resin has the following structural units.
  • Polyimides (PI-1) to (PI-3) have structural units represented by general formula (1).
  • (PI-3) also has an ethylenically unsaturated double bond group.
  • Polyimides (PI-4) to (PI-9) and (PI-12) have a structural unit represented by general formula (1) and a structural unit represented by general formula (21). (PI-12) also has an ethylenically unsaturated double bond group.
  • Polyimides (PI-10) and (PI-11) have a structural unit represented by general formula (1) and a structural unit represented by general formula (22).
  • the polyimide precursor (PIP-1) has a structural unit represented by general formula (3).
  • the content ratio of the amic acid ester structural unit to the total content ratio of the amic acid structural unit, the amic acid ester structural unit, the amic acid amide structural unit, and the imide ring-closing structural unit is 65 mol%.
  • the content ratio of the amic acid structural unit is 25 mol%
  • the content ratio of the imide ring-closing structural unit is 10 mol%.
  • the polyimide precursor (PIP-2) has a structural unit represented by general formula (3) and a structural unit represented by general formula (21).
  • the content ratio of the amic acid ester structural unit to the total content ratio of the amic acid structural unit, the amic acid ester structural unit, the amic acid amide structural unit, and the imide ring-closing structural unit is 65 mol%.
  • the content ratio of the amic acid structural unit is 25 mol%
  • the content ratio of the imide ring-closing structural unit is 10 mol%.
  • Polybenzoxazole (PB-1) has a structural unit represented by general formula (2).
  • the polybenzoxazole precursor (PBP-1) has a structural unit represented by general formula (4).
  • Polyamideimides (PAI-1) and (PAI-2) have structural units represented by general formula (5).
  • (PAI-2) also has an ethylenically unsaturated double bond group.
  • Polyamideimides (PAI-3), (PAI-4) and (PAI-5) have a structural unit represented by general formula (5) and a structural unit represented by general formula (21). (PAI-5) also has an ethylenically unsaturated double bond group.
  • Polysiloxane (PS-1) has a structural unit represented by general formula (8) and a structural unit represented by general formula (9).
  • Polysiloxanes (PS-2) and (PS-3) have a structural unit represented by general formula (8), a structural unit represented by general formula (9), and a cyclic structural unit of (AX) resin.
  • the polycyclic side chain-containing resin has a structural unit represented by general formula (41) including a structure represented by general formula (44).
  • (CR-1) also has an ethylenically unsaturated double bond group.
  • the acid-modified epoxy resins (AE-1) and (AE-2) have a structural unit represented by general formula (61) including a structure represented by general formula (66).
  • (AE-1) and (AE-2) also have an ethylenically unsaturated double bond group.
  • the acrylic resin (AC-1) has a structural unit represented by general formula (81) and a structural unit represented by general formula (82). (AC-1) also has an ethylenically unsaturated double bond group.
  • the phenolic resin (PR-1) has a structural unit represented by general formula (36).
  • the phenolic resin (PR-2) has a structural unit represented by the general formula (36) and a cyclic structural unit of the (AX) resin.
  • PHS-1 Polyhydroxystyrene (PHS-1) has a structural unit represented by general formula (91).
  • Bk-CBF1 Bk-CBF2
  • e-1 ADP (Cl-1) cyclopropylmethyl chloride (Cl-2) tetrabutylammonium chloride (Br-1) benzyl bromide (S-1) p-toluenethiol (S-2) dimethylsulfoxide (P-1) triphenylphosphine .
  • ⁇ Preparation of cured product of composition> After applying the prepared composition 1 on an ITO/Ag substrate by spin coating at an arbitrary number of rotations using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), a buzzer hot plate (HPD-3000BZN; AS ONE Co., Ltd. ) and prebaked at 120° C. for 120 seconds to prepare a prebaked film having a film thickness of about 1.8 ⁇ m.
  • a spin coater MS-A100; manufactured by Mikasa Co., Ltd.
  • HPD-3000BZN buzzer hot plate
  • the prepared pre-baked film is developed by spraying with a 2.38% by mass TMAH aqueous solution using a small developing device for photolithography (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.), and the pre-baked film (unexposed area) is completely dissolved.
  • the time (Breaking Point; hereinafter referred to as "BP") required to do so was measured.
  • a pre-baked film is prepared in the same manner as described above, and the prepared pre-baked film is subjected to a sensitivity measurement gray scale mask (MDRM Patterning exposure was performed with i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of an extra-high pressure mercury lamp via MODEL 4000-5-FS; manufactured by Opto-Line International).
  • the exposure amount was set to the exposure amount (i-line illuminometer value) capable of forming a space pattern corresponding to an opening with a dimension width of 18 ⁇ m in a 20 ⁇ m line-and-space pattern.
  • the film After exposure, using a small developing device for photolithography (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.), the film was developed with a 2.38% by mass TMAH aqueous solution and rinsed with water for 30 seconds to form a film of Composition 1 after development. made. The development time was BP+20 seconds. After development, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the composition was thermally cured at 250° C. to prepare a cured product of composition 1 having a film thickness of about 1.2 ⁇ m. As for the heat curing conditions, heat curing was performed at 250° C. for 60 minutes in a nitrogen atmosphere.
  • the cured product obtained by methods such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, and time-of-flight secondary ion mass spectrometry was analyzed to analyze the structural units of the resin and the structure of the compound contained in the cured product. . It was confirmed that the cured product obtained by curing composition 1 by the method described above contained the following resins and compounds. That is, the cured product obtained by curing composition 1 contains a compound having a structure derived from each component contained in composition 1 .
  • (X-DL) resin A resin having a structural unit represented by general formula (21).
  • (I-DL) resin A resin having a structural unit represented by general formula (1).
  • (II-DL) resin a resin having a structural unit represented by general formula (24).
  • (III-DL) resin a resin having a structural unit represented by general formula (36).
  • (IV-DL) Phosphate-based structure a compound having a phosphonate ester structure.
  • B1 Structure derived from compound A compound having a structure represented by general formula (141).
  • D1a Black pigment: (D1a-1a) A benzofuranone-based black pigment having a structure represented by general formula (161).
  • Examples 2 to 83 and Comparative Examples 1 to 5 Compositions 2 to 88 were prepared in the same manner as in Example 1 with the compositions shown in Tables 3-1 to 10. Numerical values in parentheses in Tables 3-1 to 10 indicate parts by mass of the solid content of each component.
  • At least one resin selected from the group consisting of (AX) resin, (A1) resin, (A2) resin and (A3) resin is changed as (A) alkali-soluble resin.
  • Various properties were evaluated with the composition obtained.
  • Table 4 various properties were evaluated for compositions in which the (F) compound and/or the (H) compound were changed.
  • various properties were evaluated for the compositions in which the (G) compound was changed.
  • Table 6 various characteristics were evaluated for compositions in which one or more compounds selected from the group consisting of (B) compound, (C) photosensitizer and (C1-1) compound were changed.
  • (D1a) compositions with different types of black pigments were evaluated for various properties.
  • Examples 69 to 70 various properties were evaluated for compositions containing no (D) colorant and (E) dispersant.
  • Examples 71 and 72 various properties were evaluated for compositions having positive photosensitivity and containing (D) a colorant and (E) a dispersant in different amounts.
  • Table 8 various properties were evaluated for compositions with different additives containing elemental chlorine, bromine, sulfur, or phosphorus. Table 8 shows the content of elemental chlorine, elemental bromine, elemental sulfur, and elemental phosphorus.
  • (I) compositions with different inorganic particles were evaluated for various properties.
  • Comparative Examples 1 to 5 evaluated various properties of compositions containing no (AX) resin.
  • the development time is 60 seconds, 90 seconds, or 120 seconds, and a gray scale mask (MDRM MODEL 4000-5-FS; Opto-Line International Co., Ltd.) for sensitivity measurement. (manufacturer), the optimum exposure dose (i-line illuminance meter value) that can form a space pattern corresponding to an opening with a dimension width of 18 ⁇ m in a line and space pattern of 20 ⁇ m was determined. .
  • the heat curing conditions were such that the composition was heat cured at 200° C. for 60 minutes in a nitrogen atmosphere.
  • the content of elemental chlorine, bromine, sulfur or phosphorus was determined by combustion ion chromatography.
  • the composition was combusted and decomposed in the combustion tube of the analyzer, and after the generated gas was absorbed in the absorbing liquid, a portion of the absorbing liquid was analyzed by ion chromatography.
  • the element content of each example and comparative example is described below. If there is no description of element content, it means that the element was not detected.
  • the elemental phosphorus content of Examples 1-36, 40-55, 57, 59-65, 67, 68 and Comparative Examples 1-4 was 72 ppm.
  • the elemental phosphorus content of Example 37 was 39 ppm.
  • the elemental phosphorus content of Example 38 was 19 ppm.
  • the elemental phosphorus content of Example 39 was 135 ppm.
  • the elemental phosphorus content of Example 56 was 72 ppm and the elemental sulfur content was 598 ppm.
  • the elemental phosphorus content of Example 58 was 70 ppm and the elemental sulfur content was 114 ppm.
  • the elemental phosphorus content of Example 66 was 57 ppm.
  • the elemental phosphorus content of Examples 69 and 70 was 219 ppm.
  • the elemental sulfur content of Example 71 was 449 ppm.
  • the elemental sulfur content of Example 72 was 632 ppm.

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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  • Electroluminescent Light Sources (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne une composition de résine photosensible qui est capable d'éliminer les résidus après le développement ainsi que la variation de la taille de motif d'ouverture après le développement, et ce tout en ayant d'excellentes caractéristiques de demi-ton. De plus, un but de la présente invention est de fournir un produit durci qui permet d'obtenir un bon équilibre entre l'amélioration de la fiabilité d'un élément électroluminescent dans un dispositif d'affichage électroluminescent organique et l'excitation de l'élément électroluminescent à basse tension.　La composition de résine photosensible contient une résine soluble en milieu alcalin (A) et un sensibilisateur (C), la résine soluble en milieu alcalin (A) contenant au moins la résine (AX) décrite ci-après, tout en contenant également une ou plusieurs résines sélectionnées parmi la résine (A1), la résine (A2) et la résine (A3) décrites ci-dessous. Résine (AX) : une résine qui comporte un motif constitutif qui comprend une structure cyclique ayant au moins trois atomes d'azote Résine (A1) : une résine qui comporte un motif constitutif qui comprend une ou plusieurs structures sélectionnées parmi une structure imide, une structure amide, une structure oxazole et une structure siloxane, tout en n'ayant pas de groupe à double liaison éthyléniquement insaturée Résine (A2) : une résine qui comporte un groupe à double liaison éthyléniquement insaturée Résine (A3) : une résine qui comporte un groupe hydroxyle phénolique
PCT/JP2022/023438 2021-06-14 2022-06-10 Composition de résine photosensible, produit durci, procédé de production de produit durci, et dispositif d'affichage WO2022264934A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009092952A (ja) * 2007-10-09 2009-04-30 Toppan Printing Co Ltd 感光性着色組成物、これを用いたカラーフィルタ、及び液晶表示装置
JP2016191905A (ja) * 2015-03-30 2016-11-10 東京応化工業株式会社 感光性樹脂組成物、パターン形成方法、硬化膜、絶縁膜、カラーフィルタ、及び表示装置
WO2018159384A1 (fr) * 2017-03-03 2018-09-07 東レ株式会社 Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur
JP2020070352A (ja) * 2018-10-31 2020-05-07 東レ株式会社 顔料分散液、ネガ型感光性組成物および硬化物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009092952A (ja) * 2007-10-09 2009-04-30 Toppan Printing Co Ltd 感光性着色組成物、これを用いたカラーフィルタ、及び液晶表示装置
JP2016191905A (ja) * 2015-03-30 2016-11-10 東京応化工業株式会社 感光性樹脂組成物、パターン形成方法、硬化膜、絶縁膜、カラーフィルタ、及び表示装置
WO2018159384A1 (fr) * 2017-03-03 2018-09-07 東レ株式会社 Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur
JP2020070352A (ja) * 2018-10-31 2020-05-07 東レ株式会社 顔料分散液、ネガ型感光性組成物および硬化物

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