WO2022264934A1 - Photosensitive resin composition, cured product, method for producing cured product, and display device - Google Patents

Photosensitive resin composition, cured product, method for producing cured product, and display device 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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French (fr)
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/en

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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.

Abstract

The present invention provides a photosensitive resin composition which is capable of suppressing residues after development and variation in the opening pattern size after development, while having excellent half-tone characteristics at the same time. In addition, one purpose of the present invention is to provide a cured product which enables the achievement of a good balance between reliability improvement of a light emitting element in an organic EL display and driving of the light emitting element at a low voltage.　A photosensitive resin composition which contains an alkali-soluble resin (A) and a sensitizer (C), wherein the alkali-soluble resin (A) contains at least the resin (AX) described below, while additionally containing one or more resins that are selected from the group consisting of the resin (A1), the resin (A2) and the resin (A3) described below. Resin (AX): a resin which has a structural unit that comprises a cyclic structure having at least three nitrogen atoms Resin (A1): a resin which has a structural unit that comprises one or more structures that are selected from the group consisting of an imide structure, an amide structure, an oxazole structure and a siloxane structure, while having no ethylenically unsaturated double bond group Resin (A2): a resin which has an ethylenically unsaturated double bond group Resin (A3): a resin which has a phenolic hydroxyl group

Description

感光性樹脂組成物、硬化物及び硬化物の製造方法並びに表示装置Photosensitive resin composition, cured product, method for producing cured product, and display device
　本発明は、感光性樹脂組成物、硬化物および硬化物の製造方法ならびに表示装置に関する。表示装置に関して、詳しくは、有機エレクトロルミネッセンス（以下、「有機ＥＬ」）ディスプレイ、量子ドットディスプレイ、またはマイクロ発光ダイオード（以下、「マイクロＬＥＤ」）ディスプレイに関する。特に、有機ＥＬディスプレイに関する。 The present invention relates to a photosensitive resin composition, a cured product, a method for producing the cured product, and a display device. As to 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. In particular, it relates to organic EL displays.
　近年、スマートフォン、タブレットＰＣおよびテレビなど、薄型ディスプレイを有する表示装置において、有機ＥＬディスプレイ、量子ドットディスプレイ、またはマイクロＬＥＤディスプレイに関する技術が盛んに研究されており、それらを用いた製品が多く開発されている。 In recent years, in display devices having thin displays such as smartphones, tablet PCs, and televisions, technologies related to organic EL displays, quantum dot displays, or micro LED displays have been actively researched, and many products using these have been developed. there is
　有機ＥＬディスプレイの発光特性向上および信頼性向上のために、有機ＥＬディスプレイの画素分割層、薄層トランジスタ（以下、「ＴＦＴ」）平坦化層もしくはＴＦＴ保護層またはＴＦＴアレイ形成における層間絶縁層もしくはゲート絶縁層には、高耐熱性の感光性組成物が用いられる。第１電極上に形成される画素分割層を形成する際、フォトリソグラフィーによってアノード（陽極）となる第１電極を露出させる開口部を、画素分割層に設ける必要がある。そのため、感光性組成物には、開口部のアノード表面における現像残渣を抑制することが求められる。また、有機ＥＬディスプレイの発光特性向上の観点からは、発光素子を高信頼性化すれば有機ＥＬディスプレイの耐久性向上を実現できる。加えて、発光素子を低電圧駆動できるようにすれば、高輝度化および省電力化を実現できる。そのため、感光性組成物には、発光素子の信頼性向上および低電圧駆動が可能な特性も求められる。 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 A highly heat-resistant photosensitive composition is used for the insulating layer. When forming the pixel division layer formed on the first electrode, it is necessary to provide an opening in the pixel division layer through photolithography to expose the first electrode, which will be the anode. Therefore, 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. In addition, if the light-emitting element can be driven at a low voltage, high luminance and low power consumption can be achieved. Therefore, the photosensitive composition is also required to have properties capable of improving the reliability of the light-emitting element and enabling low-voltage driving.
　また、画素分割層を形成した後、蒸着マスクを介して発光材料を蒸着によって成膜し、その後、第２電極を蒸着によって成膜するのが一般的である。なお、発光材料を蒸着によって成膜する際の蒸着マスクの支持台として、画素分割層の一部に膜厚の厚い領域（以下、「厚膜部」）を形成することも一般的である。このような厚膜部は、画素分割層を形成した後、その上層に感光性組成物を再度成膜してパターン加工する二層成膜プロセスで形成可能である。一方で、このような二層成膜プロセスでは、工程数増加による生産性低下および歩留まり低下が懸念される。そのため、画素分割層をフォトリソグラフィーによって形成する際、ハーフトーンフォトマスクを用いることで、画素分割層に厚膜部とそれ以外の部分（以下、「薄膜部」）とを一括形成するプロセスが適用されている。 Further, after forming the pixel dividing layer, it is common to form 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. Such 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. On the other hand, in such a two-layer film formation process, there is a concern that the increase in the number of steps will lead to a decrease in productivity and a decrease in yield. Therefore, when forming the pixel division layer by photolithography, a process is applied in which the thick film portion and the other portion (hereinafter referred to as the “thin film portion”) are collectively formed in the pixel division layer by using a halftone photomask. It is
　ところで、有機ＥＬディスプレイは自発光素子を有するため、屋外における太陽光などの外光が入射すると、その外光の反射によって視認性およびコントラストが低下する。そのため、外光を遮断して外光反射を低減する技術として、画素分割層を形成する感光性組成物中に着色剤を含有させて遮光性を向上させることが一般的である。 By the way, since 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.
　感光性組成物としては、アミドイミド樹脂を含有するネガ型感光性組成物（特許文献１参照）、およびポリイミドなどの第１の樹脂と、カルド系樹脂などの第２の樹脂とを含有するネガ型感光性組成物（特許文献２参照）などが挙げられる。 Examples of the photosensitive composition 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).
特開２０２０－１４８８１５号公報JP 2020-148815 A 国際公開第２０１７／１５９８７６号WO2017/159876
　上述した画素分割層の開口部のアノード（第１電極）表面における現像残渣は、感光性組成物の塗膜形成プロセスにおいて、プリベーク時の熱反応により塗膜中の成分のアルカリ溶解性が低下することが支配的要因になって発生する場合がある。特に、ネガ型の感光性組成物の場合、開口部は未露光部に相当するため、プリベーク時の塗膜のアルカリ溶解性低下は顕著な現像残渣悪化の要因となる。加えて、開口部のアノード表面における現像残渣は、所望の電流密度を得るにあたって必要な駆動電圧が高くなる要因になるばかりでなく、該現像残渣を起点としたダークスポットの発生の要因、および該現像残渣からのアウトガスによって、発光素子の信頼性を低下させる要因となる。 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. In particular, in the case of a negative photosensitive composition, since 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. In addition, 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.
　また、上述した画素分割層層の一部に厚膜部を形成するプロセスにおいて、感光性組成物の特性によっては、ハーフトーンフォトマスクを介したパターン露光により厚膜部と薄膜部とを所望の膜厚で一括形成する特性（以下、「ハーフトーン特性」）が不十分な場合がある。ハーフトーンフォトマスクを用いても、厚膜部と薄膜部との膜厚差を形成できない場合や、薄膜部が現像時に消失する場合がある。これはハーフトーンフォトマスクのハーフトーン部を介した比較的露光量の小さな光に対する、感光性組成物の感度が支配的要因となって発生すると考えられる。ポジ型の感光性組成物の場合、ハーフトーン部を介した光に対する感度が過剰であると、薄膜部が現像時に消失しやすい。一方、ネガ型の感光性組成物の場合、ハーフトーン部を介した光に対する感度が過剰であると、厚膜部と薄膜部との膜厚差が形成困難となりやすい。特に、ネガ型の感光性組成物の場合、比較的露光量が小さい領域では不十分な光硬化となりやすく、薄膜部が現像時に消失することも多いため、安定的なパターン加工が困難である。 In the process of forming the thick film portion in part of the pixel dividing layer described above, depending on the characteristics of the photosensitive composition, the thick film portion and the thin film portion may be formed into desired portions by pattern exposure through a halftone photomask. In some cases, the characteristics of batch formation by film thickness (hereinafter referred to as “halftone characteristics”) are insufficient. Even if a halftone photomask is used, there are cases where a film thickness difference between the thick film portion and the thin film portion cannot be formed, or the thin film portion disappears during development. It is considered that this is caused mainly by the sensitivity of the photosensitive composition to light with a relatively small amount of exposure through the halftone portion of the halftone photomask. In the case of a positive photosensitive composition, if the sensitivity to light through the halftone portion is excessive, the thin film portion tends to disappear during development. On the other hand, in the case of a negative photosensitive composition, excessive sensitivity to light through the halftone portion tends to make it difficult to form a film thickness difference between the thick film portion and the thin film portion. In particular, in the case of a negative photosensitive composition, insufficient photocuring tends to occur in areas where the exposure amount is relatively small, and the thin film portion often disappears during development, making stable pattern processing difficult.
　感光性組成物を用いたフォトリソグラフィーによる開口部の形成において、開口パターン寸法のバラツキが大きい場合、アノード上の発光画素領域の設計誤差に繋がるため、有機ＥＬディスプレイの発光特性バラツキなどの悪影響を及ぼす。例えば、開口パターン寸法によって電流密度が変化するため、発光素子の輝度バラツキおよび駆動電圧バラツキの要因となる。開口パターン寸法のバラツキは、パターン露光時の照度バラツキなどの装置による影響もあると考えられるが、材料特性によっても大きく左右される。 In the formation of openings by photolithography using a photosensitive composition, large variations in the dimensions of the opening pattern lead to design errors in the luminescent pixel regions on the anode, which adversely affects the luminescent characteristics of the organic EL display. . For example, since the current density changes depending on the size of the opening pattern, it becomes a factor of luminance variation and driving voltage variation of the light emitting element. Variation in aperture pattern size is considered to be affected by apparatus such as variation in illuminance during pattern exposure, but is also greatly affected by material properties.
　ポジ型の感光性組成物の場合、露光部の塗膜のアルカリ溶解性向上が、基板上の面内においてどの程度のバラツキがあるかの程度が、開口パターン寸法のバラツキに影響を与える。一般に、露光部の塗膜のアルカリ溶解性が過剰な場合に、開口パターン寸法のバラツキが大きくなりやすい。また、塗膜深部におけるアルカリ溶解性向上にバラツキがある場合も、開口パターン寸法のバラツキが大きくなりやすい。 In the case of a positive photosensitive composition, 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. In general, when the alkali solubility of the coating film in the exposed area is excessive, the size of the opening pattern tends to vary greatly. In addition, when there is variation in the improvement of alkali solubility in the deep part of the coating film, the variation in opening pattern dimensions tends to increase.
　一方、ネガ型の感光性組成物の場合、露光部の塗膜の光硬化によるアルカリ溶解性低下が、基板上の面内においてどの程度のバラツキがあるかの程度が、開口パターン寸法のバラツキに影響を与える。一般に、露光部の光硬化が過剰な場合、フォトマスクのパターン寸法以上の光硬化によってバラツキが大きくなりやすい。一方、露光部の光硬化が不十分な場合、アルカリ現像時の塗膜深部のサイドエッチングによってバラツキが大きくなりやすい。 On the other hand, in the case of a negative photosensitive composition, 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. In general, when the photo-curing of the exposed portion is excessive, the photo-curing over the pattern dimension of the photomask tends to cause large variations. On the other hand, if 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.
　さらに、ネガ型の感光性組成物を用いて上述したハーフトーンフォトマスクを介したパターン露光をする場合、ハーフトーン部を介した比較的露光量の小さな光が塗膜深部まで十分に到達しないため、塗膜深部の光硬化が不十分となりやすい。すなわち、ハーフトーンフォトマスクを用いてパターン加工する場合は、さらに開口パターン寸法のバラツキが大きくなりやすい。 Furthermore, when a negative photosensitive composition is used for pattern exposure through the above-mentioned halftone photomask, light with a relatively small exposure amount through the halftone portion does not sufficiently reach the deep portion of the coating film. , the photocuring of the deep part of the coating tends to be insufficient. That is, when patterning is performed using a halftone photomask, variations in opening pattern dimensions tend to increase.
　従って、感光性組成物には、現像後の残渣抑制、優れたハーフトーン特性および現像後における開口パターン寸法のバラツキ抑制を兼ね備える材料特性が要求される。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化を両立できる硬化物を提供可能な材料特性も要求される。しかしながら、上記の文献に記載の感光性組成物はいずれも、上記いずれかの特性が不十分であった。 Therefore, 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. In addition, there is also a demand for 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. However, all of the photosensitive compositions described in the above documents are insufficient in any of the above properties.
　上述した課題を解決するために、本発明の第一の態様である感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂および（Ｃ）感光剤を含有する感光性樹脂組成物であって、
前記（Ａ）アルカリ可溶性樹脂が、少なくとも以下の（ＡＸ）樹脂を含み、
さらに以下の（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂からなる群より選ばれる一種類以上の樹脂を含有する、感光性樹脂組成物である。
（ＡＸ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂。
（Ａ１）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
（Ａ２）樹脂：エチレン性不飽和二重結合基を有する樹脂。
（Ａ３）樹脂：フェノール性水酸基を有する樹脂。 In order to solve the above-described problems, 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.
　本発明の第二の態様である表示装置は、基板、第１電極、第２電極および画素分割層を少なくとも有し、
さらに、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層を有する表示装置であって、
前記画素分割層は、前記第１電極の上に第１電極の一部と重なるように形成され、
前記発光層を含む有機ＥＬ層および／または前記発光層を含む光取り出し層は、前記第１電極上、かつ前記第１電極および該第２電極の間に形成され、
前記画素分割層が、少なくとも以下の（Ｘ－ＤＬ）樹脂を有し、
さらに以下の（Ｉ－ＤＬ）樹脂、（ＩＩ－ＤＬ）樹脂および（ＩＩＩ－ＤＬ）樹脂からなる群より選ばれる一種類以上の樹脂を有する表示装置である。
（Ｘ－ＤＬ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂。
（Ｉ－ＤＬ）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する樹脂。
（ＩＩ－ＤＬ）樹脂：一般式（２４）で表される構造単位を有する樹脂。
（ＩＩＩ－ＤＬ）樹脂：フェノール樹脂、ポリヒドロキシスチレン、フェノール基変性エポキシ樹脂およびフェノール基変性アクリル樹脂からなる群より選ばれる一種類以上の樹脂。 A display device according to a second aspect of the present invention 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.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（２４）において、Ｒ６７～Ｒ６９は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表す。ａは０または１である。＊１は樹脂中の結合点を表す。 In general formula (24), 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.
　本発明の第一の態様である感光性樹脂組成物によれば、現像後の残渣抑制、優れたハーフトーン特性、および現像後における開口パターン寸法のバラツキ抑制を兼ね備える感光性樹脂組成物を提供可能である。加えて、本発明の第一の態様である感光性樹脂組成物によれば、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化を両立できる硬化物を提供可能である。 According to 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. In addition, according to 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.
　本発明の第二の態様である表示装置によれば、発光素子の信頼性向上および発光素子の低電圧駆動化を兼ね備える表示装置を提供可能である。 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.
図１は、本発明の第一の態様の感光性樹脂組成物の硬化物を用いた有機ＥＬディスプレイにおける工程１～工程７の製造プロセスを模式的断面で例示する工程図である。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. 図２は、パターン寸法バラツキ評価に用いたハーフトーンフォトマスクにおける、透光部、遮光部、および半透光部の、配置および寸法の概略図である。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. 図３は、ハーフトーン特性評価に用いたハーフトーンフォトマスクにおける、透光部、遮光部、および半透光部の、配置および寸法を例示する概略図である。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. 図４は、発光特性評価に用いた有機ＥＬディスプレイの基板における工程１～工程４の製造プロセスを平面図で例示する概略図である。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.
　以下、本発明の第一の態様である感光性樹脂組成物について述べる。また本発明の第二の態様である表示装置についても述べる。なお本発明の感光性樹脂組成物と記載する場合、本発明の第一の態様である感光性樹脂組成物に関する記載である。また本発明の表示装置と記載する場合、本発明の第二の態様である表示装置、および、本発明の第一の態様である感光性樹脂組成物を硬化した硬化物を具備する表示装置に関する記載である。 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. When describing 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. Further, when describing 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.
　＜第一の態様の感光性樹脂組成物＞
　本発明の第一の態様である感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂および（Ｃ）感光剤を含有する感光性樹脂組成物であって、
前記（Ａ）アルカリ可溶性樹脂が、少なくとも以下の（ＡＸ）樹脂を含み、
さらに以下の（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂からなる群より選ばれる一種類以上の樹脂を含有する、感光性樹脂組成物である。
（ＡＸ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂。
（Ａ１）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
（Ａ２）樹脂：エチレン性不飽和二重結合基を有する樹脂。
（Ａ３）樹脂：フェノール性水酸基を有する樹脂。 <Photosensitive resin composition of the first aspect>
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.
　＜（Ａ）アルカリ可溶性樹脂；（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂＞
　本発明の第一の態様の感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂を含有し、（Ａ）アルカリ可溶性樹脂が、少なくとも（ＡＸ）樹脂を含み、さらに以下の（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂からなる群より選ばれる一種類以上の樹脂を含有する。
（Ａ１）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
（Ａ２）樹脂：エチレン性不飽和二重結合基を有する樹脂。
（Ａ３）樹脂：フェノール性水酸基を有する樹脂。
エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。 <(A) alkali-soluble resin; (A1) resin, (A2) resin and (A3) resin>
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.
　（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂からなる群より選ばれる一種類以上の樹脂を含有することで、現像後の残渣抑制、およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著となる。 (A) 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.
　（Ａ１）樹脂とは、樹脂の主鎖、樹脂の側鎖および樹脂の末端にエチレン性不飽和二重結合基を有さず、樹脂の構造単位中にイミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を有する樹脂をいう。
本発明において、イミド構造とは、後述のポリイミド前駆体構造も含むものとする。また、オキサゾール構造とは、後述のポリベンゾオキサゾール前駆体構造も含むものとする。 (A1) 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. A resin having one or more structures selected from the group consisting of structures.
In the present invention, the imide structure also includes the polyimide precursor structure described below. The oxazole structure also includes the polybenzoxazole precursor structure described below.
　（Ａ２）樹脂とは、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにエチレン性不飽和二重結合基を有する樹脂をいう。 (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.
　（Ａ３）樹脂とは、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにフェノール性水酸基を有する樹脂であって、（Ａ１）樹脂および（Ａ２）樹脂とは異なる樹脂をいう。 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.
　なお、（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂は、これらの中で、それぞれが、別の樹脂を構成する構造や基を有する場合は、以下の規則によりいずれかに分類するものとする。本発明においては、樹脂の構造単位中にイミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を有し、かつ、エチレン性不飽和二重結合基を有さない樹脂がフェノール性水酸基を有する場合、（Ａ１）樹脂に分類する。また、樹脂の構造単位中にイミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を有する樹脂が、エチレン性不飽和二重結合基を有し、かつ、フェノール性水酸基を有しない場合、（Ａ２）樹脂に分類する。エチレン性不飽和二重結合基を有する樹脂がフェノール性水酸基を有しない場合、（Ａ２）樹脂に分類する。一方、エチレン性不飽和二重結合基を有する樹脂がフェノール性水酸基を有する場合、（Ａ３）樹脂に分類する。なお、イミド構造、アミド構造、オキサゾール構造、およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有し、エチレン性不飽和二重結合基を有し、さらにフェノール性水酸基を有する樹脂は、（Ａ２）樹脂に分類する。なお、樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、他の構造にかかわらず、全て（ＡＸ）樹脂に分類するものとする。すなわち、樹脂の構造単位中にイミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を有する樹脂、エチレン性不飽和二重結合基を有する樹脂またはフェノール性水酸基を有する樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂には含めず、（ＡＸ）樹脂に分類する。 In addition, (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. and In the present invention, 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. Further, 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. When a resin having an ethylenically unsaturated double bond group does not have a phenolic hydroxyl group, it is classified as (A2) resin. On the other hand, when a resin having an ethylenically unsaturated double bond group has a phenolic hydroxyl group, it is classified as (A3) resin. In addition, it 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. That is, 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, a resin having an ethylenically unsaturated double bond group, or a phenolic hydroxyl group in the structural unit of the resin. When 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.
　（Ａ）アルカリ可溶性樹脂は、前記（Ａ１）樹脂および／または前記（Ａ３）樹脂を含有することが好ましい。 The (A) alkali-soluble resin preferably contains the (A1) resin and/or the (A3) resin.
　（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂および／または（Ａ３）樹脂を含有することで、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上、および発光素子の低電圧駆動化の効果が顕著となる。（Ａ）アルカリ可溶性樹脂は、（Ａ１）樹脂を含有することがより好ましく、（Ａ１）樹脂および（Ａ３）樹脂を含有することがさらに好ましく、フェノール性水酸基を有する（Ａ１）樹脂を含有することが最も好ましい。 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.
　上述した通り、ポジ型の感光性組成物の場合、露光部のアルカリ溶解性が過剰な場合に、現像後における開口パターン寸法のバラツキが大きくなりやすい。フェノール性水酸基を有する（Ａ３）樹脂を含有させることで、フェノール性水酸基の適度なアルカリ溶解促進作用によって、露光部がアルカリ溶解性過剰となり難く、現像後における開口パターン寸法のバラツキ抑制がされると考えられる。また、未露光部ではフェノール性水酸基の温和な酸性度によって、現像時にハーフトーン露光部が緩やかな膜減りをするためハーフトーン加工性が向上すると推定される。剛直な骨格であるイミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する（Ａ１）樹脂を含有させることで、剛直な骨格によるアルカリ溶解阻害により露光部がアルカリ溶解性過剰となり難く、またハーフトーン露光部が緩やかな現像膜減りをするため、現像後における開口パターン寸法のバラツキ抑制およびハーフトーン特性向上がされると考えられる。 As described above, in the case of a positive photosensitive composition, if the exposed area has excessive alkali solubility, the size of the opening pattern tends to vary greatly after development. 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. In the unexposed area, 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. Inhibition of alkaline dissolution by a rigid skeleton by containing the (A1) resin having a structural unit containing one or more types of structures selected from the group consisting of an imide structure, an amide structure, an oxazole structure, and a siloxane structure, which are rigid skeletons. Due to this, the exposed area is unlikely to become excessively soluble in alkali, and the developed film is gradually reduced in the halftone exposed area.
　一方、ネガ型の感光性組成物の場合、一般にパターン露光時に発生したラジカルによる光硬化の影響で開口パターン寸法のバラツキが発生しやすい。フェノール性水酸基を有する（Ａ３）樹脂を含有させることで、フェノール性水酸基の適度なアルカリ溶解促進作用によって、露光部におけるアルカリ現像時の膜深部のサイドエッチングが抑制され、現像後における開口パターン寸法のバラツキ抑制がされると考えられる。また、フェノール性水酸基によって露光部における過度な光硬化を制御することで、露光量に対する光硬化度の勾配を緩やかにできると考えられる。加えて、フェノール性水酸基の温和な酸性度によって、現像時にハーフトーン露光部が緩やかな膜減りをするためハーフトーン加工性が向上すると推定される。剛直な骨格であるイミド構造、アミド構造、オキサゾール構造、およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する（Ａ１）樹脂を含有させることで、剛直な骨格による立体障害や分子運動阻害により露光部における過度な光硬化が制御される。さらに、剛直な骨格によるアルカリ溶解阻害により露光部におけるアルカリ現像時の膜深部におけるサイドエッチングが抑制され、またハーフトーン露光部が緩やかな現像膜減りをするなどの効果が顕著となる。そのため、現像後における開口パターン寸法のバラツキ抑制およびハーフトーン特性向上がされると考えられる。 On the other hand, in the case of a negative photosensitive composition, the size of the opening pattern tends to vary due to photocuring caused by radicals generated during pattern exposure. By containing 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. In addition, it is considered that 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. In addition, it is presumed that the mild acidity of the phenolic hydroxyl group causes gradual film reduction in the halftone-exposed areas during development, thereby improving the halftone workability. By containing 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. In addition, due to the inhibition of alkali dissolution by the rigid skeleton, side etching in the deep portion of the film during alkali development in the exposed area is suppressed, and effects such as gradual reduction of the developed film in the halftone exposed area are remarkable. Therefore, it is considered that the variation in the size of the opening pattern after development is suppressed and the halftone characteristics are improved.
　前記（Ａ１）樹脂は、以下の（Ａ１－１）樹脂、（Ａ１－２）樹脂、（Ａ１－３）樹脂、（Ａ１－４）樹脂、（Ａ１－５）樹脂および（Ａ１－６）樹脂からなる群より選ばれる一種類以上の樹脂を含有することが好ましい。これにより、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。
（Ａ１－１）樹脂：ポリイミド。
（Ａ１－２）樹脂：ポリイミド前駆体。
（Ａ１－３）樹脂：ポリベンゾオキサゾール。
（Ａ１－４）樹脂：ポリベンゾオキサゾール前駆体。
（Ａ１－５）樹脂：ポリアミドイミド。
（Ａ１－６）樹脂：ポリシロキサン。 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.
(A1-1) Resin: polyimide.
(A1-2) Resin: polyimide precursor.
(A1-3) Resin: Polybenzoxazole.
(A1-4) Resin: Polybenzoxazole precursor.
(A1-5) Resin: polyamideimide.
(A1-6) Resin: Polysiloxane.
　（Ａ１）樹脂は、（Ａ１－１）樹脂、（Ａ１－２）樹脂、（Ａ１－３）樹脂、（Ａ１－４）樹脂および（Ａ１－５）樹脂からなる群より選ばれる一種類以上の樹脂を含有することがより好ましく、（Ａ１－１）樹脂および／または（Ａ１－５）樹脂を含有することがさらに好ましい。（Ａ１）樹脂は、単一の樹脂および共重合体のいずれであっても構わない。 (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. (A1) The resin may be either a single resin or a copolymer.
　（Ａ３）樹脂は、（Ａ３－１）フェノール樹脂、（Ａ３－２）ポリヒドロキシスチレン、（Ａ３－３）フェノール基変性エポキシ樹脂および（Ａ３－４）フェノール基変性アクリル樹脂からなる群より選ばれる一種類以上の樹脂を含有することが好ましい。これによって、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の低電圧駆動化の効果が顕著となる。（Ａ３）樹脂は、（Ａ３－１）樹脂および／または（Ａ３－３）樹脂を含有することがより好ましく、（Ａ３－１）樹脂を含有することがさらに好ましい。（Ａ３）樹脂は、単一の樹脂および共重合体のいずれであっても構わない。 (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.
　＜（Ａ）アルカリ可溶性樹脂；（Ａ３ａ）樹脂および（Ａ３ｂ）樹脂＞
　本発明の第一の態様の感光性樹脂組成物は、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、（Ａ３）樹脂が、（Ａ３－１）樹脂、（Ａ３－２）樹脂、（Ａ３－３）樹脂および（Ａ３－４）樹脂からなる群より選ばれる一種類以上の樹脂であって、以下の（Ａ３ｂ）樹脂に該当する樹脂を含有することも好ましい。
（Ａ３ｂ）樹脂：（Ａ３）樹脂のうち、フェノール性水酸基、およびエチレン性不飽和二重結合基を有する樹脂。 <(A) alkali-soluble resin; (A3a) resin and (A3b) resin>
In the photosensitive resin composition of the first aspect of the present invention, from the viewpoint of improving sensitivity during exposure, suppressing residue after development, and suppressing variation in opening pattern dimensions after development, (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.
　（Ａ３ｂ）樹脂とは、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにフェノール性水酸基を有し、かつ、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにエチレン性不飽和二重結合基を有する樹脂であって、（Ａ１）樹脂とは異なる樹脂をいう。 (A3b) 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).
　（Ａ３ｂ）樹脂が有するエチレン性不飽和二重結合基は、露光時の感度向上の観点から、ラジカル重合性基であることが好ましく、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基であることがより好ましい。光反応性基としては、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基が好ましく、（メタ）アクリロイル基がより好ましい。炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基が好ましく、ビニル基またはアリル基がより好ましい。 (A3b) 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. Examples of the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms 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.
　（Ａ３ｂ）樹脂の二重結合当量は、ハーフトーン特性向上の観点から、５００ｇ／ｍｏｌ以上が好ましく、７００ｇ／ｍｏｌ以上がより好ましく、１，０００ｇ／ｍｏｌ以上がさらに好ましい。一方、二重結合当量は、露光時の感度向上、および現像後における開口パターン寸法のバラツキ抑制の観点から、３，０００ｇ／ｍｏｌ以下が好ましく、２，０００ｇ／ｍｏｌ以下がより好ましく、１，５００ｇ／ｍｏｌ以下がさらに好ましい。 (A3b) 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. On the other hand, 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.
　本発明の第一の態様の感光性樹脂組成物は、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、（Ａ３）樹脂が、（Ａ３－１）樹脂、（Ａ３－２）樹脂、（Ａ３－３）樹脂および（Ａ３－４）樹脂からなる群より選ばれる一種類以上の樹脂であって、以下の（Ａ３ａ）樹脂に該当する樹脂を含有することも好ましい。
（Ａ３ａ）樹脂：（Ａ３）樹脂のうち、フェノール性水酸基を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
ここで、（Ａ３ａ）樹脂がエチレン性不飽和二重結合基を有しないとは、ラジカル重合性基であるエチレン性不飽和二重結合基を有しないことを意味する。 In the photosensitive resin composition of the first aspect of the present invention, from the viewpoint of suppressing residue after development, improving halftone characteristics, and suppressing variation in opening pattern dimensions after development, (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.
Here, (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.
　（Ａ３ａ）樹脂とは、樹脂の主鎖、樹脂の側鎖および樹脂の末端にエチレン性不飽和二重結合基を有さず、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにフェノール性水酸基を有する樹脂であって、（Ａ１）樹脂および（Ａ２）樹脂とは異なる樹脂をいう。なお、（Ａ）アルカリ可溶性樹脂が上述した（Ａ３ｂ）樹脂を含有する場合、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、（Ａ）アルカリ可溶性樹脂が、さらに上述した（Ａ３ａ）樹脂を含有することが好ましい。 (A3a) 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). When (A) 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, (A) The alkali-soluble resin preferably further contains the above-described (A3a) resin.
　（Ａ）アルカリ可溶性樹脂は、前記（Ａ２）樹脂を含有することも好ましい。（Ａ）アルカリ可溶性樹脂が、（Ａ２）樹脂を含有することで、露光時の感度向上、現像後の残渣抑制およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著となる。
（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂および／または（Ａ３）樹脂を含有し、さらに前記（Ａ２）樹脂を含有することがより好ましい。（Ａ）アルカリ可溶性樹脂は、（Ａ１）樹脂および（Ａ２）樹脂を含有することがより好ましく、（Ａ１）樹脂、（Ａ３）樹脂、および（Ａ２）樹脂を含有することがさらに好ましい。 (A) The alkali-soluble resin preferably contains the (A2) resin. When 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.
(A) Alkali-soluble resin more preferably contains (A1) resin and/or (A3) resin, and further contains (A2) resin. (A) Alkali-soluble resin more preferably contains (A1) resin and (A2) resin, and more preferably contains (A1) resin, (A3) resin and (A2) resin.
　（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂および／または（Ａ３）樹脂を含有し、さらに（Ａ２）樹脂を含有することで、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上、および発光素子の低電圧駆動化の効果が顕著となる。 (A) 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.
　（Ａ２）樹脂が有するエチレン性不飽和二重結合基は、露光時の感度向上の観点から、ラジカル重合性基であることが好ましく、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基であることがより好ましい。光反応性基としては、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基が好ましく、（メタ）アクリロイル基がより好ましい。炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基が好ましく、ビニル基またはアリル基がより好ましい。 (A2) 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. Examples of the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms 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）樹脂は、以下の（Ａ２－ａ）樹脂、（Ａ２－ｂ）樹脂、（Ａ２－ｃ）樹脂、（Ａ２－ｄ）樹脂、（Ａ２－ｅ）樹脂、（Ａ２－ｆ）樹脂、（Ａ２－１）樹脂、（Ａ２－２）樹脂および（Ａ２－３）樹脂からなる群より選ばれる一種類以上の樹脂を含有することが好ましい。
（Ａ２－ａ）樹脂：エチレン性不飽和二重結合基含有ポリイミド。
（Ａ２－ｂ）樹脂：エチレン性不飽和二重結合基含有ポリイミド前駆体。
（Ａ２－ｃ）樹脂：エチレン性不飽和二重結合基含有ポリベンゾオキサゾール。
（Ａ２－ｄ）樹脂：エチレン性不飽和二重結合基含有ポリベンゾオキサゾール前駆体。
（Ａ２－ｅ）樹脂：エチレン性不飽和二重結合基含有ポリアミドイミド。
（Ａ２－ｆ）樹脂：エチレン性不飽和二重結合基含有ポリシロキサン。
（Ａ２－１）樹脂：多環側鎖含有樹脂。
（Ａ２－２）樹脂：酸変性エポキシ樹脂。
（Ａ２－３）樹脂：アクリル樹脂。 (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.
(A2-b) Resin: Ethylenically unsaturated double bond group-containing polyimide precursor.
(A2-c) Resin: Ethylenically unsaturated double bond group-containing polybenzoxazole.
(A2-d) 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.
(A2-3) Resin: acrylic resin.
　現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、（Ａ２）樹脂は、（Ａ２－ａ）樹脂、（Ａ２－ｂ）樹脂、（Ａ２－ｃ）樹脂、（Ａ２－ｄ）樹脂、（Ａ２－ｅ）樹脂および（Ａ２－ｆ）樹脂からなる群より選ばれる一種類以上の樹脂を含有することがより好ましく、（Ａ２－ａ）樹脂、（Ａ２－ｂ）樹脂、（Ａ２－ｃ）樹脂、（Ａ２－ｄ）樹脂および（Ａ２－ｅ）樹脂からなる群より選ばれる一種類以上の樹脂を含有することがさらに好ましく、（Ａ２－ａ）樹脂および／または（Ａ２－ｅ）樹脂を含有することが特に好ましい。一方、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、（Ａ２）樹脂は、（Ａ２－１）樹脂、（Ａ２－２）樹脂および（Ａ２－３）樹脂からなる群より選ばれる一種類以上の樹脂を含有することがより好ましく、（Ａ２－１）樹脂および／または（Ａ２－２）樹脂を含有することがさらに好ましい。 From the viewpoint of suppressing residues after development, improving halftone characteristics, suppressing variations in opening pattern dimensions after development, improving the reliability of light-emitting elements in organic EL displays, and driving light-emitting elements at low voltage, (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. On the other hand, from the viewpoint of improving sensitivity during exposure, suppressing residue after development, and suppressing variation in opening pattern dimensions after development, (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.
　また、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、（Ａ２）樹脂は、（Ａ２－ａ）樹脂、（Ａ２－ｂ）樹脂、（Ａ２－ｃ）樹脂、（Ａ２－ｄ）樹脂、（Ａ２－ｅ）樹脂、および（Ａ２－ｆ）樹脂からなる群より選ばれる一種類以上の樹脂を含有し、さらに（Ａ２－１）樹脂、（Ａ２－２）樹脂、および（Ａ２－３）樹脂からなる群より選ばれる一種類以上の樹脂を含有することも好ましい。（Ａ２）樹脂は、単一の樹脂および共重合体のいずれであっても構わない。 In addition, from the viewpoint of improving sensitivity during exposure, suppressing residue after development, improving halftone characteristics, suppressing variations in opening pattern dimensions after development, improving reliability of light-emitting elements in organic EL displays, and driving light-emitting elements at low voltage. From the viewpoint, (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. (A2) The resin may be either a single resin or a copolymer.
　＜（Ａ）アルカリ可溶性樹脂；（ＡＸ）樹脂＞
　前記（Ａ）アルカリ可溶性樹脂は、少なくとも以下の（ＡＸ）樹脂を含む。
（ＡＸ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂。 <(A) alkali-soluble resin; (AX) resin>
The (A) alkali-soluble 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.
　（Ａ）アルカリ可溶性樹脂とは、後述のアルカリ可溶性基を有する樹脂をいう。アルカリ可溶性樹脂は、アルカリ可溶性基を有することによって、アルカリ現像液に対する溶解性を有する。（Ａ）アルカリ可溶性樹脂は、後述する（Ｃ）感光剤によって、組成物にポジ型またはネガ型の感光性が付与され、アルカリ現像液で現像することでポジ型またはネガ型のパターンを形成可能な溶解性を有する樹脂が好ましい。 (A) 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. (A) 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.
　（Ａ）アルカリ可溶性樹脂が、少なくとも（ＡＸ）樹脂を含有することで、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。 When 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. 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.
　（ＡＸ）樹脂とは、樹脂の構造単位中に窒素原子を少なくとも３つ有する環状構造を含む構造単位（以下、「（ＡＸ）樹脂の環状構造単位」）を有する樹脂をいう。窒素原子を少なくとも３つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましく、イソシアヌル酸構造がより好ましい。 (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.
　（ＡＸ）樹脂としては、イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する樹脂（以下、「特定の（ＡＸ）樹脂」）が好ましい。すなわち、（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有することが好ましい。（ＡＸ）樹脂が、イソシアヌル酸構造を含む構造単位を有することがより好ましい。 As 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. . That is, 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂および／または（Ａ３）樹脂を含有し、（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有することが好ましい。（ＡＸ）樹脂は、イソシアヌル酸構造を含む構造単位を有することがより好ましい。 In the photosensitive resin composition of the first aspect of the present invention, (A) 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.
　（ＡＸ）樹脂が、これらの構造単位を有することで、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。 By having these structural units in the (AX) resin, 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 driving the light-emitting element at a low voltage becomes remarkable.
　本発明の第一の態様の感光性樹脂組成物において、（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂および／または（Ａ３）樹脂を含有し、（ＡＸ）樹脂がイソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位が、脂肪族構造、脂環式構造および芳香族構造からなる群より選ばれる一種類以上の構造を有する有機基を、少なくとも２つ有することが好ましい。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　（ＡＸ）樹脂が、これらの構造を有することで、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。脂肪造構造は、炭素数１～２０の脂肪族構造が好ましく、炭素数１～２０のアルキレン基がより好ましく、炭素数１～１０のアルキレン基がさらに好ましい。脂環式構造は、炭素数４～２０の脂環式構造が好ましく、炭素数４～２０のシクロアルキレン基がより好ましく、炭素数４～１０のシクロアルキレン基がさらに好ましい。芳香族構造は、炭素数６～３０の芳香族構造が好ましく、炭素数６～３０のアリーレン基がより好ましく、炭素数６～１５のアリーレン基がさらに好ましい。 When the (AX) resin has these structures, the effects of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development are 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 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.
　本発明の第一の態様の感光性樹脂組成物は、（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、以下の（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂、（ＡＸ－５）樹脂および（ＡＸ－６）樹脂からなる群より選ばれる一種類以上の樹脂（以下、「特に好適な（ＡＸ）樹脂」ということがある）を含有することが好ましい。 In the photosensitive resin composition of the first aspect of the present invention, 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").
　本発明の第一の態様の感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂が、（Ａ１）樹脂および／または（Ａ３）樹脂を含有し、（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、以下の（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂、（ＡＸ－５）樹脂および（ＡＸ－６）樹脂からなる群より選ばれる一種類以上の樹脂を含有することが好ましい。（ＡＸ）樹脂は、イソシアヌル酸構造を含む構造単位を有することがより好ましい。
（ＡＸ－１）樹脂：窒素環含有ポリイミド。
（ＡＸ－２）樹脂：窒素環含有ポリイミド前駆体。
（ＡＸ－３）樹脂：窒素環含有ポリベンゾオキサゾール。
（ＡＸ－４）樹脂：窒素環含有ポリベンゾオキサゾール前駆体。
（ＡＸ－５）樹脂：窒素環含有ポリアミドイミド。
（ＡＸ－６）樹脂：窒素環含有ポリシロキサン。 In the photosensitive resin composition of the first aspect of the present invention, (A) 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）樹脂が、（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂、（ＡＸ－５）樹脂および（ＡＸ－６）樹脂からなる群より選ばれる一種類以上の樹脂を含有することで、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上、および発光素子の低電圧駆動化の効果が顕著となる。（ＡＸ）樹脂は、（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂および（ＡＸ－５）樹脂からなる群より選ばれる一種類以上の樹脂を含有することがより好ましく、（ＡＸ－１）樹脂および／または（ＡＸ－５）樹脂を含有することがさらに好ましい。（ＡＸ）樹脂は、単一の樹脂および共重合体のいずれであっても構わない。ここでいう窒素環とは、「（ＡＸ）樹脂の環状構造単位」、すなわち、窒素原子を少なくとも３つ有する環状構造を含む構造単位をいう。なお、（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂、（ＡＸ－５）樹脂および（ＡＸ－６）樹脂は、窒素環としてイソシアヌル酸構造および／またはトリアジン構造を有する。 (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 By containing one or more selected resins, the effects of suppressing post-development residues, 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 driving the light-emitting element at a low voltage becomes remarkable. (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. The term "nitrogen ring" as used herein refers to a "(AX) resin cyclic structural unit", that is, a structural unit containing a cyclic structure having at least three nitrogen atoms. In addition, (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.
　＜（Ａ）アルカリ可溶性樹脂；（ＡＸａ）樹脂および（ＡＸｂ）樹脂＞
　（Ａ）アルカリ可溶性樹脂が、以下の（ＡＸｂ）樹脂を含有することが好ましい。
（ＡＸｂ）樹脂：（ＡＸ）樹脂のうち、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、さらにエチレン性不飽和二重結合基を有する樹脂。 <(A) alkali-soluble resin; (AXa) resin and (AXb) resin>
(A) 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.
　（Ａ）アルカリ可溶性樹脂が、（ＡＸｂ）樹脂を含有することで、露光時の感度向上、現像後の残渣抑制、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。（ＡＸｂ）樹脂とは、樹脂の構造単位中に（ＡＸ）樹脂の環状構造単位を有し、かつ、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにエチレン性不飽和二重結合基を有する樹脂をいう。 When the (A) alkali-soluble resin contains the (AXb) resin, the effects of improving sensitivity during exposure, suppressing residues after development, and suppressing variations in opening pattern dimensions after development become remarkable. 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.
　（ＡＸｂ）樹脂が有するエチレン性不飽和二重結合基は、露光時の感度向上の観点から、ラジカル重合性基であることが好ましく、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基であることがより好ましい。光反応性基は、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基が好ましく、（メタ）アクリロイル基がより好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基は、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基が好ましく、ビニル基またはアリル基がより好ましい。 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. On the other hand, 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.
　（Ａ）アルカリ可溶性樹脂が、以下の（ＡＸａ）樹脂を含有することが好ましい。
（ＡＸａ）樹脂：（ＡＸ）樹脂のうち、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
ここで、（ＡＸａ）樹脂がエチレン性不飽和二重結合基を有しないとは、ラジカル重合性基である、エチレン性不飽和二重結合基を有しないことを意味する。 (A) 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.
Here, 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.
　（Ａ）アルカリ可溶性樹脂が、（ＡＸａ）樹脂を含有することで、現像後の残渣抑制、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。（ＡＸａ）樹脂とは、樹脂の構造単位中に（ＡＸ）樹脂の環状構造単位を有し、かつ、樹脂の主鎖、樹脂の側鎖および樹脂の末端にエチレン性不飽和二重結合基を有しない樹脂をいう。 When 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
　（Ａ）アルカリ可溶性樹脂が、前記（ＡＸｂ）樹脂および前記（ＡＸａ）樹脂含有することが好ましい。 (A) The alkali-soluble resin preferably contains the (AXb) resin and the (AXa) resin.
　（Ａ）アルカリ可溶性樹脂が、（ＡＸａ）樹脂および（ＡＸｂ）樹脂を含有することで、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。 (A) 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.
　＜アルカリ可溶性基＞
　（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基として酸性基を有する。（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂は、酸性基を有する構造単位および酸性基を有する末端構造のうち少なくとも１つを有することが好ましい。（Ａ１）樹脂、（Ａ２）樹脂および（ＡＸ）樹脂において、酸性基としては、カルボキシ基、カルボン酸無水物基、フェノール性水酸基、ヒドロキシイミド基、ヒドロキシアミド基、シラノール基、１，１－ビス（トリフルオロメチル）メチロール基、スルホン酸基またはメルカプト基が好ましい。ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、フェノール性水酸基、ヒドロキシイミド基、ヒドロキシアミド基、シラノール基または１，１－ビス（トリフルオロメチル）メチロール基がより好ましく、フェノール性水酸基またはシラノール基がさらに好ましく、フェノール性水酸基が特に好ましい。一方、現像後の残渣抑制の観点から、カルボキシ基またはカルボン酸無水物基が好ましい。 <Alkali-soluble group>
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. In the (A1) resin, (A2) resin and (AX) resin, 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. On the other hand, a carboxy group or a carboxylic anhydride group is preferred from the viewpoint of suppressing residue after development.
　（ＡＸ）樹脂の酸当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、２００ｇ／ｍｏｌ以上が好ましく、２５０ｇ／ｍｏｌ以上がより好ましく、３００ｇ／ｍｏｌ以上がさらに好ましい。一方、酸当量は、現像後の残渣抑制の観点から、６００ｇ／ｍｏｌ以下が好ましく、５００ｇ／ｍｏｌ以下がより好ましく、４５０ｇ／ｍｏｌ以下がさらに好ましい。 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. On the other hand, 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.
　（Ａ１）樹脂の酸当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、２００ｇ／ｍｏｌ以上が好ましく、２５０ｇ／ｍｏｌ以上がより好ましく、３００ｇ／ｍｏｌ以上がさらに好ましい。一方、酸当量は、現像後の残渣抑制の観点から、６００ｇ／ｍｏｌ以下が好ましく、５００ｇ／ｍｏｌ以下がより好ましく、４５０ｇ／ｍｏｌ以下がさらに好ましい。 (A1) 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. On the other hand, 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.
　（Ａ２）樹脂の酸当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、３００ｇ／ｍｏｌ以上が好ましく、３５０ｇ／ｍｏｌ以上がより好ましく、４００ｇ／ｍｏｌ以上がさらに好ましい。一方、酸当量は、現像後の残渣抑制の観点から、７００ｇ／ｍｏｌ以下が好ましく、６００ｇ／ｍｏｌ以下がより好ましく、５５０ｇ／ｍｏｌ以下がさらに好ましい。 (A2) 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. On the other hand, 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.
　（Ａ３）樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基としてフェノール性水酸基を有する。（Ａ３）樹脂は、フェノール性水酸基を有する構造単位およびフェノール性水酸基を有する末端構造のうち少なくとも１つを有することが好ましい。また、その他の酸性基を有しても構わない。その他の酸性基としては、カルボキシ基、カルボン酸無水物基、ヒドロキシイミド基、ヒドロキシアミド基、シラノール基、１，１－ビス（トリフルオロメチル）メチロール基、スルホン酸基またはメルカプト基が好ましく、ハーフトーン特性向上の観点から、ヒドロキシイミド基、ヒドロキシアミド基、シラノール基または１，１－ビス（トリフルオロメチル）メチロール基が好ましい。一方、現像後の残渣抑制の観点から、カルボキシ基またはカルボン酸無水物基が好ましい。 (A3) 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. (A3) 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. On the other hand, a carboxy group or a carboxylic anhydride group is preferred from the viewpoint of suppressing residue after development.
　（Ａ３）樹脂の酸当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、７０ｇ／ｍｏｌ以上が好ましく、８０ｇ／ｍｏｌ以上がより好ましく、９０ｇ／ｍｏｌ以上がさらに好ましい。一方、酸当量は、現像後の残渣抑制の観点から、４５０ｇ／ｍｏｌ以下が好ましく、３５０ｇ／ｍｏｌ以下がより好ましく、３００ｇ／ｍｏｌ以下がさらに好ましい。 (A3) 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. On the other hand, 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.
　＜（Ａ）アルカリ可溶性樹脂；（ＡＸ１）樹脂、（ＡＸ２）樹脂および（ＡＸ３）樹脂＞
　（Ａ）アルカリ可溶性樹脂が、（ＡＸ）樹脂として、以下の（ＡＸ１）樹脂、（ＡＸ２）樹脂および（ＡＸ３）樹脂からなる群より選ばれる一種類以上の樹脂を含有することが好ましい。
（ＡＸ１）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
（ＡＸ２）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、さらにエチレン性不飽和二重結合基を有する樹脂。
（ＡＸ３）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、さらにフェノール性水酸基を有する樹脂。 <(A) Alkali-soluble resin; (AX1) resin, (AX2) resin and (AX3) resin>
(A) 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.
　上述した（Ａ１－１）樹脂、（Ａ１－２）樹脂、（Ａ１－３）樹脂、（Ａ１－４）樹脂、（Ａ１－５）樹脂および（Ａ１－６）樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、それらの樹脂は（ＡＸ）樹脂に分類される。そのような樹脂を、それぞれ以下の（ＡＸ１－１）樹脂、（ＡＸ１－２）樹脂、（ＡＸ１－３）樹脂、（ＡＸ１－４）樹脂、（ＡＸ１－５）樹脂および（ＡＸ１－６）樹脂というものとする。
（ＡＸ１－１）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリイミド。
（ＡＸ１－２）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリイミド前駆体。
（ＡＸ１－３）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリベンゾオキサゾール。
（ＡＸ１－４）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリベンゾオキサゾール前駆体。
（ＡＸ１－５）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリアミドイミド。
（ＡＸ１－６）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリシロキサン。 The above-mentioned (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.
(AX1-5) Resin: Nitrogen ring-containing polyamideimide having no ethylenically unsaturated double bond group.
(AX1-6) Resin: Nitrogen ring-containing polysiloxane having no ethylenically unsaturated double bond group.
　上述した（Ａ２－ａ）樹脂（Ａ２－ｂ）樹脂、（Ａ２－ｃ）樹脂、（Ａ２－ｄ）樹脂、（Ａ２－ｅ）樹脂および（Ａ２－ｆ）樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、それらの樹脂は（ＡＸ）樹脂に分類される。そのような樹脂を、それぞれ以下の（ＡＸ２－ａ）樹脂（ＡＸ２－ｂ）樹脂、（ＡＸ２－ｃ）樹脂、（ＡＸ２－ｄ）樹脂、（ＡＸ２－ｅ）樹脂および（ＡＸ２－ｆ）樹脂というものとする。
（ＡＸ２－ａ）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリイミド。
（ＡＸ２－ｂ）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリイミド前駆体。
（ＡＸ２－ｃ）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリベンゾオキサゾール。
（ＡＸ２－ｄ）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリベンゾオキサゾール前駆体。
（ＡＸ２－ｅ）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリアミドイミド。
（ＡＸ２－ｆ）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリシロキサン。 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.
(AX2-e) Resin: Ethylenically unsaturated double bond group-containing polyamideimide having a nitrogen ring.
(AX2-f) Resin: Polysiloxane containing an ethylenically unsaturated double bond group having a nitrogen ring.
　また、上述した（Ａ２－１）樹脂、（Ａ２－２）樹脂および（Ａ２－３）樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、それらの樹脂は（ＡＸ）樹脂に分類される。そのような樹脂を、それぞれ以下の（ＡＸ２－１）樹脂、（ＡＸ２－２）樹脂、および（ＡＸ２－３）樹脂というものとする。
（ＡＸ２－１）樹脂：窒素環を有する多環側鎖含有樹脂。
（ＡＸ２－２）樹脂：窒素環を有する酸変性エポキシ樹脂。
（ＡＸ２－３）樹脂：窒素環を有するアクリル樹脂。 Further, when the above-mentioned (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.
(AX2-2) Resin: acid-modified epoxy resin having a nitrogen ring.
(AX2-3) Resin: an acrylic resin having a nitrogen ring.
　上述した（Ａ３－１）樹脂、（Ａ３－２）樹脂、（Ａ３－３）樹脂および（Ａ３－４）樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、それらの樹脂は（ＡＸ）樹脂に分類される。そのような樹脂を、それぞれ以下の（ＡＸ３－１）樹脂、（ＡＸ３－２）樹脂、（ＡＸ３－３）樹脂および（ＡＸ３－４）樹脂というものとする。
（ＡＸ３－１）樹脂：窒素環を有するフェノール樹脂。
（ＡＸ３－２）樹脂：窒素環を有するポリヒドロキシスチレン。
（ＡＸ３－３）樹脂：窒素環を有するフェノール基変性エポキシ樹脂。
（ＡＸ３－４）樹脂：窒素環を有するフェノール基変性アクリル樹脂。 When the above-mentioned (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.
(AX3-1) Resin: Phenolic resin having a nitrogen ring.
(AX3-2) Resin: polyhydroxystyrene having a nitrogen ring.
(AX3-3) Resin: phenol group-modified epoxy resin having a nitrogen ring.
(AX3-4) Resin: phenol group-modified acrylic resin having a nitrogen ring.
　また、上述した（Ａ３ａ）樹脂および（Ａ３ｂ）樹脂が、窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する場合、それらの樹脂は（ＡＸ）樹脂に分類される。そのような樹脂を、それぞれ以下の（ＡＸ３ａ）樹脂および（ＡＸ３ｂ）樹脂というものとする。
（ＡＸ３ａ）樹脂：（ＡＸ３）樹脂のうち、窒素環およびフェノール性水酸基を有し、かつエチレン性不飽和二重結合基を有しない樹脂。
（ＡＸ３ｂ）樹脂：（ＡＸ３）樹脂のうち、窒素環、フェノール性水酸基およびエチレン性不飽和二重結合基を有する樹脂。 Further, 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.
　以下、（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂に共通する内容について述べる。 The contents common to (A1) resin, (A2) resin, (A3) resin and (AX) resin will be described below.
　＜（Ａ）アルカリ可溶性樹脂；ポリイミド、およびポリイミド前駆体＞
　以下、ポリイミドである（Ａ１－１）樹脂、（ＡＸ１－１）樹脂、（Ａ２－ａ）樹脂、および（ＡＸ２－ａ）樹脂について、まとめて記載する。同様に、ポリイミド前駆体である（Ａ１－２）樹脂、（ＡＸ１－２）樹脂、（Ａ２－ｂ）樹脂、および（ＡＸ２－ｂ）樹脂について、まとめて記載する。 <(A) alkali-soluble resin; polyimide and polyimide precursor>
The (A1-1) resin, (AX1-1) resin, (A2-a) resin, and (AX2-a) resin, which are polyimides, are collectively described below. Similarly, the polyimide precursors (A1-2) resin, (AX1-2) resin, (A2-b) resin, and (AX2-b) resin will be collectively described.
　ポリイミド前駆体としては、例えば、テトラカルボン酸または対応するテトラカルボン酸二無水物などと、ジアミンまたはジイソシアネート化合物などとを反応させることで得られる、ポリアミド酸、ポリアミド酸エステル、ポリアミド酸アミド、またはポリイソイミドが挙げられる。ポリイミドとしては、例えば、ポリイミド前駆体を加熱または触媒を用いた反応により、脱水閉環させることで得られる樹脂が挙げられる。ポリイミドおよびポリイミド前駆体は、樹脂を合成する反応において、さらにジカルボン酸または対応するジカルボン酸活性ジエステルなどを用いることで得られる、ポリアミドとの共重合体であっても構わない。 Examples of polyimide precursors 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. is mentioned. 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.
　ポリイミドは、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（１）で表される構造単位を有することが好ましい。ポリイミド中の全構造単位に占める、一般式（１）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 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%.
　ポリイミド前駆体は、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（３）で表される構造単位を有することが好ましい。ポリイミド前駆体中の全構造単位に占める、一般式（３）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 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%.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　一般式（１）および一般式（３）において、Ｒ１およびＲ９は、それぞれ独立して、４～１０価の有機基を表す。Ｒ２およびＲ１０は、それぞれ独立して、２～１０価の有機基を表す。Ｒ３、Ｒ４、およびＲ１３は、それぞれ独立して、フェノール性水酸基、スルホン酸基、メルカプト基、または一般式（６）もしくは一般式（７）で表される置換基を表す。Ｒ１１は、一般式（６）または一般式（７）で表される置換基を表す。Ｒ１２は、フェノール性水酸基、スルホン酸基、またはメルカプト基を表す。ｐは０～６の整数を表す。ｑは０～８の整数を表す。ｔは２～８の整数を表し、ｕは０～６の整数を表し、２≦ｔ＋ｕ≦８である。ｖは０～８の整数を表す。ただし、Ｒ３またはＲ４がフェノール性水酸基を表す場合、フェノール性水酸基と結合するＲ１またはＲ２は芳香族構造を表す。また、Ｒ１２またはＲ１３がフェノール性水酸基を表す場合、フェノール性水酸基と結合するＲ９またはＲ１０は芳香族構造を表す。 In general formulas (1) and (3), 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. p represents an integer of 0 to 6; q represents an integer of 0 to 8; t represents an integer of 2 to 8, u represents an integer of 0 to 6, and 2≦t+u≦8. v represents an integer from 0 to 8; However, when 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. Further, when 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.
　一般式（１）および一般式（３）において、Ｒ１およびＲ９としては、それぞれ独立して、炭素数２～２０の脂肪族構造、炭素数４～２０の脂環式構造、または炭素数６～３０の芳香族構造を有する４～１０価の有機基が好ましい。Ｒ２およびＲ１０としては、それぞれ独立して、炭素数２～２０の脂肪族構造、炭素数４～２０の脂環式構造、または炭素数６～３０の芳香族構造を有する２～１０価の有機基が好ましい。ｑは１～８の整数が好ましい。ｖは１～８の整数が好ましい。Ｒ１およびＲ９は、それぞれ独立して、テトラカルボン酸残基またはテトラカルボン酸誘導体残基を表す。Ｒ２およびＲ１０は、それぞれ独立して、ジアミン残基またはジアミン誘導体残基を表す。テトラカルボン酸誘導体としては、テトラカルボン酸二無水物、テトラカルボン酸二塩化物、またはテトラカルボン酸活性ジエステルが挙げられる。ジアミン誘導体としては、ジイソシアネート化合物またはトリメチルシリル化ジアミンが挙げられる。上述した脂肪族構造、脂環式構造、および芳香族構造は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (1) and (3), 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.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　一般式（６）および一般式（７）において、Ｒ２５～Ｒ２７は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数２～６のアシル基、または炭素数６～１５のアリール基を表す。一般式（６）および一般式（７）において、Ｒ２５～Ｒ２７としては、それぞれ独立して、水素原子、炭素数１～６のアルキル基、炭素数２～４のアシル基、または炭素数６～１０のアリール基が好ましい。上述したアルキル基、アシル基、およびアリール基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (6) and (7), 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. In general formulas (6) and (7), 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.
　ポリイミド前駆体において、一般式（３）で表される構造単位におけるＲ１１が、一般式（６）で表される置換基であり、Ｒ２５が水素原子である場合をアミド酸構造単位という。一般式（３）で表される構造単位におけるＲ１１が、一般式（６）で表される置換基であり、Ｒ２５が炭素数１～１０のアルキル基、炭素数２～６のアシル基または炭素数６～１５のアリール基である場合を、アミド酸エステル構造単位という。一般式（３）で表される構造単位におけるＲ１１が、一般式（７）で表される置換基である場合を、アミド酸アミド構造単位という。ポリイミド前駆体は、現像後における開口パターン寸法のバラツキ抑制の観点から、アミド酸エステル構造単位および／またはアミド酸アミド構造単位を有することが好ましい。アミド酸エステル構造単位および／またはアミド酸アミド構造単位を有するポリイミド前駆体としては、テトラカルボン酸残基および／またはテトラカルボン酸誘導体残基であるカルボキシ基の一部を、エステル化および／またはアミド化させることで得られる樹脂が挙げられる。また、ポリイミド前駆体は、アミド酸構造単位、アミド酸エステル構造単位、およびアミド酸アミド構造単位の一部がイミド閉環したイミド閉環構造単位を有しても構わない。アミド酸構造単位、アミド酸エステル構造単位、アミド酸アミド構造単位、およびイミド閉環構造単位の含有比率の合計に占める、アミド酸エステル構造単位およびアミド酸アミド構造単位の含有比率の合計は、現像後における開口パターン寸法のバラツキ抑制の観点から、１０ｍｏｌ％以上が好ましく、３０ｍｏｌ％以上がより好ましく、５０ｍｏｌ％以上がさらに好ましい。一方、アミド酸エステル構造単位およびアミド酸アミド構造単位の含有比率の合計は、現像後の残渣抑制の観点から、１００ｍｏｌ％以下が好ましく、９０ｍｏｌ％以上がより好ましく、８０ｍｏｌ％以上がさらに好ましい。 In the polyimide precursor, the case where 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 is called an amic acid structural unit. R 11 in the structural unit represented by general formula (3) is a substituent represented by general formula (6), and R 25 is an alkyl group having 1 to 10 carbon atoms and an acyl group having 2 to 6 carbon atoms. Alternatively, 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. As 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 Also, 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. On the other hand, 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.
　＜（Ａ）アルカリ可溶性樹脂；ポリベンゾオキサゾール前駆体およびポリベンゾオキサゾール＞
　以下、ポリベンゾオキサゾールである（Ａ１－３）樹脂、（ＡＸ１－３）樹脂、（Ａ２－ｃ）樹脂および（ＡＸ２－ｃ）樹脂について、まとめて記載する。同様に、ポリベンゾオキサゾール前駆体である（Ａ１－４）樹脂、（ＡＸ１－４）樹脂、（Ａ２－ｄ）樹脂および（ＡＸ２－ｄ）樹脂について、まとめて記載する。 <(A) Alkali-soluble resin; polybenzoxazole precursor and polybenzoxazole>
Hereinafter, (A1-3) resin, (AX1-3) resin, (A2-c) resin and (AX2-c) resin, which are polybenzoxazoles, will be collectively described. Similarly, the polybenzoxazole precursors (A1-4) resin, (AX1-4) resin, (A2-d) resin and (AX2-d) resin will be collectively described.
　ポリベンゾオキサゾール前駆体としては、例えば、ジカルボン酸または対応するジカルボン酸活性ジエステルなどと、ジアミンとしてビスアミノフェノール化合物などとを反応させることで得られるポリヒドロキシアミドが挙げられる。ポリベンゾオキサゾールとしては、例えば、ポリベンゾオキサゾール前駆体を加熱または触媒を用いた反応により、脱水閉環させることで得られる樹脂が挙げられる。ポリベンゾオキサゾールおよびポリベンゾオキサゾール前駆体は、樹脂を合成する反応において、さらにジアミンまたはジイソシアネート化合物などを用いることで得られる、ポリアミドとの共重合体であっても構わない。 Examples of 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. Examples of 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.
　ポリベンゾオキサゾールは、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（２）で表される構造単位を有することが好ましい。ポリベンゾオキサゾール中の全構造単位に占める、一般式（２）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 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%.
　ポリベンゾオキサゾール前駆体は、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（４）で表される構造単位を有することが好ましい。ポリベンゾオキサゾール前駆体中の全構造単位に占める、一般式（４）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 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.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　一般式（２）および一般式（４）において、Ｒ５およびＲ１４は、それぞれ独立して、２～１０価の有機基を表す。Ｒ６およびＲ１５は、それぞれ独立して、芳香族構造を有する４～１０価の有機基を表す。Ｒ７、Ｒ８、およびＲ１６は、それぞれ独立して、フェノール性水酸基、スルホン酸基、メルカプト基、または上述した一般式（６）もしくは一般式（７）で表される置換基を表す。Ｒ１７はフェノール性水酸基を表す。Ｒ１８は、スルホン酸基、メルカプト基、または上述した一般式（６）もしくは一般式（７）で表される置換基を表す。ｒは０～８の整数を表す。ｓは０～６の整数を表す。ｗは０～８の整数を表す。ｘは２～８の整数を表し、ｙは０～６の整数を表し、２≦ｘ＋ｙ≦８である。ただし、Ｒ７がフェノール性水酸基を表す場合、フェノール性水酸基と結合するＲ５は芳香族構造を表す。また、Ｒ１６がフェノール性水酸基を表す場合、フェノール性水酸基と結合するＲ１４は芳香族構造を表す。 In general formulas (2) and (4), 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. r represents an integer of 0 to 8; s represents an integer of 0 to 6; w represents an integer from 0 to 8; x represents an integer of 2 to 8, y represents an integer of 0 to 6, and 2≦x+y≦8. However, when R7 represents a phenolic hydroxyl group, R5 bonding to the phenolic hydroxyl group represents an aromatic structure. Also, when R 16 represents a phenolic hydroxyl group, R 14 bonding to the phenolic hydroxyl group represents an aromatic structure.
　一般式（２）および一般式（４）において、Ｒ５およびＲ１４としては、それぞれ独立して、炭素数２～２０の脂肪族構造、炭素数４～２０の脂環式構造または炭素数６～３０の芳香族構造を有する２～１０価の有機基が好ましい。Ｒ６およびＲ１５としては、それぞれ独立して、炭素数６～３０の芳香族構造を有する４～１０価の有機基が好ましい。ｓは１～６の整数が好ましい。Ｒ５およびＲ１４は、それぞれ独立して、ジカルボン酸残基またはジカルボン酸誘導体残基を表す。Ｒ６およびＲ１５は、それぞれ独立して、ビスアミノフェノール化合物残基またはビスアミノフェノール化合物誘導体残基を表す。ジカルボン酸誘導体としては、ジカルボン酸無水物、ジカルボン酸塩化物、ジカルボン酸活性エステル、ジホルミル化合物が挙げられる。上述した脂肪族構造、脂環式構造、および芳香族構造は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (2) and (4), 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.
　＜（Ａ）アルカリ可溶性樹脂；ポリアミドイミド＞
　以下、ポリアミドイミドである（Ａ１－５）樹脂、（ＡＸ１－５）樹脂、（Ａ２－ｅ）樹脂および（ＡＸ２－ｅ）樹脂について、まとめて記載する。ポリアミドイミドとしては、例えば、トリカルボン酸または対応するトリカルボン酸無水物などと、ジアミンまたはジイソシアネート化合物などとを反応させることで得られる樹脂が挙げられる。得られた樹脂を、さらに加熱または触媒を用いた反応により、脱水閉環させることで得られる樹脂も挙げられる。ポリアミドイミドは、樹脂を合成する反応において、さらにジカルボン酸または対応するジカルボン酸活性ジエステルなどを用いることで得られる、ポリアミドとの共重合体であっても構わない。 <(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.
　ポリアミドイミドは、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（５）で表される構造単位を有することが好ましい。ポリアミドイミド中の全構造単位に占める、一般式（５）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 From the viewpoint of suppressing variations in opening pattern dimensions after development, 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%.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　一般式（５）において、Ｒ１９は、３～１０価の有機基を表す。Ｒ２０は、２～１０価の有機基を表す。Ｒ２１およびＲ２２は、それぞれ独立して、フェノール性水酸基、スルホン酸基、メルカプト基または上述した一般式（６）もしくは一般式（７）で表される置換基を表す。ｍは０～７の整数を表す。ｎは０～８の整数を表す。ただし、Ｒ２１またはＲ２２がフェノール性水酸基を表す場合、フェノール性水酸基と結合するＲ１９またはＲ２０は芳香族構造を表す。 In general formula (5), 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; However, when 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.
　一般式（５）において、Ｒ１９としては、炭素数２～２０の脂肪族構造、炭素数４～２０の脂環式構造または炭素数６～３０の芳香族構造を有する３～１０価の有機基が好ましい。Ｒ２０としては、炭素数２～２０の脂肪族構造、炭素数４～２０の脂環式構造または炭素数６～３０の芳香族構造を有する２～１０価の有機基が好ましい。ｎは１～８の整数が好ましい。Ｒ１９は、トリカルボン酸残基またはトリカルボン酸誘導体残基を表す。Ｒ２０は、ジアミン残基またはジアミン誘導体残基を表す。トリカルボン酸誘導体としては、トリカルボン酸無水物、トリカルボン酸塩化物またはトリカルボン酸活性エステルが挙げられる。ジアミン誘導体としては、ジイソシアネート化合物またはトリメチルシリル化ジアミンが挙げられる。上述した脂肪族構造、脂環式構造、および芳香族構造は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formula (5), 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.
　＜フッ素原子を有する構造単位＞
　ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体およびポリアミドイミド（以下、「ポリイミド系の樹脂」）は、露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、フッ素原子を有する構造単位を有することが好ましい。ここでいう露光とは、活性化学線（放射線）の照射のことであり、例えば、可視光線、紫外線、電子線またはＸ線などの照射が挙げられる。以降、露光とは、活性化学線（放射線）の照射をいう。 <Structural Unit Having Fluorine Atom>
Polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and polyamideimides (hereinafter referred to as "polyimide-based resins") 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. The term "exposure" as used herein means irradiation with actinic rays (radiation), and examples thereof include irradiation with visible light, ultraviolet rays, electron beams, X-rays, and the like. Hereinafter, exposure refers to irradiation with actinic rays (radiation).
　ポリイミド系の樹脂において、それぞれの樹脂の全構造単位のうち、カルボン酸に由来する構造単位またはカルボン酸誘導体に由来する構造単位および／またはアミンに由来する構造単位またはアミン誘導体に由来する構造単位にフッ素原子を有する場合、樹脂の全構造単位に占める、フッ素原子を有する構造単位の含有比率の合計は、１０～１００ｍｏｌ％が好ましく、３０～１００ｍｏｌ％がより好ましく、５０～１００ｍｏｌ％がさらに好ましい。 In 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 When fluorine atoms are present, 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%.
　＜アルカリ可溶性基＞
　ポリイミド系の樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基として酸性基を有する。これらの樹脂は、カルボン酸に由来する構造単位またはジアミンに由来する構造単位に酸性基を有すること、または酸性基を有する末端構造を有することが好ましい。また、それぞれの樹脂が有する一部のヒドロキシ基などと、多官能カルボン酸二無水物とを反応させて得られる樹脂も好ましく、それぞれの樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応により酸性基を導入した樹脂も好ましい。 <Alkali-soluble group>
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. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　（Ａ２）樹脂である（Ａ２－ａ）樹脂、（Ａ２－ｂ）樹脂、（Ａ２－ｃ）樹脂、（Ａ２－ｄ）樹脂および（Ａ２－ｅ）樹脂（以下、「ポリイミド系の（Ａ２）樹脂」）ならびに（ＡＸ２）樹脂である（ＡＸ２－ａ）樹脂、（ＡＸ２－ｂ）樹脂、（ＡＸ２－ｃ）樹脂、（ＡＸ２－ｄ）樹脂および（ＡＸ２－ｅ）樹脂（以下、「ポリイミド系の（ＡＸ２）樹脂」）は、エチレン性不飽和二重結合基を有する。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。これらの（Ａ２）樹脂および（ＡＸ２）樹脂としては、（Ａ１－１）樹脂、（Ａ１－２）樹脂、（Ａ１－３）樹脂、（Ａ１－４）樹脂および（Ａ１－５）樹脂（以下、「ポリイミド系の（Ａ１）樹脂」）ならびに（ＡＸ１－１）樹脂、（ＡＸ１－２）樹脂、（ＡＸ１－３）樹脂、（ＡＸ１－４）樹脂および（ＡＸ１－５）樹脂（以下、「ポリイミド系の（ＡＸ１）樹脂」）において、それぞれの樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有する化合物とを反応させて得られる樹脂が好ましい。また、それぞれの樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりエチレン性不飽和二重結合基を導入した樹脂も好ましい。エチレン性不飽和二重結合基を有する化合物としては、エチレン性不飽和二重結合基を有する求電子性化合物が好ましい。求電子性化合物としては、反応性および化合物の利用性の観点から、イソシアネート化合物、エポキシ化合物、アルコール化合物、アルデヒド化合物、ケトン化合物またはカルボン酸無水物が好ましく、イソシアネート化合物、エポキシ化合物またはアルコール化合物がより好ましい。 <Ethylenically unsaturated double bond group>
(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. These (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. Also preferred is 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. As the compound having an ethylenically unsaturated double bond group, 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.
　上述したポリイミド系の（Ａ２）樹脂およびポリイミド系の（ＡＸ２）樹脂の二重結合当量は、ハーフトーン特性向上の観点から、５００ｇ／ｍｏｌ以上が好ましく、７００ｇ／ｍｏｌ以上がより好ましく、１，０００ｇ／ｍｏｌ以上がさらに好ましい。一方、二重結合当量は、露光時の感度向上および現像後における開口パターン寸法のバラツキ抑制の観点から、３，０００ｇ／ｍｏｌ以下が好ましく、２，０００ｇ／ｍｏｌ以下がより好ましく、１，５００ｇ／ｍｏｌ以下がさらに好ましい。 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. On the other hand, 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂および（ＡＸ－５）樹脂（以下、「ポリイミド系の（ＡＸ）樹脂」）は、（ＡＸ）樹脂に含まれる。これらの樹脂としては、（Ａ１）樹脂の項で説明したポリイミド系の樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含むテトラカルボン酸もしくは対応するテトラカルボン酸二無水物；窒素原子を少なくとも３つ有する環状構造を含むジカルボン酸もしくは対応するジカルボン酸活性ジエステル；窒素原子を少なくとも３つ有する環状構造を含むトリカルボン酸もしくは対応するトリカルボン酸無水物；窒素原子を少なくとも３つ有する環状構造を含むジアミン、ジイソシアネート化合物、トリアミン、もしくはトリイソシアネート化合物；または；窒素原子を少なくとも３つ有する環状構造を含むジアミンとしてビスアミノフェノール化合物などを用いることで得られる樹脂が好ましい。 <(AX) Cyclic Structural Unit of Resin>
The above-mentioned (AX-1) resin, (AX-2) resin, (AX-3) resin, (AX-4) resin and (AX-5) resin (hereinafter referred to as "polyimide-based (AX) resin") , (AX) contained in the resin. 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 diamine, diisocyanate compound, triamine, or triisocyanate compound containing;
　中でも、窒素原子を少なくとも３つ有する環状構造を含むジアミン、ジイソシアネート化合物、トリアミンまたはトリイソシアネート化合物を用いることで得られる樹脂がより好ましい。 Among them, 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.
　また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造は、イソシアヌル酸構造および／またはトリアジン構造が好ましい。窒素原子を少なくとも３つ有する環状構造を有する化合物としては、求電子性化合物または求核性化合物が好ましい。求電子性化合物としては、イソシアネート化合物、エポキシ化合物、アルコール化合物、アルデヒド化合物、ケトン化合物、カルボン酸無水物、（メタ）アクリロイル化合物、ビニル化合物、アリル化合物またはアルコキシシラン化合物が好ましく、イソシアネート化合物、エポキシ化合物またはアルコール化合物がより好ましい。求核性化合物としては、アルコール化合物、アミン化合物、チオール化合物またはカルボン酸化合物が好ましく、アルコール化合物またはアミン化合物がより好ましい。また、求核性化合物としては、イソシアヌル酸に由来する窒素原子に結合した水素原子を有するイソシアヌル酸化合物またはシアヌル酸に由来する酸素原子（トリアジン構造に結合した酸素原子）に結合した水素原子を有するシアヌル酸化合物が好ましい。イソシアヌル酸化合物およびシアヌル酸化合物は、置換基を有しても構わない。 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. As the compound having a cyclic structure having at least three nitrogen atoms, an electrophilic compound or a nucleophilic compound is preferred. As 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. In addition, as the nucleophilic 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.
　＜イソシアヌル酸構造および／またはトリアジン構造を含む構造単位＞
　ポリイミド系の（ＡＸ）樹脂は、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有することが好ましく、イソシアヌル酸構造および／またはトリアジン構造を含むジアミン、ジイソシアネート化合物、トリアミンまたはトリイソシアネート化合物に由来する構造単位を有することがより好ましい。また、ポリイミド系の（ＡＸ）樹脂は、（ＡＸ－１）樹脂および／または（ＡＸ－５）樹脂を含有することが好ましい。 <Structural Unit Containing Isocyanuric Acid Structure and/or Triazine Structure>
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.
　ポリイミド系の（ＡＸ）樹脂において、それぞれの樹脂の全構造単位のうち、全アミンに由来する構造単位または全アミン誘導体に由来する構造単位にイソシアヌル酸構造および／またはトリアジン構造を含む場合、全アミンに由来する構造単位および全アミン誘導体に由来する構造単位の合計に占める、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位の含有比率の合計は、１０～１００ｍｏｌ％が好ましく、３０～１００ｍｏｌ％がより好ましく、５０～１００ｍｏｌ％がさらに好ましい。 In the 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.
　ポリイミド系の（ＡＸ）樹脂は、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位が、脂肪族構造、脂環式構造および芳香族構造からなる群より選ばれる一種類以上の構造を有する有機基を、少なくとも２つ有することが好ましく、少なくとも３つ有することがより好ましい。 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.
　ポリイミド系の（ＡＸ）樹脂が、これらの構造を有することで、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。脂肪造構造としては、炭素数１～２０の脂肪族構造が好ましく、炭素数１～２０のアルキレン基がより好ましく、炭素数１～１０のアルキレン基がさらに好ましい。脂環式構造としては、炭素数４～２０の脂環式構造が好ましく、炭素数４～２０のシクロアルキレン基がより好ましく、炭素数４～１０のシクロアルキレン基がさらに好ましい。芳香族構造としては、炭素数６～３０の芳香族構造が好ましく、炭素数６～３０のアリーレン基がより好ましく、炭素数６～１５のアリーレン基がさらに好ましい。 When the polyimide-based (AX) resin has these structures, the effects of suppressing residues after development, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development are 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 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.
　ポリイミド系の（ＡＸ）樹脂は、イソシアヌル酸構造および／またはトリアジン構造を含むジアミン、ジイソシアネート化合物、トリアミンまたはトリイソシアネートに由来する構造単位として、一般式（２１）で表される構造単位および／または一般式（２２）で表される構造単位を有することが好ましく、一般式（２１）で表される構造単位を有することがより好ましい。 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).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　一般式（２１）および一般式（２２）において、Ｗ４８～Ｗ５０は、それぞれ独立して、直接結合または酸素原子を表す。Ｙ４５～Ｙ５０は、それぞれ独立して、直接結合または炭素数１～２０の脂肪族構造を表す。Ｚ４５～Ｚ５０は、それぞれ独立して、直接結合、炭素数４～２０の脂環式構造または炭素数６～３０の芳香族構造を表す。Ｒ４７およびＲ５０は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基または結合点を表す。＊１～＊４は、それぞれ独立して、結合点を表す。なお、「結合点」とは、他の構造と結合する点を意味する。上述した脂肪族構造、脂環式構造および芳香族構造は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。一般式（２１）および一般式（２２）において、Ｙ４５～Ｙ５０のうち、少なくとも１つは、炭素数１～２０の脂肪族構造であることが好ましい。Ｚ４５～Ｚ５０のうち、少なくとも１つは、炭素数４～２０の脂環式構造または炭素数６～３０の芳香族構造であることが好ましい。また、Ｙ４５～Ｙ５０としては、それぞれ独立して、直接結合または炭素数１～１０の脂肪族構造が好ましく、直接結合または炭素数１～１０のアルキレン基がより好ましい。Ｚ４５～Ｚ５０としては、それぞれ独立して、直接結合、炭素数４～１０の脂環式構造または炭素数６～１５の芳香族構造が好ましく、直接結合、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基がより好ましい。 In general formulas (21) and (22), 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. In addition, 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. In general formulas (21) and (22), 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.
　イソシアヌル酸構造および／またはトリアジン構造を含むジアミン、ジイソシアネート化合物、トリアミン、またはトリイソシアネート化合物としては、１，３－ビス（４－アミノフェニル）イソシアヌル酸、１，３－ビス［４－［２－（４－アミノフェニル）］エチニルフェニル］イソシアヌル酸、１，３，５－トリス（４－アミノフェニル）イソシアヌル酸、１，３，５－トリス（４－アミノ－２－メチルフェニル）イソシアヌル酸、１，３，５－トリス［４－［２－（４－アミノフェニル）］エチニルフェニル］イソシアヌル酸、２，４－ジアミノ－６－フェニル－１，３，５－トリアジン、２，４－ビス（４－アミノフェノキシ）－６－ヒドロキシ－１，３，５－トリアジンまたは２，４，６－トリス（４－アミノフェノキシ）－１，３，５－トリアジンが好ましい。 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)-1,3,5-triazine are preferred.
　ポリイミド系の（ＡＸ）樹脂は、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、イソシアヌル酸構造および／またはトリアジン構造を含み、さらに脂環式構造を有する構造単位を有することが好ましい。また、イソシアヌル酸構造および／またはトリアジン構造を含み、さらに脂環式構造を有するジアミン、ジイソシアネート化合物、トリアミンまたはトリイソシアネート化合物に由来する構造単位（以下、「（ＡＸ）樹脂の特定構造単位」）を有することがより好ましい。一般式（２１）および一般式（２２）において、Ｚ４５～Ｚ５０のうち、少なくとも１つが炭素数４～２０の脂環式構造である場合、ポリイミド系の（ＡＸ）樹脂は、（ＡＸ）樹脂の特定構造単位を有する。 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. It is preferable to have a structural unit having In addition, 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 (hereinafter, "(AX) resin specific structural unit") It is more preferable to have In general formulas (21) and (22), when at least one of Z 45 to Z 50 is an alicyclic structure having 4 to 20 carbon atoms, the polyimide-based (AX) resin is (AX) It has a specific structural unit of resin.
　イソシアヌル酸構造および／またはトリアジン構造を含み、さらに脂環式構造を有するジアミン、ジイソシアネート化合物、トリアミンまたはトリイソシアネート化合物としては、イソホロンジイソシアネートのイソシアヌル酸変性体（イソシアヌル酸型トリイソシアネート）、イソホロンジイソシアネートのイソシアヌル酸変性体をトリアミンに変換した化合物（イソシアヌル酸型トリイソシアネートのトリアミン体）、イソホロンジイソシアネートとシアヌル酸との縮合物（ウレタン結合を有するトリアジン型トリイソシアネート）またはイソホロンジイソシアネートとシアヌル酸との縮合物をトリアミンに変換した化合物（ウレタン結合を有するトリアジン型トリイソシアネートのトリアミン体）が好ましい。 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 A compound converted to triamine (a triamine form of triazine-type triisocyanate having a urethane bond) is preferred.
　同様の観点から、上述したポリイミドおよびポリイミド前駆体は、脂環式構造を有するテトラカルボン酸または対応するテトラカルボン酸二無水物に由来する構造単位を有することが好ましい。また、上述したポリベンゾオキサゾールおよびポリベンゾオキサゾール前駆体は、脂環式構造を有するジカルボン酸または対応するジカルボン酸活性ジエステルに由来する構造単位を有することが好ましい。上述したポリアミドイミドは、脂環式構造を有するトリカルボン酸または対応するトリカルボン酸無水物に由来する構造単位を有することが好ましい。 From the same point of view, 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. Moreover, 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.
　ポリイミドおよびポリイミド前駆体において、全カルボン酸に由来する構造単位および全カルボン酸誘導体に由来する構造単位の合計に占める、脂環式構造を有するテトラカルボン酸または対応するテトラカルボン酸二無水物に由来する構造単位の含有比率の合計は、１０～１００ｍｏｌ％が好ましく、３０～１００ｍｏｌ％がより好ましく、５０～１００ｍｏｌ％がさらに好ましい。 Derived from a tetracarboxylic acid having an alicyclic structure or a corresponding tetracarboxylic acid dianhydride, which accounts for the total number of structural units derived from all carboxylic acids and all structural units derived from all carboxylic acid derivatives in polyimides and polyimide precursors 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%.
　ポリベンゾオキサゾールおよびポリベンゾオキサゾール前駆体において、全カルボン酸に由来する構造単位および全カルボン酸誘導体に由来する構造単位の合計に占める、脂環式構造を有するジカルボン酸または対応するジカルボン酸活性ジエステルに由来する構造単位の含有比率の合計は、１０～１００ｍｏｌ％が好ましく、３０～１００ｍｏｌ％がより好ましく、５０～１００ｍｏｌ％がさらに好ましい。 In polybenzoxazole and polybenzoxazole precursors, 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%.
　ポリアミドイミドにおいて、全カルボン酸に由来する構造単位および全カルボン酸誘導体に由来する構造単位の合計に占める、脂環式構造を有するトリカルボン酸または対応するトリカルボン酸無水物に由来する構造単位の含有比率は、１０～１００ｍｏｌ％が好ましく、３０～１００ｍｏｌ％がより好ましく、５０～１００ｍｏｌ％がさらに好ましい。 In polyamideimide, 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 %.
　上述した（ＡＸ）樹脂の特定構造単位および脂環式構造を有するトリカルボン酸または対応するトリカルボン酸無水物に由来する構造単位を有するポリアミドイミドとしては、例えば、“ＵＮＩＤＩＣ”（登録商標）ＥＭＧ－７９３、同Ｖ－８０００、同Ｖ－８００２、同Ｖ－８００４もしくは同Ｖ－８００５または“ＬＵＸＹＤＩＲ”（登録商標）Ｖ－８０００ＢＭ、同ＥＭＧ－１０１５、同ＥＬＧ－１３０２、同ＥＱＧ－１１７０（以上、いずれもＤＩＣ（株）製）が挙げられる。 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).
　＜イソシアヌル酸構造および／またはトリアジン構造を含む側鎖構造、および末端構造＞
　ポリイミド系の（ＡＸ）樹脂は、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、イソシアヌル酸構造および／またはトリアジン構造を含む、側鎖構造および／または末端構造を有することが好ましい。これらの側鎖構造および末端構造を有する樹脂としては、反応性基を含む側鎖構造または反応性基を含む末端構造を有するポリイミド系の（ＡＸ）樹脂に、イソシアヌル酸化合物および／またはトリアジン化合物を反応させることで得られる樹脂が好ましい。反応性基を含む側鎖構造としては、エチレン性不飽和二重結合基を有する側鎖構造が好ましい。反応性基を含む末端構造としては、マレイミド基を有する末端構造が好ましい。 <Side chain structure containing isocyanuric acid structure and/or triazine structure, and terminal structure>
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. As 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. As the side chain structure containing a reactive group, a side chain structure having an ethylenically unsaturated double bond group is preferred. As a terminal structure containing a reactive group, a terminal structure having a maleimide group is preferred.
　またイソシアヌル酸構造および／またはトリアジン構造は、イソシアヌル酸構造の窒素原子に結合した水素原子および／またはトリアジン構造の酸素原子に結合した水素原子を有することがより好ましい。これらの側鎖構造および末端構造を有する樹脂としては、上述した反応において、窒素原子に結合した水素原子を少なくとも２つ有するイソシアヌル酸化合物または酸素原子に結合した水素原子を少なくとも２つ有するトリアジン化合物を反応させることで得られる樹脂が好ましい。 Further, 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.
　＜その他の構造単位、末端封止剤および分子量＞
　ポリイミド系の樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族カルボン酸に由来する構造単位または芳香族ジアミンに由来する構造単位などの芳香族基を有する構造単位も好ましい。また、パターン形状の低テーパー化の観点から、シリコーンジアミンに由来する構造単位などのシリル基もしくはシロキサン結合を有する構造単位またはオキシアルキレンジアミンに由来する構造単位などのオキシアルキレン骨格を有する構造単位も好ましい。また、樹脂の末端が、モノアミンまたはジカルボン酸無水物などの末端封止剤で封止された構造を有することも好ましい。 <Other structural units, terminal blockers and molecular weights>
As 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.
　ポリイミド系の樹脂の重量平均分子量（以下、「Ｍｗ」）は、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」）で測定されるポリスチレン換算で、１，０００以上が好ましく、３，０００以上がより好ましく、５，０００以上がさらに好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、１００，０００以下が好ましく、５０，０００以下がより好ましく、３０，０００以下がさらに好ましく、２０，０００以下が特に好ましい。なお、前記（ＡＸ－５）樹脂のＭｗは、現像後の残渣抑制ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましく、２，０００以上がさらに好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、３０，０００以下がより好ましく、２０，０００以下がさらに好ましく、１０，０００以下がさらにより好ましく、５，０００以下が特に好ましい。 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. , is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. On the other hand, 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. In addition, 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. On the other hand, 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.
　ポリイミド系の樹脂は公知の方法で合成できる。それぞれの樹脂の合成に用いられるテトラカルボン酸、トリカルボン酸、ジカルボン酸およびそれらの誘導体ならびにジアミン、ビスアミノフェノール化合物、モノアミンおよびそれらの誘導体としては、例えば、国際公開第２０１７／０５７２８１号または国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 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.
　＜（Ａ）アルカリ可溶性樹脂；ポリシロキサン＞
　以下、ポリシロキサンである（Ａ１－６）樹脂、（ＡＸ１－６）樹脂、（Ａ２－ｆ）樹脂および（ＡＸ２－ｆ）樹脂について、まとめて記載する。ポリシロキサンとしては、例えば、三官能オルガノシラン、四官能オルガノシラン、二官能オルガノシランおよび一官能オルガノシランからなる群より選ばれる一種類以上の化合物を加水分解し、脱水縮合させて得られる樹脂が挙げられる。 <(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.
　ポリシロキサンは、現像後における開口パターン寸法のバラツキ抑制の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、一般式（８）で表される三官能オルガノシラン単位および／または一般式（９）で表される四官能オルガノシラン単位を有することが好ましい。 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).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（８）および一般式（９）において、Ｒ２９は、水素原子または有機基を表す。＊１～＊３は、それぞれ独立して、樹脂中の結合点を表す。Ｒ２９としては、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のハロゲン化アルキル基、炭素数４～１０のハロゲン化シクロアルキル基または炭素数６～１５のハロゲン化アリール基が好ましい。上述したアルキル基、シクロアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化シクロアルキル基およびハロゲン化アリール基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (8) and (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. The 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.
　ポリシロキサンに占める、一般式（８）で表される三官能オルガノシラン単位の含有比率は、Ｓｉ原子ｍｏｌ比で５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。三官能オルガノシラン単位としては、現像後の残渣抑制の観点から、エポキシ基を有するオルガノシラン単位が好ましい。 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. From the viewpoint of suppressing residue after development, the trifunctional organosilane unit is preferably an organosilane unit having an epoxy group.
　ポリシロキサンに占める、一般式（９）で表される四官能オルガノシラン単位の含有比率は、現像後の残渣抑制の観点から、Ｓｉ原子ｍｏｌ比で１ｍｏｌ％以上が好ましく、５ｍｏｌ％以上がより好ましく、１０ｍｏｌ％以上がさらに好ましい。一方、一般式（９）で表される四官能オルガノシラン単位の含有比率は、パターン形状の低テーパー化の観点から、Ｓｉ原子ｍｏｌ比で４０ｍｏｌ％以下が好ましく、３０ｍｏｌ％以下がより好ましく、２０ｍｏｌ％以下がさらに好ましい。 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. On the other hand, 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.
　＜アルカリ可溶性基＞
　ポリシロキサンは、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基として酸性基を有する。酸性基としては、前記（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂の項で説明したものが挙げられる。 <Alkali-soluble group>
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. Examples of the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
　ポリシロキサンとしては、酸性基を有するオルガノシラン単位を有する樹脂が好ましい。また、樹脂が有する一部のヒドロキシ基などと、多官能カルボン酸二無水物とを反応させて得られる樹脂も好ましく、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応により酸性基を導入した樹脂も好ましい。 A resin having an organosilane unit having an acidic group is preferable as the polysiloxane. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　（Ａ２）樹脂である（Ａ２－ｆ）樹脂および（ＡＸ２）樹脂である（ＡＸ２－ｆ）樹脂は、エチレン性不飽和二重結合基を有する。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。（Ａ２－ｆ）樹脂および（ＡＸ２－ｆ）樹脂としては、エチレン性不飽和二重結合基を有するオルガノシラン単位を有する樹脂が好ましい。また、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有する化合物とを反応させて得られる樹脂も好ましく、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりエチレン性不飽和二重結合基を導入した樹脂も好ましい。（Ａ２－ｆ）樹脂および（ＡＸ２－ｆ）樹脂の二重結合当量は、ハーフトーン特性向上の観点から、５００ｇ／ｍｏｌ以上が好ましく、７００ｇ／ｍｏｌ以上がより好ましく、１，０００ｇ／ｍｏｌ以上がさらに好ましい。一方、二重結合当量は、露光時の感度向上および現像後における開口パターン寸法のバラツキ抑制の観点から、３，０００ｇ／ｍｏｌ以下が好ましく、２，０００ｇ／ｍｏｌ以下がより好ましく、１，５００ｇ／ｍｏｌ以下がさらに好ましい。 <Ethylenically unsaturated double bond group>
(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. As (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. Resins into which ethylenically unsaturated double bond groups have been introduced by reaction using a catalyst are also preferred. From the viewpoint of improving the halftone characteristics, 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. On the other hand, 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ１－６）樹脂および（ＡＸ２－ｆ）樹脂は、（ＡＸ）樹脂に含まれる。これらの樹脂としては、上述したポリシロキサンを合成する反応において、窒素原子を少なくとも３つ有する環状構造を含むオルガノシランなどを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造は、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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.
　イソシアヌル酸構造および／またはトリアジン構造を含むオルガノシランとしては、１，３，５－トリス（３－トリメトキシシリルプロピル）イソシアヌル酸、１，３，５－トリス（３－トリエトキシシリルプロピル）イソシアヌル酸、２，４，６－トリス［（３－トリメトキシシリルプロピル）アミノ］－１，３，５－トリアジン、２，４，６－トリス［（３－トリエトキシシリルプロピル）アミノ］－１，３，５－トリアジン、２，４－ジアミノ－６－（２－トリエトキシシリルエチル）アミノ－１，３，５－トリアジンまたは２，４－ジアミノ－６－（２－トリエトキシシリルエトキシ）－１，３，５－トリアジンが好ましい。 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.
　＜その他の構造単位、および分子量＞
　ポリシロキサンが有する構造単位としては、パターン形状の低テーパー化の観点から、二官能オルガノシラン単位または一官能オルガノシラン単位も好ましい。また、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族基を有するオルガノシラン単位も好ましい。各オルガノシラン単位は、規則的な配列または不規則的な配列のいずれであっても構わない。規則的な配列としては、例えば、交互共重合、周期的共重合、ブロック共重合またはグラフト共重合などが挙げられる。不規則的な配列としては、例えば、ランダム共重合などが挙げられる。また、各オルガノシラン単位は、二次元的な配列または三次元的な配列のいずれであっても構わない。二次元的な配列としては、例えば、直鎖状が挙げられる。三次元的な配列としては、例えば、梯子状、籠状または網目状などが挙げられる。 <Other structural units and molecular weights>
As a structural unit possessed by polysiloxane, a bifunctional organosilane unit or a monofunctional organosilane unit is also preferable from the viewpoint of reducing the taper of the pattern shape. Moreover, an organosilane unit having an aromatic group is also preferable from the viewpoint of improving the reliability of a light-emitting element in an organic EL display. 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.
　ポリシロキサンのＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、１０，０００以下がより好ましい。ポリシロキサンは公知の方法で合成できる。オルガノシランとしては、例えば、国際公開第２０１７／０５７２８１号または国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 From the viewpoint of improving the reliability of light-emitting elements in organic EL displays, 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.
　＜（Ａ）アルカリ可溶性樹脂；多環側鎖含有樹脂＞
　以下、多環側鎖含有樹脂である（Ａ２－１）樹脂および（ＡＸ２－１）樹脂について、まとめて記載する。多環側鎖含有樹脂としては、例えば、以下の（１－ａ２－１）～（６－ａ２－１）で得られる樹脂が挙げられる。必要に応じて、いずれかの反応段階において多官能アルコール化合物をさらに反応させても構わない。
（１－ａ２－１）多官能フェノール化合物と多官能カルボン酸二無水物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる樹脂。
（２－ａ２－１）多官能フェノール化合物とエポキシ化合物とを反応させて得られる化合物に、多官能カルボン酸二無水物を反応させて得られる樹脂。
（３－ａ２－１）環状骨格含有多官能アルコール化合物と多官能カルボン酸二無水物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる樹脂。
（４－ａ２－１）環状骨格含有多官能アルコール化合物とエポキシ化合物とを反応させて得られる化合物に、多官能カルボン酸二無水物を反応させて得られる樹脂。
（５－ａ２－１）多官能エポキシ化合物と多官能カルボン酸化合物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる樹脂。
（６－ａ２－１）多官能エポキシ化合物とカルボン酸化合物とを反応させて得られる化合物に、多官能カルボン酸二無水物を反応させて得られる樹脂。 <(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.
　多環側鎖含有樹脂は、樹脂の構造単位中に、主鎖と環状骨格を有する嵩高い側鎖とが１つの原子で繋がれた構造を有する。また、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（４１）で表される構造単位を有することが好ましい。 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. In addition, from the viewpoint of suppressing variations in opening pattern dimensions after development, it is preferable to have a structural unit represented by general formula (41).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　一般式（４１）において、Ｘ４１およびＸ４２は、それぞれ独立して、直接結合、一般式（４２）または一般式（４３）で表される置換基を表す。Ｙ４１は、カルボン酸残基またはカルボン酸誘導体残基である３～４価の有機基を表す。Ｗ１は、芳香族基を少なくとも２つ有する有機基を表す。Ｒ１０１およびＲ１０２は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表し、Ｒ１０３およびＲ１０４は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基またはエチレン性不飽和二重結合基を有する有機基を表す。ａおよびｂは、それぞれ独立して、０～１０の整数を表す。ｃは０または１を表す。一般式（４２）および一般式（４３）において、Ｒ１０５およびＲ１０６は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基またはエチレン性不飽和二重結合基を有する有機基を表す。＊１および＊２は、それぞれ独立して、一般式（４１）中のＷ１との結合点または炭素原子との結合点を表す。＊３および＊４は、それぞれ独立して、一般式（４１）中の酸素原子との結合点を表す。 In 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, and 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. a and b each independently represent an integer of 0 to 10; c represents 0 or 1; In general formulas (42) and (43), 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).
　一般式（４１）において、Ｙ４１としては、炭素数２～２０の脂肪族構造、炭素数４～２０の脂環式構造または炭素数６～３０の芳香族構造を有する３～４価の有機基が好ましい。現像後における開口パターン寸法のバラツキ抑制および発光素子の信頼性向上の観点から、Ｗ１としては、一般式（４４）～（４９）のいずれかで表される置換基が好ましい。Ｒ１０３およびＲ１０４としては、それぞれ独立して、水素原子またはエチレン性不飽和二重結合基を有する有機基が好ましい。一般式（４１）～（４３）中、Ｒ１０３～Ｒ１０６におけるエチレン性不飽和二重結合基を有する有機基としては、（メタ）アクリロイル基または一般式（５０）で表される置換基が好ましい。上述したアルキル基、脂肪族構造、脂環式構造および芳香族構造は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In the 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. In general formulas (41) to (43), 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). preferable. The alkyl groups, aliphatic structures, alicyclic structures and aromatic structures described above may have heteroatoms and may be unsubstituted or substituted.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　一般式（４４）～（４９）において、Ｘ４３～Ｘ５２は、それぞれ独立して、単環式または縮合多環式の炭化水素環を表す。Ｙ４３およびＹ５３は、それぞれ独立して、直接結合、炭素原子、窒素原子、酸素原子または硫黄原子を表す。Ｒ１０７～Ｒ１１７は、それぞれ独立して、ハロゲン原子または炭素数１～１０のアルキル基を表す。Ｒ１１８～Ｒ１２４は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～４の整数を表す。ｅおよびｆは、それぞれ独立して、０～５の整数を表す。ｇ、ｈおよびｉは、それぞれ独立して、０～４の整数を表す。ｊおよびｋは、それぞれ独立して、０～３の整数を表す。Ｙ４３が直接結合、酸素原子または硫黄原子の場合、ｌは０である。Ｙ４３が窒素原子の場合、ｌは１である。Ｙ４３が炭素原子の場合、ｌは２である。Ｙ５３が直接結合、酸素原子または硫黄原子の場合、ｍは０である。Ｙ５３が窒素原子の場合、ｍは１である。Ｙ５３が炭素原子の場合、ｍは２である。＊１～＊６は、それぞれ独立して、上述した一般式（４７）中のＸ４１との結合点または酸素原子との結合点を表す。＊７～＊１２は、それぞれ独立して、上述した一般式（４７）中のＸ４２との結合点または酸素原子との結合点を表す。 In general formulas (44) to (49), 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.
　一般式（４４）～（４９）において、Ｘ４３～Ｘ５２としては、それぞれ独立して、炭素数６～１５の単環式または縮合多環式の炭化水素環が好ましい。Ｙ４３およびＹ５３としては、それぞれ独立して、直接結合または酸素原子が好ましい。上述したアルキル基、シクロアルキル基、アリール基および単環式もしくは縮合多環式の芳香族炭化水素環は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (44) to (49), 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.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　一般式（５０）において、Ｘ５４は、直接結合、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基を表す。Ｒ１２５は、ビニル基、アリル基、クロトニル基、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基を表す。Ｒ１２６は、水素原子、炭素数１～１０のアルキル基またはカルボキシ基を有するカルボン酸誘導体残基を表す。上述したアルキレン基、シクロアルキレン基およびアリーレン基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formula (50), 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.
　多環側鎖含有樹脂は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、縮合多環式構造を有する構造単位または縮合多環式ヘテロ環構造を有する構造単位を有することが好ましい。縮合多環式構造または縮合多環式ヘテロ環構造としては、フルオレン骨格、キサンテン骨格またはイソインドリノン骨格が好ましい。上述した一般式（４１）において、Ｗ１が一般式（４４）または一般式（４９）であり、Ｙ４３が直接結合または酸素原子であると、フルオレン骨格を有する構造単位またはキサンテン骨格を有する構造単位を有する。また、上述した一般式（４１）において、Ｗ１が一般式（４８）であると、イソインドリノン骨格を有する構造単位を有する。 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. As the condensed polycyclic structure or condensed polycyclic heterocyclic structure, a fluorene skeleton, a xanthene skeleton or an isoindolinone skeleton is preferred. In the above general formula (41), when W 1 is general formula (44) or general formula (49) and Y 43 is a direct bond or an oxygen atom, a structural unit having a fluorene skeleton or a structure having a xanthene skeleton has units. Further, in the general formula (41) described above, when W 1 is the general formula (48), it has a structural unit having an isoindolinone skeleton.
　＜アルカリ可溶性基＞
　多環側鎖含有樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基として酸性基を有する。酸性基としては、前記（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂の項で説明したものが挙げられる。 <Alkali-soluble group>
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. Examples of the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
　多環側鎖含有樹脂は、多官能カルボン酸化合物に由来する構造単位、多官能カルボン酸二無水物に由来する構造単位および酸性基を有する末端構造のうち少なくとも１つを有することが好ましい。また、樹脂が有する一部のヒドロキシ基などと、多官能カルボン酸二無水物とを反応させて得られる樹脂も好ましく、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応により酸性基を導入した樹脂も好ましい。 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. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　（Ａ２）樹脂である（Ａ２－１）樹脂と（ＡＸ２）樹脂である（ＡＸ２－１）樹脂は、エチレン性不飽和二重結合基を有する。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。（Ａ２－１）樹脂および（ＡＸ２－１）樹脂は、エチレン性不飽和二重結合基を有するエポキシ化合物に由来する構造単位、エチレン性不飽和二重結合基を有するカルボン酸化合物に由来する構造単位およびエチレン性不飽和二重結合基を有する末端構造のうち少なくとも１つを有することが好ましい。また、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有する化合物とを反応させて得られる樹脂も好ましく、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりエチレン性不飽和二重結合基を導入した樹脂も好ましい。（Ａ２－１）樹脂および（ＡＸ２－１）樹脂の二重結合当量は、ハーフトーン特性向上の観点から、３００ｇ／ｍｏｌ以上が好ましく、４００ｇ／ｍｏｌ以上がより好ましく、５００ｇ／ｍｏｌ以上がさらに好ましい。一方、二重結合当量は、露光時の感度向上および現像後における開口パターン寸法のバラツキ抑制の観点から、１，５００ｇ／ｍｏｌ以下が好ましく、１，０００ｇ／ｍｏｌ以下がより好ましく、７００ｇ／ｍｏｌ以下がさらに好ましい。 <Ethylenically unsaturated double bond group>
(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. 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. Resins into which ethylenically unsaturated double bond groups have been introduced by reaction using a catalyst are also preferred. From the viewpoint of improving halftone characteristics, 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. . On the other hand, 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ２－１）樹脂は、（ＡＸ）樹脂に含まれる。（ＡＸ２－１）樹脂としては、上述した多環側鎖含有樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含む多官能フェノール化合物、環状骨格含有多官能アルコール化合物、多官能エポキシ化合物、多官能カルボン酸化合物、多官能カルボン酸二無水物、エポキシ化合物またはカルボン酸化合物などを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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. 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. The cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
　＜その他の構造単位、末端封止剤および分子量＞
　多環側鎖含有樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族多官能カルボン酸化合物に由来する構造単位または芳香族多官能カルボン酸二無水物に由来する構造単位などの芳香族基を有する構造単位も好ましい。また、樹脂の末端が、モノカルボン酸、ジカルボン酸無水物またはトリカルボン酸無水物などの末端封止剤で封止された構造を有することも好ましい。 <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.
　多環側鎖含有樹脂のＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、１０，０００以下がより好ましい。多環側鎖含有樹脂は公知の方法で合成できる。フェノール化合物、アルコール化合物、エポキシ化合物、カルボン酸無水物およびカルボン酸化合物としては、例えば、国際公開第２０１７／０５７２８１号または国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 From the viewpoint of improving the reliability of light-emitting elements in organic EL displays, 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. 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. 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.
　多環側鎖含有樹脂としては、例えば、“ＡＤＥＫＡ　ＡＲＫＬＳ”（登録商標）ＷＲ－１０１もしくは同ＷＲ－３０１（以上、いずれも（株）ＡＤＥＫＡ製）または“ＯＧＳＯＬ”（登録商標）ＣＲ－１０３０（大阪ガスケミカル（株）製）が挙げられる。 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.).
　＜（Ａ）アルカリ可溶性樹脂；酸変性エポキシ樹脂＞
　以下、酸変性エポキシ樹脂である（Ａ２－２）樹脂および（ＡＸ２－２）樹脂について、まとめて記載する。酸変性エポキシ樹脂としては、例えば、以下の（１－ａ２－２）～（２－ａ２－２）で得られる樹脂が挙げられる。必要に応じて、いずれかの反応段階において多官能アルコール化合物をさらに反応させても構わない。
（１－ａ２－２）多官能エポキシ化合物と多官能カルボン酸化合物とを反応させて得られる化合物に、エポキシ化合物を反応させて得られる樹脂。
（２－ａ２－２）多官能エポキシ化合物とカルボン酸化合物とを反応させて得られる化合物に、多官能カルボン酸二無水物を反応させて得られる樹脂。 <(A) alkali-soluble resin; acid-modified epoxy resin>
The acid-modified epoxy resins (A2-2) and (AX2-2) are collectively described below. 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.
　酸変性エポキシ樹脂は、樹脂の構造単位中に環状骨格を有する。また、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（６１）、（６２）および（６３）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造単位を有することが好ましい。 　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
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　一般式（６１）～（６３）において、Ｘ６１およびＸ６２は、それぞれ独立して、炭素数１～６の脂肪族構造を表す。Ｘ６３は、炭素数１～６のアルキレン基を表す。Ｗ２は、芳香族基を少なくとも１つ有する有機基を表す。Ｒ１４１およびＲ１４２は、それぞれ独立して、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。Ｒ１４３は、ハロゲン原子または炭素数１～１０のアルキル基を表す。Ｒ１４４～Ｒ１４６は、それぞれ独立して、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基または一般式（６９）で表される置換基を表す。Ｒ１４７は、水素原子または一般式（７０）で表される置換基を表す。Ｒ１４８およびＲ１４９は、それぞれ独立して、エチレン性不飽和二重結合基を有する有機基を表す。ａおよびｂは、それぞれ独立して、０～１０の整数を表す。ｃは０～１４の整数を表す。ｄは０～３の整数を表す。ｅおよびｆは、それぞれ独立して、０～４の整数を表す。 In general formulas (61) to (63), 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;
　一般式（６１）において、現像後における開口パターン寸法のバラツキ抑制および発光素子の信頼性向上の観点から、Ｗ２としては、一般式（６４）～（６８）のいずれかで表される置換基が好ましい。一般式（６１）～（６３）中、Ｒ１４８およびＲ１４９におけるエチレン性不飽和二重結合基を有する有機基としては、（メタ）アクリロイル基または一般式（７２）もしくは一般式（７３）で表される置換基が好ましい。上述した脂肪族構造、アルキレン基、アルキル基、シクロアルキル基およびアリール基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In the general formula (61), 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. In general formulas (61) to (63), 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.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　一般式（６４）～（６８）において、Ｘ６４は、炭素数１～６の脂肪族構造を表す。Ｘ６５およびＸ６６は、それぞれ独立して、単環式または縮合多環式の炭化水素環を表す。Ｙ６５は、直接結合、炭素原子、窒素原子、酸素原子または硫黄原子を表す。Ｒ１５０は、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。Ｒ１５１～Ｒ１５９は、それぞれ独立して、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基または一般式（６９）で表される置換基を表す。Ｒ１６０～Ｒ１６２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。Ｒ１６３～Ｒ１６９は、それぞれ独立して、エチレン性不飽和二重結合基を有する有機基を表す。ａは０～１０の整数を表す。ｂは０～３の整数を表す。ｃは０～５の整数を表す。ｄは０～３の整数を表す。ｅ、ｆ、ｇおよびｈは、それぞれ独立して、０～４の整数を表す。ｉおよびｊは、それぞれ独立して、０～３の整数を表す。Ｙ６５が直接結合、酸素原子または硫黄原子の場合、ｋは０である。Ｙ６５が窒素原子の場合、ｋは１である。Ｙ６５が炭素原子の場合、ｋは２である。＊１～＊５は、それぞれ独立して、上述した一般式（６１）中のＸ６１との結合点を表す。＊６～＊１０は、それぞれ独立して、上述した一般式（６１）中の結合点を表す。 In general formulas (64) to (68), 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. a represents an integer of 0 to 10; b represents an integer of 0 to 3; c represents an integer of 0 to 5; d represents an integer of 0 to 3; e, f, g and h each independently represent an integer of 0-4. 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.
　一般式（６４）～（６８）において、Ｘ６５およびＸ６６としては、それぞれ独立して、炭素数６～１５の単環式または縮合多環式の炭化水素環が好ましい。Ｙ６５は、直接結合または酸素原子が好ましい。Ｒ１６３～Ｒ１６９におけるエチレン性不飽和二重結合基を有する有機基としては、（メタ）アクリロイル基または一般式（７２）もしくは一般式（７３）で表される置換基が好ましい。上述した脂肪族構造、アルキル基、シクロアルキル基、アリール基および単環式もしくは縮合多環式の芳香族炭化水素環は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (64) to (68), 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.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　一般式（６９）および一般式（７０）において、Ｒ１７０およびＲ１７２は、それぞれ独立して、一般式（７２）または一般式（７３）で表される置換基を表す。Ｒ１７１は、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基または一般式（６９）もしくは一般式（７１）で表される置換基を表す。ａは０～４の整数を表す。一般式（７１）において、Ｒ１７３およびＲ１７４は、それぞれ独立して、水素原子、ハロゲン原子または炭素数１～１０のアルキル基を表す。Ｒ１７５は、ハロゲン原子、炭素数１～１０のアルキル基または一般式（６９）で表される置換基を表す。ｂは０～５の整数を表す。一般式（７２）および一般式（７３）において、Ｘ６７およびＸ６８は、それぞれ独立して、直接結合、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基を表す。Ｒ１７６およびＲ１７７は、それぞれ独立して、ビニル基、アリル基、クロトニル基、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基を表す。Ｒ１７８およびＲ１７９は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基または一般式（７４）で表される置換基を表す。一般式（７４）において、Ｘ６９は、炭素数１～６のアルキレン基、炭素数２～６のアルケニレン基、炭素数４～１０のシクロアルキレン基、炭素数４～１０のシクロアルケニレン基または炭素数６～１５のアリーレン基を表す。Ｘ６９は、カルボン酸無水物残基であることが好ましい。上述したアルキル基、シクロアルキル基、アリール基、アルキレン基、アルケニレン基、シクロアルキレン基、シクロアルケニレン基およびアリーレン基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (69) and (70), 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; In general formula (71), 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; In general formulas (72) and (73), 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). In the 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. The 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.
　酸変性エポキシ樹脂は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、縮合多環式構造を有する構造単位、縮合多環式ヘテロ環構造を有する構造単位、芳香環骨格および脂環式骨格が直接連結された構造を有する構造単位または少なくとも２つの芳香環骨格が直接連結された構造を有する構造単位を有することが好ましい。縮合多環式構造または縮合多環式ヘテロ環構造としては、ナフタレン骨格、フルオレン骨格またはキサンテン骨格が好ましい。脂環式骨格としては、トリシクロ［５．２．１．０２，６］デカン骨格が好ましい。少なくとも２つの芳香環骨格が直接連結された構造としては、ビフェニル骨格が好ましい。上述した一般式（６１）において、Ｗ２が一般式（６５）～（６７）のいずれかで表される置換基であり、Ｙ６５が直接結合または酸素原子であると、ナフタレン骨格を有する構造単位、ビフェニル骨格を有する構造単位、フルオレン骨格を有する構造単位またはキサンテン骨格を有する構造単位を有する。また、上述した一般式（６２）であると、芳香環骨格およびトリシクロ［５．２．１．０２，６］デカン骨格が直接連結された構造を有する構造単位を有する。 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. As the condensed polycyclic structure or condensed polycyclic heterocyclic structure, a naphthalene skeleton, a fluorene skeleton or a xanthene skeleton is preferable. As the alicyclic skeleton, 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. In general formula (61) above, when 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. Moreover, 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.
　＜アルカリ可溶性基＞
　酸変性エポキシ樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基として酸性基を有する。酸性基としては、前記（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂の項で説明したものが挙げられる。 <Alkali-soluble group>
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.
　酸変性エポキシ樹脂は、多官能カルボン酸化合物に由来する構造単位、多官能カルボン酸二無水物に由来する構造単位および酸性基を有する末端構造のうち少なくとも１つを有することが好ましい。また、酸変性エポキシ樹脂を製造する方法としては、例えば、酸性基を有しない樹脂に酸性基を導入する方法も挙げられる。より具体的には、例えば、樹脂が有する一部のヒドロキシ基などと、多官能カルボン酸二無水物とを反応させる方法や、カルボキシ基を有しない樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応により酸性基を導入する方法などが挙げられる。 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. Moreover, as 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. More specifically, for example, a method of reacting a portion of the hydroxy group of the resin with a polyfunctional carboxylic acid dianhydride, a method of reacting the main chain of the resin having no carboxy group, the side chain of the resin and Examples include a method of introducing an acidic group to at least one of the terminals by a reaction using a catalyst.
　＜エチレン性不飽和二重結合基＞
　（Ａ２）樹脂である（Ａ２－２）樹脂と（ＡＸ２）樹脂である（ＡＸ２－２）樹脂は、エチレン性不飽和二重結合基を有する。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。（Ａ２－２）樹脂および（ＡＸ２－２）樹脂は、エチレン性不飽和二重結合基を有するエポキシ化合物に由来する構造単位、エチレン性不飽和二重結合基を有するカルボン酸化合物に由来する構造単位およびエチレン性不飽和二重結合基を有する末端構造のうち少なくとも１つを有することが好ましい。また、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有する化合物とを反応させて得られる樹脂も好ましく、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりエチレン性不飽和二重結合基を導入した樹脂も好ましい。（Ａ２－２）樹脂および（ＡＸ２－２）樹脂の二重結合当量は、ハーフトーン特性向上の観点から、３００ｇ／ｍｏｌ以上が好ましく、４００ｇ／ｍｏｌ以上がより好ましく、５００ｇ／ｍｏｌ以上がさらに好ましい。一方、二重結合当量は、露光時の感度向上および現像後における開口パターン寸法のバラツキ抑制の観点から、１，５００ｇ／ｍｏｌ以下が好ましく、１，０００ｇ／ｍｏｌ以下がより好ましく、７００ｇ／ｍｏｌ以下がさらに好ましい。 <Ethylenically unsaturated double bond group>
(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. 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. Resins into which ethylenically unsaturated double bond groups have been introduced by reaction using a catalyst are also preferred. From the viewpoint of improving halftone characteristics, 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. . On the other hand, 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ２－２）樹脂は、（ＡＸ）樹脂に含まれる。（ＡＸ２－２）樹脂としては、上述した酸変性エポキシ樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含む多官能エポキシ化合物、多官能カルボン酸化合物、多官能カルボン酸二無水物、エポキシ化合物またはカルボン酸化合物などを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造は、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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. 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.
　＜その他の構造単位、末端封止剤および分子量＞
　酸変性エポキシ樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族多官能カルボン酸化合物に由来する構造単位または芳香族多官能カルボン酸二無水物に由来する構造単位などの芳香族基を有する構造単位も好ましい。また、樹脂の末端が、モノカルボン酸、ジカルボン酸無水物またはトリカルボン酸無水物などの末端封止剤で封止された構造を有することも好ましい。 <Other structural units, terminal blockers and molecular weights>
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. 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.
　酸変性エポキシ樹脂のＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、２０，０００以下がより好ましい。酸変性エポキシ樹脂は公知の方法で合成できる。エポキシ化合物、カルボン酸無水物およびカルボン酸化合物としては、例えば、国際公開第２０１７／０５７２８１号または国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 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. 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. 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.
　酸変性エポキシ樹脂としては、例えば、“ＫＡＹＡＲＡＤ”（登録商標）ＰＣＲ－１２２２Ｈ、同ＣＣＲ－１１７１Ｈ、同ＴＣＲ－１３４８Ｈ、同ＺＡＲ－１４９４Ｈ、同ＺＦＲ－１４０１Ｈ、同ＺＣＲ－１７９８Ｈ、同ＺＸＲ－１８０７Ｈ、同ＺＣＲ－６００２Ｈ、または同ＺＣＲ－８００１Ｈ（以上、いずれも日本化薬（株）製）が挙げられる。 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.).
　＜（Ａ）アルカリ可溶性樹脂；アクリル樹脂＞
　以下、アクリル樹脂である（Ａ２－３）樹脂および（ＡＸ２－３）樹脂について、まとめて記載する。アクリル樹脂としては、例えば、（メタ）アクリル酸誘導体、（メタ）アクリル酸エステル誘導体、スチレン誘導体およびその他の共重合成分からなる群より選ばれる一種類以上のモノマーをラジカル共重合させて得られる樹脂が挙げられる。アクリル樹脂は、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（８１）で表される構造単位および／または一般式（８２）で表される構造単位を有することが好ましい。 <(A) alkali-soluble resin; acrylic resin>
The acrylic resins (A2-3) and (AX2-3) are collectively described below. Examples of 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.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（８１）および一般式（８２）において、Ｘ８１は、直接結合または炭素数１～１０のアルキレン基を表す。Ｘ８２は、直接結合、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基を表す。Ｒ２０１～Ｒ２０６は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表す。Ｒ２０７は、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のハロゲン化アルキル基、炭素数４～１０のハロゲン化シクロアルキル基または炭素数６～１５のハロゲン化アリール基を表す。Ｒ２０８は、ビニル基、アリル基、クロトニル基、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基を表す。Ｒ２０９は、水素原子、炭素数１～１０のアルキル基または一般式（８３）で表される置換基を表す。一般式（８３）において、Ｘ８３は、炭素数１～６のアルキレン基、炭素数２～６のアルケニレン基、炭素数４～１０のシクロアルキレン基、炭素数４～１０のシクロアルケニレン基または炭素数６～１５のアリーレン基を表す。Ｘ８３は、カルボン酸無水物残基であることが好ましい。一般式（８１）において、Ｘ８１が直接結合であり、Ｒ２０７が水素原子であることが好ましい。上述したアルキル基、シクロアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化シクロアルキル基、ハロゲン化アリール基、アルキレン基、アルケニレン基、シクロアルキレン基、シクロアルケニレン基およびアリーレン基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (81) and (82), 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). In the 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. In general formula (81), it is preferred that X 81 is a direct bond and R 207 is a hydrogen atom. The above-mentioned 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.
　＜アルカリ可溶性基＞
　アクリル樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基として酸性基を有する。酸性基としては、前記（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂の項で説明したものが挙げられる。 <Alkali-soluble group>
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. Examples of the acidic group include those described in the sections of (A1) resin, (A2) resin, (A3) resin and (AX) resin.
　アクリル樹脂は、（メタ）アクリル酸誘導体に由来する構造単位または酸性基を有する末端構造を有することが好ましい。また、樹脂が有する一部のヒドロキシ基などと、多官能カルボン酸二無水物とを反応させて得られる樹脂も好ましく、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応により酸性基を導入した樹脂も好ましい。 The acrylic resin preferably has a structural unit derived from a (meth)acrylic acid derivative or a terminal structure having an acidic group. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　（Ａ２）樹脂である（Ａ２－３）樹脂と（ＡＸ２）樹脂である（ＡＸ２－３）樹脂は、エチレン性不飽和二重結合基を有する。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。
（Ａ２－３）樹脂および（ＡＸ２－３）樹脂としては、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有するエポキシ化合物などとを反応させて得られる樹脂が好ましい。また、樹脂が有するエポキシ基などと、エチレン性不飽和二重結合基を有するカルボン酸化合物などとを反応させて得られる樹脂も好ましい。また、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりエチレン性不飽和二重結合基を導入した樹脂も好ましい。（Ａ２－３）樹脂および（ＡＸ２－３）樹脂の二重結合当量は、ハーフトーン特性向上の観点から、５００ｇ／ｍｏｌ以上が好ましく、７００ｇ／ｍｏｌ以上がより好ましく、１，０００ｇ／ｍｏｌ以上がさらに好ましい。一方、二重結合当量は、露光時の感度向上および現像後における開口パターン寸法のバラツキ抑制の観点から、４，０００ｇ／ｍｏｌ以下が好ましく、３，０００ｇ／ｍｏｌ以下がより好ましく、２，０００ｇ／ｍｏｌ以下がさらに好ましく、１，５００ｇ／ｍｏｌ以下が特に好ましい。 <Ethylenically unsaturated double bond group>
(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.
As (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. 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. From the viewpoint of improving halftone characteristics, 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. On the other hand, 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ２－３）樹脂は、（ＡＸ）樹脂に含まれる。（ＡＸ２－３）樹脂としては、上述した酸変性エポキシ樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含む（メタ）アクリル酸誘導体、（メタ）アクリル酸エステル誘導体、スチレン誘導体またはその他の共重合成分などを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造は、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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. 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.
　＜その他の構造単位および分子量＞
　アクリル樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族（メタ）アクリル酸エステル誘導体に由来する構造単位またはスチレン誘導体に由来する構造単位などの芳香族基を有する構造単位も好ましく、脂環式（メタ）アクリル酸エステル誘導体に由来する構造単位などの脂環式基を有する構造単位も好ましい。 <Other structural units and molecular weights>
From the viewpoint of improving the reliability of light-emitting elements in organic EL displays, 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.
　アクリル樹脂のＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、１，０００以上が好ましく、３，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、２０，０００以下がより好ましい。アクリル樹脂は公知の方法で合成できる。（メタ）アクリル酸誘導体、（メタ）アクリル酸エステル誘導体、スチレン誘導体およびその他の共重合成分としては、例えば、国際公開第２０１７／０５７２８１号または国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 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. 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. 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. .
　＜（Ａ）アルカリ可溶性樹脂；フェノール樹脂＞
　以下、フェノール樹脂である（Ａ３－１）樹脂および（ＡＸ３－１）樹脂について、まとめて記載する。フェノール樹脂としては、例えば、フェノール化合物などと、アルデヒド化合物、ケトン化合物、アルコキシメチル化合物およびメチロール化合物からなる群より選ばれる一種類以上の化合物とを反応させて得られる樹脂が挙げられる。フェノール樹脂は、ノボラック樹脂および／またはレゾール樹脂を含有することが好ましい。ノボラック樹脂とは、酸触媒下にて反応させて得られる樹脂をいう。レゾール樹脂とは、塩基触媒下にて反応させて得られる樹脂をいう。 <(A) Alkali-soluble resin; phenolic resin>
Hereinafter, the (A3-1) resin and (AX3-1) resin, which are phenolic resins, will be collectively described. Examples of 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.
　フェノール樹脂は、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（３６）で表される構造単位を有することが好ましい。フェノール樹脂の全構造単位に占める、一般式（３６）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 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%.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　一般式（３６）において、Ｘ３８は、炭素数１～６の脂肪族構造を表す。Ｒ９４は、ハロゲン原子、炭素数１～１０のアルキル基、炭素数６～１５のアリール基、炭素数２～１０のアルケニル基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルケニルオキシ基、炭素数１～１０のアシル基、カルボキシ基、アミノ基または環を形成する基を表す。環を形成する基によって連結する環は、単環式または縮合多環式の炭化水素環を表す。Ｒ９５は、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。ａは１～４の整数を表す。ｂは０～３の整数を表す。αは０～４の整数を表す。上述した脂肪族構造、アルキル基、アリール基、アルケニル基、アルコキシ基、アシル基、環を形成する基およびアルキレン基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。環を形成する基によって形成される縮合多環式の炭化水素環としては、ナフタレン環、アントラセン環、ピレン環、インダン環、インデン環、テトラヒドロナフタレン環、フルオレン環、キサンテン環またはイソインドリノン環が好ましい。 In general formula (36), 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; α 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.
　＜アルカリ可溶性基＞
　フェノール樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基としてフェノール性水酸基を有する。フェノール樹脂としては、フェノール化合物と、アルデヒド化合物、アルコキシメチル化合物およびメチロール化合物からなる群より選ばれる一種類以上の化合物とを反応させて得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりフェノール性水酸基を導入した樹脂も好ましい。なお、カルボキシ基および／またはカルボン酸無水物基を有しても構わない。例えば、樹脂が有するフェノール性水酸基とカルボン酸無水物とを反応させて得られる樹脂またはフェノール化合物としてカルボキシ基および／またはカルボン酸無水物基を有するフェノール化合物を反応させて得られる樹脂が挙げられる。 <Alkali-soluble group>
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. Also preferred is 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. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　フェノール樹脂は、以下の（Ａ３ｂ－１）樹脂および／または（ＡＸ３ｂ－１）樹脂を含有することが好ましい。（Ａ３ｂ－１）樹脂は、少なくとも１つのエチレン性不飽和二重結合基を有する（Ａ３ｂ）樹脂である。（ＡＸ３ｂ－１）樹脂は、（ＡＸ）樹脂の環状構造単位、および少なくとも１つのエチレン性不飽和二重結合基を有する（ＡＸ３ｂ）樹脂である。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。
（Ａ３ｂ－１）樹脂：エチレン性不飽和二重結合基含有フェノール樹脂。
（ＡＸ３ｂ－１）樹脂：窒素環を有するエチレン性不飽和二重結合基含有フェノール樹脂。 <Ethylenically unsaturated double bond group>
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）樹脂および（ＡＸ３ｂ－１）樹脂としては、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有するエポキシ化合物などとを反応させて得られる樹脂が好ましい。また、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりエチレン性不飽和二重結合基を導入した樹脂も好ましい。なお、（Ａ）アルカリ可溶性樹脂が（Ａ３ｂ－１）樹脂および／または（ＡＸ３ｂ－１）樹脂を含有する場合、（Ａ）アルカリ可溶性樹脂が、さらに以下の（Ａ３ａ－１）樹脂および／または（ＡＸ３ａ－１）樹脂を含有することが好ましい。（Ａ３ａ－１）樹脂および（ＡＸ３ａ－１）樹脂は、エチレン性不飽和二重結合基を有しない。すなわち（Ａ３ａ－１）樹脂および（ＡＸ３ａ－１）樹脂は、ラジカル重合性基であるエチレン性不飽和二重結合基を有しない。
（Ａ３ａ－１）樹脂：エチレン性不飽和二重結合基を有しないフェノール樹脂。
（ＡＸ３ａ－１）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有フェノール樹脂。 As (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. In addition, when (A) 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ３－１）樹脂、（ＡＸ３ａ－１）樹脂、および（ＡＸ３ｂ－１）樹脂は、（ＡＸ）樹脂に含まれる。これらの樹脂としては、上述したフェノール樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含むフェノール化合物、アルデヒド化合物、ケトン化合物、アルコキシメチル化合物、またはメチロール化合物、などを用いることで得られる樹脂が好ましく、窒素原子を少なくとも３つ有する環状構造を含むフェノール化合物、アルコキシメチル化合物、またはメチロール化合物を用いることで得られる樹脂がより好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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. 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. The cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
　イソシアヌル酸構造および／またはトリアジン構造を含むフェノール化合物としては、１，３－ビス（４－ヒドロキシフェニル）イソシアヌル酸、１，３，５－トリス（４－ヒドロキシフェニル）イソシアヌル酸、２，４－ビス（４－ヒドロキシフェノキシ）－６－ヒドロキシ－１，３，５－トリアジン、２，４，６－トリス（４－ヒドロキシフェノキシ）－１，３，５－トリアジン、２，４，６－トリス（４－ヒドロキシフェニル）アミノ－１，３，５－トリアジン、１，３，５，７－テトラキス［（２－ヒドロキシフェニル）メチル］グリコールウリルが好ましい。 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.
　イソシアヌル酸構造および／またはトリアジン構造を含むアルコキシメチル化合物またはメチロール化合物としては、２，４，６－トリス［Ｎ，Ｎ－ビス（メトキシメチル）アミノ］－１，３，５－トリアジン、２，４，６－トリス［Ｎ，Ｎ－ビス（ブトキシメチル）アミノ］－１，３，５－トリアジン、２，４，６－トリス［Ｎ，Ｎ－ビス（ヒドロキシメチル）アミノ］－１，３，５－トリアジン、２，４，６－トリス［Ｎ－（メトキシメチル）アミノ］－１，３，５－トリアジン、２，４－ビス［Ｎ，Ｎ－ビス（メトキシメチル）アミノ］－６－フェニル－１，３，５－トリアジン、１，３，５，７－テトラキス（メトキシメチル）グリコールウリル、または１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリドンが好ましい。 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.
　＜その他の構造単位および分子量＞
　フェノール樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族アルデヒド化合物に由来する構造単位または芳香族ケトン化合物に由来する構造単位などの芳香族基を有する構造単位も好ましく、脂環式アルデヒド化合物に由来する構造単位、脂環式ケトン化合物に由来する構造単位、脂環式アルコキシメチル化合物に由来する構造単位、または脂環式メチロール化合物に由来する構造単位などの脂環式基を有する構造単位も好ましい。 <Other structural units and molecular weights>
As the structural unit of the phenolic resin, from the viewpoint of improving the reliability of the light-emitting element in the organic EL display, 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.
　フェノール樹脂のＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、３０，０００以下がより好ましく、１０，０００以下がさらに好ましく、５，０００以下がさらにより好ましく、３，０００以下が特に好ましい。フェノール樹脂は公知の方法で合成できる。フェノール化合物、アルデヒド化合物、ケトン化合物、アルコキシメチル化合物およびメチロール化合物としては、例えば、国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 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. On the other hand, 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.
　＜（Ａ）アルカリ可溶性樹脂；ポリヒドロキシスチレン＞
　以下、ポリヒドロキシスチレンである（Ａ３－２）樹脂および（ＡＸ３－２）樹脂について、まとめて記載する。ポリヒドロキシスチレンとしては、例えば、ヒドロキシスチレン誘導体などと、スチレン誘導体および／またはその他の共重合成分とをラジカル共重合させて得られる樹脂が挙げられる。その他の共重合成分としては、（メタ）アクリル酸誘導体または（メタ）アクリル酸エステル誘導体などが挙げられる。ポリヒドロキシスチレンは、現像後における開口パターン寸法のバラツキ抑制の観点から、一般式（９１）で表される構造単位および／または一般式（９２）で表される構造単位を有することが好ましい。ポリヒドロキシスチレンの全構造単位に占める、一般式（９１）で表される構造単位および一般式（９２）で表される構造単位の含有比率は、５０～１００ｍｏｌ％が好ましく、６０～１００ｍｏｌ％がより好ましく、７０～１００ｍｏｌ％がさらに好ましい。 <(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.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　一般式（９１）および一般式（９２）において、Ｘ１２１は、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基を表す。Ｒ２２１～Ｒ２２６は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表す。Ｒ２２７およびＲ２２８は、それぞれ独立して、ハロゲン原子、炭素数１～１０のアルキル基、炭素数６～１５のアリール基、炭素数２～１０のアルケニル基、炭素数１～１０のアルコキシ基、炭素数２～１０のアルケニルオキシ基、炭素数１～１０のアシル基、カルボキシ基、アミノ基または環を形成する基を表す。環を形成する基によって連結する環は、単環式または縮合多環式の炭化水素環を表す。ａおよびｂは、それぞれ独立して、１～５の整数を表す。ｃおよびｄは、それぞれ独立して、０～４の整数を表す。上述したアルキル基、アリール基、アルケニル基、アルコキシ基、アシル基、環を形成する基、アルキレン基、シクロアルキレン基およびアリーレン基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。環を形成する基によって形成される縮合多環式の炭化水素環としては、ナフタレン環、アントラセン環、ピレン環、インダン環、インデン環、テトラヒドロナフタレン環、フルオレン環、キサンテン環またはイソインドリノン環が好ましい。 In general formulas (91) and (92), 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. , an alkenyloxy group having 2 to 10 carbon atoms, 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. 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.
　＜アルカリ可溶性基＞
　ポリヒドロキシスチレンは、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基としてフェノール性水酸基を有する。ポリヒドロキシスチレンとしては、少なくともヒドロキシスチレン誘導体を含む共重合成分をラジカル共重合させて得られる樹脂が好ましい。また、さらにエポキシ基などの反応性基を有する（メタ）アクリル酸エステルを含む共重合成分をラジカル共重合させて得られた樹脂において、樹脂が有するエポキシ基などと、カルボキシ基を有するフェノール化合物などとを反応させて得られる樹脂も好ましく、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりフェノール性水酸基を導入した樹脂も好ましい。なお、カルボキシ基および／またはカルボン酸無水物基を有しても構わない。例えば、樹脂が有するフェノール性水酸基とカルボン酸無水物とを反応させて得られる樹脂またはその他の共重合成分としてカルボキシ基および／またはカルボン酸無水物基を有する共重合成分を反応させて得られる樹脂が挙げられる。 <Alkali-soluble group>
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. In addition, it may have a carboxy group and/or a carboxylic acid anhydride group. For example, 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.
　＜エチレン性不飽和二重結合基＞
　ポリヒドロキシスチレンは、以下の（Ａ３ｂ－２）樹脂および／または（ＡＸ３ｂ－２）樹脂を含有することが好ましい。（Ａ３ｂ－２）樹脂は、少なくとも１つのエチレン性不飽和二重結合基を有する（Ａ３ｂ）樹脂である。（ＡＸ３ｂ－２）樹脂は、（ＡＸ）樹脂の環状構造単位および少なくとも１つのエチレン性不飽和二重結合基を有する（ＡＸ３ｂ）樹脂である。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。
（Ａ３ｂ－２）樹脂：エチレン性不飽和二重結合基含有ポリヒドロキシスチレン。
（ＡＸ３ｂ－２）樹脂：窒素環を有するエチレン性不飽和二重結合基含有ポリヒドロキシスチレン。 <Ethylenically unsaturated double bond group>
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: Ethylenically unsaturated double bond group-containing polyhydroxystyrene.
(AX3b-2) Resin: Polyhydroxystyrene containing an ethylenically unsaturated double bond group having a nitrogen ring.
　（Ａ３ｂ－２）樹脂および（ＡＸ３ｂ－２）樹脂としては、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有するエポキシ化合物などとを反応させて得られる樹脂が好ましい。また、樹脂が有するエポキシ基などと、エチレン性不飽和二重結合基を有するカルボン酸化合物などとを反応させて得られる樹脂も好ましい。なお、（Ａ）アルカリ可溶性樹脂が（Ａ３ｂ－２）樹脂および／または（ＡＸ３ｂ－２）樹脂を含有する場合、（Ａ）アルカリ可溶性樹脂が、さらに以下の（Ａ３ａ－２）樹脂および／または（ＡＸ３ａ－２）樹脂を含有することが好ましい。（Ａ３ａ－２）樹脂および（ＡＸ３ａ－２）樹脂は、エチレン性不飽和二重結合基を有しない。すなわち（Ａ３ａ－２）樹脂および（ＡＸ３ａ－２）樹脂は、ラジカル重合性基であるエチレン性不飽和二重結合基を有しない。
（Ａ３ａ－２）樹脂：エチレン性不飽和二重結合基を有しないポリヒドロキシスチレン。
（ＡＸ３ａ－２）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有ポリヒドロキシスチレン。 As (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. In addition, when (A) 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.
(AX3a-2) Resin: Nitrogen ring-containing polyhydroxystyrene having no ethylenically unsaturated double bond group.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ３－２）樹脂、（ＡＸ３ａ－２）樹脂、および（ＡＸ３ｂ－２）樹脂は、（ＡＸ）樹脂に含まれる。これらの樹脂としては、上述したポリヒドロキシスチレンを合成する反応において、窒素原子を少なくとも３つ有する環状構造を含むヒドロキシスチレン誘導体、スチレン誘導体またはその他の共重合成分などを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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. . 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. The cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
　＜その他の構造単位および分子量＞
　ポリヒドロキシスチレンが有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族（メタ）アクリル酸エステル誘導体に由来する構造単位などの芳香族基を有する構造単位も好ましく、脂環式（メタ）アクリル酸エステル誘導体に由来する構造単位などの脂環式基を有する構造単位も好ましい。 <Other structural units and molecular weights>
As a structural unit possessed by polyhydroxystyrene, 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.
　ポリヒドロキシスチレンのＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、２０，０００以下がより好ましい。ポリヒドロキシスチレンは公知の方法で合成できる。ヒドロキシスチレン誘導体、スチレン誘導体およびその他の共重合成分としては、例えば、国際公開第２０１７／１５９８７６号に記載の化合物が挙げられる。 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.
　＜（Ａ）アルカリ可溶性樹脂；フェノール基変性エポキシ樹脂＞
　以下、フェノール基変性エポキシ樹脂である（Ａ３－３）樹脂および（ＡＸ３－３）樹脂について、まとめて記載する。フェノール基変性エポキシ樹脂としては、例えば、以下の（１－ａ３－３）～（２－ａ３－３）で得られる樹脂が挙げられる。必要に応じて、いずれかの反応段階において多官能アルコール化合物をさらに反応させても構わない。フェノール基変性エポキシ樹脂は、樹脂の構造単位中に環状骨格を有する。
（１－ａ３－３）多官能エポキシ化合物と、エポキシ反応性基を有するフェノール化合物とを反応させて得られる樹脂。
（２－ａ３－３）上述した（１－ａ３－３）の樹脂に、さらに多官能カルボン酸二無水物または多官能カルボン酸化合物を反応させて得られる樹脂。 <(A) Alkali-soluble resin; phenol group-modified epoxy resin>
Hereinafter, the (A3-3) resin and (AX3-3) resin, which are phenol group-modified epoxy resins, will be collectively described. Examples of 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.
　＜アルカリ可溶性基＞
　フェノール基変性エポキシ樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基としてフェノール性水酸基を有する。フェノール基変性エポキシ樹脂としては、多官能エポキシ化合物などと、カルボキシ基を有するフェノール化合物とを反応させて得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりフェノール性水酸基を導入した樹脂も好ましい。なお、カルボキシ基および／またはカルボン酸無水物基を有しても構わない。例えば、樹脂が有するヒドロキシ基とカルボン酸無水物とを反応させて得られる樹脂が挙げられる。 <Alkali-soluble group>
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. As the phenol group-modified epoxy resin, a resin obtained by reacting a polyfunctional epoxy compound or the like with a phenol compound having a carboxy group is preferable. Also preferred is 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. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　フェノール基変性エポキシ樹脂は、以下の（Ａ３ｂ－３）樹脂および／または（ＡＸ３ｂ－３）樹脂を含有することが好ましい。（Ａ３ｂ－３）樹脂は、少なくとも１つのエチレン性不飽和二重結合基を有する（Ａ３ｂ）樹脂である。（ＡＸ３ｂ－３）樹脂は、（ＡＸ）樹脂の環状構造単位および少なくとも１つのエチレン性不飽和二重結合基を有する（ＡＸ３ｂ）樹脂である。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。
（Ａ３ｂ－３）樹脂：エチレン性不飽和二重結合基含有フェノール基変性エポキシ樹脂。
（ＡＸ３ｂ－３）樹脂：窒素環を有するエチレン性不飽和二重結合基含有フェノール基変性エポキシ樹脂。 <Ethylenically unsaturated double bond group>
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.
　（Ａ３ｂ－３）樹脂および（ＡＸ３ｂ－３）樹脂としては、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有するエポキシ化合物などとを反応させて得られる樹脂が好ましい。また、樹脂が有するエポキシ基などと、エチレン性不飽和二重結合基を有するカルボン酸化合物などとを反応させて得られる樹脂も好ましい。なお、（Ａ）アルカリ可溶性樹脂が（Ａ３ｂ－３）樹脂および／または（ＡＸ３ｂ－３）樹脂を含有する場合、（Ａ）アルカリ可溶性樹脂が、さらに以下の（Ａ３ａ－３）樹脂および／または（ＡＸ３ａ－３）樹脂を含有することが好ましい。（Ａ３ａ－３）樹脂および（ＡＸ３ａ－３）樹脂は、エチレン性不飽和二重結合基を有しない。すなわち（Ａ３ａ－３）樹脂および（ＡＸ３ａ－３）樹脂は、ラジカル重合性基であるエチレン性不飽和二重結合基を有しない。
（Ａ３ａ－３）樹脂：エチレン性不飽和二重結合基を有しないフェノール基変性エポキシ樹脂。
（ＡＸ３ａ－３）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有フェノール基変性エポキシ樹脂。 As the (A3b-3) resin and (AX3b-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. In addition, when (A) 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.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ３－３）樹脂、（ＡＸ３ａ－３）樹脂および（ＡＸ３ｂ－３）樹脂は、（ＡＸ）樹脂に含まれる。これらの樹脂としては、上述したフェノール基変性エポキシ樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含む多官能エポキシ化合物と、エポキシ反応性基を有するフェノール化合物、多官能カルボン酸二無水物または多官能カルボン酸化合物などを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
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. 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. The cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
　＜その他の構造単位および分子量＞
　フェノール基変性エポキシ樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族多官能カルボン酸化合物に由来する構造単位または芳香族多官能カルボン酸二無水物に由来する構造単位などの芳香族基を有する構造単位も好ましい。 <Other structural units and molecular weights>
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
　フェノール基変性エポキシ樹脂のＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、５００以上が好ましく、１，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、２０，０００以下がより好ましい。フェノール基変性エポキシ樹脂は公知の方法で合成できる。 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. 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. A phenol group-modified epoxy resin can be synthesized by a known method.
　＜（Ａ）アルカリ可溶性樹脂；フェノール基変性アクリル樹脂＞
　以下、フェノール基変性アクリル樹脂である（Ａ３－４）樹脂および（ＡＸ３－４）樹脂について、まとめて記載する。フェノール基変性アクリル樹脂としては、例えば、以下の（１－ａ３－４）～（２－ａ３－４）で得られる樹脂が挙げられる。
（１－ａ３－４）（メタ）アクリル酸誘導体、（メタ）アクリル酸エステル誘導体、スチレン誘導体、およびその他の共重合成分からなる群より選ばれる一種類以上のモノマーをラジカル共重合させて得られる樹脂に、さらに付加反応性基を有するフェノール化合物を反応させて得られる樹脂。
（２－ａ３－４）上述した（１－ａ３－４）の樹脂に、さらに多官能カルボン酸二無水物または多官能カルボン酸化合物を反応させて得られる樹脂。 <(A) Alkali-soluble resin; phenol group-modified acrylic resin>
Hereinafter, the (A3-4) resin and (AX3-4) resin, which are phenol group-modified acrylic resins, will be collectively described. Examples of 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; A resin obtained by reacting a resin with a phenol compound having an addition-reactive group.
(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.
　＜アルカリ可溶性基＞
　フェノール基変性アクリル樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基としてフェノール性水酸基を有する。フェノール基変性アクリル樹脂としては、エポキシ基などの反応性基を有する（メタ）アクリル酸エステルを含む共重合成分をラジカル共重合させて得られた樹脂において、樹脂が有するエポキシ基などと、カルボキシ基を有するフェノール化合物とを反応させて得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つに、触媒を用いた反応によりフェノール性水酸基を導入した樹脂も好ましい。なお、カルボキシ基および／またはカルボン酸無水物基を有しても構わない。例えば、樹脂が有するヒドロキシ基とカルボン酸無水物とを反応させて得られる樹脂が挙げられる。 <Alkali-soluble group>
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. As 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 A resin obtained by reacting a phenol compound having Also preferred is 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. In addition, 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.
　＜エチレン性不飽和二重結合基＞
　フェノール基変性アクリル樹脂は、以下の（Ａ３ｂ－４）樹脂および／または（ＡＸ３ｂ－４）樹脂を含有することが好ましい。（Ａ３ｂ－４）樹脂は、少なくとも１つのエチレン性不飽和二重結合基を有する（Ａ３ｂ）樹脂である。（ＡＸ３ｂ－４）樹脂は、（ＡＸ）樹脂の環状構造単位、および少なくとも１つのエチレン性不飽和二重結合基を有する（ＡＸ３ｂ）樹脂である。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。
（Ａ３ｂ－４）樹脂：エチレン性不飽和二重結合基含有フェノール基変性アクリル樹脂。
（ＡＸ３ｂ－４）樹脂：窒素環を有するエチレン性不飽和二重結合基含有フェノール基変性アクリル樹脂。 <Ethylenically unsaturated double bond group>
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.
(A3b-4) Resin: phenol group-modified acrylic resin containing an ethylenically unsaturated double bond group.
(AX3b-4) Resin: A phenol group-modified acrylic resin containing an ethylenically unsaturated double bond group having a nitrogen ring.
　（Ａ３ｂ－４）樹脂および（ＡＸ３ｂ－４）樹脂としては、樹脂が有する一部の酸性基などと、エチレン性不飽和二重結合基を有するエポキシ化合物などとを反応させて得られる樹脂が好ましい。また、樹脂が有するエポキシ基などと、エチレン性不飽和二重結合基を有するカルボン酸化合物などとを反応させて得られる樹脂も好ましい。なお、（Ａ）アルカリ可溶性樹脂が（Ａ３ｂ－４）樹脂および／または（ＡＸ３ｂ－４）樹脂を含有する場合、（Ａ）アルカリ可溶性樹脂が、さらに以下の（Ａ３ａ－４）樹脂および／または（ＡＸ３ａ－４）樹脂を含有することが好ましい。（Ａ３ａ－４）樹脂および（ＡＸ３ａ－４）樹脂は、エチレン性不飽和二重結合基を有しない。すなわち（Ａ３ａ－４）樹脂および（ＡＸ３ａ－４）樹脂は、ラジカル重合性基であるエチレン性不飽和二重結合基を有しない。
（Ａ３ａ－４）樹脂：エチレン性不飽和二重結合基を有しないフェノール基変性アクリル樹脂。
（ＡＸ３ａ－４）樹脂：エチレン性不飽和二重結合基を有しない窒素環含有フェノール基変性アクリル樹脂。 As the (A3b-4) resin and (AX3b-4) 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. In addition, when (A) 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.
(A3a-4) Resin: A phenol group-modified acrylic resin having no ethylenically unsaturated double bond group.
(AX3a-4) Resin: nitrogen ring-containing phenol group-modified acrylic resin having no ethylenically unsaturated double bond group.
　＜（ＡＸ）樹脂の環状構造単位＞
　上述した（ＡＸ３－４）樹脂、（ＡＸ３ａ－４）樹脂および（ＡＸ３ｂ－４）樹脂は、（ＡＸ）樹脂に含まれる。これらの樹脂としては、上述したフェノール基変性アクリル樹脂を合成する反応において、窒素原子を少なくとも３つ有する環状構造を含むフェノール化合物、（メタ）アクリル酸誘導体、（メタ）アクリル酸エステル誘導体、スチレン誘導体、その他の共重合成分、付加反応性基を有するフェノール化合物、多官能カルボン酸二無水物または多官能カルボン酸化合物などを用いることで得られる樹脂が好ましい。また、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうちの少なくとも１つに、触媒を用いた反応により窒素原子を少なくとも３つ有する環状構造を有する化合物を反応させて、窒素原子を少なくとも３つ有する環状構造を導入した樹脂も好ましい。窒素原子を少なくとも３つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 <(AX) Cyclic Structural Unit of Resin>
The (AX3-4) resin, (AX3a-4) resin and (AX3b-4) resin described above are included in the (AX) resin. Examples of 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. 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. The cyclic structure having at least three nitrogen atoms is preferably an isocyanuric acid structure and/or a triazine structure.
　＜その他の構造単位、および分子量＞
　フェノール基変性アクリル樹脂が有する構造単位としては、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、芳香族（メタ）アクリル酸エステル誘導体に由来する構造単位またはスチレン誘導体に由来する構造単位などの芳香族基を有する構造単位も好ましく、脂環式（メタ）アクリル酸エステル誘導体に由来する構造単位などの脂環式基を有する構造単位も好ましい。 <Other structural units and molecular weights>
From the viewpoint of improving the reliability of light-emitting elements in organic EL displays, 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.
　フェノール基変性アクリル樹脂のＭｗは、有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、ＧＰＣで測定されるポリスチレン換算で、１，０００以上が好ましく、３，０００以上がより好ましい。一方、Ｍｗは、現像後の残渣抑制、およびパターン形状の低テーパー化の観点から、５０，０００以下が好ましく、２０，０００以下がより好ましい。フェノール基変性アクリル樹脂は公知の方法で合成できる。 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. 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. A phenol group-modified acrylic resin can be synthesized by a known method.
　＜（Ａ）アルカリ可溶性樹脂の含有比率＞
　本発明の感光性樹脂組成物において、（Ａ）アルカリ可溶性樹脂の合計１００質量％に占める、（ＡＸ）樹脂の含有比率の合計は、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点、ならびに、有機ＥＬディスプレイにおける発光素子の信頼性向上、および発光素子の低電圧駆動化の観点から、５質量％以上が好ましく、１５質量％以上がより好ましく、２５質量％以上がさらに好ましい。一方、（ＡＸ）樹脂の含有比率の合計は、パターン形状の低テーパー化の観点から、９５質量％以下が好ましく、８５質量％以下がより好ましく、７５質量％以下がさらに好ましく、６５質量％以下がさらにより好ましく、５５質量％以下が特に好ましい。 <(A) content ratio of alkali-soluble resin>
In the photosensitive resin composition of the present invention, 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. On the other hand, 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.
　本発明の感光性樹脂組成物において、（Ａ）アルカリ可溶性樹脂の合計１００質量％に占める、（Ａ１）樹脂および（ＡＸ１）樹脂の含有比率の合計は、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、５質量％以上が好ましく、１５質量％以上がより好ましく、２５質量％以上がさらに好ましい。一方、（Ａ１）樹脂および（ＡＸ１）樹脂の含有比率の合計は、パターン形状の低テーパー化の観点から、９５質量％以下が好ましく、８５質量％以下がより好ましく、７５質量％以下がさらに好ましく、６５質量％以下がさらにより好ましく、５５質量％以下が特に好ましい。 In the photosensitive resin composition of the present invention, 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. And from the viewpoint of suppressing variation in opening pattern dimensions after development and improving the reliability of light-emitting elements in organic EL displays, 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. On the other hand, 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.
　本発明の感光性樹脂組成物において、（Ａ）アルカリ可溶性樹脂の合計１００質量％に占める、（Ａ２）樹脂および（ＡＸ２）樹脂の含有比率の合計は、露光時の感度向上および現像後における開口パターン寸法のバラツキ抑制の観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上がさらに好ましい。一方、（Ａ２）樹脂および（ＡＸ２）樹脂の含有比率の合計は、ハーフトーン特性向上およびパターン形状の低テーパー化の観点から、６５質量％以下が好ましく、５５質量％以下がより好ましく、４５質量％以下がさらに好ましい。 In the photosensitive resin composition of the present invention, 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. On the other hand, 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.
　本発明の感光性樹脂組成物において、（Ａ）アルカリ可溶性樹脂の合計１００質量％に占める、（Ａ３）樹脂および（ＡＸ３）樹脂の含有比率の合計は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上がさらに好ましい。一方、（Ａ３）樹脂および（ＡＸ３）樹脂の含有比率の合計は、現像後の残渣抑制およびハーフトーン特性向上の観点から、８５質量％以下が好ましく、７５質量％以下がより好ましく、６５質量％以下がさらに好ましく、５５質量％以下がさらにより好ましく、４５質量％以下が特に好ましい。 In the photosensitive resin composition of the present invention, 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 From the viewpoint of suppressing dimensional variation, 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. On the other hand, 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.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ａ）アルカリ可溶性樹脂の含有比率は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、１０質量％以上が好ましく、２０質量％以上がより好ましく、２５質量％以上がさらに好ましい。一方、（Ａ）アルカリ可溶性樹脂の含有比率は、露光時の感度向上および現像後の残渣抑制の観点から、７５質量％以下が好ましく、６５質量％以下がより好ましく、５５質量％以下がさらに好ましい。なお、本発明において固形分とは、感光性樹脂組成物中の溶剤を除く全成分を言う。 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.
　また、本発明の感光性樹脂組成物が、（Ａ）アルカリ可溶性樹脂および後述の（Ｂ）ラジカル重合性化合物を含有する場合、（Ａ）アルカリ可溶性樹脂の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）ラジカル重合性化合物の合計を１００質量部とした場合において、２５質量部以上が好ましく、３５質量部以上がより好ましく、４５質量部以上がさらに好ましい。一方、（Ａ）アルカリ可溶性樹脂の含有量は、８５質量部以下が好ましく、８０質量部以下がより好ましく、７５質量部以下がさらに好ましい。 Further, when 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) When 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. On the other hand, 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.
　＜（Ｂ）ラジカル重合性化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｂ）ラジカル重合性化合物（以下、「（Ｂ）化合物」）を含有することが好ましい。（Ｂ）化合物とは、少なくとも２つのエチレン性不飽和二重結合基を有する化合物をいう。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。 <(B) Radically polymerizable compound>
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.
　本発明の感光性樹脂組成物がネガ型の感光性を有する場合、該組成物から得られる膜をパターン露光した時、後述する（Ｃ１）光重合開始剤から発生するラジカルによって（Ｂ）化合物のラジカル重合が進行し、膜の露光部がアルカリ現像液に対して不溶化することで、ネガ型のパターンを形成できる。また、露光時の光硬化が促進され、露光時の感度向上の効果が顕著となる。 When the photosensitive resin composition of the present invention has negative photosensitivity, when the film obtained from the composition is pattern-exposed, 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. In addition, photocuring at the time of exposure is accelerated, and the effect of improving the sensitivity at the time of exposure becomes remarkable.
　一方、本発明の感光性樹脂組成物がポジ型の感光性を有する場合、パターン露光時の未露光部において、現像後露光時または熱硬化時に（Ｂ）化合物のラジカル重合が進行し、組成物から得られる膜の架橋度が向上することで、熱硬化後のパターン形状制御の効果が顕著となる。 On the other hand, when 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.
　（Ｂ）化合物のエチレン性不飽和二重結合基は、ラジカル重合が進行しやすい観点から、（メタ）アクリロイル基を有することが好ましい。（Ｂ）化合物は、後述する（Ｂ１）疎水性骨格含有ラジカル重合性化合物、（Ｂ２）柔軟骨格含有ラジカル重合性化合物および（Ｂ３）環状骨格含有ラジカル重合性化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。 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
　（Ｂ）化合物の二重結合当量は、ハーフトーン特性向上の観点から、８０ｇ／ｍｏｌ以上が好ましく、９０ｇ／ｍｏｌ以上がより好ましい。一方、二重結合当量は、露光時の感度向上の観点から、８００ｇ／ｍｏｌ以下が好ましく、６００ｇ／ｍｏｌ以下がより好ましい。 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. On the other hand, 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.
　本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｂ）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、露光時の感度向上および現像後の残渣抑制の観点から、１５質量部以上が好ましく、２０質量部以上がより好ましく、２５質量部以上がさらに好ましい。一方、（Ｂ）化合物の含有量は、ハーフトーン特性向上の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、７５質量部以下が好ましく、６５質量部以下がより好ましく、５５質量部以下がさらに好ましい。 When the photosensitive resin composition of the present invention contains the (B) compound, 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. On the other hand, 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:
　＜（Ｂ）ラジカル重合性化合物；（Ｂ１）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｂ１）疎水性骨格含有ラジカル重合性化合物（以下、「（Ｂ１）化合物」）を含有することが好ましい。（Ｂ１）化合物とは、以下の（Ｉ－ｂ１）構造および（ＩＩ－ｂ１）構造を有し、かつ、（ＩＩ－ｂ１）構造を少なくとも２つ有する化合物を言う。
（Ｉ－ｂ１）構造：フルオレン構造、インダン構造、縮合多環脂環式構造、インドリノン構造およびイソインドリノン構造からなる群より選ばれる一種類以上の構造を含む構造。
（ＩＩ－ｂ１）構造：エチレン性不飽和二重結合基を有する少なくとも２つの有機基。 <(B) radically polymerizable compound; (B1) compound>
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.
　エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。エチレン性不飽和二重結合基は、（メタ）アクリロイル基を有することが好ましい。（Ｂ１）化合物を含有させることで、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。 The ethylenically unsaturated double bond group is preferably a radically polymerizable group. The ethylenically unsaturated double bond group preferably has a (meth)acryloyl group. By containing the compound (B1), the effect of improving the halftone characteristics and suppressing the variation in the dimension of the opening pattern after development becomes remarkable.
　（Ｂ１）化合物は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、上述した（Ｉ－ｂ１）構造が、一般式（１４１）～（１４７）のいずれかで表される構造であることが好ましい。 In the compound (B1), 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.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　一般式（１４１）～（１４７）において、Ｘ２０１～Ｘ２０８は、それぞれ独立して、単環式または縮合多環式の炭化水素環を表す。Ｘ２１０～Ｘ２１４は、それぞれ独立して、炭素数１～６の脂肪族構造を表す。Ｙ２０１およびＹ２０９は、それぞれ独立して、直接結合、炭素原子、窒素原子、酸素原子または硫黄原子を表す。Ｒ３０１～Ｒ３０９は、それぞれ独立して、ハロゲン原子または炭素数１～１０のアルキル基を表す。Ｒ３１０～Ｒ３１６は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。Ｒ３１７およびＲ３１８は、それぞれ独立して、ハロゲン原子または炭素数１～１０のアルキル基を表す。ａ、ｂ、ｃ、ｄ、ｅ、ｆおよびｇは、それぞれ独立して、０～４の整数を表す。ｈおよびｉは、それぞれ独立して、０～３の整数を表す。Ｙ２０１が直接結合、酸素原子または硫黄原子の場合、ｊは０である。Ｙ２０１が窒素原子の場合、ｊは１である。Ｙ２０１が炭素原子の場合、ｊは２である。Ｙ２０９が直接結合、酸素原子または硫黄原子の場合、ｋは０である。Ｙ２０９が窒素原子の場合、ｋは１である。Ｙ２０９が炭素原子の場合、ｋは２である。ｌおよびｍは、それぞれ独立して、０～１４の整数を表す。ｎは０～２の整数を表す。＊１～＊１５は、それぞれ独立して、上述した（ＩＩ－ｂ１）構造との結合点を表す。 In general formulas (141) to (147), 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.
　一般式（１４１）～（１４７）において、Ｘ２０１～Ｘ２０８としては、それぞれ独立して、炭素数６～１５の単環式または縮合多環式の炭化水素環が好ましい。Ｙ２０１およびＹ２０９としては、それぞれ独立して、直接結合または酸素原子が好ましい。上述した脂肪族構造、アルキル基、シクロアルキル基、アリール基および単環式もしくは縮合多環式の芳香族炭化水素環は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (141) to (147), 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.
　（Ｂ１）化合物は、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、（Ｉ－ｂ１）構造、（ＩＩ－ｂ１）構造ならびに以下の（ＩＩＩ－ｂ１）構造または（ＩＶ－ｂ１）構造を有することがより好ましい。
（ＩＩＩ－ｂ１）構造：アルキレンカルボニル基、オキシアルキレンカルボニル基またはアミノアルキレンカルボニル基。
（ＩＶ－ｂ１）構造：ヒドロキシ基を含むアルキレン基またはヒドロキシ基を含むオキシアルキレン基。 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.
　（Ｂ１）化合物が有する（ＩＩＩ－ｂ１）構造または（ＩＶ－ｂ１）構造の数の合計は、２個以上が好ましく、３個以上がより好ましく、４個以上がさらに好ましい。一方、（ＩＩＩ－ｂ１）構造または（ＩＶ－ｂ１）構造の数の合計は、１０個以下が好ましく、８個以下がより好ましく、６個以下がさらに好ましい。（Ｂ１）化合物は、（ＩＩＩ－ｂ１）構造を有することが好ましい。（ＩＩＩ－ｂ１）構造としては、ラクトン化合物に由来する構造またはラクタム化合物に由来する構造が好ましい。（Ｂ１）化合物が（ＩＩＩ－ｂ１）構造または（ＩＶ－ｂ１）構造を有する場合、上述した一般式（１４１）～（１４７）において、＊１～＊１５は、それぞれ独立して、上述した（ＩＩ－ｂ１）構造との結合点、上述した（ＩＩＩ－ｂ１）構造との結合点または上述した（ＩＶ－ｂ１）構造との結合点を表す。 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. (B1) When the compound has the (III-b1) structure or (IV-b1) structure, in the above general formulas (141) to (147), * 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.
　（Ｂ１）化合物が後述する一般式（１５７）で表される構造を有する場合、上述した（ＩＩＩ－ｂ１）構造を有する。また、（Ｂ１）化合物が後述する一般式（１５６）で表される構造を有し、Ｘ２３１がヒドロキシ基を含む炭素数１～１０のアルキレン基を表す場合、上述した（ＩＶ－ｂ１）構造を有する。なお、一般式（１５６）および一般式（１５７）において、＊１および＊２は、それぞれ独立して、上述した（Ｉ－ｂ１）構造との結合点を表す。＊３および＊４は、それぞれ独立して、上述した（ＩＩ－ｂ１）構造との結合点を表す。一般式（１５７）において、＊１および＊２は、それぞれ独立して、上述した一般式（１４１）～（１４７）中の酸素原子との結合点であることが好ましい。 When the compound (B1) has a structure represented by general formula (157) described later, it has the structure (III-b1) described above. Further, when 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 In general formulas (156) and (157), * 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. In general formula (157), * 1 and * 2 are each independently preferably a bonding point with the oxygen atom in general formulas (141) to (147) described above.
　（Ｂ１）化合物の二重結合当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、１５０ｇ／ｍｏｌ以上が好ましく、１９０ｇ／ｍｏｌ以上がより好ましい。一方、二重結合当量は、現像後の残渣抑制の観点から、６００ｇ／ｍｏｌ以下が好ましく、４００ｇ／ｍｏｌ以下がより好ましい。 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. On the other hand, 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.
　本発明の感光性樹脂組成物が、（Ｂ１）化合物を含有する場合、（Ｂ１）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、５質量部以上が好ましく、１０質量部以上がより好ましい。一方、（Ｂ１）化合物の含有量は、現像後の残渣抑制の観点から、２５質量部以下が好ましく、２０質量部以下がより好ましい。 When the photosensitive resin composition of the present invention contains the (B1) compound, 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. On the other hand, 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.
　＜（Ｂ）ラジカル重合性化合物；（Ｂ２）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｂ２）柔軟骨格含有ラジカル重合性化合物（以下、「（Ｂ２）化合物」）を含有し、（Ｂ２）化合物が、以下の（Ｉ－ｂ２）構造、（ＩＩ－ｂ２）構造および（ＩＩＩ－ｂ２）構造を有し、（ＩＩ－ｂ２）構造を少なくとも２つ有することが好ましい。
（Ｉ－ｂ２）構造：少なくとも２つのヒドロキシ基を有する化合物に由来する構造。
（ＩＩ－ｂ２）構造：エチレン性不飽和二重結合基を有する有機基。
（ＩＩＩ－ｂ２）構造：アルキレン基、オキシアルキレン基、ヒドロキシ基を含むアルキレン基、ヒドロキシ基を含むオキシアルキレン基、アルキレンカルボニル基、オキシアルキレンカルボニル基またはアミノアルキレンカルボニル基。 <(B) radically polymerizable compound; (B2) compound>
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.
　エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。エチレン性不飽和二重結合基は、（メタ）アクリロイル基を有することが好ましい。（Ｂ２）化合物を含有させることで、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。 The ethylenically unsaturated double bond group is preferably a radically polymerizable group. The ethylenically unsaturated double bond group preferably has a (meth)acryloyl group. By containing the compound (B2), the effects of improving the sensitivity during exposure, suppressing residues after development, and suppressing variations in opening pattern dimensions after development become remarkable.
　（Ｂ２）化合物において、（Ｉ－ｂ２）構造としては、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、以下の（Ｉ－ｂ２ｘ）構造がより好ましい。
（Ｉ－ｂ２ｘ）構造：脂肪族多官能アルコールに由来する構造、脂環式構造およびヘテロ脂環式構造からなる群より選ばれる一種類以上の構造を含む構造。 In the compound (B2), 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. preferable.
(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.
　（Ｂ２）化合物は、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、上述した（Ｉ－ｂ２ｘ）構造が、一般式（１５１）～（１５４）のいずれかで表される構造であることが好ましい。 From the viewpoint of improving sensitivity during exposure, suppressing residue after development, and suppressing variation in opening pattern dimensions after development, 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.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　一般式（１５１）～（１５４）において、Ｘ２２１～Ｘ２２８は、それぞれ独立して、炭素数１～６の脂肪族構造を表す。Ｒ３２１～Ｒ３２５は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基または炭素数４～１０のシクロアルキル基を表す。ａおよびｂは、それぞれ独立して、０～５の整数を表す。＊１～＊１６は、それぞれ独立して、上述した（ＩＩ－ｂ２）構造との結合点または上述した（ＩＩＩ－ｂ２）構造との結合点を表す。上述した脂肪族構造、アルキル基およびシクロアルキル基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (151) to (154), 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.
　（Ｂ２）化合物が上述した（Ｉ－ｂ２ｘ）構造を有する化合物を含有する場合、ハーフトーン特性向上およびパターン形状の低テーパー化の観点から、（Ｂ２）化合物は、さらに、上述した（Ｉ－ｂ２）構造として、一般式（１５５）で表される構造を有する化合物を含有することが好ましい。 When 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).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　一般式（１５５）において、Ｘ２２９およびＸ２３０は、それぞれ独立して、炭素数１～６の脂肪族構造を表す。Ｙ２２９は、直接結合、窒素原子、または酸素原子を表す。Ｒ３２６は、水素原子、ハロゲン原子、炭素数１～１０のアルキル基または炭素数４～１０のシクロアルキル基を表す。Ｙ２２９が直接結合または酸素原子の場合、ａは０である。Ｙ２２９が窒素原子の場合、ａは１である。＊１および＊２は、それぞれ独立して、上述した（ＩＩＩ－ｂ２）構造との結合点を表す。上述した脂肪族構造は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In 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.
　（Ｂ２）化合物は、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、以下の（ＩＩＩ－ｂ２ｘ）構造を有することがより好ましい。
（ＩＩＩ－ｂ２ｘ）構造：アルキレンカルボニル基、オキシアルキレンカルボニル基またはアミノアルキレンカルボニル基。 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.
　（Ｂ２）化合物が有する（ＩＩＩ－ｂ２）構造の数および（ＩＩＩ－ｘ）構造の数の合計は、２個以上が好ましく、３個以上がより好ましく、４個以上がさらに好ましい。一方、（ＩＩＩ－ｂ２）構造の数および（ＩＩＩ－ｂ２ｘ）構造の数の合計は、１２個以下が好ましく、１０個以下がより好ましく、８個以下がさらに好ましい。アルキレン基、オキシアルキレン基、ヒドロキシ基を含むアルキレン基およびヒドロキシ基を含むオキシアルキレン基としては、エポキシ化合物に由来する構造またはアルキレングリコールに由来する構造が好ましい。（Ｂ２）化合物は、（ＩＩＩ－ｂ２ｘ）構造を有することが好ましい。（ＩＩＩ－ｂ２ｘ）構造としては、ラクトン化合物に由来する構造またはラクタム化合物に由来する構造が好ましい。 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. On the other hand, 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.
　（Ｂ２）化合物は、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、上述した（ＩＩＩ－ｂ２）構造は、一般式（１５６）および一般式（１５７）のいずれかで表される構造からなる群より選ばれる一種類以上の構造であることが好ましい。 (B2) compound, from the viewpoint of improving the sensitivity at the time of exposure, suppressing residue after development, and suppressing variation in opening pattern size after development, 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).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　一般式（１５６）および一般式（１５７）において、Ｘ２３１およびＸ２３２は、それぞれ独立して、炭素数１～１０のアルキレン基またはヒドロキシ基を含む炭素数１～１０のアルキレン基を表す。Ｙ２３１およびＹ２３２は、それぞれ独立して、直接結合、窒素原子または酸素原子を表す。Ｒ３２７は、水素原子、ハロゲン原子、炭素数１～１０のアルキル基または炭素数４～１０のシクロアルキル基を表す。ａおよびｂは、それぞれ独立して、１～４の整数を表す。Ｙ２３２が直接結合または酸素原子の場合、ｃは０である。Ｙ２３２が窒素原子の場合、ｃは１である。＊１および＊２は、それぞれ独立して、上述した（Ｉ－ｂ２）構造との結合点を表す。＊３および＊４は、それぞれ独立して、上述した（ＩＩ－ｂ２）構造との結合点を表す。一般式（１５６）および一般式（１５７）において、＊１および＊２は、それぞれ独立して、一般式（１５１）～（１５４）中の酸素原子との結合点であることが好ましい。上述したアルキレン基、アルキル基およびシクロアルキル基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。（Ｂ２）化合物が一般式（１５７）で表される構造を有する場合、上述した（ＩＩＩ－ｂ２ｘ）構造を有する。 In general formulas (156) and (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. In general formulas (156) and (157), * 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. When the compound (B2) has the structure represented by the general formula (157), it has the structure (III-b2x) described above.
　（Ｂ２）化合物が有するエチレン性不飽和二重結合基数は、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、２個以上が好ましく、３個以上がより好ましく、４個以上がさらに好ましい。一方、エチレン性不飽和二重結合基数は、ハーフトーン特性向上およびパターン形状の低テーパー化の観点から、１２個以下が好ましく、１０個以下がより好ましく、８個以下がさらに好ましい。また、二重結合当量は、ハーフトーン特性向上およびパターン形状の低テーパー化の観点から、１００ｇ／ｍｏｌ以上が好ましく、１２０ｇ／ｍｏｌ以上がより好ましい。一方、二重結合当量は、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、６００ｇ／ｍｏｌ以下が好ましく、４００ｇ／ｍｏｌ以下がより好ましい。（Ｂ２）化合物は、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、少なくとも３つの（ＩＩ－ｂ２）構造を有する化合物および２つの（ＩＩ－ｂ２）構造を有する化合物を含有することがより好ましい。 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. On the other hand, 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. In addition, 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. On the other hand, 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.
　本発明の感光性樹脂組成物が、（Ｂ２）化合物を含有する場合、（Ｂ２）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、露光時の感度向上、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の観点から、１０質量部以上が好ましく、２０質量部以上がより好ましい。一方、（Ｂ２）化合物の含有量は、ハーフトーン特性向上およびパターン形状の低テーパー化の観点から、４０質量部以下が好ましく、３５質量部以下がより好ましい。 When the photosensitive resin composition of the present invention contains the (B2) compound, 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. On the other hand, 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.
　＜（Ｂ）ラジカル重合性化合物；（Ｂ３）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｂ３）環状骨格含有ラジカル重合性化合物（以下、「（Ｂ３）化合物」）を含有し、（Ｂ３）化合物が、以下の（Ｉ－ｂ３）構造および（ＩＩ－ｂ３）構造を有し、（ＩＩ－ｂ３）構造を少なくとも２つ有することが好ましい。
（Ｉ－ｂ３）構造：脂環式構造および／またはヘテロ脂環式構造を含む構造。
（ＩＩ－ｂ３）構造：エチレン性不飽和二重結合基を有する有機基。 <(B) radically polymerizable compound; (B3) compound>
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.
　（Ｂ３）化合物は、（Ｂ１）化合物および（Ｂ２）化合物とは異なる化合物である。なお、（Ｂ１）化合物および（Ｂ２）化合物の両方に該当する化合物は、（Ｂ１）化合物に含まれるものとする。エチレン性不飽和二重結合基は、ラジカル重合性基であることが好ましい。エチレン性不飽和二重結合基は、（メタ）アクリロイル基を有することが好ましい。（Ｂ３）化合物を含有させることで、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。 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. By containing the (B3) compound, the effect of improving the halftone characteristics and suppressing the variation in the dimension of the opening pattern after development becomes remarkable.
　（Ｂ３）化合物は、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、上述した（Ｉ－ｂ３）構造が、窒素原子を少なくとも２つ有する環状構造を含む構造であることが好ましい。窒素原子を少なくとも２つ有する環状構造としては、イソシアヌル酸構造および／またはトリアジン構造が好ましい。 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.
　（Ｂ３）化合物の二重結合当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、１５０ｇ／ｍｏｌ以上が好ましく、１９０ｇ／ｍｏｌ以上がより好ましい。一方、二重結合当量は、現像後の残渣抑制の観点から、６００ｇ／ｍｏｌ以下が好ましく、４００ｇ／ｍｏｌ以下がより好ましい。 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. On the other hand, 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.
　本発明の感光性樹脂組成物が、（Ｂ３）化合物を含有する場合、（Ｂ３）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、５質量部以上が好ましく、１０質量部以上がより好ましい。一方、（Ｂ３）化合物の含有量は、現像後の残渣抑制の観点から、２５質量部以下が好ましく、２０質量部以下がより好ましい。 When the photosensitive resin composition of the present invention contains the (B3) compound, 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.
　＜（Ｃ）感光剤＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ）感光剤を含有する。（Ｃ）感光剤とは、露光によって結合開裂、反応または構造変化して別の化合物を発生させることで、組成物にポジ型またはネガ型の感光性を付与する化合物をいう。（Ｃ）感光剤は、（Ｃ１）光重合開始剤（以下、「（Ｃ１）化合物」）、（Ｃ２）光酸発生剤および（Ｃ３）ナフトキノンジアジド化合物（以下、「（Ｃ３）化合物」）からなる群より選ばれる一種類以上の化合物を含有することが好ましい。組成物にネガ型の感光性を付与する場合、（Ｃ１）化合物を含有することが好ましく、さらに、（Ｃ２）光酸発生剤および／または（Ｃ３）化合物を含有することが好ましい。組成物にポジ型の感光性を付与する場合、（Ｃ３）化合物を含有することが好ましく、さらに、（Ｃ１）化合物および／または（Ｃ２）光酸発生剤を含有することが好ましい。 <(C) Photosensitizer>
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. (C) 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: 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.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｃ）感光剤の含有比率は、露光時の感度向上の観点から、０．３質量％以上が好ましく、１．０質量％以上がより好ましく、２．０質量％以上がさらに好ましい。一方、（Ｃ）感光剤の含有比率は、現像後の残渣抑制の観点から、２５質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましい。 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. On the other hand, 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.
　＜（Ｃ）感光剤；（Ｃ１）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ）感光剤が、（Ｃ１）化合物を含有することが好ましい。（Ｃ１）化合物とは、前記のとおり、光重合開始剤、すなわち、露光によって結合開裂および／または反応してラジカルを発生する化合物をいう。露光時、（Ｃ１）化合物から発生するラジカルが僅かな量であっても、上述した（Ｂ）化合物などのラジカル重合が連鎖的に進行するため、低露光量の光でのネガ型のパターン形成に好適であり、露光時の感度向上の効果が顕著となる。 <(C) Photosensitizer; (C1) Compound>
In the photosensitive resin composition of the first aspect of the present invention, 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）化合物としては、ベンジルケタール系化合物、α－ヒドロキシケトン系化合物、α－アミノケトン系化合物、アシルホスフィンオキシド系化合物、ビイミダゾール系化合物、オキシムエステル系化合物、アクリジン系化合物、チタノセン系化合物、ベンゾフェノン系化合物、アセトフェノン系化合物、芳香族ケトエステル系化合物または安息香酸エステル系化合物が好ましい。露光時の感度向上の観点から、α－ヒドロキシケトン系化合物、α－アミノケトン系化合物、アシルホスフィンオキシド系化合物、ビイミダゾール系化合物またはオキシムエステル系化合物がより好ましく、露光時の感度向上、ハーフトーン特性向上および現像後の残渣抑制の観点から、オキシムエステル系化合物がさらに好ましい。 (C1) compounds include benzyl ketal-based compounds, α-hydroxyketone-based compounds, α-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, α-hydroxyketone compounds, α-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.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｃ１）化合物の含有比率は、露光時の感度向上の観点から、０．３質量％以上が好ましく、１．０質量％以上がより好ましく、２．０質量％以上がさらに好ましい。一方、（Ｃ１）化合物の含有比率は、現像後の残渣抑制の観点から、２５質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましい。また、本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｃ１）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、１質量部以上が好ましく、３質量部以上がより好ましく、５質量部以上がさらに好ましい。一方、（Ｃ１）化合物の含有量は、３０質量部以下が好ましく、２５質量部以下がより好ましく、２０質量部以下がさらに好ましい。 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. On the other hand, 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. Further, when the photosensitive resin composition of the present invention contains the (B) compound, 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. On the other hand, 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.
　＜（Ｃ）感光剤；（Ｃ１－１）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ１）化合物が、（Ｃ１－１）オキシムエステル系化合物（以下、「（Ｃ１－１）化合物」）を含有することが好ましい。（Ｃ１－１）化合物とは、露光によって結合開裂および／または反応してラジカルを発生する骨格として、オキシムエステル構造を有する化合物をいう。（Ｃ１－１）化合物を含有させることで、露光時の感度向上、ハーフトーン特性向上および現像後の残渣抑制の効果が顕著となる。 <(C) Photosensitizer; (C1-1) Compound>
In the photosensitive resin composition of the first aspect of the present invention, 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. By containing the (C1-1) compound, the effect of improving sensitivity during exposure, improving halftone characteristics, and suppressing residue after development becomes remarkable.
　本発明の第一の態様の感光性樹脂組成物は、露光時の感度向上、ハーフトーン特性向上および現像後の残渣抑制の観点から、（Ｃ１）化合物が、（Ｃ１－１）化合物を含有し、さらに、上述した（Ｂ）化合物を含有することが好ましい。（Ｃ１－１）化合物は、露光時の光に対する吸光度が高いため、高効率的なラジカル発生に好適であり、（Ｂ）化合物のラジカル重合の反応速度向上が顕著となる。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　（Ｃ１－１）化合物は、縮合多環式構造、縮合多環式ヘテロ環構造またはジフェニルスルフィド構造を有することが好ましい。（Ｃ１－１）化合物は、縮合多環式構造、縮合多環式へテロ環構造またはジフェニルスルフィド構造に、少なくとも１つのオキシムエステル構造が結合した構造（α－オキシム構造）または少なくとも１つのオキシムエステルカルボニル構造が結合した構造（すなわち、カルボニル構造を介してオキシムエステル構造が結合した構造；β－オキシム構造）を有することが好ましく、少なくとも１つのオキシムエステル構造が結合した構造を有することがより好ましい。縮合多環式構造としては、フルオレン構造、ベンゾフルオレン構造、ジベンゾフルオレン構造、インデン構造、インダン構造、ベンゾインデン構造またはベンゾインダン構造が好ましく、フルオレン構造、ベンゾフルオレン構造またはジベンゾフルオレン構造がより好ましい。縮合多環式ヘテロ環構造としては、カルバゾール構造、ジベンゾフラン構造、ジベンゾチオフェン構造、ベンゾカルバゾール構造、インドール構造、インドリン構造、ベンゾインドール構造、ベンゾインドリン構造、フェノチアジン構造またはフェノチアジンオキシド構造が好ましく、カルバゾール構造、ベンゾカルバゾール構造、インドール構造またはベンゾインドール構造がより好ましい。露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、（Ｃ１－１）化合物は、フルオレン構造、ベンゾフルオレン構造、ジベンゾフルオレン構造、ベンゾカルバゾール構造、インドール構造またはベンゾインドール構造を有することが好ましい。 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 (α-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 β-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. From the viewpoint of improving sensitivity during exposure, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development, 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ）感光剤が、（Ｃ１）化合物を含み、（Ｃ１）化合物が、（Ｃ１－１）化合物を含有し、（Ｃ１－１）化合物が、ニトロ基、ナフチルカルボニル構造、トリメチルベンゾイル構造、チオフェニルカルボニル構造、フリルカルボニル構造、少なくとも２つのオキシムエステル構造および少なくとも２つのオキシムエステルカルボニル構造からなる群より選ばれる一種類以上の構造を有することが好ましい。 In the photosensitive resin composition of the first aspect of the present invention, (C) 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）化合物が、ニトロ基、ナフチルカルボニル構造、トリメチルベンゾイル構造、チオフェニルカルボニル構造、フリルカルボニル構造、少なくとも２つのオキシムエステル構造および少なくとも２つのオキシムエステルカルボニル構造からなる群より選ばれる一種類以上の構造を有することで、露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。中でも、縮合多環式構造、縮合多環式へテロ環構造またはジフェニルスルフィド構造に、これらの構造が結合した構造を有することが好ましい。 (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; By having the above structure, the effects of improving sensitivity during exposure, improving halftone characteristics, and suppressing variations in opening pattern dimensions after development become remarkable. Among them, it is preferable to have a structure in which these structures are bonded to a condensed polycyclic structure, a condensed polycyclic heterocyclic structure or a diphenylsulfide structure.
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ１－１）化合物が、ニトロ基、ナフチルカルボニル構造、トリメチルベンゾイル構造、チオフェニルカルボニル構造、フリルカルボニル構造および少なくとも２つのオキシムエステル構造からなる群より選ばれる一種類以上の構造を有し、かつ、フルオレン骨格、ベンゾフルオレン骨格、およびジベンゾフルオレン骨格からなる群より選ばれる一種類以上の構造を有することが好ましい。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　（Ｃ１－１）化合物が、フルオレン骨格、ベンゾフルオレン骨格およびジベンゾフルオレン骨格からなる群より選ばれる一種類以上の構造を有することで、（Ｃ１－１）化合物がフォトブリーチング性を有するため、露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。フォトブリーチング性とは、露光によって結合開裂および／または反応することで、紫外領域の波長（例えば、４００ｎｍ以下）の吸光度および／または可視光線の波長（３８０～７８０ｎｍ）の吸光度が低下することをいう。同様に、フォトブリーチング性を有する観点から、（Ｃ１－１）化合物は、ジフェニルスルフィド構造、インドール構造またはベンゾインドール構造を有することも好ましく、縮合多環式構造または縮合多環式へテロ環構造に、オキシムエステルカルボニル構造が結合した構造を有することも好ましい。 Since 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. Similarly, from the viewpoint of photobleaching, 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 .
　（Ｃ１－１）化合物は、露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、ハロゲン原子で置換された基を有することが好ましく、フッ素原子で置換された基を有することがより好ましい。上述した（Ａ）アルカリ可溶性樹脂がハロゲン原子を有する構造単位を有する場合、樹脂と光重合開始剤との相溶性向上により、露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。なお、上述したポリイミド系の樹脂は、上述したフッ素原子を有する構造単位を有することが好ましい。ハロゲン原子で置換された基としては、トリフルオロメチル基、トリフルオロプロピル基、トリクロロプロピル基、テトラフルオロプロピル基、フルオロシクロペンチル基、フルオロフェニル基、ペンタフルオロフェニル基、トリフルオロプロポキシ基、テトラフルオロプロポキシ基またはペンタフルオロフェノキシ基が好ましい。 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. When 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.
　（Ｃ１－１）化合物は、露光時の感度向上、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基を有することが好ましい。中でも、縮合多環式構造、縮合多環式へテロ環構造またはジフェニルスルフィド構造に、少なくとも１つの炭素数１～５のアルケニル基が結合した構造を有することが好ましい。光反応性基としては、ラジカル重合性基が好ましく、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基がより好ましく、（メタ）アクリロイル基がさらに好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ラジカル重合性基が好ましく、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基がより好ましく、ビニル基またはアリル基がさらに好ましい。 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. On the other hand, 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.
　縮合多環式構造、縮合多環式ヘテロ環構造またはジフェニルスルフィド構造を有する（Ｃ１－１）化合物は、露光時の感度向上、ハーフトーン特性向上および現像後の残渣抑制の観点から、一般式（１７）、（１８）および（１９）のいずれかで表される化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましく、一般式（１８）で表される化合物を含有することがより好ましい。なお、縮合多環式構造を有する場合、一般式（１７）および一般式（１８）において、Ｙ１およびＹ２は、それぞれ独立して、炭素原子である。また、縮合多環式ヘテロ環構造を有する場合、一般式（１７）および一般式（１８）において、Ｙ１およびＹ２は、それぞれ独立して、窒素原子、酸素原子または硫黄原子を表す。 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. In the case of having a condensed polycyclic structure, Y 1 and Y 2 are each independently a carbon atom in general formulas (17) and (18). In the case of having a condensed polycyclic heterocyclic structure, Y 1 and Y 2 each independently represent a nitrogen atom, an oxygen atom or a sulfur atom in general formulas (17) and (18).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　一般式（１７）～（１９）において、Ｘ１、Ｘ２、Ｘ４、Ｘ５およびＸ６は、それぞれ独立して、直接結合、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基を表す。Ｙ１およびＹ２は、それぞれ独立して、炭素原子、窒素原子、酸素原子または硫黄原子を表す。Ｒ４５１～Ｒ４５６は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のアルコキシ基または炭素数１～１０のヒドロキシアルキル基を表す。Ｒ４５７～Ｒ４５９は、それぞれ独立して、一般式（３７）～（４０）のいずれかで表される置換基またはニトロ基を表す。Ｒ４６０～Ｒ４６７は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基または炭素数４～１０の環を形成する基を表す。Ｒ４６８およびＲ４６９は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のアルケニル基、炭素数１～１０のアルコキシ基、炭素数１～１０のハロアルキル基、炭素数１～１０のハロアルコキシ基または炭素数２～１５のアシル基を表す。Ｒ４７１～Ｒ４７３は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のアルケニル基、炭素数１～１０のアルコキシ基、炭素数１～１０のハロアルキル基、炭素数１～１０のハロアルコキシ基、炭素数４～１０の複素環基、炭素数４～１０の複素環オキシ基、炭素数２～１０のアシル基またはニトロ基を表す。Ｒ４７４～Ｒ４７６は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。ａは０～３の整数を表す。ｃは０～５の整数を表す。ｂおよびｄは、それぞれ独立して、０または１を表す。ｅおよびｆは、それぞれ独立して、０～２の整数を表す。Ｙ１およびＹ２が、それぞれ独立して、炭素原子の場合、ｇおよびｈは、それぞれ独立して、２である。Ｙ１およびＹ２が、それぞれ独立して、窒素原子の場合、ｇおよびｈは、それぞれ独立して、１である。Ｙ１およびＹ２が、それぞれ独立して、酸素原子または硫黄原子の場合、ｇおよびｈは、それぞれ独立して、０である。ｊ、ｋ、およびｌは、それぞれ独立して、０または１を表す。ｍ、ｎおよびｏは、それぞれ独立して、１～１０の整数を表す。ｐ、ｑおよびｒは、それぞれ独立して、１～４の整数を表す。ｘ、ｙおよびｚは、それぞれ独立して、１～４の整数を表す。 In general formulas (17) to (19), 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. group, alkoxy group having 1 to 10 carbon atoms, haloalkyl group having 1 to 10 carbon atoms, haloalkoxy group having 1 to 10 carbon atoms, heterocyclic group having 4 to 10 carbon atoms, heterocyclic oxy group having 4 to 10 carbon atoms , represents an acyl group or a nitro group having 2 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; p, q and r each independently represents an integer of 1 to 4; x, y and z each independently represents an integer of 1 to 4;
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　一般式（３７）～（４０）において、Ｒ４７７～Ｒ４８０は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基、炭素数１～１０のアルコキシ基、炭素数１～１０のヒドロキシアルキル基または環を形成する基を表す。複数のＲ４７７～Ｒ４８０で形成する環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、シクロペンタン環またはシクロヘキサン環が挙げられる。ａは０～７の整数を表す。ｂは０～２の整数を表す。ｃおよびｄは、それぞれ独立して、０～３の整数を表す。複数のＲ４７７～Ｒ４８０で形成する環としては、ベンゼン環またはナフタレン環が好ましい。 In general formulas (37) to (40), 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 represents an integer of 0 to 7; b represents an integer of 0 to 2; c and d each independently represent an integer of 0 to 3; A benzene ring or a naphthalene ring is preferable as the ring formed by a plurality of R 477 to R 480 .
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｃ１－１）化合物の含有比率は、露光時の感度向上およびハーフトーン特性向上の観点から、０．３質量％以上が好ましく、１．０質量％以上がより好ましく、２．０質量％以上がさらに好ましい。一方、（Ｃ１－１）化合物の含有比率は、現像後の残渣抑制の観点から、２５質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましい。また、本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｃ１－１）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、１質量部以上が好ましく、３質量部以上がより好ましく、５質量部以上がさらに好ましい。一方、（Ｃ１－１）化合物の含有量は、３０質量部以下が好ましく、２５質量部以下がより好ましく、２０質量部以下がさらに好ましい。 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. On the other hand, 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. Further, when 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. On the other hand, 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.
　＜（Ｃ）感光剤；（Ｃ２）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ）感光剤が、（Ｃ２）光酸発生剤を含有しても構わない。（Ｃ２）光酸発生剤とは、露光によって結合開裂および／または反応して酸を発生する化合物をいう。露光時、（Ｃ２）光酸発生剤から発生する酸が僅かな量であっても、カチオン重合性化合物のカチオン重合、および／または、後述する（Ｇ）架橋剤などと樹脂との架橋が連鎖的に進行するため、低露光量でのネガ型のパターン形成に好適であり、露光時の感度向上の効果が顕著となる。（Ｃ）感光剤が、上述した（Ｃ１）化合物および（Ｃ２）光酸発生剤を含有することも好ましい。一方、（Ｃ）感光剤が後述する（Ｃ３）化合物および（Ｃ２）光酸発生剤を含有する場合、アルカリ現像後かつ熱硬化前における露光時、（Ｃ２）光酸発生剤から酸を発生できる。発生した酸により、その後の熱硬化時における後述する（Ｃ）架橋剤などと樹脂との架橋を促進できるため、硬化物の耐熱性向上および硬化物の耐薬品性向上の効果が顕著となる。 <(C) Photosensitizer; (C2) Compound>
In the photosensitive resin composition of the first aspect of the present invention, (C) 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. (C) The photosensitive agent preferably contains the above-described (C1) compound and (C2) photoacid generator. On the other hand, when 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.
　（Ｃ２）光酸発生剤としては、例えば、イオン性化合物または非イオン性化合物が挙げられる。イオン性化合物としては、トリオルガノスルホニウム塩系化合物が好ましい。非イオン性化合物としては、ハロゲン含有化合物、ジアゾメタン化合物、スルホン化合物、スルホン酸エステル化合物、カルボン酸エステル化合物、スルホンイミド化合物、リン酸エステル化合物またはスルホンベンゾトリアゾール化合物が好ましい。 (C2) Photoacid generators include, for example, ionic compounds and nonionic compounds. As the 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.
　＜（Ｃ）感光剤；（Ｃ３）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｃ）感光剤が、（Ｃ３）ナフトキノンジアジド化合物（以下、「（Ｃ３）化合物」）を含有することが好ましい。（Ｃ３）化合物とは、露光によって構造変化してインデンカルボン酸および／またはスルホインデンカルボン酸を発生する化合物をいう。露光時、（Ｃ３）化合物が構造変化した酸性化合物により、組成物から得られる膜の露光部がアルカリ現像液に対して可溶化することで、ポジ型のパターンを形成できる。また、露光部のアルカリ現像液に対する溶解性が選択的に向上し、現像後の解像度向上の効果が顕著となる。一方、本発明の第一の態様の感光性樹脂組成物がネガ型の感光性を有する場合、（Ｃ）感光剤が、上述した（Ｃ１）化合物および（Ｃ３）化合物を含有することで、現像時のパターン形状変化抑制およびパターン形状の低テーパー化の効果が顕著となる。 <(C) Photosensitizer; (C3) compound>
In the photosensitive resin composition of the first aspect of the present invention, (C) 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. At the time of exposure, 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. In addition, the solubility of the exposed portion in an alkaline developer is selectively improved, and the effect of improving the resolution after development becomes remarkable. On the other hand, when the photosensitive resin composition of the first aspect of the present invention has negative photosensitivity, 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.
　（Ｃ３）化合物としては、フェノール性水酸基の有する化合物の５－ナフトキノンジアジドスルホン酸エステル体または４－ナフトキノンジアジドスルホン酸エステル体が好ましい。（Ｃ３）化合物を製造する方法としては、例えば、フェノール性水酸基を有する化合物と、ナフトキノンジアジドスルホン酸とをエステル化反応させる方法や、フェノール性水酸基を有する化合物と、ナフトキノンジアジドスルホン酸クロリドとをエステル化反応させる方法などが挙げられる。ナフトキノンジアジドスルホン酸クロリドとしては、５－ナフトキノンジアジドスルホン酸クロリドまたは４－ナフトキノンジアジドスルホン酸クロリドが好ましい。 The (C3) compound is preferably a 5-naphthoquinonediazidesulfonic acid ester or a 4-naphthoquinonediazidesulfonic acid ester of a compound having a phenolic hydroxyl group. As 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. As the naphthoquinonediazidesulfonic acid chloride, 5-naphthoquinonediazidesulfonic acid chloride or 4-naphthoquinonediazidesulfonic acid chloride is preferred.
　＜（Ｄ）着色剤；（Ｄａ）化合物および（Ｄｂ）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｄ）着色剤を含有することが好ましい。（Ｄ）着色剤は、（Ｄａ）黒色剤を含むことが好ましい。 <(D) Colorant; (Da) Compound and (Db) Compound>
The photosensitive resin composition of the first aspect of the present invention preferably further contains (D) a colorant. (D) The colorant preferably contains (Da) a black agent.
　（Ｄ）着色剤とは、可視光線の波長（３８０～７８０ｎｍ）の光を吸収することで組成物を着色させる化合物をいう。（Ｄ）着色剤を含有させることで、組成物から得られる硬化物を透過する光または組成物から得られる硬化物から反射する光を所望の色に着色できる。また、組成物から得られる硬化物に遮光性を付与できる。（Ｄ）着色剤としては、（Ｄ１）顔料または（Ｄ２）染料などが好ましい。特に、可視光線の遮光性が必要な場合、（Ｄ）着色剤として（Ｄａ）黒色剤が好ましい。（Ｄａ）黒色剤とは、可視光線の波長の光を吸収することで組成物を黒色化させる化合物をいう。（Ｄａ）黒色剤を含有させることで、組成物から得られる硬化物の遮光性向上、および有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著となる。（Ｄａ）黒色剤を含有する組成物から得られる硬化物は、外光反射抑制による高コントラスト化、隣接画素からの光漏れ防止またはＴＦＴの誤作動防止などが要求される用途に好適であり、有機ＥＬディスプレイの画素分割層、ＴＦＴ平坦化層、ＴＦＴ保護層、層間絶縁層またはゲート絶縁層として特に好ましく用いられる。また、ブラックマトリックスまたはブラックカラムスペーサーとしても好ましく用いられる。 (D) The colorant refers to a compound that colors the composition by absorbing light with a visible wavelength (380 to 780 nm). 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. In addition, a light-shielding property can be imparted to a cured product obtained from the composition. (D) Colorant is preferably (D1) pigment or (D2) dye. In particular, when light-shielding properties against visible light are required, (Da) a black agent is preferable as the (D) coloring agent. (Da) The blackening agent is a compound that blackens the composition by absorbing visible light. (Da) By containing a black agent, the effect of improving the light shielding property of the cured product obtained from the composition and improving the reliability of the light-emitting element in the organic EL display becomes remarkable. (Da) 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ｄａ）黒色剤および上述した（ＡＸ）樹脂を含有することで、現像後の残渣抑制および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。これは、上述した（ＡＸ）樹脂と（Ｄａ）黒色剤との相互作用により、基板表面における（Ｄａ）黒色剤のアルカリ現像液に対する溶解性が向上したためと考えられる。また、上述した（ＡＸ）樹脂の作用により、アルカリ現像時の膜深部のサイドエッチングが抑制されたためと推定される。 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.
　なお、感光性樹脂組成物は、（Ｄａ）黒色剤を含有し、さらに（Ｄｂ）黒色以外の着色剤を含有しても構わない。（Ｄｂ）黒色以外の着色剤を含有させることで、組成物から得られる硬化物を所望の色座標に調色できる。 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）染料とは、対象物の表面構造に化学吸着等をして着色させる化合物をいい、一般に溶剤等に可溶である。（Ｄ２）染料としては、例えば、アントラキノン系染料、アゾ系染料、アジン系染料、フタロシアニン系染料、メチン系染料、オキサジン系染料、キノリン系染料、インジゴ系染料、インジゴイド系染料、カルボニウム系染料、スレン系染料、ペリノン系染料、ペリレン系染料、トリアリールメタン系染料またはキサンテン系染料が挙げられる。 (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）着色剤における黒色とは、Ｃｏｌｏｕｒ　Ｉｎｄｅｘ　Ｇｅｎｅｒｉｃ　Ｎａｍｅ（以下、「Ｃ．Ｉ．ナンバー」）に“ＢＬＡＣＫ”が含まれるものをいう。Ｃ．Ｉ．ナンバーが付与されていないものを含有するときは、硬化物とした場合に、黒色であるものをいう。硬化物とした場合における黒色とは、（Ｄ）着色剤を含有する組成物の硬化物の透過スペクトルにおいて、波長５５０ｎｍにおける膜厚１．０μｍあたりの透過率をランベルト・ベールの式に基づいて、波長５５０ｎｍにおける透過率が１０％となるように膜厚を０．１～１．５μｍの範囲内で換算した場合に、換算後の透過スペクトルにおける波長４５０～６５０ｎｍにおける透過率が２５％以下であることをいう。硬化物の透過スペクトルは、国際公開第２０１９／０８７９８５号の段落［０２８５］に記載の方法に基づき、求めることができる。 (D) Black in colorants refers to those that include "BLACK" in the Color Index Generic Name (hereinafter "C.I. number"). C. I. 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 μm 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 μm 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. Say things. The transmission spectrum of the cured product can be obtained based on the method described in paragraph [0285] of WO2019/087985.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｄ）着色剤の含有比率は、遮光性向上の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、５質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましい。一方、（Ｄ）着色剤の含有比率は、露光時の感度向上の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、７０質量％以下が好ましく、５０質量％以下がより好ましい。本発明の感光性樹脂組成物において、（Ｄａ）黒色剤の好ましい含有比率は、上述した（Ｄ）着色剤の好ましい含有比率の通りである。 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. On the other hand, 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. In the photosensitive resin composition of the present invention, the preferred content ratio of (Da) the black agent is the same as the preferred content ratio of (D) the colorant described above.
　＜（Ｄ）着色剤；（Ｄ１ａ）化合物および（Ｄ１ｂ）化合物＞
　（Ｄａ）黒色剤は、（Ｄ１ａ）黒色顔料を含有することが好ましい。（Ｄ１ａ）黒色顔料とは、可視光線の波長の光を吸収することで組成物を黒色化させる顔料をいう。顔料とは、対象物の表面に物理吸着または相互作用等をして着色させる化合物をいい、一般に溶剤等に不溶である。（Ｄ１ａ）黒色顔料を含有させることで、組成物から得られる膜の遮光性向上および有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著となる。なお、（Ｄ１ａ）黒色顔料が、後述する（Ｄ１ａ－１）有機黒色顔料および／または（Ｄ１ａ－２）無機黒色顔料を含む場合、さらに（Ｄ１ｂ）黒色以外の顔料を含有しても構わない。（Ｄ１ｂ）黒色以外の顔料を含有させることで、組成物から得られる膜を所望の色座標に調色できる。（Ｄ１ｂ）黒色以外の顔料は、後述する青色顔料、赤色顔料、黄色顔料、紫色顔料、橙色顔料および緑色顔料からなる群より選ばれる一種類以上の顔料であることが好ましい。本発明の感光性樹脂組成物において、（Ｄ１ａ）黒色顔料の好ましい含有比率は、上述した（Ｄ）着色剤の好ましい含有比率の通りである。 <(D) Colorant; (D1a) Compound and (D1b) Compound>
(Da) The black agent preferably contains (D1a) a black pigment. (D1a) 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. When (D1a) 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. (D1b) 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. In the photosensitive resin composition of the present invention, the preferred content ratio of (D1a) black pigment is the same as the preferred content ratio of (D) colorant described above.
　＜（Ｄ）着色剤；（Ｄ１ａ－１）化合物、（Ｄ１ａ－２）化合物および（Ｄ１ａ－３）化合物＞
　（Ｄ１ａ）黒色顔料は、（Ｄ１ａ－１）有機黒色顔料（以下、「（Ｄ１ａ－１）化合物」）、（Ｄ１ａ－２）無機黒色顔料（以下、「（Ｄ１ａ－２）化合物」）および（Ｄ１ａ－３）二色以上の着色顔料混合物（以下、「（Ｄ１ａ－３）化合物」）からなる群より選ばれる一種類以上の顔料であることが好ましい。有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、（Ｄ１ａ－１）化合物および／または（Ｄ１ａ－３）化合物であることがより好ましく、（Ｄ１ａ－１）化合物がさらに好ましい。 <(D) colorant; (D1a-1) compound, (D1a-2) compound and (D1a-3) compound>
(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.
　（Ｄ１ａ－１）化合物としては、例えば、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料、（Ｄ１ａ－１ｂ）ペリレン系黒色顔料、（Ｄ１ａ－１ｃ）アゾ系黒色顔料、アントラキノン系黒色顔料、アニリン系黒色顔料、アゾメチン系黒色顔料またはカーボンブラックが挙げられる。（Ｄ１ａ－２）化合物としては、例えば、グラファイトもしくは銀スズ合金またはチタン、銅、鉄、マンガン、コバルト、クロム、ニッケル、亜鉛、カルシウムもしくは銀などの金属を含む微粒子、酸化物、複合酸化物、硫化物、硫酸塩、硝酸塩、炭酸塩、窒化物、炭化物もしくは酸窒化物が挙げられる。（Ｄ１ａ－３）化合物とは、二色以上の顔料を組み合わせて含むことで、擬似的に黒色を呈する顔料混合物をいう。二色以上の顔料を混合するため、組成物から得られる膜を所望の色座標に調色できる。 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.
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｄ１ａ－１）化合物および／または（Ｄ１ａ－３）化合物を含有し、
（Ｄ１ａ－１）化合物が、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料、（Ｄ１ａ－１ｂ）ペリレン系黒色顔料および（Ｄ１ａ－１ｃ）アゾ系黒色顔料からなる群より選ばれる一種類以上の顔料を含み、
（Ｄ１ａ－３）化合物が、赤、橙、黄、緑、青および紫色の顔料からなる群より選ばれる二色以上の顔料を含むことが好ましい。 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ｄ１ａ）黒色顔料として、遮光性の高いこれらの顔料を含む場合においても、上述した（ＡＸ）樹脂を含有することにより、上述した（ＡＸ）樹脂と（Ｄ１ａ）黒色顔料との相互作用により、基板表面における（Ｄ１ａ）黒色顔料のアルカリ現像液に対する溶解性が向上するので好ましい。また、上述した（ＡＸ）樹脂の作用により、アルカリ現像時の膜深部のサイドエッチングが抑制されるので好ましい。 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 ( The interaction between the 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.
　（Ｄ１ａ－３）化合物は、赤、橙、黄、緑、青および紫色の顔料からなる群より選ばれる二色以上の顔料を含むことが好ましい。（Ｄ１ａ－３）化合物は、露光時の感度向上、およびハーフトーン特性向上の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、（Ｉ－ｄ１）青色顔料、赤色顔料および黄色顔料を含む着色顔料混合物、（ＩＩ－ｄ１）青色顔料、赤色顔料および橙色顔料を含む着色顔料混合物、（ＩＩＩ－ｄ１）青色顔料、紫色顔料および橙色顔料を含む着色顔料混合物または（ＩＶ－ｄ１）紫色顔料および黄色顔料を含む着色顔料混合物であることが好ましい。 (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 or (IV-d1) a purple pigment and a yellow pigment.
　（Ｄ１ａ－３）二色以上の着色顔料混合物において、青色顔料としては、Ｃ．Ｉ．ピグメントブルー１５：４、Ｃ．Ｉ．ピグメントブルー１５：６またはＣ．Ｉ．ピグメントブルー６０が好ましく、赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１２３、Ｃ．Ｉ．ピグメントレッド１４９、Ｃ．Ｉ．ピグメントレッド１７７、Ｃ．Ｉ．ピグメントレッド１７９またはＣ．Ｉ．ピグメントレッド１９０が好ましく、黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１２０、Ｃ．Ｉ．ピグメントイエロー１５１、Ｃ．Ｉ．ピグメントイエロー１７５、Ｃ．Ｉ．ピグメントイエロー１８０、Ｃ．Ｉ．ピグメントイエロー１８１、Ｃ．Ｉ．ピグメントイエロー１９２またはＣ．Ｉ．ピグメントイエロー１９４が好ましく、紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１９、Ｃ．Ｉ．ピグメントバイオレット２９またはＣ．Ｉ．ピグメントバイオレット３７が好ましく、橙色顔料としては、Ｃ．Ｉ．ピグメントオレンジ４３、Ｃ．Ｉ．ピグメントオレンジ６４またはＣ．Ｉ．ピグメントオレンジ７２が好ましい（数値はいずれもＣ．Ｉ．ナンバー）。本発明の感光性樹脂組成物において、（Ｄ１ａ－１）化合物、（Ｄ１ａ－２）化合物および（Ｄ１ａ－３）化合物の含有比率の合計は、上述した（Ｄ）着色剤の好ましい含有比率の通りである。 (D1a-3) In the mixture of two or more color pigments, 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). In the photosensitive resin composition of the present invention, 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.
　＜（Ｄ）着色剤；（Ｄ１ａ－１ａ）化合物、（Ｄ１ａ－１ｂ）化合物および（Ｄ１ａ－１ｃ）化合物＞
　（Ｄ１ａ－１）化合物は、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料、（Ｄ１ａ－１ｂ）ペリレン系黒色顔料および（Ｄ１ａ－１ｃ）アゾ系黒色顔料からなる群より選ばれる一種類以上の顔料（以下、「特定の（Ｄ１ａ－１）有機黒色顔料」）を含有することが好ましく、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料を含有することがより好ましい。特定の（Ｄ１ａ－１）有機黒色顔料は、一般的な有機顔料と比較して組成物中の顔料の単位含有比率当たりの遮光性に優れるとともに、紫外領域の波長（例えば、４００ｎｍ以下）の透過率が高いため、露光時の感度向上、現像後の残渣抑制、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の低電圧駆動化の効果が顕著となる。また、一般的な有機顔料や無機顔料と比較して絶縁性および低誘電性に優れるため、有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著となる。 <(D) colorant; (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.
　本発明の第一の態様の感光性樹脂組成物において、上述した（ＡＸ）樹脂と組み合わせることに好適な（Ｄ１ａ－１）化合物としては、顔料の可視光線の波長における高い遮光性および顔料の紫外領域の波長における高い透過率の観点から、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料が特に好ましい。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ｄ１ａ－１）化合物を含有し、（Ｄ１ａ－１）化合物が、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料を含むことが好ましい。 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.
　（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料は、ベンゾフラン－２（３Ｈ）－オン構造またはベンゾフラン－３（２Ｈ）－オン構造を有することが好ましく、一般式（１６１）および一般式（１６２）のいずれかで表される化合物、それらの幾何異性体、それらの塩またはそれらの幾何異性体の塩を有することがより好ましい。 (D1a-1a) 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.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　一般式（１６１）および一般式（１６２）において、Ｒ３４１～Ｒ３４４は、それぞれ独立して、水素原子、ハロゲン原子または炭素数１～１０のアルキル基を表す。Ｒ３４５～Ｒ３４８は、それぞれ独立して、ハロゲン原子、Ｒ３５３、ＣＯＯＨ、ＣＯＯＲ３５３、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ３５３、ＣＯＮＲ３５３Ｒ３５４、ＣＮ、ＯＨ、ＯＲ３５３、ＯＣＯＲ３５３、ＯＣＯＮＨ２、ＯＣＯＮＨＲ３５３、ＯＣＯＮＲ３５３Ｒ３５４、ＮＯ２、ＮＨ２、ＮＨＲ３５３、ＮＲ３５３Ｒ３５４、ＮＨＣＯＲ３５３、ＮＲ３５３ＣＯＲ３５４、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ３５３、Ｎ＝ＣＲ３５３Ｒ３５４、ＳＨ、ＳＲ３５３、ＳＯＲ３５３、ＳＯ２Ｒ３５３、ＳＯ３Ｒ３５３、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ３５３またはＳＯ２ＮＲ３５３Ｒ３５４を表す。Ｒ３５３およびＲ３５４は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数２～１０のアルケニル基、炭素数４～１０のシクロアルケニル基または炭素数２～１０のアルキニル基を表す。複数のＲ３４５～Ｒ３４８は、互いに直接結合または酸素原子ブリッジ、硫黄原子ブリッジ、ＮＨブリッジもしくはＮＲ３５３ブリッジにより環を形成しても構わない。Ｒ３４９～Ｒ３５２は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基または炭素数６～１５のアリール基を表す。ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～４の整数を表す。上述したアルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基およびアリール基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (161) and (162), 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 each independently represent a halogen atom, R 353 , COOH, COOR 353 , COO − , CONH 2 , CONHR 353 , CONR 353 R 354 , CN, OH, OR 353 , OCOR 353 , OCONH 2 , OCONHR353 , OCONR353R354 , NO2 , NH2 , NHR353 , NR353R354 , NHCOR353 , NR353COR354 , N = CH2 , N= CHR353 , N = CR353R354 , SH , SR 353 , SOR 353 , SO 2 R 353 , SO 3 R 353 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 353 or SO 2 NR 353 R 354 ; R 353 and R 354 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 4 to 10 carbon atoms, or It represents an alkynyl group having 2 to 10 carbon atoms. A plurality of 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）ペリレン系黒色顔料としては、ペリレン構造を有し、一般式（１６４）～（１６６）のいずれかで表される化合物またはそれらの塩が好ましい。 As (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.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　一般式（１６４）～（１６６）において、Ｘ２４１およびＸ２４２は、それぞれ独立して、直接結合または炭素数１～１０のアルキレン基を表す。Ｙ２４１およびＹ２４２は、それぞれ独立して、直接結合または炭素数６～１５のアリーレン基を表す。Ｒ３６１およびＲ３６２は、それぞれ独立して、水素原子、ヒドロキシ基、炭素数１～１０のアルキル基、炭素数１～６のアルコキシ基または炭素数２～６のアシル基を表す。Ｒ３６３～Ｒ３６９は、それぞれ独立して、ヒドロキシ基、炭素数１～１０のアルキル基、炭素数１～６のアルコキシ基、炭素数２～６のアシル基、ハロゲン原子、Ｒ３７０、ＣＯＯＨ、ＣＯＯＲ３７０、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ３７０、ＣＯＮＲ３７０Ｒ３７１、ＣＮ、ＯＨ、ＯＲ３７０、ＯＣＯＲ３７０、ＯＣＯＮＨ２、ＯＣＯＮＨＲ３７０、ＯＣＯＮＲ３７０Ｒ３７１、ＮＯ２、ＮＨ２、ＮＨＲ３７０、ＮＲ３７０Ｒ３７１、ＮＨＣＯＲ３７０、ＮＲ３７０ＣＯＲ３７１、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ３７０、Ｎ＝ＣＲ３７０Ｒ３７１、ＳＨ、ＳＲ３７０、ＳＯＲ３７０、ＳＯ２Ｒ３７０、ＳＯ３Ｒ３７０、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ３７０、またはＳＯ２ＮＲ３７０Ｒ３７１を表す。Ｒ３７０およびＲ３７１は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数２～１０のアルケニル基、炭素数４～１０のシクロアルケニル基、または炭素数２～１０のアルキニル基を表す。複数のＲ３６７～Ｒ３６９は、互いに直接結合、または、酸素原子ブリッジ、硫黄原子ブリッジ、ＮＨブリッジ、もしくはＮＲ３７０ブリッジにより環を形成しても構わない。ａおよびｂは、それぞれ独立して、０～５の整数を表す。ｃ、ｄ、ｅ、およびｆは、それぞれ独立して、０～４の整数を表す。ｇ、ｈ、およびｉは、それぞれ独立して、０～８の整数を表す。Ｘ２４１およびＸ２４２が直接結合であって、Ｙ２４１およびＹ２４２が直接結合の場合、Ｒ３６１およびＲ３６２は、それぞれ独立して、水素原子または炭素数１～１０のアルキル基が好ましく、ａおよびｂは１である。Ｘ２４１およびＸ２４２が炭素数１～１０のアルキレン基であって、Ｙ２４１およびＹ２４２が直接結合の場合、Ｒ３６１およびＲ３６２はヒドロキシ基が好ましく、ａおよびｂは１である。Ｘ２４１およびＸ２４２が炭素数１～１０のアルキレン基であって、Ｙ２４１およびＹ２４２が炭素数６～１５のアリーレン基の場合、Ｒ３６１およびＲ３６２は、それぞれ独立して、ヒドロキシ基、炭素数１～６のアルコキシ基または炭素数２～６のアシル基が好ましく、ａおよびｂは、それぞれ独立して、０～５の整数を表す。上述したアルキレン基、アリーレン基、アルキル基、アルコキシ基およびアシル基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (164) to (166), 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. R 363 to R 369 are each independently a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, a halogen atom, R 370 , COOH, COOR370 , COO- , CONH2 , CONHR370 , CONR370R371 , CN, OH, OR370 , OCOR370 , OCONH2 , OCONHR370 , OCONR370R371 , NO2 , NH2 , NHR370 , NR370R 371 , NHCOR 370 , NR 370 COR 371 , N=CH 2 , N=CHR 370 , N=CR 370 R 371 , SH, SR 370 , SOR 370 , SO 2 R 370 , SO 3 R 370 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 370 , or SO 2 NR 370 R 371 ; R 370 and R 371 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 4 to 10 carbon atoms, Or represents an alkynyl group having 2 to 10 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; When X 241 and X 242 are direct bonds and Y 241 and Y 242 are direct bonds, 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. When X 241 and X 242 are C 1-10 alkylene groups and Y 241 and Y 242 are direct bonds, R 361 and R 362 are preferably hydroxy groups, and a and b are 1. When X 241 and X 242 are C 1-10 alkylene groups and Y 241 and Y 242 are C 6-15 arylene groups, 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.
　（Ｄ１ａ－１ｃ）アゾ系黒色顔料としては、分子内にアゾ基を有し、一般式（１６８）で表される化合物またはその塩が好ましい。 (D1a-1c) As the azo black pigment, a compound having an azo group in the molecule and represented by general formula (168) or a salt thereof is preferable.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　一般式（１６８）において、Ｘ２５１は、炭素数６～１５のアリーレン基を表す。Ｙ２５１は、炭素数６～１５のアリーレン基を表す。Ｒ３８１～Ｒ３８３は、それぞれ独立して、ハロゲン原子、Ｒ３９０、ＣＯＯＨ、ＣＯＯＲ３９０、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ３９０、ＣＯＮＲ３９０Ｒ３９１、ＣＮ、ＯＨ、ＯＲ３９０、ＯＣＯＲ３９０、ＯＣＯＮＨ２、ＯＣＯＮＨＲ３９０、ＯＣＯＮＲ３９０Ｒ３９１、ＮＯ２、ＮＨ２、ＮＨＲ３９０、ＮＲ３９０Ｒ３９１、ＮＨＣＯＲ３９０、ＮＲ３９０ＣＯＲ３９１、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ３９０、Ｎ＝ＣＲ３９０Ｒ３９１、ＳＨ、ＳＲ３９０、ＳＯＲ３９０、ＳＯ２Ｒ３９０、ＳＯ３Ｒ３９０、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ３９０、またはＳＯ２ＮＲ３９０Ｒ３９１を表す。Ｒ３９０およびＲ３９１は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数２～１０のアルケニル基、炭素数４～１０のシクロアルケニル基、または炭素数２～１０のアルキニル基を表す。複数のＲ３８１～Ｒ３８３は、互いに直接結合、または、酸素原子ブリッジ、硫黄原子ブリッジ、ＮＨブリッジ、もしくはＮＲ３９０ブリッジにより環を形成しても構わない。Ｒ３８４は、ハロゲン原子、炭素数１～１０のアルキル基、炭素数１～６のアルコキシ基またはニトロ基を表す。Ｒ３８５は、ハロゲン原子、炭素数１～１０のアルキル基、炭素数１～６のアルコキシ基、炭素数２～１０のアシルアミノ基またはニトロ基を表す。Ｒ３８６～Ｒ３８９は、それぞれ独立して、水素原子または炭素数１～１０のアルキル基を表す。ａは０～４の整数を表す。ｂは０～２の整数を表す。ｃは０～４の整数を表す。ｄおよびｅは、それぞれ独立して、０～８の整数を表す。ｎは１～４の整数を表す。上述したアリーレン基、アルキル基、アルコキシ基およびアシルアミノ基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formula (168), 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 each independently represent a halogen atom, R 390 , COOH, COOR 390 , COO − , CONH 2 , CONHR 390 , CONR 390 R 391 , CN, OH, OR 390 , OCOR 390 , OCONH 2 , OCONHR390 , OCONR390R391 , NO2 , NH2 , NHR390 , NR390R391 , NHCOR390 , NR390COR391 , N = CH2 , N= CHR390 , N = CR390R391 , SH , SR 390 , SOR 390 , SO 2 R 390 , SO 3 R 390 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 390 , or SO 2 NR 390 R 391 ; R 390 and R 391 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 4 to 10 carbon atoms, Or represents an alkynyl group having 2 to 10 carbon atoms. A plurality of 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. a represents an integer of 0 to 4; b represents an integer of 0 to 2; c represents an integer of 0 to 4; d and e each independently represent an integer of 0 to 8; n represents an integer of 1 to 4; The arylene group, alkyl group, alkoxy group and acylamino group described above may have a heteroatom and may be unsubstituted or substituted.
　（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料としては、例えば、“ＩＲＧＡＰＨＯＲ”（登録商標）ＢＬＡＣＫ　Ｓ０１００ＣＦ（ＢＡＳＦ社製）、国際公開第２０１０／０８１６２４号記載の黒色顔料、または国際公開第２０１０／０８１７５６号記載の黒色顔料が挙げられる。また、（Ｄ１ａ－１ｂ）ペリレン系黒色顔料としては、例えば、Ｃ．Ｉ．ピグメントブラック３１またはＣ．Ｉ．ピグメントブラック３２が挙げられる（数値はいずれもＣ．Ｉ．ナンバー）。上述した以外に、“ＰＡＬＩＯＧＥＮ”（登録商標）ＢＬＡＣＫ　Ｓ００８４、同Ｋ００８４、同Ｌ００８６、同Ｋ００８６、同Ｋ００８７、同Ｋ００８８、同ＥＨ０７８８、同ＦＫ４２８０または同ＦＫ４２８１（以上、いずれもＢＡＳＦ社製）が挙げられる。また、（Ｄ１ａ－１ｃ）アゾ系黒色顔料としては、例えば、“ＣＨＲＯＭＯＦＩＮＥ”（登録商標）ＢＬＡＣＫ　Ａ１１０３（大日精化工業（株）製）、特開平０１－１７０６０１号公報に記載された黒色顔料、または特開平０２－０３４６６４号公報に記載された黒色顔料が挙げられる。本発明の感光性樹脂組成物において、特定の（Ｄ１ａ－１）有機黒色顔料の含有比率の合計は、上述した（Ｄ）着色剤の好ましい含有比率の通りである。 (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). In addition to the above, "PALIOGEN" (registered trademark) BLACK S0084, K0084, L0086, K0086, K0087, K0088, EH0788, FK4280, or FK4281 (all manufactured by BASF) can be mentioned. . In addition, (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. In the photosensitive resin composition of the present invention, 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.
　＜（ＤＣ）被覆層＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｄ１ａ－１）化合物が、さらに（ＤＣ）被覆層を含有することが好ましい。（ＤＣ）被覆層とは、例えば、シランカップリング剤による表面処理、ケイ酸塩による表面処理、金属アルコキシドによる表面処理または樹脂による被覆処理などの処理で形成される顔料表面を被覆する層をいう。（ＤＣ）被覆層を含有させることで、（Ｄ１ａ－１）化合物の耐酸性、耐アルカリ性、耐溶剤性、分散安定性または耐熱性を向上でき、現像後の残渣抑制、ハーフトーン特性向上および有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著となる。特に、上述した（Ｄ１ａ－１）化合物が、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料を含有する場合、（ＤＣ）被覆層を含有させることで、顔料に起因する現像後の残渣抑制、現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。（Ｄ１ａ－１）化合物に対する、（ＤＣ）被覆層による平均被覆率は、現像後の残渣抑制の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、５０～１００％が好ましく、７０～１００％がより好ましく、９０～１００％がさらに好ましい。（Ｄ１ａ－１）化合物に対する、（ＤＣ）被覆層による平均被覆率は、国際公開第２０１９／０８７９８５号の段落［０３４９］に記載の方法に基づき、求めることができる。 <(DC) coating layer>
In the photosensitive resin composition of the first aspect of the present invention, 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. . By containing the (DC) coating layer, 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. In particular, when 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. 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 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.
　＜（ＤＣ）被覆層；（ＤＣ－１）被覆層、（ＤＣ－２）被覆層および（ＤＣ－３）被覆層＞
　（ＤＣ）被覆層は、現像後の残渣抑制の観点、および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、（ＤＣ－１）シリカ被覆層（以下、「（ＤＣ－１）被覆層」）、（ＤＣ－２）金属酸化物被覆層（以下、「（ＤＣ－２）被覆層」）および（ＤＣ－３）金属水酸化物被覆層（以下、「（ＤＣ－３）被覆層」）からなる群より選ばれる一種類を含有することが好ましく、（ＤＣ－１）被覆層を含有することがより好ましい。（ＤＣ－１）被覆層におけるシリカとしては、例えば、二酸化ケイ素またはその含水物が挙げられる。（ＤＣ－２）被覆層における金属酸化物には、金属酸化物そのものだけでなく、例えば、金属酸化物の水和物なども含まれる。金属酸化物としては、例えば、アルミナ（Ａｌ２Ｏ３）またはアルミナ水和物（Ａｌ２Ｏ３・ｎＨ２Ｏ）が挙げられる。（ＤＣ－３）被覆層における金属水酸化物としては、例えば、水酸化アルミニウム（Ａｌ（ＯＨ）３）が挙げられる。 <(DC) coating layer; (DC-1) coating layer, (DC-2) coating layer and (DC-3) coating layer>
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. (DC-2) The metal oxide in the coating layer includes not only the metal oxide itself but also, for example, a hydrate of the metal oxide. Examples of 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 ).
　本発明の感光性樹脂組成物において、（ＤＣ－１）被覆層の含有量は、（Ｄ１ａ－１）化合物を１００質量部とした場合において、現像後の残渣抑制の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、１質量部以上が好ましく、５質量部以上がより好ましい。一方、（ＤＣ－１）被覆層の含有量は、現像後の残渣抑制の観点から、２０質量部以下が好ましく、１０質量部以下がより好ましい。また、本発明の感光性樹脂組成物において、（ＤＣ－２）被覆層および（ＤＣ－３）被覆層の含有量の合計は、（Ｄ１ａ－１）化合物を１００質量部とした場合において、現像後の残渣抑制の観点および有機ＥＬディスプレイにおける発光素子の信頼性向上の観点から、０．１質量部以上が好ましく、０．５質量部以上がより好ましい。一方、（ＤＣ－２）被覆層および（ＤＣ－３）被覆層の含有量の合計は、現像後の残渣抑制の観点から、２０質量部以下が好ましく、１０質量部以下がより好ましい。 In the photosensitive resin composition of the present invention, 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. On the other hand, 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. Further, in the photosensitive resin composition of the present invention, 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. On the other hand, 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.
　＜（Ｅ）分散剤＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｅ）分散剤を含有することが好ましい。（Ｅ）分散剤とは、上述した（Ｄ１）顔料などの表面と相互作用する表面親和性基と、分散安定性を向上させる分散安定化構造とを有する化合物をいう。分散安定化構造としては、例えば、静電反発によって分散安定化させるイオン性置換基や極性置換基または立体障害によって分散安定化させるポリマー鎖などが挙げられる。（Ｄ１）顔料の数平均粒子径が５００ｎｍ以下である場合、表面積の増大によって分散安定性が低下し、粒子の凝集が発生しやすくなる。（Ｅ）分散剤を含有させることで、現像後の残渣抑制および現像後の解像度向上の効果が顕著となる。 <(E) Dispersant>
The photosensitive resin composition of the first aspect of the present invention preferably further contains (E) a dispersant. (E) 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. By containing (E) a dispersant, the effects of suppressing residue after development and improving resolution after development become remarkable.
　（Ｅ）分散剤は、現像後の残渣抑制の観点から、塩基性基、酸性基、塩基性基の塩構造、および酸性基の塩構造からなる群より選ばれる一種類以上の構造を有することが好ましく、塩基性基および／または塩基性基の塩構造を有することがより好ましい。（Ｅ）分散剤としては、現像後の残渣抑制の観点から、塩基性基のみを有する分散剤、塩基性基および酸性基を有する分散剤、塩基性基が酸と塩形成した構造を有する分散剤または酸性基が塩基と塩形成した構造を有する分散剤が好ましく、塩基性基のみを有する分散剤または塩基性基および酸性基を有する分散剤がより好ましい。なお、酸性基のみを有する分散剤または塩基性基および酸性基のいずれも有しない分散剤を含有しても構わない。 (E) 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. (E) As the dispersant, from the viewpoint of suppressing residue after development, 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.
　（Ｅ）分散剤が有する塩基性基としては、三級アミノ基またはピロリジン骨格、ピロール骨格、イミダゾール骨格もしくはピペリジン骨格などの含窒素環骨格を有する基が好ましい。（Ｅ）分散剤が有する酸性基としては、カルボキシ基、スルホン酸基、リン酸基またはフェノール性水酸基が好ましい。（Ｅ）分散剤が有する塩基性基が酸と塩形成した構造としては、四級アンモニウム塩構造または上述した含窒素環骨格が塩形成した構造が好ましい。塩基性基の塩構造におけるカウンターアニオンとしては、カルボン酸アニオン、スルホン酸アニオン、フェノキシアニオン、硫酸アニオン、硝酸アニオン、リン酸アニオン、またはハロゲンアニオンが好ましく、カルボン酸アニオンがより好ましい。ポリマー鎖を有する（Ｅ）分散剤としては、アクリル樹脂系分散剤、ポリオキシアルキレンエーテル系分散剤、ポリエステル系分散剤、ポリウレタン系分散剤、ポリオール系分散剤、ポリアルキレンアミン系分散剤、ポリエチレンイミン系分散剤またはポリアリルアミン系分散剤が好ましい。 (E) 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. (E) 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. (E) 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. (E) 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.
　＜（Ｅ）分散剤；（Ｅ１）化合物＞
　（Ｅ）分散剤は、（Ｅ１）塩基性基を有する顔料分散剤（以下、「（Ｅ１）化合物」）を含有することが好ましく、（Ｅ１）化合物が、一般式（２６）、（２７）、（２８）および（２９）のいずれかで表される構造からなる群より選ばれる一種類以上の構造ならびにポリオキシアルキレン構造を有することがより好ましい。（Ｅ１）化合物は、顔料分散液の保管時の粘度上昇抑制、硬化物の平坦性向上および現像後の残渣抑制の観点から、一般式（２６）で表される構造およびポリオキシアルキレン構造を有することがさらに好ましい。また、（Ｅ１）塩基性基を有する顔料分散剤は、顔料の分散性向上、および顔料分散液の冷凍保管時における顔料凝集物抑制の観点から、一般式（２９）で表される構造、およびポリオキシアルキレン構造を有することもさらに好ましい。 <(E) dispersant; (E1) compound>
(E) 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. In addition, (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.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　一般式（２６）～（２８）において、Ｒ５６～Ｒ５９は、それぞれ独立して、炭素数１～６のアルキル基を表す。ｎは１～９の整数を表す。＊１～＊６は、それぞれ独立して、ポリオキシアルキレン構造との結合点を表す。一般式（２９）において、Ｘ５６およびＸ５７は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表す。Ｙ５６～Ｙ５９は、それぞれ独立して、炭素数１～６のアルキレン基を表す。ａおよびｂは、それぞれ独立して、１～１００の整数を表す。ｃおよびｄは、それぞれ独立して、０～１００の整数を表す。＊７は、炭素原子または窒素原子との結合点を表す。ａおよびｂは、それぞれ独立して、５～６０の整数が好ましく、１０～４０の整数がより好ましい。ｃおよびｄは、それぞれ独立して、０～２０の整数が好ましく、０～１０の整数がより好ましい。 In general formulas (26) to (28), 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. In general formula (29), 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. Preferably, 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.
　（Ｅ）分散剤（（Ｅ１）化合物を含む）のアミン価は、現像後の残渣抑制の観点から、５ｍｇＫＯＨ／ｇ以上が好ましく、１０ｍｇＫＯＨ／ｇ以上がより好ましい。一方、アミン価は、現像後の残渣抑制の観点から、１００ｍｇＫＯＨ／ｇ以下が好ましく、７０ｍｇＫＯＨ／ｇ以下がより好ましい。ここでいうアミン価とは、（Ｅ）分散剤１ｇ当たりと反応する酸と当量の水酸化カリウムの質量をいい、単位はｍｇＫＯＨ／ｇである。 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.
　（Ｅ）分散剤（（Ｅ１）化合物を含む）の酸価は、現像後の残渣抑制の観点から、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましい。一方、酸価は、現像後の残渣抑制の観点から、１００ｍｇＫＯＨ／ｇ以下が好ましく、７０ｍｇＫＯＨ／ｇ以下がより好ましい。ここでいう酸価とは、（Ｅ）分散剤１ｇ当たりと反応する水酸化カリウムの質量をいい、単位はｍｇＫＯＨ／ｇである。 The acid value of the (E) dispersant (including the (E1) compound) is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, from the viewpoint of suppressing residue after development. On the other hand, 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.
　本発明の感光性樹脂組成物が（Ｄ１）顔料および（Ｅ）分散剤を含有する場合、（Ｅ）分散剤（（Ｅ１）化合物を含む）の含有量は、（Ｄ１）顔料を１００質量部とした場合において、現像後の残渣抑制の観点から、５質量部以上が好ましく、１５質量部以上がより好ましい。一方、（Ｅ）分散剤の含有量は、現像後の残渣抑制の観点から、５０質量部以下が好ましく、４０質量部以下がより好ましい。 When the photosensitive resin composition of the present invention contains (D1) pigment and (E) dispersant, the content of (E) dispersant (including (E1) compound) 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. On the other hand, 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.
　＜（Ｆ）化合物；（Ｆ０）化合物および（ＦＢ）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、以下の（Ｆ０）化合物および／または（ＦＢ）化合物を含有することが好ましい。
（Ｆ０）化合物：リン原子を含む酸性基および／またはリン原子を含む酸性基の塩を有する化合物（以下、「（Ｆ０）化合物」）。
（ＦＢ）化合物：リン原子を含むベタイン構造を有する化合物（以下、「（ＦＢ）化合物」）。 <(F) compound; (F0) compound and (FB) compound>
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").
　なお、（Ｆ０）化合物、（ＦＢ）化合物、後述する（ＦＣ１）化合物および後述する（ＦＴ）化合物をまとめて、以下、「（Ｆ）化合物」という場合もある。 In addition, 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ｆ０）化合物が、以下の（Ｉ－ｆ０）構造を有することが好ましい。
（Ｉ－ｆ０）構造：炭素数４～３０の１～２価の脂肪族基、炭素数１０～３０のアルキルアリール基および炭素数６～１５のアリール基が結合したオキシアルキレン基からなる群より選ばれる一種類以上の基。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　本発明の第一の態様の感光性樹脂組成物は、（ＦＢ）化合物が、以下の（Ｉ－ｆｂ）構造を有することが好ましい。
（Ｉ－ｆｂ）構造：アンモニウムカチオン構造を有する炭素数１～６の１～２価の脂肪族基。 In the photosensitive resin composition of the first aspect of the present invention, 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）化合物および／または（ＦＢ）化合物を含有させることで、現像後の残渣抑制、およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。（Ｆ０）化合物および／または（ＦＢ）化合物は、二種類以上の化合物を含有することも好ましく、二種類以上の（Ｆ０）化合物および二種類以上の（ＦＢ）化合物を含有することも好ましい。（Ｆ０）化合物および（ＦＢ）化合物を含有することが特に好ましい。 By containing the (F0) compound and/or the (FB) compound, the effect of suppressing residue after development and improving halftone characteristics becomes 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. (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.
　＜（Ｆ）化合物；（Ｆ１）化合物および（ＦＢ１）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｆ０）化合物および／または（ＦＢ）化合物を含有し、（Ｆ０）化合物が、以下の（Ｆ１）化合物を含み、かつ、（ＦＢ）化合物が、以下の（ＦＢ１）化合物を含むことが好ましい。
（Ｆ１）化合物：リン酸化合物、ホスホン酸化合物、ホスフィン酸化合物およびそれらの塩からなる群より選ばれる一種類以上の化合物（以下、「（Ｆ１）化合物」）。
（ＦＢ１）化合物：リン酸ベタイン化合物、ホスホン酸ベタイン化合物およびホスフィン酸ベタイン化合物からなる群より選ばれる一種類以上の化合物（以下、「（ＦＢ１）化合物」）。 <(F) compound; (F1) compound and (FB1) 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").
　本発明の第一の態様の感光性樹脂組成物は、（Ｆ１）化合物が、以下の（Ｉ－ｆ１）構造および／または（ＩＩ－ｆ１）構造を有することが好ましい。
（Ｉ－ｆ１）構造：炭素数４～３０の１価の脂肪族基、炭素数６～３０の２価の脂肪族基および炭素数１０～３０のアルキルアリール基からなる群より選ばれる一種類以上の基。
（ＩＩ－ｆ１）構造：炭素数４～３０の１価の脂肪族基が結合したオキシアルキレン基、炭素数１０～３０のアルキルアリール基が結合したオキシアルキレン基および炭素数６～１５のアリール基が結合した炭素数４～１５のオキシアルキレン基からなる群より選ばれる一種類以上の基。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　本発明の第一の態様の感光性樹脂組成物は、（ＦＢ１）化合物が、以下の（Ｉ－ｆｂ１）構造を有することが好ましい。
（Ｉ－ｆｂ１）構造：アンモニウムカチオン構造を有する炭素数１～６の１～２価の脂肪族基。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　（Ｆ１）化合物および／または（ＦＢ１）化合物を含有させることで、現像後の残渣抑制、およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。（Ｆ１）化合物および／または（ＦＢ１）化合物は、二種類以上の化合物を含有することも好ましく、二種類以上の（Ｆ１）化合物および二種類以上の（ＦＢ１）化合物を含有することも好ましい。（Ｆ１）化合物および（ＦＢ１）化合物を含有することが特に好ましい。 By containing the (F1) compound and/or the (FB1) compound, the effects of 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 and lowering the driving voltage of the light-emitting element becomes remarkable. 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.
　（Ｆ１）化合物は、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基として、以下の（Ｉ－ｆ１）構造および／または（ＩＩ－ｆ１）構造を有することが好ましい。 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）構造としては、以下の（Ｉ－ｆ１ｘ）構造が好ましい。
（Ｉ－ｆ１ｘ）構造：炭素数６～１２の１価の脂肪族基、炭素数６～１２の２価の脂肪族基および炭素数１４～２６のアルキルアリール基からなる群より選ばれる一種類以上の基。 As the (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.
　１価の脂肪族基としては、アルキル基、アルケニル基またはアルキニル基が好ましい。２価の脂肪族基としては、アルキレン基、アルケニレン基またはアルキニレン基が好ましい。また、（Ｉ－ｆ１）構造は、直鎖構造および／または分岐構造であることも好ましい。 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. Also, the (I-f1) structure is preferably a linear structure and/or a branched structure.
　（ＩＩ－ｆ１）構造としては、以下の（ＩＩ－ｆ１ｘ）構造が好ましい。
（ＩＩ－ｆ１ｘ）構造：炭素数６～１２の１価の脂肪族基が結合したオキシアルキレン基、炭素数１４～２６のアルキルアリール基が結合したオキシアルキレン基および炭素数６～１０のアリール基が結合した炭素数６～１２のオキシアルキレン基からなる群より選ばれる一種類以上の基。 As the (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.
　１価の脂肪族基としては、アルキル基、アルケニル基またはアルキニル基が好ましい。また、（ＩＩ－ｆ１）構造は、直鎖構造および／または分岐構造であることも好ましい。 The monovalent aliphatic group is preferably an alkyl group, an alkenyl group or an alkynyl group. Also, the (II-f1) structure is preferably a linear structure and/or a branched structure.
　（Ｆ０）化合物におけるリン原子を含む酸性基の塩としては、リン原子を含む酸性基と、カチオン構造を有する化合物との塩が挙げられる。同様に、（Ｆ１）化合物におけるリン酸化合物の塩、ホスホン酸化合物の塩、またはホスフィン酸化合物の塩としては、リン酸化合物、ホスホン酸化合物、およびホスフィン酸化合物と、カチオン構造を有する化合物との塩が挙げられる。カチオン構造を有する化合物としては、金属原子のカチオン、アンモニウムカチオン、ホスホニウムカチオン、およびスルホニウムカチオンからなる群より選ばれる一種類以上の構造を有する化合物が挙げられ、アンモニウムカチオンを有する化合物が好ましい。アンモニウムカチオンとしては、一級アンモニウムカチオン、二級アンモニウムカチオン、三級アンモニウムカチオン、または四級アンモニウムカチオンが好ましく、四級アンモニウムカチオンがより好ましい。アンモニウムカチオンは、少なくとも１つの炭素数１～３０の脂肪族基を有することが好ましく、炭素数１～１５の脂肪族基を有することがより好ましく、炭素数１～１０の脂肪族基を有することがさらに好ましく、炭素数１～６の脂肪族基を有することが特に好ましい。脂肪族基としては、１～２価の直鎖構造および／または分岐構造の脂肪族基が好ましく、直鎖構造のアルキル基、アルケニル基、およびアルキニル基からなる群より選ばれる基が好ましく、直鎖構造のアルキル基がさらに好ましい。 (F0) 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. Similarly, 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.
　（Ｆ１）化合物は、一般式（１１）、（１２）および（１３）のいずれかで表される化合物およびそれらの塩からなる群より選ばれる一種類以上の化合物を含有することが好ましい。一般式（１１）、（１２）および（１３）のいずれかで表される化合物およびそれらの塩からなる群より選ばれる二種類以上の化合物を含有することも好ましい。（Ｆ１）化合物は、現像後の残渣抑制およびハーフトーン特性向上の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、少なくとも一般式（１２）で表される化合物および／またはその塩を含むことが特に好ましい。 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.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　一般式（１１）～（１３）において、Ｚ１１～Ｚ１３は、それぞれ独立して、直接結合、炭素数６～３０の２価の脂肪族基または一般式（１４）で表される基を表す。Ｚ１４～Ｚ１６は、それぞれ独立して、直接結合、炭素数６～３０の２価の脂肪族基または一般式（１５）で表される基を表す。一般式（１１）におけるＺ１１が直接結合の場合、対応するＲ３１は、炭素数４～３０の１価の脂肪族基または炭素数１０～３０のアルキルアリール基を表す。一般式（１２）および一般式（１３）における、Ｚ１２および対応するＲ３２、ならびに、Ｚ１３および対応するＲ３３においても一般式（１１）におけるＺ１１および対応するＲ３１の関係と同様である。一般式（１１）におけるＺ１４が直接結合の場合、対応するＲ３４は、水素原子、炭素数４～３０の１価の脂肪族基、炭素数１０～３０のアルキルアリール基、光反応性基、炭素数２～５のアルケニル基、炭素数２～５のアルキニル基または熱反応性基を表す。一般式（１２）および一般式（１３）における、Ｚ１５および対応するＲ３５ならびにＺ１６および対応するＲ３６においても一般式（１１）におけるＺ１４および対応するＲ３４の関係と同様である。一般式（１１）におけるＺ１１とＺ１４の少なくともいずれかが、炭素数６～３０の２価の脂肪族基の場合、対応するＲ３１および／またはＲ３４は、それぞれ独立して、水素原子、ヒドロキシ基または炭素数１～１５の１価の有機基を表す。一般式（１２）および一般式（１３）における、Ｚ１２とＺ１５および対応するＲ３２とＲ３５ならびにＺ１３とＺ１６および対応するＲ３３とＲ３６においても一般式（１１）におけるＺ１１とＺ１４および対応するＲ３１とＲ３４の関係と同様である。一般式（１１）におけるＺ１１が、一般式（１４）で表される基の場合、対応するＲ３１は、炭素数４～３０の１価の脂肪族基、炭素数１０～３０のアルキルアリール基または炭素数６～１５のアリール基を表す。一般式（１２）および一般式（１３）における、Ｚ１２および対応するＲ３２ならびにＺ１３および対応するＲ３３においても一般式（１１）におけるＺ１１および対応するＲ３１の関係と同様である。一般式（１１）におけるＺ１４が、一般式（１５）で表される基の場合、対応するＲ３４は、水素原子、炭素数４～３０の１価の脂肪族基、炭素数１０～３０のアルキルアリール基、炭素数６～１５のアリール基、光反応性基、炭素数２～５のアルケニル基、炭素数２～５のアルキニル基または熱反応性基を表す。一般式（１２）および一般式（１３）における、Ｚ１５および対応するＲ３５ならびにＺ１６および対応するＲ３６においても一般式（１１）におけるＺ１４および対応するＲ３４の関係と同様である。光反応性基、炭素数２～５のアルケニル基、および炭素数２～５のアルキニル基は、ラジカル重合性基であることが好ましい。熱反応性基としては、アルコキシメチル基、メチロール基、エポキシ基、オキセタニル基、またはブロックイソシアネート基が好ましい。 In general formulas (11) to (13), 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). show. 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). When 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. In general formulas (12) and (13), 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). be. When 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. , represents an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or a thermally reactive 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). When at least one of 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. In general formulas (12) and (13), 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. When 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). When 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. is an alkylaryl group, an aryl group having 6 to 15 carbon atoms, a photoreactive group, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms or a thermally reactive 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). 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. As the heat-reactive group, an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, or a blocked isocyanate group is preferred.
　一般式（１４）および一般式（１５）において、Ｙ１１およびＹ１２は、それぞれ独立して、炭素数１～１５のアルキレン基を表す。Ｒ３７およびＲ３８は、それぞれ独立して、炭素数１～６のアルキル基を表す。ｍおよびｎは、それぞれ独立して、１～１５の整数を表す。ｐおよびｑは、それぞれ独立して、０～４の整数を表す。＊１は、一般式（１１）中の酸素原子との結合点、一般式（１２）中のリン原子との結合点または一般式（１３）中のリン原子との結合点を表す。＊２は、一般式（１１）中のＲ３１との結合点、一般式（１２）中のＲ３２との結合点または一般式（１３）中のＲ３３との結合点を表す。＊３は、一般式（１１）中の酸素原子との結合点、一般式（１２）中の酸素原子との結合点または一般式（１３）中のリン原子との結合点を表す。＊４は、一般式（１１）中のＲ３４との結合点、一般式（１２）中のＲ３５との結合点または一般式（１３）中のＲ３６との結合点を表す。 In general formulas (14) and (15), 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).
　本発明の第一の態様の感光性樹脂組成物が、後述するアセテート結合を有する溶剤としてプロピレングリコールモノアルキルエーテルアセテートを含有し、かつ、（Ｆ１）化合物が、上述した一般式（１１）～（１３）中、Ｚ１１～Ｚ１３が直接結合または一般式（１４）で表される基の場合、Ｒ３１～Ｒ３３における炭素数４～３０の１価の脂肪族基が、それぞれ独立して炭素数６～１２の１価の脂肪族基であり、上述した一般式（１１）～（１３）中、Ｚ１４～Ｚ１６が直接結合の場合、Ｒ３４～Ｒ３６は水素原子であることが好ましい。 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.
　このような（Ｆ１）化合物を、以下、「特定の（Ｆ１）化合物」という。なお（Ｆ１）化合物が、上述した（Ｉ－ｆ１）構造として、炭素数６～１２の１価の脂肪族基および／または上述した（ＩＩ－ｆ１）構造として、炭素数６～１２の１価の脂肪族基が結合したオキシアルキレン基を有する場合、同様にこのような化合物を、以下、「特定の（Ｆ１）化合物」という。 Such (F1) compounds are hereinafter referred to as "specific (F1) compounds". Note that 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. When the aliphatic group of has an attached oxyalkylene group, such compounds are also referred to hereinafter as "specific (F1) compounds".
　（Ｆ１）化合物が、特定の（Ｆ１）化合物を含有することで、特異的に（Ｆ１）化合物のプロピレングリコールモノアルキルエーテルアセテートへの溶解性を顕著に向上できる。それにより、現像後の残渣抑制およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。なお、プロピレングリコールモノアルキルエーテルアセテートとしては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートが好ましく、プロピレングリコールモノメチルエーテルアセテートがより好ましい。 By containing the specific (F1) compound in the (F1) compound, the solubility of the (F1) compound in propylene glycol monoalkyl ether acetate can be significantly improved. As a result, the effects of suppressing residues 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 and lowering the driving voltage of the light-emitting element becomes remarkable. As 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.
　（Ｆ１）化合物は、ハーフトーン特性向上の観点から、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基として、前記（Ｉ－ｆ１）構造および／または（ＩＩ－ｆ１）構造に加えて、さらに以下の（ＩＩＩ－ｆ１）構造を有することも好ましい。
（ＩＩＩ－ｆ１）構造：光反応性基、炭素数２～５のアルケニル基、および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基。 From the viewpoint of improving halftone characteristics, 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.
　（ＩＩＩ－ｆ１）構造において、光反応性基としては、ラジカル重合性基が好ましく、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基がより好ましく、（メタ）アクリロイル基がさらに好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ラジカル重合性基が好ましく、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基がより好ましく、ビニル基またはアリル基がさらに好ましい。 In structure (III-f1), 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. On the other hand, 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.
　本発明の第一の態様の感光性樹脂組成物は、上述した（Ｆ１）化合物および／または（ＦＢ１）化合物を含み、かつ、（Ｆ１）化合物とは別の、上述した光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基を有する、リン酸化合物、ホスホン酸化合物およびホスフィン酸化合物からなる群より選ばれる一種類以上の化合物を含有することも好ましい。 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 One or more types selected from the group consisting of phosphoric acid compounds, phosphonic acid compounds and phosphinic acid compounds, having one or more groups selected from the group consisting of alkenyl groups having 2 to 5 carbon atoms and alkynyl groups having 2 to 5 carbon atoms. It is also preferred to contain a compound of
　（ＦＢ１）化合物は、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基として、以下の（Ｉ－ｆｂ１）構造を有することが好ましい。 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.
　（Ｉ－ｆｂ１）構造において、炭素数１～６の１～２価の脂肪族基としては、炭素数１～４の２価の脂肪族基が好ましい。１価の脂肪族基としては、アルキル基、アルケニル基またはアルキニル基が好ましい。２価の脂肪族基としては、アルキレン基、アルケニレン基またはアルキニレン基が好ましい。また、炭素数１～６の１～２価の脂肪族基は、直鎖構造および／または分岐構造であることも好ましい。炭素数１～６の１～２価の脂肪族基は、置換基として、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、カルボキシ基またはヒドロキシ基を有しても構わない。 In the (I-fb1) structure, 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. Also, 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. .
　（Ｉ－ｆｂ１）構造において、アンモニウムカチオン構造としては、アンモニウムカチオン、モノアルキルアンモニウムカチオン、ジアルキルアンモニウムカチオンまたはトリアルキル四級アンモニウムカチオンが好ましく、トリアルキル四級アンモニウムカチオンがより好ましい。 In the (I-fb1) structure, 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.
　（Ｉ－ｆｂ１）構造としては、少なくとも１つのヒドロキシ基および少なくとも１つのアンモニウム基またはアミノ基を有する炭素数１～６の窒素含有脂肪族アルコール化合物に由来する構造がより好ましい。そのような化合物としては、エタノールアミン、プロパノールアミン、ブタノールアミン、ペンタノールアミン、セリン、トレオニン、チオシンまたはコリンが好ましく、エタノールアミン、セリンまたはコリンがより好ましい。 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.
　本発明の第一の態様の感光性樹脂組成物は、後述するアセテート結合を有する溶剤としてプロピレングリコールモノアルキルエーテルアセテートを少なくとも含み、さらに、後述するエーテル結合を少なくとも３つ有する溶剤としてジエチレングリコールジアルキルエーテルおよび／または後述するアルコール性水酸基を有する溶剤としてプロピレングリコールモノアルキルエーテル、乳酸アルキル、ヒドロキシ酢酸アルキルおよび酢酸ヒドロキシアルキルからなる群より選ばれる一種類以上の溶剤を含有する場合（以下、「特定の溶剤を含有する場合」）において、（ＦＢ１）化合物は、上述した（Ｉ－ｆｂ１）構造において、トリアルキル四級アンモニウムカチオン構造を有することが好ましい。 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. / Or 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.
　トリアルキル四級アンモニウムカチオン構造は、炭素数１～６のアルキル基を３つ有することが好ましく、炭素数１～４のアルキル基を３つ有することがより好ましい。このような（ＦＢ１）化合物を、以下、「特定の（ＦＢ１）化合物」という。 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".
　特定の溶剤を含有する場合において、（ＦＢ１）化合物が、特定の（ＦＢ１）化合物を含有することで、特異的に（ＦＢ１）化合物の溶剤への溶解性を顕著に向上できる。それにより、現像後の残渣抑制およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。 When a specific solvent is contained, the (FB1) compound containing the specific (FB1) compound can significantly improve the solubility of the (FB1) compound in the solvent. As a result, the effects of suppressing residues 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 and lowering the driving voltage of the light-emitting element becomes remarkable.
　なお、プロピレングリコールモノアルキルエーテルアセテートとしては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートが好ましく、プロピレングリコールモノメチルエーテルアセテートがより好ましい。 As the 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.
　また、ジエチレングリコールジアルキルエーテルとしては、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルおよびジエチレングリコールエチルメチルエーテルが好ましく、ジエチレングリコールエチルメチルエーテルがより好ましい。 As the 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.
　また、プロピレングリコールモノアルキルエーテル、乳酸アルキル、ヒドロキシ酢酸アルキルまたは酢酸ヒドロキシアルキルとしては、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、乳酸メチル、乳酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、酢酸２－ヒドロキシメチルおよび酢酸２－ヒドロキシエチルが好ましく、プロピレングリコールモノメチルエーテル、乳酸エチル、ヒドロキシ酢酸エチルまたは酢酸２－ヒドロキシエチルがより好ましい。 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.
　（ＦＢ１）化合物は、現像後の残渣抑制およびハーフトーン特性向上の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基として、前記（Ｉ－ｆｂ１）構造に加えて、さらに以下の（ＩＩ－ｆｂ１）構造を有することが好ましい。
（ＩＩ－ｆｂ１）構造：炭素数６～３０の脂肪酸化合物に由来する脂肪酸エステル構造および／または炭素数６～３０の脂肪族アルコールに由来する脂肪族エーテル構造。 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.
　（ＩＩ－ｆｂ１）構造は、炭素数６～３０の１～２価の脂肪族基を有することが好ましく、炭素数１０～２０の１～２価の脂肪族基を有することがより好ましい。１価の脂肪族基としては、アルキル基、アルケニル基またはアルキニル基が好ましい。２価の脂肪族基としては、アルキレン基、アルケニレン基またはアルキニレン基が好ましい。また、炭素数６～３０の１～２価の脂肪族基は、直鎖構造および／または分岐構造であることも好ましい。なお、上述した特定の溶剤を含有する場合において、（ＦＢ１）化合物が、上述した（ＩＩ－ｆｂ１）構造を有することで、さらに特異的に（ＦＢ１）化合物の溶剤への溶解性を顕著に向上できる。 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. Also, the monovalent to divalent aliphatic group having 6 to 30 carbon atoms preferably has a linear structure and/or a branched structure. In addition, when the above-mentioned specific solvent is contained, 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.
　（ＦＢ１）化合物は、現像後の残渣抑制およびハーフトーン特性向上の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、（Ｉ－ｆｂ１）構造を有し、さらに以下の（ＩＶ－ｆｂ１）構造または（Ｖ－ｆｂ１）構造を有する化合物（以下、「ベタイン型のリン脂質の（ＦＢ１）化合物」）を含有することが好ましい。
（ＩＶ－ｆｂ１）構造：少なくとも３つのヒドロキシ基を有する、炭素数２～６の脂肪族多官能アルコール化合物に由来するエステル構造。
（Ｖ－ｆｂ１）構造：少なくとも２つのヒドロキシ基、ならびに、少なくとも１つのアミノ基または少なくとも１つのアルキルアミド基を有する、炭素数１５～２０の窒素含有脂肪族アルコール化合物に由来するエステル構造。 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.
　なお、上述した特定の溶剤を含有する場合において、（ＦＢ１）化合物が、ベタイン型リン脂質の（ＦＢ１）化合物を含有することで、さらに特異的に（ＦＢ１）化合物の溶剤への溶解性を顕著に向上できる。 In the case where the above-mentioned specific solvent is contained, 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
　（ＦＢ１）化合物は、ベタイン型リン脂質の（ＦＢ１）化合物として、グリセロリン脂質および／またはスフィンゴリン脂質を含むことが特に好ましい。ベタイン型リン脂質の（ＦＢ１）化合物は、ホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルセリン、スフィンゴミエリン、水添ホスファチジルコリン、水添ホスファチジルエタノールアミン、水添ホスファチジルセリン、水添スフィンゴミエリン、リゾホスファチジルコリン、リゾホスファチジルエタノールアミン、リゾホスファチジルセリン、リゾスフィンゴミエリン、レシチン、水添レシチン、リゾレシチン、セファリン、水添セファリン、リゾセファリン、プラズマローゲン、血小板活性化因子および（トリメチルアンモニオ）エチルホスホン酸セラミドからなる群より選ばれる一種類以上の化合物を含有することが特に好ましい。 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, hydrogenated cephalin, lysocephalin, plasmalogen, platelet-activating factor and (trimethylammonio) ethylphosphonate ceramide It is particularly preferable to contain the above compounds.
　（ＦＢ１）化合物は、ハーフトーン特性向上の観点から、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基として、前記（Ｉ－ｆｂ１）構造に加えて、さらに以下の（ＩＩＩ－ｆｂ１）構造を有することも好ましい。
（ＩＩＩ－ｆｂ１）構造：光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基。 From the viewpoint of improving halftone characteristics, 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.
　また、（ＦＢ１）化合物が二種類以上の（ＦＢ１）化合物を含有し、上述した（ＩＩ－ｆｂ１）構造、上述した（ＩＶ－ｆｂ１）構造および上述した（Ｖ－ｆｂ１）構造からなる群より選ばれる一種類以上の構造を有する化合物を含み、さらに（ＩＩＩ－ｆｂ１）構造を有する化合物を含むことも好ましい。 Further, 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.
　（ＩＩＩ－ｆｂ１）構造において、光反応性基としては、ラジカル重合性基が好ましく、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基がより好ましく、（メタ）アクリロイル基がさらに好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ラジカル重合性基が好ましく、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基がより好ましく、ビニル基またはアリル基がさらに好ましい。 In structure (III-fb1), 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. On the other hand, 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.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｆ１）化合物および（ＦＢ１）化合物の含有比率の合計は、現像後の残渣抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、０．０２質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１５質量％以上がさらに好ましく、０．２５質量％以上が特に好ましい。一方、（Ｆ１）化合物および（ＦＢ１）化合物の含有比率の合計は、現像後の残渣抑制の観点ならびに有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の観点から、１．８質量％以下が好ましく、１．５質量％以下がより好ましく、１．３質量％以下がさらに好ましく、１．０質量％以下が特に好ましい。また、本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｆ１）化合物および（ＦＢ１）化合物の含有量の合計は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、０．０５質量部以上が好ましく、０．１０質量部以上がより好ましく、０．３０質量部以上がさらに好ましく、０．５０質量部以上が特に好ましい。一方、（Ｆ１）化合物および（ＦＢ１）化合物の含有量の合計は、３．０質量部以下が好ましく、２．５質量部以下がより好ましく、２．０質量部以下がさらに好ましく、１．５質量部以下が特に好ましい。 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. from the viewpoint of suppressing residue after development and from the viewpoint of improving the reliability of the light-emitting element in the organic EL display and driving the light-emitting element at a low voltage. 8% by mass or less is preferable, 1.5% by mass or less is more preferable, 1.3% by mass or less is even more preferable, and 1.0% by mass or less is particularly preferable. Further, when 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. On the other hand, 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.
　＜（Ｆ）化合物；（ＦＣ１）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（ＦＣ１）非ベタイン型リン脂質（以下、「（ＦＣ１）化合物」）を含有することが好ましい。（ＦＣ１）化合物を含有させることで、現像後の残渣抑制およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。（ＦＣ１）化合物は、二種類以上の化合物を含有することも好ましく、（Ｆ１）化合物および／または（ＦＢ１）化合物を含み、さらに（ＦＣ１）化合物を含有することが特に好ましい。 <(F) compound; (FC1) compound>
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"). By containing the (FC1) compound, the effects of 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 and lowering the driving voltage of the light-emitting element becomes remarkable. 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.
　（ＦＣ１）化合物は、少なくとも以下の（Ｉ－ｆｃ１）構造ならびに（ＩＩ－ｆｃ１）構造を有する。
（Ｉ－ｆｃ１）構造：リン原子を含む酸性基、リン原子を含むアニオン構造およびリン原子を含む酸性基の塩からなる群より選ばれる一種類以上の構造。
（ＩＩ－ｆｃ１）構造：炭素数６～３０の脂肪酸化合物に由来する脂肪酸エステル構造および／または炭素数６～３０の脂肪族アルコールに由来する脂肪族エーテル構造。 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.
　（Ｉ－ｆｃ１）構造が、リン原子を含む酸性基および／またはリン原子を含むアニオン構造である場合、（ＦＣ１）化合物は、アンモニウムカチオン構造を有しないことが好ましい。上述したリン原子を含むアニオン構造は、リン原子を含む酸性基に由来するアニオン構造が好ましい。（ＦＣ１）化合物は、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基として、（Ｉ－ｆｃ１）構造、および、（ＩＩ－ｆｃ１）構造を有することが好ましい。 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.
　（Ｉ－ｆｃ１）構造としては、リン酸基、ホスホン酸基もしくはホスフィン酸基および／またはリン酸アニオン、ホスホン酸アニオンもしくはホスフィン酸アニオンが好ましい。 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.
　（ＩＩ－ｆｃ１）構造は、炭素数６～３０の１～２価の脂肪族基を有することが好ましく、炭素数１０～２０の１～２価の脂肪族基を有することがより好ましい。１価の脂肪族基としては、アルキル基、アルケニル基またはアルキニル基が好ましい。２価の脂肪族基としては、アルキレン基、アルケニレン基またはアルキニレン基が好ましい。また、炭素数６～３０の１～２価の脂肪族基は、直鎖構造および／または分岐構造であることも好ましい。 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. Also, the monovalent to divalent aliphatic group having 6 to 30 carbon atoms preferably has a linear structure and/or a branched structure.
　（ＦＣ１）化合物は、ホスファチジン酸、ホスファチジルグリセロール、リゾホスファチジン酸、リゾホスファチジルグリセロール、ホスファチジルイノシトール、リゾホスファチジルイノシトール、ジホスファチジルグリセロール、カルジオリピン、スフィンゴシン－１－リン酸およびホスファチジル－シチジン一リン酸からなる群より選ばれる一種類以上の化合物を含有することが特に好ましい。 (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.
　本発明の感光性樹脂組成物において、（Ｆ１）化合物、（ＦＢ１）化合物および（ＦＣ１）化合物の含有比率の合計は、上述した（Ｆ１）化合物および（ＦＢ１）化合物の好ましい含有比率の通りである。また、本発明の感光性樹脂組成物が、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物を含有する場合、（Ｆ１）化合物、（ＦＢ１）化合物および（ＦＣ１）化合物の含有量の合計は、上述した（Ｆ１）化合物および（ＦＢ１）化合物の好ましい含有量の通りである。 In the photosensitive resin composition of the present invention, 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. . Further, when 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.
　＜（Ｆ）化合物；（ＦＴ）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（ＦＴ）反応性基を有する、リン原子を含む酸性基のエステル化合物（以下、「（ＦＴ）化合物」）を含有することが好ましい。（ＦＴ）化合物を含有させることで、ハーフトーン特性向上および現像後のパターン剥がれ抑制の効果が顕著となる。（ＦＴ）化合物は、二種類以上の化合物を含有することも好ましく、（Ｆ１）化合物および／または（ＦＢ１）化合物を含み、さらに（ＦＴ）化合物を含有することが特に好ましい。 <(F) compound; (FT) compound>
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. 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.
　（ＦＴ）化合物は、ラジカル重合性基を有することが好ましく、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基を有することがより好ましい。（ＦＴ）化合物が有する、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基の数を（Ｘ）とし、（ＦＴ）化合物が有する、１～２価の脂肪族基、１～２価の脂環式基、１～２価の芳香族基および置換基が結合したオキシアルキレン基からなる群より選ばれる一種類以上の基の数を（Ｙ）とするとき、（Ｘ）および（Ｙ）が、次の一般式（ＦＴ－α）～（ＦＴ－γ）を全て満たすことが好ましい。
Ｘ＋Ｙ＝３　（ＦＴ－α）。
１≦Ｘ≦３　（ＦＴ－β）。
０≦Ｙ≦２　（ＦＴ－γ）。 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. It is more preferable to have (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 When the number of groups is (Y), (X) and (Y) preferably satisfy all of the following general formulas (FT-α) to (FT-γ).
X+Y=3 (FT-α).
1≤X≤3 (FT-β).
0≦Y≦2 (FT−γ).
　上記一般式（ＦＴ－α）～（ＦＴ－γ）において、Ｘは、１～３の整数が好ましく、２または３であることがより好ましく、３であることがさらに好ましい。Ｙは、０～２の整数が好ましく、０または１であることがより好ましい。 In the general formulas (FT-α) to (FT-γ), 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.
　（ＦＴ）化合物は、リン原子に結合する置換基および／またはＰ－Ｏ結合上の酸素原子に結合する置換基を有し、該置換基が、ラジカル重合性基を有することが好ましく、光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基を有することがより好ましい。また、該置換基が、１～２価の脂肪族基、１～２価の脂環式基、１～２価の芳香族基および置換基が結合したオキシアルキレン基からなる群より選ばれる一種類以上の基を有することも好ましい。 (FT) compound has a substituent that binds to the phosphorus atom and / or a substituent that binds to the oxygen atom on the PO bond, 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.
　本発明の第一の態様の感光性樹脂組成物は、さらに以下の（ＦＴ１）化合物、（Ｆ１）化合物として上述した（ＩＩＩ－ｆ１）構造を有する化合物および（ＦＢ１）化合物として上述した（ＩＩＩ－ｆｂ１）構造を有する化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。
（ＦＴ１）化合物：光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基を少なくとも３つ有する、リン原子を含む酸性基のエステル化合物。 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.
　（ＦＴ）化合物において、光反応性基としては、ラジカル重合性基が好ましく、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基がより好ましく、（メタ）アクリロイル基がさらに好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ラジカル重合性基が好ましく、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基がより好ましく、ビニル基またはアリル基がさらに好ましい。 In the (FT) 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. On the other hand, 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.
　（ＦＴ）化合物は、上述した光反応性基、炭素数２～５のアルケニル基および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基を有する、リン酸トリエステル化合物、亜リン酸トリエステル化合物、ホスホン酸ジエステル化合物、次亜リン酸ジエステル化合物およびホスフィン酸モノエステル化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。 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.
　本発明の感光性樹脂組成物において、（Ｆ１）化合物、（ＦＢ１）化合物および（ＦＴ）化合物の含有比率の合計は、上述した（Ｆ１）化合物および（ＦＢ１）化合物の好ましい含有比率の通りである。また、本発明の感光性樹脂組成物が、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物を含有する場合、（Ｆ１）化合物、（ＦＢ１）化合物および（ＦＴ）化合物の含有量の合計は、上述した（Ｆ１）化合物および（ＦＢ１）化合物の好ましい含有量の通りである。 In the photosensitive resin composition of the present invention, 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. . Further, when 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.
　＜（Ｇ）架橋剤＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｇ）架橋剤を含有することが好ましい。（Ｇ）架橋剤とは、樹脂などと結合可能な架橋性基を有する化合物またはカチオン重合性基を有する化合物をいう。一般に、架橋性基による樹脂などとの架橋反応およびカチオン重合性基によるカチオン重合は、酸および／または熱によって促進可能であり、硬化物の耐熱性向上、および硬化物の耐薬品性向上に好適である。（Ｇ）架橋剤としては、アルコキシアルキル基、ヒドロキシアルキル基、エポキシ基、オキセタニル基、ビニル基およびアリル基からなる群より選ばれる一種類以上の基を少なくとも２つ有する化合物が好ましい（ただし、上述した（Ｂ）化合物は除く）。アルコキシアルキル基としては、アルコキシメチル基が好ましく、メトキシメチル基がより好ましい。ヒドロキシアルキル基としては、メチロール基が好ましい。 <(G) Crosslinking agent>
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. In general, 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. (G) 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). As the alkoxyalkyl group, an alkoxymethyl group is preferable, and a methoxymethyl group is more preferable. A methylol group is preferred as the hydroxyalkyl group.
　＜（Ｇ）架橋剤；（Ｇ１）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、（Ｇ１）疎水性骨格含有エポキシ架橋剤（以下、「（Ｇ１）化合物」）を含有することが好ましい。（Ｇ１）化合物とは、以下の（Ｉ－ｇ１）構造および（ＩＩ－ｇ１）構造を有し、（ＩＩ－ｇ１）構造を少なくとも２つ有する化合物をいう。
（Ｉ－ｇ１）構造：縮合多環式構造、縮合多環式ヘテロ環構造、芳香環骨格および脂環式骨格が直接連結された構造ならびに少なくとも２つの芳香環骨格が直接連結された構造からなる群より選ばれる一種類以上の構造を含む構造。
（ＩＩ－ｇ１）構造：エポキシ基を有する有機基。 <(G) Crosslinking Agent; (G1) Compound>
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 A structure containing one or more structures selected from the group.
(II-g1) structure: an organic group having an epoxy group.
　（Ｇ１）化合物を含有させることで、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。 By containing the (G1) compound, the effect of improving halftone characteristics and suppressing variations in opening pattern dimensions after development becomes remarkable.
　（Ｇ１）化合物は、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の観点から、上述した（Ｉ－ｇ１）構造が、フルオレン構造、インダン構造、インドリノン構造、イソインドリノン構造、キサンテン構造、トリシクロ［５．２．１．０２，６］デカン構造およびビナフチル構造からなる群より選ばれる一種類以上の構造を含む構造であることが好ましい。 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.
　（Ｇ１）化合物のエポキシ基当量は、現像後の残渣抑制の観点から、１５０ｇ／ｍｏｌ以上が好ましく、１７０ｇ／ｍｏｌ以上がより好ましく、１９０ｇ／ｍｏｌ以上がさらに好ましい。一方、エポキシ基当量は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、８００ｇ／ｍｏｌ以下が好ましく、６００ｇ／ｍｏｌ以下がより好ましく、５００ｇ／ｍｏｌ以下がさらに好ましい。 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. On the other hand, 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.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｇ１）化合物の含有比率は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点から、０．３質量％以上が好ましく、１．０質量％以上がより好ましく、２．０質量％以上がさらに好ましい。一方、（Ｇ１）化合物の含有比率は、現像後の残渣抑制の観点から、２５質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましい。また、本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｇ１）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、１質量部以上が好ましく、３質量部以上がより好ましく、５質量部以上がさらに好ましい。一方、（Ｇ１）化合物の含有量は、３０質量部以下が好ましく、２５質量部以下がより好ましく、２０質量部以下がさらに好ましい。 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. On the other hand, 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. Further, when the photosensitive resin composition of the present invention contains the (B) compound, 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. On the other hand, 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.
　＜（Ｇ）架橋剤；（Ｇ２）化合物および（Ｇ３）化合物＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、以下の（Ｇ２）化合物および／または（Ｇ３）化合物を含有し、架橋性基が、アルコキシアルキル基、ヒドロキシアルキル基、エポキシ基、オキセタニル基、ビニル基およびアリル基からなる群より選ばれる一種類以上の基を含むことが好ましい。アルコキシアルキル基としては、アルコキシメチル基が好ましく、メトキシメチル基がより好ましい。ヒドロキシアルキル基としては、メチロール基が好ましい。
（Ｇ２）化合物：少なくとも２つのフェノール性水酸基および少なくとも２つの架橋性基を有する化合物。
（Ｇ３）化合物：窒素原子を少なくとも２つ有する環状構造および少なくとも２つの架橋性基を有する化合物。 <(G) Crosslinking Agent; (G2) Compound and (G3) Compound>
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. As 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.
(G3) Compound: a compound having a cyclic structure having at least two nitrogen atoms and at least two crosslinkable groups.
　（Ｇ２）化合物および／または（Ｇ３）化合物を含有させることで、現像後の残渣抑制、およびハーフトーン特性向上の効果が顕著となる。加えて、有機ＥＬディスプレイにおける発光素子の低電圧駆動化の効果が顕著となる。（Ｇ２）化合物または（Ｇ３）化合物が有する架橋性基数は、２つ以上が好ましく、３つ以上がより好ましく、４つ以上がさらに好ましい。一方、架橋性基数は、８つ以下が好ましく、７つ以下がより好ましく、６つ以下がさらに好ましい。 By containing the (G2) compound and/or the (G3) compound, the effect of suppressing residue after development and improving halftone characteristics becomes remarkable. In addition, the effect of low-voltage driving of the light-emitting elements in the organic EL display becomes remarkable. 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. On the other hand, the number of crosslinkable groups is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
　（Ｇ２）化合物は、以下の（Ｉ－ｇ２）構造を少なくとも２つ有することが好ましい。また（Ｇ２）化合物は、以下の（Ｉ－ｇ２ｘ）構造を少なくとも２つ有することがより好ましい。
（Ｉ－ｇ２）構造：１つの芳香族構造にフェノール性水酸基および架橋性基が結合した構造。
（Ｉ－ｇ２ｘ）構造：１つの芳香族構造にフェノール性水酸基および少なくとも２つの架橋性基が結合した構造。 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.
　（Ｇ２）化合物が有する（Ｉ－ｇ２）構造の数および（Ｉ－ｇ２ｘ）構造の数の合計は、２つ以上が好ましく、３つ以上がより好ましく、４つ以上がさらに好ましい。一方、（Ｉ－ｇ２）構造の数および（Ｉ－ｇ２ｘ）構造の数の合計は、８つ以下が好ましく、７つ以下がより好ましく、６つ以下がさらに好ましい。（Ｇ２）化合物は、芳香族構造などの疎水性骨格を有することが好ましい。疎水性骨格としては、フルオレン構造、インダン構造、縮合多環脂環式構造、少なくとも２つの芳香環骨格が脂肪族基で連結された構造および少なくとも２つの芳香環骨格が直接連結された構造からなる群より選ばれる一種類以上の構造を含む構造が好ましい。 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. On the other hand, 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.
　現像後の残渣抑制、ハーフトーン特性向上および有機ＥＬディスプレイにおける発光素子の低電圧駆動化の観点から、（Ｇ２）化合物が有するフェノール性水酸基数は、２つ以上が好ましく、３つ以上がより好ましく、４つ以上がさらに好ましい。一方、フェノール性水酸基数は、８つ以下が好ましく、７つ以下がより好ましく、６つ以下がさらに好ましい。 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. On the other hand, the number of phenolic hydroxyl groups is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
　（Ｇ３）化合物は、以下の（Ｉ－ｇ３）構造を有することが好ましい。また（Ｇ３）化合物は、以下の（Ｉ－ｇ３ｘ）構造を有することがより好ましい。
（Ｉ－ｇ３）構造：窒素原子を少なくとも２つ有する環状骨格に、架橋性基が結合した構造。
（Ｉ－ｇ３ｘ）構造：窒素原子を少なくとも２つ有する環状骨格に、少なくとも２つの架橋性基が結合した構造。 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.
　（Ｇ３）化合物が有する（Ｉ－ｇ３ｘ）構造における架橋性基数は、２つ以上が好ましく、３つ以上がより好ましく、４つ以上がさらに好ましい。一方、架橋性基数は、８つ以下が好ましく、７つ以下がより好ましく、６つ以下がさらに好ましい。 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. On the other hand, the number of crosslinkable groups is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less.
　現像後の残渣抑制、ハーフトーン特性向上および有機ＥＬディスプレイにおける発光素子の低電圧駆動化の観点から、（Ｇ３）化合物が有する窒素原子を少なくとも２つ有する環状骨格としては、イソシアヌル酸構造、トリアジン構造、グリコールウリル構造、イミダゾリドン構造、ピラゾール構造、イミダゾール構造、トリアゾール構造、テトラゾール構造およびプリン構造からなる群より選ばれる一種類以上の構造が好ましく、イソシアヌル酸構造、トリアジン構造およびグリコールウリル構造からなる群より選ばれる一種類以上の構造がより好ましく、イソシアヌル酸構造および／またはトリアジン構造がさらに好ましい。 From the viewpoint of suppressing residue after development, improving halftone characteristics, and driving a light-emitting element in an organic EL display at low voltage, the cyclic skeleton having at least two nitrogen atoms possessed by the (G3) compound includes an isocyanuric acid structure and a triazine structure. , a glycoluril structure, an imidazolidone structure, a pyrazole structure, an imidazole structure, a triazole structure, a tetrazole structure and a purine structure. One or more selected structures are more preferred, and an isocyanuric acid structure and/or a triazine structure are even more preferred.
　（Ｇ２）化合物は、一般式（１８１）、（１８２）、（１８３）および（１８４）のいずれかで表される化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。 (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).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　一般式（１８１）～（１８４）において、Ｙ３１１は、直接結合、炭素原子、窒素原子、酸素原子または硫黄原子を表す。Ｒ４１１～Ｒ４２３は、それぞれ独立して、ハロゲン原子または炭素数１～１０のアルキル基を表す。Ｒ４２４～Ｒ４３０は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基または炭素数６～１５のアリール基を表す。Ｒ４３１～Ｒ４４０は、それぞれ独立して、炭素数２～１０のアルコキシアルキル基、炭素数１～６のヒドロキシアルキル基、エポキシ基を有する炭素数１～６のアルキル基、エポキシ基を有する炭素数２～１０のアルコキシアルキル基、オキセタニル基を有する炭素数１～８のアルキル基、オキセタニル基を有する炭素数２～１２のアルコキシアルキル基、ビニル基またはアリル基を表す。ａおよびｂは、それぞれ独立して、０～４の整数を表す。ｃおよびｄは、それぞれ独立して、０～２の整数を表す。ｅ、ｆ、ｇ、ｈ、ｉ、ｊ、ｋおよびｌは、それぞれ独立して、０～３の整数を表す。ｍは０～４の整数を表す。Ｙ３１１が直接結合、酸素原子、または硫黄原子の場合、ｎは０である。Ｙ３１１が窒素の場合、ｎは１である。Ｙ３１１が炭素原子の場合、ｎは２である。ｏ、ｐ、αおよびβは、それぞれ独立して、１～３の整数を表し、２≦ｏ＋α≦４であり、２≦ｐ＋β≦４である。ｑ、ｒ、γおよびδは、それぞれ独立して、１～４の整数を表し、２≦ｑ＋γ≦５であり、２≦ｒ＋δ≦５である。ｓ、ｔ、ｕ、ε、ζおよびηは、それぞれ独立して、１～４の整数を表し、２≦ｓ＋ε≦５であり、２≦ｔ＋ζ≦５であり、２≦ｕ＋η≦５である。ｖ、ｗ、ｘ、θ、λおよびπは、それぞれ独立して、１～４の整数を表し、２≦ｖ＋θ≦５であり、２≦ｗ＋λ≦５であり、２≦ｘ＋π≦５である。Ｙ３１１としては、直接結合または酸素原子が好ましい。上述したアルキル基、シクロアルキル基、アリール基、アルコキシアルキル基およびヒドロキシアルキル基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (181) to (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, α and β each independently represent an integer of 1 to 3, 2≦o+α≦4, and 2≦p+β≦4. q, r, γ and δ each independently represent an integer of 1 to 4, 2≦q+γ≦5 and 2≦r+δ≦5. s, t, u, ε, ζ, and η each independently represent an integer of 1 to 4, 2≦s+ε≦5, 2≦t+ζ≦5, and 2≦u+η≦5. v, w, x, θ, λ and π each independently represent an integer of 1 to 4, 2≦v+θ≦5, 2≦w+λ≦5, and 2≦x+π≦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）化合物は、一般式（１７１）、（１７２）および（１７３）のいずれかで表される化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。 (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).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　一般式（１７１）～（１７３）において、Ｙ２６４～Ｙ２６６は、それぞれ独立して、直接結合、酸素原子または窒素原子を表す。Ｒ２６１～Ｒ２７０は、それぞれ独立して、一般式（１７４）～（１７８）のいずれかで表される基、水素原子、炭素数１～１０のアルキル基、炭素数４～１０のシクロアルキル基、炭素数６～１５のアリール基またはヒドロキシ基を表す。一般式（１７４）～（１７８）において、Ｘ２７１は、炭素数１～６のアルキレン基を表す。Ｘ２７２～Ｘ２７４およびＸ２７６は、それぞれ独立して、直接結合または炭素数１～１０のアルキレン基を表す。Ｘ２７５は、直接結合、炭素数１～６のアルキレン基、または炭素数６～１５のアリーレン基を表す。Ｙ２７２は、直接結合または炭素数１～１０のアルキレン基を表す。Ｚ２７２およびＺ２７３は、直接結合、炭素数１～１０のアルキレン基、炭素数４～１０のシクロアルキレン基または炭素数６～１５のアリーレン基を表す。Ｒ２７１は、水素原子または炭素数１～６のアルキル基を表す。Ｒ２７２およびＲ２７３は、それぞれ独立して、一般式（１７９）または一般式（１８０）で表される基を表す。Ｒ２７４は、水素原子または炭素数１～１０のアルキル基を表す。Ｒ２７５およびＲ２７６は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基またはヒドロキシ基を表す。Ｙ２６４～Ｙ２６６が、それぞれ独立して、直接結合または酸素原子の場合、ａ、ｂおよびｃは１である。Ｙ２６４～Ｙ２６６が、それぞれ独立して、窒素原子の場合、ａ、ｂおよびｃは２である。ｄは０または１を表す。ｅは０または１を表す。ｆは１～４の整数を表す。ｅが１の場合、ｄは１であり、Ｙ２７２は、炭素数１～１０のアルキレン基を表す。ｇは１～４の整数を表す。ｈは１～６の整数を表す。＊１～＊７は、それぞれ独立して、結合点を表す。上述したアルキル基、シクロアルキル基、アリール基、アルキレン基、シクロアルキレン基およびアリーレン基は、ヘテロ原子を有してもよく、無置換体または置換体のいずれであっても構わない。 In general formulas (171) to (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. In general formulas (174) to (178), 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; When e is 1, d is 1 and Y 272 represents an alkylene group having 1 to 10 carbon atoms. g represents an integer of 1 to 4; h represents an integer of 1 to 6; * 1 to * 7 each independently represent a point of attachment. 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.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｇ２）化合物および（Ｇ３）化合物の含有比率の合計は、現像後の残渣抑制およびハーフトーン特性向上の観点ならびに有機ＥＬディスプレイにおける発光素子の低電圧駆動化の観点から、０．３質量％以上が好ましく、１．０質量％以上がより好ましく、２．０質量％以上がさらに好ましい。一方、（Ｇ２）化合物および（Ｇ３）化合物の含有比率の合計は、現像後の残渣抑制、および露光時の感度向上の観点から、２５質量％以下が好ましく、２０質量％以下がより好ましく、１５質量％以下がさらに好ましい。また、本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｇ２）化合物および（Ｇ３）化合物の含有量の合計は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、１質量部以上が好ましく、３質量部以上がより好ましく、５質量部以上がさらに好ましい。一方、（Ｇ２）化合物および（Ｇ３）化合物の含有量の合計は、３０質量部以下が好ましく、２５質量部以下がより好ましく、２０質量部以下がさらに好ましい。 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. On the other hand, 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. Further, when the photosensitive resin composition of the present invention contains the (B) compound, 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. On the other hand, 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.
　＜（Ｈ）溶解促進剤＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｈ）溶解促進剤（以下、「（Ｈ）化合物」）を含有することが好ましい。（Ｈ）化合物とは、アルカリ現像液へ溶解可能な酸性基および／または親水性基を有する化合物をいう。酸性基としては、前記（Ａ１）樹脂、（Ａ２）樹脂、（Ａ３）樹脂および（ＡＸ）樹脂の項で説明したものが挙げられる。親水性基としては、ヒドロキシ基およびオキシアルキレン基が挙げられる。（Ｈ）化合物を含有させることで現像後の残渣抑制の効果が顕著となる。（Ｈ）化合物は、多官能カルボン酸化合物、多官能フェノール化合物、ヒドロキシイミド化合物ならびにヒドロキシ基およびオキシアルキレン基を有する化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。 <(H) Dissolution accelerator>
Preferably, 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 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. By including the compound (H), the effect of suppressing residue after development becomes remarkable. 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）化合物としては、炭素数１～１０の１～２価の脂肪族基；炭素数６～１５のアリール基；炭素数７～２５のアリールアルキル基；炭素数７～２５のアルキルアリール基；および炭素数７～２５のアリールアルキル基が少なくとも２つ結合した炭素数６～１５のアリール基；からなる群より選ばれる基にオキシアルキレン基が結合している化合物が好ましい。炭素数７～２５のアリールアルキル基としては、炭素数６～１５のアリール基を有する炭素数２～５のアルケニル基が好ましい。（Ｈ）化合物が有するオキシアルキレン基としては、炭素数１～６のオキシアルキレン基が好ましく、オキシエチレン基またはオキシプロピレン基がより好ましく、オキシエチレン基がさらに好ましい。（Ｈ）化合物が有するオキシアルキレン基の繰り返し数は、２個以上が好ましく、３個以上がより好ましく、４個以上がさらに好ましい。一方、オキシアルキレン基数は、２０個以下が好ましく、１５個以下がより好ましく、１０個以下がさらに好ましい。 (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. As 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. On the other hand, the number of oxyalkylene groups is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less.
　溶剤を除く、本発明の感光性樹脂組成物の全固形分中に占める（Ｈ）化合物の含有比率は、現像後の残渣抑制の観点から、０．２質量％以上が好ましく、０．３質量％以上がより好ましく、１．０質量％以上がさらに好ましい。一方、（Ｈ）化合物の含有比率は、現像後のパターン剥がれ抑制の観点から、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下がさらに好ましい。また、本発明の感光性樹脂組成物が、（Ｂ）化合物を含有する場合、（Ｈ）化合物の含有量は、（Ａ）アルカリ可溶性樹脂および（Ｂ）化合物の合計を１００質量部とした場合において、０．５質量％以上が好ましく、１質量部以上がより好ましく、３質量部以上がさらに好ましい。一方、（Ｈ）化合物の含有量は、２５質量部以下が好ましく、２０質量部以下がより好ましく、１５質量部以下がさらに好ましい。 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. On the other hand, 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. Further, when the photosensitive resin composition of the present invention contains the (B) compound, 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. On the other hand, 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.
　＜（Ｉ）無機粒子＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｉ）無機粒子を含有することが好ましい。（Ｉ）無機粒子とは、金属元素、半金属元素、および半導体元素からなる群より選ばれる元素を含む粒子をいう。（Ｉ）無機粒子としては、例えば、水を除いた質量のうち金属化合物、半金属化合物、および半導体化合物からなる群より選ばれる化合物の含有比率が９０質量％以上の粒子が挙げられる。金属化合物、半金属化合物、または半導体化合物としては、例えば、上記元素のハロゲン化物、酸化物、窒化物、水酸化物、炭酸塩、硫酸塩、硝酸塩、またはメタケイ酸塩が挙げられる。 <(I) Inorganic particles>
The photosensitive resin composition of the first aspect of the present invention preferably further contains (I) inorganic particles. (I) Inorganic particles refer to particles containing an element selected from the group consisting of metal elements, metalloid elements, and semiconductor elements. (I) 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.
　（Ｉ）無機粒子を含有させることで、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。また（Ｉ）無機粒子を含有させることで、感光性組成物の硬化物は、（Ｉ）無機粒子の堅牢な構造が導入されるため耐熱性が顕著に向上し、画素分割層等からのアウトガスが抑制される。その結果、発光素子の劣化が抑制されるため、発光素子の信頼性向上の効果が顕著となる。 (I) By including inorganic particles, the effects of improving halftone characteristics and suppressing variations in opening pattern dimensions after development become remarkable. In addition, by including (I) inorganic particles, the cured product of the photosensitive composition is remarkably improved in heat resistance due to the introduction of the robust structure of (I) inorganic particles, and outgassing from the pixel dividing layer etc. is suppressed. As a result, deterioration of the light-emitting element is suppressed, so that the effect of improving the reliability of the light-emitting element becomes remarkable.
　ポジ型の感光性組成物の場合、（Ｉ）無機粒子の堅牢な構造よるアルカリ溶解阻害により露光部がアルカリ溶解性過剰となりづらく、またハーフトーン露光部が緩やかな現像膜減りをするため、現像後における開口パターン寸法のバラツキ抑制、およびハーフトーン特性向上の効果が顕著になると考えられる。一方、ネガ型の感光性組成物の場合、（Ｉ）無機粒子の堅牢な構造による立体障害や分子運動阻害により露光部における過度な光硬化が制御される。さらに、堅牢な構造によるアルカリ溶解阻害により露光部におけるアルカリ現像時の膜深部におけるサイドエッチングが抑制され、またハーフトーン露光部が緩やかな現像膜減りをするなどの効果が顕著となる。そのため、現像後における開口パターン寸法のバラツキ抑制、およびハーフトーン特性向上の効果が顕著になると考えられる。 In the case of a positive photosensitive composition, (I) the strong structure of the inorganic particles inhibits alkali dissolution, making it difficult for the exposed area to become excessively soluble in alkali. It is considered that the effect of suppressing variations in opening pattern dimensions and improving the halftone characteristics afterward will become remarkable. On the other hand, in the case of a negative photosensitive composition, excessive photocuring in the exposed area is controlled by (I) steric hindrance and molecular motion inhibition due to the rigid structure of the inorganic particles. Furthermore, side etching in the deep portion of the film during alkali development in the exposed area is suppressed due to alkali dissolution inhibition due to the robust structure, and effects such as gradual reduction of the developed film in the halftone exposed area are remarkable. Therefore, it is considered that the effect of suppressing the variation in the dimension of the opening pattern after development and the improvement of the halftone characteristics become remarkable.
　本発明の感光性組成物は、さらに、（Ｉ）無機粒子を含有し、（Ｉ）無機粒子が、Ｓｉ、Ａｌ、Ｔｉ、Ｖ、Ｚｎ、Ｚｒ、Ｎｂ、Ｓｎ、Ｌｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｓｒ、Ａｇ、Ｂａ、Ｌａ、Ｃｅ、Ｔａ、Ｗ、またはＲｅを主成分の元素として含むことが好ましく、ケイ素、アルミニウム、チタン、バナジウム、クロム、鉄、コバルト、銅、亜鉛、ジルコニウム、ニオブ、スズ、またはセリウムを主成分の元素として含むことがより好ましく、ケイ素を主成分の元素として含むことがさらに好ましい。（Ｉ）無機粒子における主成分の元素とは、（Ｉ）無機粒子を構成する金属元素、半金属元素、および半導体元素からなる群より選ばれる構成元素において最も多く含まれる元素をいう。なお上記の元素のうち、いずれか単独での質量を基準に主成分を判断するものとする。これらの元素を主成分の元素として含むことで、画素分割層等からのアウトガスが抑制されるため、発光素子の信頼性向上の効果が顕著となる。（Ｉ）無機粒子としては、シリカ粒子、アルミナ粒子、チタニア粒子、酸化バナジウム粒子、酸化クロム粒子、酸化鉄粒子、酸化コバルト粒子、酸化亜鉛粒子、酸化ジルコニウム粒子、酸化ニオブ粒子、酸化スズ粒子、または酸化セリウム粒子が好ましく、シリカ粒子がより好ましい。 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. (I) 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. (I) 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.
　（Ｉ）無機粒子は、主成分の元素に加えて、Ｓｉ、Ａｌ、Ｔｉ、Ｖ、Ｚｎ、Ｚｒ、Ｎｂ、Ｓｎ、Ｌｉ、Ｎａ、Ｍｇ、Ｋ、Ｃａ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｓｒ、Ｙ、Ａｇ、Ｂａ、Ｌａ、Ｃｅ、Ｈｆ、Ｔａ、Ｗ、およびＲｅからなる群より選ばれる一種類以上の元素をさらに含むことが好ましく、ケイ素、アルミニウム、チタン、バナジウム、クロム、鉄、コバルト、銅、亜鉛、ジルコニウム、ニオブ、スズ、セリウム、ナトリウム、マグネシウム、カリウム、カルシウム、およびハフニウムからなる群より選ばれる一種類以上の元素を含むことがより好ましく、ケイ素元素を含むことがさらに好ましい。 (I) Inorganic particles, in addition to the elements of the main component, Si, Al, Ti, V, Zn, Zr, Nb, Sn, Li, Na, Mg, K, Ca, Cr, Mn, Fe, Co, Ni , Cu, Sr, Y, Ag, Ba, La, Ce, Hf, Ta, W, and Re. , iron, cobalt, copper, zinc, zirconium, niobium, tin, cerium, sodium, magnesium, potassium, calcium, and hafnium. is more preferred.
　（Ｉ）無機粒子は、表面にラジカル重合性基、熱反応性基、シラノール基、アルコキシシリル基、アルキルシリル基、ジアルキルシリル基、トリアルキルシリル基、フェニルシリル基、およびジフェニルシリル基からなる群より選ばれる一種類以上の官能基を有することが好ましく、露光時の感度向上、ハーフトーン特性向上、および現像後における開口パターン寸法のバラツキ抑制の観点、ならびに、発光素子の信頼性向上および発光素子の駆動電圧のバラツキ抑制の観点から、ラジカル重合性基および／または熱反応性基を有することが好ましい。 (I) 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. It is preferable to have one or more kinds of functional groups selected from the above, from the viewpoint of improving sensitivity during exposure, improving halftone characteristics, suppressing variations in opening pattern dimensions after development, improving reliability of light emitting elements and light emitting elements From the viewpoint of suppressing variation in driving voltage, it preferably has a radically polymerizable group and/or a thermally reactive group.
　ラジカル重合性基および／または熱反応性基を有する（Ｉ）無機粒子を含有させることで、ラジカル重合性基または熱反応性基の架橋構造により、ポジ型の感光性組成物の場合の露光部における過剰なアルカリ溶解抑制、または、ネガ型の感光性組成物の場合の露光部におけるアルカリ現像時の膜深部におけるサイドエッチング抑制により、上記の効果が顕著になると推定される。また、（メタ）アクリロイル基などのラジカル重合性基がラジカル重合した架橋構造が導入されるため、感光性組成物の硬化物は架橋密度向上により耐熱性向上の効果が顕著となる。その結果、画素分割層等からのアウトガスが抑制されるため、発光素子の信頼性向上の効果が顕著になると推定される。 By containing the (I) inorganic particles having a radically polymerizable group and/or a thermally reactive group, 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. In addition, 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.
　ラジカル重合性基としては、エチレン性不飽和二重結合基が好ましい。ラジカル重合性基としては、光反応性基、炭素数２～５のアルケニル基、および炭素数２～５のアルキニル基からなる群より選ばれる一種類以上の基がより好ましい。光反応性基としては、スチリル基、シンナモイル基、マレイミド基、または（メタ）アクリロイル基が好ましく、（メタ）アクリロイル基がより好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基、または２－プロパルギル基が好ましく、ビニル基またはアリル基がより好ましい。熱反応性基としては、アルコキシメチル基、メチロール基、エポキシ基、オキセタニル基、またはブロックイソシアネート基が好ましい。 As the radically polymerizable group, an ethylenically unsaturated double bond group is preferred. As 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. On the other hand, 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. As the heat-reactive group, an alkoxymethyl group, a methylol group, an epoxy group, an oxetanyl group, or a blocked isocyanate group is preferred.
　溶剤を除く、本発明の感光性組成物の全固形分中に占める（Ｉ）無機粒子の含有比率は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点、ならびに、発光素子の信頼性向上の観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上が特に好ましい。一方、（Ｉ）無機粒子の含有比率は、発光素子の信頼性向上の観点から、５０質量％以下が好ましく、４０質量％以下がより好ましい。 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.
　＜（Ｉ）無機粒子；（Ｉ１）シリカ粒子＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、（Ｉ）無機粒子を含有し、（Ｉ）無機粒子が、（Ｉ１）シリカ粒子を含有することが好ましい。 <(I) inorganic particles; (I1) silica particles>
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.
　このような構成とすることで、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の効果が顕著となる。加えて、発光素子の信頼性向上の効果が顕著となる。（Ｉ１）シリカ粒子を含有させることで、（Ｉ１）シリカ粒子の堅牢な構造により、ポジ型の感光性組成物の場合の露光部における過剰なアルカリ溶解抑制、または、ネガ型の感光性組成物の場合の露光部におけるアルカリ現像時の膜深部におけるサイドエッチング抑制により、上記の効果が顕著になると推定される。また（Ｉ１）シリカ粒子を含有させることで、感光性組成物の硬化物は、（Ｉ１）シリカ粒子の堅牢な構造が導入されるため耐熱性が顕著に向上し、画素分割層等からのアウトガスが抑制される。その結果、発光素子の劣化が抑制されるため、発光素子の信頼性向上の効果が顕著となる。また硬化物の表面における入射した外光の反射および散乱が低減されるため、外光反射抑制の効果が顕著となる。 By adopting such a structure, the effect of improving the halftone characteristics and suppressing variations in opening pattern dimensions after development becomes remarkable. In addition, the effect of improving the reliability of the light-emitting element becomes remarkable. (I1) By containing silica particles, (I1) the robust structure of the silica particles suppresses excessive alkali dissolution in the exposed area in the case of a positive photosensitive composition, or a negative photosensitive composition. It is presumed that the above effect becomes remarkable due to suppression of side etching in the deep portion of the film during alkaline development in the exposed portion in the case of . In addition, by containing (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. As a result, deterioration of the light-emitting element is suppressed, so that the effect of improving the reliability of the light-emitting element becomes remarkable. In addition, since 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.
　（Ｉ１）シリカ粒子とは、ケイ素を主成分の元素として含む無機粒子をいう。（Ｉ１）シリカ粒子としては、例えば、水を除いた質量のうち二酸化ケイ素の純分が９０質量％以上の粒子、二酸化ケイ素（無水ケイ酸）からなる粒子、二酸化ケイ素水和物（含水ケイ酸またはホワイトカーボン）からなる粒子、石英ガラスからなる粒子、または、オルトケイ酸、メタケイ酸、およびメタ二ケイ酸からなる粒子が挙げられる。（Ｉ１）シリカ粒子としては、有機溶媒および／または水を分散媒としたシリカ粒子分散液を組成物に添加することが好ましい。 (I1) Silica particles refer to inorganic particles containing silicon as the main component element. (I1) 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. (I1) 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.
　これらの粒子の構造は特に限定されず、内部空隙を有していても構わない。ただし、有機顔料および無機顔料における表面処理剤または被覆層に含まれる二酸化ケイ素は、その一次粒子径やアスペクト比によらずシリカ粒子には含まれないものとする。（Ｉ１）シリカ粒子の凝集形態は特に限定されない。シリカ粒子の製法によって制御された凝集形態としては、例えば、数珠状シリカ粒子、鎖状シリカ粒子、会合状シリカ粒子、またはマリモ状シリカ粒子が挙げられる。これらの凝集形態のシリカ粒子は、複数の一次粒子から構成された二次粒子または三次粒子とみなす。 The structure of these particles is not particularly limited, and they may have internal voids. However, 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. (I1) 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.
　（Ｉ１）シリカ粒子の一次粒子径および平均一次粒子径は５～５０ｎｍであることが好ましい。（Ｉ１）シリカ粒子の一次粒子径および平均一次粒子径は、ハーフトーン特性向上および現像後における開口パターン寸法のバラツキ抑制の観点、ならびに、発光素子の信頼性向上の観点から、５ｎｍ以上が好ましく、７ｎｍ以上がより好ましく、１０ｎｍ以上がさらに好ましい。一方、（Ｉ１）シリカ粒子の一次粒子径および平均一次粒子径は、外光反射抑制および発光素子の信頼性向上の観点から、５０ｎｍ以下が好ましく、４０ｎｍ以下がより好ましく、３０ｎｍ以下がさらに好ましく、２５ｎｍ以下がさらにより好ましく、２０ｎｍ以下が特に好ましく、１５ｎｍ以下が最も好ましい。シリカ粒子の一次粒子径とは、シリカ粒子の一次粒子における長軸径をいう。シリカ粒子分散液中の（Ｉ１）シリカ粒子の平均一次粒子径の好ましい範囲は、上記の（Ｉ１）シリカ粒子の一次粒子径および平均一次粒子径の好ましい範囲の通りである。 (I1) The silica particles preferably have a primary particle size and an average primary particle size of 5 to 50 nm. (I1) 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. On the other hand, (I1) 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. 25 nm or less is even more preferred, 20 nm or less is particularly preferred, and 15 nm or less is most preferred. 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.
　（Ｉ１）シリカ粒子のアスペクト比および平均アスペクト比は、１．００以上が好ましく、１．０５以上がより好ましく、１．１０以上がさらに好ましい。一方、（Ｉ１）シリカ粒子のアスペクト比および平均アスペクト比は、１．５０以下が好ましく、１．４０以下がより好ましく、１．３０以下がさらに好ましく、１．２０以下が特に好ましい。シリカ粒子のアスペクト比とは、シリカ粒子の一次粒子径における長軸径を短軸径で除した値の小数点第三位を四捨五入した値をいう。シリカ粒子のアスペクト比が１．００～１．０５未満である場合、真球状シリカ粒子とみなす。 (I1) 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. On the other hand, 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.
　（Ｉ１）シリカ粒子の一次粒子径およびアスペクト比は、硬化物を薄く割断したものを測定試料として、イオンミリング処理により研磨して平滑性を高めた断面について、ＴＥＭを用いて硬化物の表面から深さ方向に０．２～０．８μｍの範囲に位置する箇所を倍率５０，０００倍の条件で観測した撮像を、画像解析式粒度分布測定ソフトウェア（Ｍａｃ－Ｖｉｅｗ；ＭＯＵＮＴＥＣＨ社製）を用いて測定できる。また（Ｉ１）シリカ粒子の平均一次粒子径は、測定試料の断面を撮像および解析し、（Ｉ１）シリカ粒子の一次粒子３０個を測定した平均値として算出できる。さらに、ＴＥＭ－ＥＤＸで観測することで粒子を構成する元素を判別でき、硬化物中のシリカ粒子の特定が可能である。なお、シリカ粒子分散液中の（Ｉ１）シリカ粒子の平均一次粒子径は、動的光散乱法により粒度分布を測定することで求めることができる。 (I1) 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 μm 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. (I1) 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. Furthermore, by observing with TEM-EDX, it is possible to identify the elements that constitute the particles, and to identify the silica particles in the cured product. 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.
　本発明の感光性組成物は、一次粒子径または平均一次粒子径が５～５０ｎｍの（Ｉ１）シリカ粒子を含み、さらに、一次粒子径または平均一次粒子径が５ｎｍ未満の（Ｉ１）シリカ粒子、および／または、一次粒子径または平均一次粒子径が５０ｎｍを超える（Ｉ１）シリカ粒子を含有しても構わない。また本発明の感光性組成物は、アスペクト比または平均アスペクト比が１．００～１．５０の（Ｉ１）シリカ粒子を含み、さらに、アスペクト比または平均アスペクト比が１．５０を超える（Ｉ１）シリカ粒子を含有しても構わない。 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.
　（Ｉ１）シリカ粒子は、発光素子の信頼性向上の観点から、ナトリウム元素を含むことが好ましい。ナトリウム元素の存在形態としては、例えば、イオン（Ｎａ＋）またはシラノール基との塩（Ｓｉ－ＯＮａ）が挙げられる。（Ｉ１）シリカ粒子に占めるナトリウム元素の含有量は、１ｐｐｍ以上が好ましく、５ｐｐｍ以上がより好ましく、１０ｐｐｍ以上がさらに好ましく、５０ｐｐｍ以上が特に好ましい。さらに、発光素子の信頼性向上の観点から、１００ｐｐｍ以上が好ましく、３００ｐｐｍ以上がより好ましく、５００ｐｐｍ以上がさらに好ましい。一方、（Ｉ１）シリカ粒子に占めるナトリウム元素の含有量は、１０，０００ｐｐｍ以下が好ましく、７，０００ｐｐｍ以下がより好ましく、５，０００ｐｐｍ以下がさらに好ましく、３，０００ｐｐｍ以下がさらにより好ましく、１，０００ｐｐｍ以下が特に好ましい。ナトリウム元素を含むシリカ粒子は、アルカリ条件下、ケイ素源として強アルカリであるケイ酸ナトリウムと、強酸である鉱酸との反応により得られる。本発明の感光性組成物において、（Ｉ１）シリカ粒子の好ましい含有比率は、上述した（Ｉ）無機粒子の好ましい含有比率の通りである。 (I1) 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). (I1) 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. Furthermore, from the viewpoint of improving the reliability of the light-emitting element, it is preferably 100 ppm or more, more preferably 300 ppm or more, and even more preferably 500 ppm or more. On the other hand, (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. In the photosensitive composition of the present invention, the preferred content ratio of (I1) silica particles is the same as the preferred content ratio of (I) inorganic particles described above.
　＜ハロゲン元素、硫黄元素およびリン元素の含有量＞
　本発明の第一の態様の感光性樹脂組成物は、ハロゲン元素を含む成分、硫黄元素を含む成分、およびリン元素を含む成分からなる群より選ばれる一種類以上の成分を含有し、下記（１）～（３）の条件を１つ以上満たすことが好ましい。
（１）感光性樹脂組成物中に占めるハロゲン元素の含有量が０．０１～１００ｐｐｍ。
（２）感光性樹脂組成物中に占める硫黄元素の含有量が０．０１～１００ｐｐｍ。
（３）感光性樹脂組成物中に占めるリン元素の含有量が０．０１～１００ｐｐｍ。 <Contents of Halogen Elements, Sulfur Elements and Phosphorus Elements>
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).
(1) The content of halogen elements in the photosensitive resin composition is 0.01 to 100 ppm.
(2) The sulfur element content in the photosensitive resin composition is 0.01 to 100 ppm.
(3) The content of phosphorus element in the photosensitive resin composition is 0.01 to 100 ppm.
　また、本発明の第一の態様の感光性樹脂組成物は、（１）の条件および／または（２）の条件を満たすことがより好ましく、（２）の条件を満たすことがさらに好ましい。また、本発明の第一の態様の感光性樹脂組成物は、（１）～（３）の条件からなる群より選ばれる二つ以上の条件を満たすことが好ましく、（１）の条件および（２）の条件を満たすことがより好ましく、（１）～（３）の条件を全て満たすことがさらに好ましい。 Further, 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). Moreover, 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).
　ハロゲン元素としては、塩素元素、臭素元素、ヨウ素元素、またはフッ素元素が挙げられる。ハロゲン元素は、塩素元素、臭素元素およびヨウ素元素からなる群より選ばれる一種類以上の元素を含むことが好ましく、塩素元素および／または臭素元素を含むことがより好ましく、塩素元素を含むことがさらに好ましい。 　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.
　感光性樹脂組成物がハロゲン元素を含む成分を含有する場合、感光性樹脂組成物中に占めるハロゲン元素の含有量は、０．０１ｐｐｍ以上が好ましく、０．０３ｐｐｍ以上がより好ましく、０．０５ｐｐｍ以上がさらに好ましく、０．０７ｐｐｍ以上がさらにより好ましく、０．１ｐｐｍ以上が特に好ましい。一方、ハロゲン元素の含有量は、７００ｐｐｍ以下が好ましく、５００ｐｐｍ以下がより好ましく、３００ｐｐｍ以下がさらに好ましい。さらに、発光特性向上の観点から、１００ｐｐｍ以下が好ましく、７０ｐｐｍ以下がより好ましく、５０ｐｐｍ以下がさらに好ましく、３０ｐｐｍ以下がさらにより好ましく、１０ｐｐｍ以下が特に好ましい。さらに、発光素子の低電圧駆動化の観点から、７ｐｐｍ以下が好ましく、５ｐｐｍ以下がより好ましく、３ｐｐｍ以下がさらに好ましく、１ｐｐｍ以下が特に好ましい。 When the photosensitive resin composition contains a component containing a halogen element, 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. On the other hand, the halogen element content is preferably 700 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less. Furthermore, from the viewpoint of improving light emission properties, 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.
　感光性樹脂組成物が硫黄元素を含む成分を含有する場合、感光性樹脂組成物中に占める硫黄元素の含有量は、０．０１ｐｐｍ以上が好ましく、０．０３ｐｐｍ以上がより好ましく、０．０５ｐｐｍ以上がさらに好ましく、０．０７ｐｐｍ以上がさらにより好ましく、０．１ｐｐｍ以上が特に好ましい。一方、硫黄元素の含有量は、７００ｐｐｍ以下が好ましく、５００ｐｐｍ以下がより好ましく、３００ｐｐｍ以下がさらに好ましい。さらに、発光特性向上の観点から、１００ｐｐｍ以下が好ましく、７０ｐｐｍ以下がより好ましく、５０ｐｐｍ以下がさらに好ましく、３０ｐｐｍ以下がさらにより好ましく、１０ｐｐｍ以下が特に好ましい。さらに、発光素子の低電圧駆動化の観点から、７ｐｐｍ以下が好ましく、５ｐｐｍ以下がより好ましく、３ｐｐｍ以下がさらに好ましく、１ｐｐｍ以下が特に好ましい。 When the photosensitive resin composition contains a component containing sulfur element, 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. On the other hand, the sulfur element content is preferably 700 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less. Furthermore, from the viewpoint of improving light emission properties, 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.
　感光性樹脂組成物がリン元素を含む成分を含有する場合、感光性樹脂組成物中に占めるリン元素の含有量は、０．０１ｐｐｍ以上が好ましく、０．０３ｐｐｍ以上がより好ましく、０．０５ｐｐｍ以上がさらに好ましく、０．０７ｐｐｍ以上がさらにより好ましく、０．１ｐｐｍ以上が特に好ましい。一方、リン元素の含有量は、７００ｐｐｍ以下が好ましく、５００ｐｐｍ以下がより好ましく、３００ｐｐｍ以下がさらに好ましい。さらに、発光特性向上の観点から、１００ｐｐｍ以下が好ましく、７０ｐｐｍ以下がより好ましく、５０ｐｐｍ以下がさらに好ましく、３０ｐｐｍ以下がさらにより好ましく、１０ｐｐｍ以下が特に好ましい。さらに、発光素子の低電圧駆動化の観点から、７ｐｐｍ以下が好ましく、５ｐｐｍ以下がより好ましく、３ｐｐｍ以下がさらに好ましく、１ｐｐｍ以下が特に好ましい。 When the photosensitive resin composition contains a component containing phosphorus element, 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. On the other hand, the phosphorus element content is preferably 700 ppm or less, more preferably 500 ppm or less, and even more preferably 300 ppm or less. Furthermore, from the viewpoint of improving light emission properties, 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.
　感光性樹脂組成物が、ハロゲン元素を含む成分、硫黄元素を含む成分、およびリン元素を含む成分からなる群より選ばれる一種類以上の成分を含有し、感光性樹脂組成物中に占めるハロゲン元素、硫黄元素、およびリン元素からなる群より選ばれる一種類以上の元素の含有量を特定範囲とすることで、有機ＥＬディスプレイにおける発光素子の信頼性向上、および発光素子の低電圧駆動化の効果が顕著となる。これは、感光性樹脂組成物中にこれらの元素を含む成分を微量含有させることで、例えば有機ＥＬディスプレイにおける画素分割層を形成する工程において、第１電極の表面がこれらの元素によって表面改質されると考えられる。または、画素分割層を形成した後、画素分割層に含まれるこれらの元素が遷移することで、第１電極の表面がこれらの元素によって表面改質されると考えられる。そのため、第１電極の仕事関数差の調整によって、有機ＥＬディスプレイにおける発光素子の低電圧駆動化の効果が顕著になると推定される。また、意図的にこれらの元素を含む成分を微量含有させることで、例えば有機ＥＬディスプレイにおける画素分割層中における分極構造や電荷バランスが制御されると考えられる。それにより、発光特性に悪影響を及ぼす金属不純物やイオン不純物に起因するイオンマイグレーションやエレクトロマイグレーションを抑制することで、有機ＥＬディスプレイにおける発光素子の信頼性向上の効果が顕著になると推定される。 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. This is because, for example, in the step of forming a pixel dividing layer in an organic EL display, 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. is considered to be Alternatively, it is considered that 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. In addition, it is believed that by intentionally including a small amount of components containing these elements, for example, the polarization structure and charge balance in the pixel division layer in an organic EL display can be controlled. As a result, it is presumed that by suppressing ion migration and electromigration caused by metal impurities and ion impurities that adversely affect the light emission characteristics, the effect of improving the reliability of the light emitting element in the organic EL display becomes remarkable.
　感光性樹脂組成物が含有するハロゲン元素を含む成分、硫黄元素を含む成分、およびリン元素を含む成分は、単体、イオン、化合物、または化合物イオンであることが好ましい。すなわち、感光性樹脂組成物が、ハロゲン元素の単体、ハロゲン元素のイオン、ハロゲン元素を含む化合物、ハロゲン元素を含む化合物イオン、硫黄元素の単体、硫黄元素のイオン、硫黄元素を含む化合物、硫黄元素を含む化合物イオン、リン元素の単体、リン元素のイオン、リン元素を含む化合物、またはリン元素を含む化合物イオンを含むことが好ましい。感光性樹脂組成物中に占めるハロゲン元素の含有量は、単体、イオン、化合物、または化合物イオンであるハロゲン元素の総量である。同様に、感光性樹脂組成物中に占める硫黄元素の含有量は、単体、イオン、化合物、または化合物イオンである硫黄元素の総量である。同様に、感光性樹脂組成物中に占めるリン元素の含有量は、単体、イオン、化合物、または化合物イオンであるリン元素の総量である。 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. It is preferable to include 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. Similarly, 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. Similarly, the content of elemental phosphorus in the photosensitive resin composition is the total amount of elemental elemental phosphorus, ion, compound, or compound ion.
　感光性樹脂組成物が、ハロゲン元素のイオン、ハロゲン元素を含む化合物イオン、硫黄元素のイオン、硫黄元素を含む化合物イオン、リン元素のイオン、またはリン元素を含む化合物イオンを含有する場合、カウンターカチオンまたはカウンターアニオンを含有しても構わない。カウンターカチオンとしては、金属元素イオン、アンモニウムイオン、一級アンモニウムイオン、二級アンモニウムイオン、三級アンモニウムイオン、または四級アンモニウムイオンが挙げられ、四級アンモニウムイオンが好ましい。金属元素イオンとしては、アルカリ金属イオン、アルカリ土類金属イオン、典型元素金属イオン、または遷移金属イオンが挙げられる。金属元素は、Ｌｉ、Ｂｅ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、Ｃａ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、またはＺｎが好ましい。一級アンモニウムイオン、二級アンモニウムイオン、三級アンモニウムイオン、および四級アンモニウムイオンは、それぞれ、脂肪族基、脂環式基、または芳香族基を１～４個有する。カウンターアニオンは、水酸化物イオン、カルボン酸イオン、次亜硝酸イオン、亜硝酸イオン、硝酸イオン、またはフェノキシイオンが挙げられる。 When 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 Alternatively, it may contain a counter anion. Examples of 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. Examples of 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.
　＜撥インク剤およびその他の添加剤＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、撥インク剤を含有することも好ましい。撥インク剤とは、撥水性の構造および／または撥油性の構造を有する化合物をいう。撥インク剤を含有させることで膜の撥液性を向上できるため、膜の純水に対する接触角および／または膜の有機溶剤に対する接触角を高めることができる。撥インク剤は、少なくとも２つの光反応性基、少なくとも２つの炭素数２～５のアルケニル基、少なくとも２つの炭素数２～５のアルキニル基および少なくとも２つの熱反応性基からなる群より選ばれる一種類以上の基を有することが好ましい。光反応性基としては、ラジカル重合性基が好ましく、スチリル基、シンナモイル基、マレイミド基または（メタ）アクリロイル基がより好ましく、（メタ）アクリロイル基がさらに好ましい。一方、炭素数２～５のアルケニル基または炭素数２～５のアルキニル基としては、ラジカル重合性基が好ましく、ビニル基、アリル基、２－メチル－２－プロペニル基、クロトニル基、２－メチル－２－ブテニル基、３－メチル－２－ブテニル基、２，３－ジメチル－２－ブテニル基、エチニル基または２－プロパルギル基がより好ましく、ビニル基またはアリル基がさらに好ましい。熱反応性基としては、アルコキシメチル基、メチロール基、エポキシ基、オキセタニル基またはブロックイソシアネート基が好ましい。撥インク剤は、ポリマー鎖を有することも好ましく、ポリマー鎖の繰り返し単位の側鎖に撥水性の構造、撥油性の構造、少なくとも２つの光反応性基、少なくとも２つの炭素数２～５のアルケニル基、少なくとも２つの炭素数２～５のアルキニル基および少なくとも２つの熱反応性基からなる群より選ばれる一種類以上の基を有することも好ましい。ポリマー鎖を有する撥インク剤としては、例えば、アクリル樹脂系撥インク剤、ポリオキシアルキレンエーテル系撥インク剤、ポリエステル系撥インク剤、ポリウレタン系撥インク剤、ポリオール系撥インク剤、ポリエチレンイミン系撥インク剤またはポリアリルアミン系撥インク剤が挙げられる。 <Ink repellent agent and other additives>
It is also preferred that 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. It is preferred to have more than one type of group. 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. On the other hand, 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.
　本発明の第一の態様の感光性樹脂組成物は、さらに、増感剤、連鎖移動剤、重合禁止剤、シランカップリング剤および界面活性剤からなる群より選ばれる一種類以上の添加剤を含有することも好ましい。増感剤を含有させることで露光時の感度向上の効果が顕著となる。増感剤としては、フルオレン骨格、ベンゾフルオレン骨格、フルオレノン骨格またはチオキサントン骨格を有する化合物が好ましい。連鎖移動剤を含有させることで露光時の感度向上の効果が顕著となる。連鎖移動剤としては、メルカプト基を少なくとも２つ有する化合物が好ましい。重合禁止剤を含有させることで現像後の解像度向上の効果が顕著となる。重合禁止剤としては、ヒンダードフェノール化合物、ヒンダードアミン化合物またはベンゾイミダゾール化合物が好ましい。シランカップリング剤を含有させることで硬化物と下地の基板との密着性向上の効果が顕著となる。シランカップリング剤としては、三官能オルガノシラン、四官能オルガノシランまたはシリケート化合物が好ましい。界面活性剤を含有させることで塗膜の膜厚均一性向上の効果が顕著となる。界面活性剤としては、フッ素樹脂系界面活性剤、シリコーン系界面活性剤、ポリオキシアルキレンエーテル系界面活性剤またはアクリル樹脂系界面活性剤が好ましい。界面活性剤の含有比率は、感光性樹脂組成物全体の、０．００１質量％以上が好ましく、０．００５質量％以上がより好ましい。一方、界面活性剤の含有比率は、１質量％以下が好ましく、０．５質量％以下がより好ましい。 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. By containing a sensitizer, the effect of improving the sensitivity at the time of exposure becomes remarkable. As the sensitizer, compounds having a fluorene skeleton, benzofluorene skeleton, fluorenone skeleton or thioxanthone skeleton are preferred. By containing a 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. By containing a polymerization inhibitor, the effect of improving the resolution after development becomes remarkable. As the polymerization inhibitor, a hindered phenol compound, a hindered amine compound or a benzimidazole compound is preferred. 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. By containing a surfactant, the effect of improving the film thickness uniformity of the coating film becomes remarkable. As the surfactant, 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. On the other hand, the surfactant content is preferably 1% by mass or less, more preferably 0.5% by mass or less.
　＜溶剤＞
　本発明の第一の態様の感光性樹脂組成物は、さらに、溶剤を含有することも好ましい。溶剤を含有させることで、組成物から得られる膜を基板上に所望の均一な膜厚で成膜できる。溶剤としては、各種樹脂および各種添加剤の溶解性の観点から、アルコール性水酸基を有する化合物、カルボニル基を有する化合物、エステル結合を有する化合物またはエーテル結合を少なくとも３つ有する化合物が好ましい。溶剤としては、塗膜の膜厚均一性向上の観点から、大気圧下の沸点が１１０℃以上である化合物が好ましい。一方、熱硬化時の膜収縮抑制による平坦性向上の観点から、大気圧下の沸点が２５０℃以下である化合物が好ましい。本発明の感光性樹脂組成物に占める溶剤の含有比率は、塗布方法などに応じて適宜調整可能である。例えば、スピンコーティングにより塗膜を形成する場合、感光性樹脂組成物全体の５０～９５質量％とすることが一般的である。 <Solvent>
It is also preferred that the photosensitive resin composition of the first aspect of the present invention further contains a solvent. By containing a solvent, a film obtained from the composition can be formed on a substrate with a desired uniform thickness. From the viewpoint of solubility of various resins and various additives, 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. As the solvent, 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. On the other hand, a compound having a boiling point of 250° C. or lower under atmospheric pressure is preferable from the viewpoint of improving flatness by suppressing film shrinkage during thermosetting. 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.
　本発明の第一の態様の感光性樹脂組成物は、（Ｄ）着色剤として（Ｄ１）顔料を含有する場合、溶剤として、カルボニル基を有する溶剤またはエステル結合を有する溶剤を含有することで、（Ｄ１）顔料の分散安定性向上により、現像後の残渣抑制の効果が顕著となる。カルボニル基としては、アルキルカルボニル基、ジアルキルカルボニル基、ホルミル基、カルボキシ基、アミド基、イミド基、ウレア結合またはウレタン結合が好ましい。エステル結合としては、カルボン酸エステル結合、炭酸エステル結合またはギ酸エステル結合が好ましく、カルボン酸エステル結合がより好ましい。カルボン酸エステル結合の中でも、アセテート結合、プロピオネート結合またはブチレート結合がより好ましく、アセテート結合がさらに好ましい。好ましい溶剤としては、エチレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノアルキルエーテルアセテート、またはブチレングリコールモノアルキルエーテルアセテートが挙げられ、特に好ましい溶剤としては、プロピレングリコールモノアルキルエーテルアセテートが挙げられる。 When the photosensitive resin composition of the first aspect of the present invention contains (D) a pigment (D1) as a colorant, 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. Among the carboxylic acid ester bonds, 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.
　本発明の第一の態様の感光性樹脂組成物において、溶剤に占めるカルボニル基を有する溶剤またはエステル結合を有する溶剤の含有比率の合計は、現像後の残渣抑制および現像後の解像度向上の観点から、３０～１００質量％が好ましく、５０～１００質量％がより好ましく、７０～１００質量％がさらに好ましい。 In the photosensitive resin composition of the first aspect of the present invention, 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.
　本発明の第一の態様の感光性樹脂組成物が、上述した特定の（Ｆ１）化合物を含有する場合、溶剤に占めるプロピレングリコールモノアルキルエーテルアセテートの含有比率は、３０～１００質量％が好ましく、５０～１００質量％がより好ましく、７０～１００質量％がさらに好ましい。 When the photosensitive resin composition of the first aspect of the present invention contains the specific (F1) compound described above, 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.
　本発明の第一の態様の感光性樹脂組成物が、上述した特定の（ＦＢ１）化合物を含有する場合、溶剤に占めるプロピレングリコールモノアルキルエーテルアセテートの含有比率は、３０質量％以上が好ましく、４０質量％以上がより好ましく、５０質量％以上がさらに好ましい。一方、プロピレングリコールモノアルキルエーテルアセテートの含有比率は、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下がさらに好ましい。また、溶剤に占めるジエチレングリコールジアルキルエーテルおよび／またはアルコール性水酸基を有する溶剤の含有比率の合計は、１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましい。一方、これらの溶剤の含有比率の合計は、５０質量％以下が好ましく、４０質量％以下がより好ましい。アルコール性水酸基を有する溶剤としては、アルコール性水酸基ならびにエーテル結合および／またはエステル結合を有する溶剤が好ましい。エステル結合としては、カルボン酸エステル結合、炭酸エステル結合、またはギ酸エステル結合が好ましく、カルボン酸エステル結合がより好ましい。アルコール性水酸基、ならびに、エーテル結合および／またはカルボン酸エステル結合を有する溶剤としては、プロピレングリコールモノアルキルエーテル、乳酸アルキル、ヒドロキシ酢酸アルキルおよび酢酸ヒドロキシアルキルからなる群より選ばれる一種類以上の溶剤が好ましい。 When the photosensitive resin composition of the first aspect of the present invention contains the specific (FB1) compound described above, 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. On the other hand, 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. In addition, 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. As the solvent having an alcoholic hydroxyl group, 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. As the 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. .
　＜本発明の感光性樹脂組成物の製造方法＞
　本発明の感光性樹脂組成物の代表的な製造方法について説明する。（Ｄ）着色剤が（Ｄａ）黒色剤を含み、（Ｄａ）黒色剤が（Ｄ１ａ）黒色顔料を含有する場合、（Ａ）アルカリ可溶性樹脂の溶液に必要に応じて（Ｅ）分散剤を加えた混合溶液に、分散機を用いて（Ｄ１ａ）黒色顔料を分散させ、顔料分散液を調製する。次に、この顔料分散液に、（Ａ）アルカリ可溶性樹脂、（Ｃ）感光剤、その他の添加剤および任意の溶剤を加え、２０分～３時間攪拌して均一な溶液とする。攪拌後、得られた溶液を濾過することで本発明の感光性樹脂組成物が得られる。分散機としては、現像後の残渣抑制の観点から、ビーズミルが好ましい。ビーズミルに用いるビーズとしては、例えば、チタニアビーズ、ジルコニアビーズまたはジルコンビーズが挙げられる。ビーズ径は、０．０１～６ｍｍが好ましく、０．０１５～５ｍｍがより好ましく、０．０３～３ｍｍがさらに好ましい。 <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. Next, (A) 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. After stirring, the resulting solution is filtered to obtain the photosensitive resin composition of the present invention. As the disperser, 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.
　＜硬化物と硬化物の光学濃度、テーパー角および段差形状＞
　本発明の硬化物は上記の感光性樹脂組成物を硬化したものである。硬化とは、例えば、反応によって、組成物を構成する成分に架橋構造が形成され、組成物の流動性が無くなること、また、その状態をいう。反応としては、加熱によるもの、エネルギー線の照射によるもの等、特に限定されるものではないが、加熱によるものが好ましい。加熱による硬化の場合、熱硬化という。加熱条件については後述する。 <Cured product and optical density of cured product, taper angle and step shape>
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.
　本発明の硬化物において、膜厚１μｍ当たりの可視光線の波長（３８０～７８０ｎｍ）における光学濃度は、外光反射抑制および隣接画素からの光漏れ防止の観点から、１．０～５．０が好ましい。膜厚１μｍ当たりの光学濃度は、上述した（Ｄ）着色剤の組成および含有比率により調節できる。本発明の感光性樹脂組成物を所望のパターン形状に形成した後、硬化させることにより、所望のパターン形状を有する硬化物が得られる。これを硬化パターンと呼ぶ。硬化パターンの断面における傾斜辺のテーパー角は、電極断線防止、および発光素子の信頼性向上の観点から、２０～４５°が好ましい。本発明の感光性樹脂組成物を硬化した硬化物が段差形状を有するパターンを有する場合、最も大きい厚さを有する領域（厚膜部）の膜厚と、最も小さい厚さを有する領域（薄膜部）の膜厚との膜厚差は、発光素子の信頼性向上の観点から、１．０～５μｍが好ましい。 In the cured product of the present invention, the optical density at the wavelength of visible light (380 to 780 nm) per 1 μm 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 μm 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. When the cured product obtained by curing the photosensitive resin composition of the present invention has a stepped pattern, 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 μm from the viewpoint of improving the reliability of the light emitting device.
　＜画素分割層の段差形状を有するパターン表面における接触角＞
　本発明の硬化物が、有機ＥＬディスプレイの画素分割層である場合において、上述した段差形状を有する硬化パターンを含む硬化物における、厚膜部の純水に対する接触角を（ＣＡｗＦＴ）°とし、かつ、薄膜部の純水に対する接触角を（ＣＡｗＨＴ）°とするとき、前記（ＣＡｗＦＴ）°と前記（ＣＡｗＨＴ）°との接触角差（ΔＣＡｗＦＴ－ＨＴ）°は、インクジェット塗布で有機ＥＬ層を形成する場合のインク同士の混色防止抑制の観点から、２０°以上が好ましく、４０°以上がより好ましい。一方、有機ＥＬ層の成膜不良抑制の観点から、純水に対する接触角差（ΔＣＡｗＦＴ－ＨＴ）°は、９０°以下が好ましく、７０°以下がより好ましい。 <Contact angle on pattern surface having step shape of pixel division layer>
In the case where the cured product of the present invention is a pixel dividing layer of an organic EL display, 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 )°, In addition, when the contact angle of the thin film portion with respect to pure water is (CAw HT )°, the contact angle difference (ΔCAw FT-HT )° between (CAw FT )° and (CAw HT )° can be obtained by inkjet coating. From the viewpoint of suppressing color mixing between inks when forming an organic EL layer, the angle is preferably 20° or more, more preferably 40° or more. On the other hand, from the viewpoint of suppressing poor film formation of the organic EL layer, the contact angle difference (ΔCAw FT-HT )° with respect to pure water is preferably 90° or less, more preferably 70° or less.
　本発明の硬化物が、有機ＥＬディスプレイの画素分割層である場合において、上述した段差形状を有するパターンを含む硬化物における、厚膜部のプロピレングリコールモノメチルエーテルアセテートに対する接触角を（ＣＡｐＦＴ）°とし、かつ、薄膜部のプロピレングリコールモノメチルエーテルアセテートに対する接触角を（ＣＡｐＨＴ）°とするとき、前記（ＣＡｐＦＴ）°と前記（ＣＡｐＨＴ）°との接触角差（ΔＣＡｐＦＴ－ＨＴ）°は、インクジェット塗布で有機ＥＬ層を形成する場合のインク同士の混色防止抑制の観点から、１０°以上が好ましく、３０°以上がより好ましい。一方、有機ＥＬ層の成膜不良抑制の観点から、プロピレングリコールモノメチルエーテルアセテートに対する接触角差（ΔＣＡｐＦＴ－ＨＴ）°は、７０°以下が好ましく、５０°以下がより好ましい。 In the case where the cured product of the present invention is a pixel dividing layer of an organic EL display, 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 (ΔCAp 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. On the other hand, from the viewpoint of suppressing poor film formation of the organic EL layer, the contact angle difference (ΔCAp FT-HT )° with respect to propylene glycol monomethyl ether acetate is preferably 70° or less, more preferably 50° or less.
　＜本発明の硬化物を具備する表示装置＞
　以下、本発明の硬化物を具備する表示装置、本発明の第二の態様である表示装置について述べる。本発明の表示装置としては、例えば、有機ＥＬディスプレイ、量子ドットディスプレイ、マイクロＬＥＤディスプレイ、ＬＥＤディスプレイ、液晶ディスプレイ、プラズマディスプレイまたは電界放出ディスプレイが挙げられる。有機ＥＬディスプレイ、量子ドットディスプレイまたはマイクロＬＥＤディスプレイが好ましく、有機ＥＬディスプレイがより好ましい。 <Display device provided with the cured product of the present invention>
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.
　本発明の感光性樹脂組成物は、露光時の感度向上、優れたハーフトーン特性および現像後における開口パターン寸法のバラツキ抑制を兼ね備えることが可能である。加えて、有機ＥＬディスプレイにおける発光素子の信頼性向上および発光素子の低電圧駆動化を両立できる。そのため、本発明の感光性樹脂組成物を硬化した硬化物は、有機ＥＬディスプレイの画素分割層、ＴＦＴ平坦化層、ＴＦＴ保護層、層間絶縁層またはゲート絶縁層として特に好ましく用いられる。また、ブラックマトリックスまたはブラックカラムスペーサーとしても好ましく用いられる。硬化物は、有機ＥＬディスプレイに特に好適に具備できる。その結果、発光素子の高信頼性によって有機ＥＬディスプレイの耐久性向上を実現できるとともに、発光素子の低電圧駆動化により高輝度化および省電力化を実現可能である。上述した理由により、本発明の感光性樹脂組成物は有機ＥＬディスプレイにおける画素分割層を形成するための用途において、特に好適である。さらに、優れたハーフトーン特性を有するため、有機ＥＬディスプレイにおける画素分割層の段差形状を一括形成するための用途において、特に好適である。 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. As a result, 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. For the reasons described above, 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.
　本発明の第一の態様の感光性樹脂組成物は、有機ＥＬディスプレイにおける画素分割層の段差形状を一括形成するために用いられることが好ましい。 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.
　本発明の感光性樹脂組成物において、（Ｄ）着色剤が（Ｄａ）黒色剤を含む場合、上述した通り硬化物の遮光性向上による外光反射抑制が可能となる。そのため、本発明の感光性樹脂組成物を硬化した硬化物を具備する有機ＥＬディスプレイは、発光素子の光取り出し側に直線偏光板、１／４波長板または円偏光板などの偏光フィルムを有しなくても、外光反射抑制が可能である。従って、硬化物がフレキシブル基板上に積層されている構造を有し、かつ偏光フィルムを有しない、フレキシブル性を有する有機ＥＬディスプレイに特に好適に具備できる。フレキシブル基板としては、ポリイミド基板、ポリエチレンテレフタレート基板、シクロオレフィンポリマー基板、ポリカーボネート基板またはセルローストリアセテート基板が好ましい。フレキシブル性を有する有機ＥＬディスプレイは、曲面の表示部、外側に折り曲げ可能な表示部または内側に折り曲げ可能な表示部を有することが好ましい。 In the photosensitive resin composition of the present invention, when (D) the colorant contains (Da) the black agent, it is possible to suppress external light reflection by improving the light shielding property of the cured product as described above. Therefore, 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. As 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.
　＜表示装置＞
　表示装置は、基板、第１電極、第２電極、画素分割層、発光層を含む有機層を有する表示装置であることが好ましい。画素分割層が本発明の硬化物であることが好ましい。また本発明の硬化物を具備する表示装置は、有機ＥＬディスプレイであることが好ましい。有機ＥＬディスプレイは、基板、第１電極、第２電極、画素分割層および発光層を少なくとも有し、画素分割層および発光層は第１電極上に形成され、発光層は第１電極および第２電極の間に形成された積層構造を有することが好ましい。 <Display device>
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.
　本発明の第二の態様である表示装置は、基板、第１電極、第２電極および画素分割層を少なくとも有し、さらに、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層を有する表示装置であって、前記画素分割層は、前記第１電極の上に第１電極の一部と重なるように形成され、前記発光層を含む有機ＥＬ層および／または前記発光層を含む光取り出し層は、前記第１電極上、かつ前記第１電極および前記第２電極の間に形成され、前記画素分割層が、少なくとも以下の（Ｘ－ＤＬ）樹脂を有し、さらに以下の（Ｉ－ＤＬ）樹脂、（ＩＩ－ＤＬ）樹脂および（ＩＩＩ－ＤＬ）樹脂からなる群より選ばれる一種類以上の樹脂を有する表示装置である。
（Ｘ－ＤＬ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂。
（Ｉ－ＤＬ）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する樹脂。
（ＩＩ－ＤＬ）樹脂：後述する一般式（２４）で表される構造単位を有する樹脂。
（ＩＩＩ－ＤＬ）樹脂：フェノール樹脂、ポリヒドロキシスチレン、フェノール基変性エポキシ樹脂およびフェノール基変性アクリル樹脂からなる群より選ばれる一種類以上の樹脂。 A display device according to a second aspect of the present invention 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. wherein the pixel division layer is formed on the first electrode so as to partially overlap the first electrode, and includes an organic EL layer including the light emitting layer and/or the light emitting layer The light extraction layer is formed on the first electrode and between the first electrode and the second electrode, and the pixel division layer has at least the following (X-DL) resin, and further the following ( 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.
　＜基板＞
　基板として、耐衝撃性向上の観点からはガラス基板が好ましい。基板としては、例えば、ガラス板上に、インジウム、スズ、亜鉛、アルミニウムおよびガリウムから選ばれる一種類以上の金属を含む酸化物、金属（モリブデン、銀、銅、アルミニウム、クロム、またはチタンなど）、またはＣＮＴ（Ｃａｒｂｏｎ　Ｎａｎｏ　Ｔｕｂｅ）からなる電極および／または配線が形成された基板が挙げられる。基板として、折り曲げ性向上の観点からは、ポリイミド基板などのフレキシブル基板が好ましい。 <Substrate>
As the substrate, a glass substrate is preferable from the viewpoint of improving impact resistance. Examples of 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. As the substrate, a flexible substrate such as a polyimide substrate is preferable from the viewpoint of improving bendability.
　＜第１電極および第２電極＞
　本発明の第二の態様の表示装置は、基板、第１電極および第２電極をこの順に有する。第１電極および第２電極の一方を透明電極に、他方を非透明電極にすることにより、後述する発光層における発光を片側に取り出すことができる。本発明の表示装置における、透明電極および非透明電極には、電気特性に優れること、陽極として用いる場合には効率良く正孔を注入できること、陰極として用いる場合には効率良く電子を注入できることなどの複合的な特性が求められる。 <First electrode and second electrode>
A display device according to a second aspect of the present invention has a substrate, a first electrode and a second electrode in this order. 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. In the display device of the present invention, 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.
　本発明の表示装置は、上述した第１電極の発光層側の最表層に、インジウム、スズ、亜鉛、アルミニウムおよびガリウムからなる群より選ばれる一種類以上の金属を含む透明導電性酸化膜層を有することが好ましく、少なくともインジウムを含む透明導電性酸化膜層を有することがより好ましく、少なくともインジウムを含むアモルファス性の透明導電性酸化膜層を有することがさらに好ましい。少なくともインジウムを含む透明導電性酸化膜層としては、仕事関数差の調整による発光特性の低電圧駆動化の観点から、酸化インジウムスズ（ＩＴＯ）または酸化インジウム亜鉛（ＩＺＯ）からなる層が好ましく、ＩＴＯからなる層がより好ましい。 In the display device of the present invention, 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. As the 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.
　第１電極は、単層構造または多層構造である。第１電極が単層構造の場合、第１電極は透明電極であり、インジウムを含む透明導電性酸化膜層であることが好ましい。第１電極が多層構造の場合、第１電極は透明電極または非透明電極であり、第１電極の発光層側の最表層に、少なくともインジウムを含む透明導電性酸化膜層を有することが好ましい。第２電極は、単層構造の透明電極、多層構造の透明電極、単層構造の非透明電極または多層構造の非透明電極である。表示装置がボトムエミッション型の構成である場合、第１電極が透明電極であり、第２電極は非透明電極である。一方、表示装置がトップエミッション型の構成である場合、第１電極が非透明電極であり、第２電極は透明電極である。本発明の表示装置は、上述した第１電極が、透明導電性酸化膜層および非透明導電性金属層を少なくとも含む多層構造を有し、第１電極の発光層側の最表層に、少なくともインジウムを含むアモルファス性の導電性酸化膜層を有し、非透明導電性金属層が、少なくとも銀を含む合金層を有することが好ましい
　＜画素分割層＞
　本発明の第二の態様の表示装置は、画素分割層を有し、画素分割層は、上述した第１電極の上に第１電極の一部と重なるように形成されている。すなわち、画素分割層は、第１電極と第２電極との間に形成されている。画素分割層としては、上述した感光性樹脂組成物を硬化した硬化物が好ましい。画素分割層が第１電極の一部と重なるように形成されることで、任意の画素における第１電極と第２電極とを絶縁することができ、第１電極と第２電極との短絡に起因する画素非点灯を抑制できる。また、任意の画素の第１電極と、その画素と隣接する画素の第１電極とを絶縁することができ、第１電極同士の短絡に起因する画素非点灯を抑制できる。 The first electrode has a single-layer structure or a multi-layer structure. When the first electrode has a single layer structure, the first electrode is a transparent electrode, preferably a transparent conductive oxide film layer containing indium. When the first electrode has a multilayer structure, 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. On the other hand, if the display device has a top emission configuration, the first electrode is a non-transparent electrode and the second electrode is a transparent electrode. In the display device of the present invention, 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. As the pixel division layer, a cured product obtained by curing the photosensitive resin composition described above is preferable. By forming the pixel dividing layer so as to overlap with a part of the first electrode, 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. In addition, 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.
　＜画素分割層が有する樹脂、化合物、着色剤、および無機粒子＞
　本発明の第二の態様の表示装置は、上述した画素分割層が、少なくとも以下の（Ｘ－ＤＬ）樹脂を有する。
（Ｘ－ＤＬ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂。 <Resins, Compounds, Colorants, and Inorganic Particles of Pixel Division Layer>
In the display device of the second aspect of the present invention, 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.
　（Ｘ－ＤＬ）樹脂としては、樹脂の構造単位中にイソシアヌル酸構造および／またはトリアジン構造を有する樹脂が好ましく、樹脂の構造単位中にイソシアヌル酸構造を有する樹脂がより好ましい。（Ｘ－ＤＬ）樹脂としては、樹脂の構造単位中にイミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を有する樹脂が好ましく、樹脂の構造単位中にイミド構造、アミド構造およびオキサゾール構造からなる群より選ばれる一種類以上の構造を有する樹脂がより好ましい。また、（Ｘ－ＤＬ）樹脂は、上述した（ＡＸ）樹脂に由来する構造を有する樹脂であることが好ましい。（Ｘ－ＤＬ）樹脂は、上述した一般式（２１）で表される構造単位および／または一般式（２２）で表される構造単位を有することが好ましく、一般式（２１）で表される構造単位を有することがより好ましい。また、（Ｘ－ＤＬ）樹脂は、上述した一般式（１）、（２）、（３）、（４）、（５）、（８）および（９）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造を有することが好ましく、一般式（１）で表される構造単位および／または一般式（５）で表される構造単位を有することがより好ましい。なお、（Ｘ－ＤＬ）樹脂は、上述した特定の（ＡＸ）樹脂に由来する構造を有する樹脂であることが好ましく、上述した特に好適な（ＡＸ）樹脂に由来する構造を有する樹脂であることがより好ましい。 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. Further, 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.
　画素分割層が、（Ｘ－ＤＬ）樹脂を有することで、表示装置における発光素子の信頼性向上、および発光素子の低電圧駆動化の効果が顕著となる。画素分割層がこれらの樹脂を有することで、画素分割層の開口部に相当する導電性酸化膜層が表面改質されるため、発光特性が向上すると推定される。また、画素分割層の開口部を形成する際、これらの樹脂による開口部の残渣抑制による相乗効果もあると考えられる。加えて、これらの樹脂中に多く含まれる窒素原子を少なくとも３つ有する環状構造の耐熱性による低アウトガス化により、信頼性向上に効果があると推定される。 By having the (X-DL) resin in the pixel division layer, 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.
　本発明の第二の態様の表示装置は、上述した画素分割層が、さらに以下の（Ｉ－ＤＬ）樹脂、（ＩＩ－ＤＬ）樹脂および（ＩＩＩ－ＤＬ）樹脂からなる群より選ばれる一種類以上の樹脂を有する。
（Ｉ－ＤＬ）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する樹脂。
（ＩＩ－ＤＬ）樹脂：一般式（２４）で表される構造単位を有する樹脂。
（ＩＩＩ－ＤＬ）樹脂：フェノール樹脂、ポリヒドロキシスチレン、フェノール基変性エポキシ樹脂およびフェノール基変性アクリル樹脂からなる群より選ばれる一種類以上の樹脂。 In the display device of the second aspect of the present invention, 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.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　一般式（２４）において、Ｒ６７～Ｒ６９は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表す。ａは０または１である。＊１は樹脂中の結合点を表す。 In general formula (24), 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.
　画素分割層が、これらの樹脂を有することで、表示装置における発光素子の信頼性向上、および発光素子の低電圧駆動化の効果が顕著となる。（Ｉ－ＤＬ）樹脂としては、樹脂の構造単位中にイミド構造、アミド構造およびオキサゾール構造からなる群より選ばれる一種類以上の構造を有する樹脂が好ましい。また、（Ｉ－ＤＬ）樹脂は、上述した（Ａ１）樹脂に由来する構造および／または上述した（Ａ２）樹脂に由来する構造を有する樹脂であることが好ましい。（Ｉ－ＤＬ）樹脂は、上述した一般式（１）、（２）、（３）、（４）、（５）、（８）および（９）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造単位を有することが好ましく、一般式（１）で表される構造単位および／または一般式（５）で表される構造単位を有することがより好ましい。 When the pixel division layer contains these resins, the effect of improving the reliability of the light emitting element in the display device and driving the light emitting element at a low voltage becomes remarkable. 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).
　（ＩＩＩ－ＤＬ）樹脂は、樹脂の主鎖、樹脂の側鎖および樹脂の末端のうち少なくとも１つにアルカリ可溶性基としてフェノール性水酸基を有し、樹脂の構造単位中に芳香環骨格を含む。また、（ＩＩＩ－ＤＬ）樹脂は、上述した（Ａ３）樹脂に由来する構造、上述した（Ａ１）樹脂に由来する構造、および上述した（Ａ２）樹脂に由来する構造からなる群より選ばれる一種類以上を有する樹脂であることが好ましい。（ＩＩＩ－ＤＬ）樹脂は、上述した一般式（３６）、（９１）および（９２）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造単位を有することが好ましく、一般式（３６）で表される構造単位を有することがより好ましい。 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. Further, 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).
　なお、（Ｉ－ＤＬ）樹脂および（ＩＩＩ－ＤＬ）樹脂は、樹脂中に含まれるフェノール性水酸基の一部が、他の樹脂や化合物と反応して架橋構造を形成していることも好ましい。 In the (I-DL) resin and (III-DL) resin, part of the phenolic hydroxyl groups contained in the resin preferably react with other resins or compounds to form a crosslinked structure.
　（ＩＩ－ＤＬ）樹脂は、上述した（Ａ２）樹脂に由来する構造および／または上述した（Ａ３）樹脂に由来する構造を有する樹脂であることが好ましい。（ＩＩ－ＤＬ）樹脂は、上述した一般式（１）、（２）、（３）、（４）、（５）、（８）、（９）、（４１）、（６１）、（６２）、（６３）、（８１）および（８２）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造単位を有することが好ましく、一般式（１）、（２）、（３）、（４）、（５）、（８）および（９）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造単位を有することがより好ましく、一般式（１）、（２）、（３）、（４）および（５）のいずれかで表される構造単位からなる群より選ばれる一種類以上の構造単位を有することがさらに好ましい。 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).
　本発明の表示装置は、上述した画素分割層が、（Ｉ－ＤＬ）樹脂および／または（ＩＩＩ－ＤＬ）樹脂を有する場合、さらに（ＩＩ－ＤＬ）樹脂を有することが好ましい。 In the display device of the present invention, when 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.
　画素分割層が、（Ｉ－ＤＬ）樹脂および／または（ＩＩＩ－ＤＬ）樹脂を有し、さらに（ＩＩ－ＤＬ）樹脂を有することで、表示装置における発光素子の信頼性向上および発光素子の低電圧駆動化の効果が顕著となる。 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.
　本発明の表示装置は、遮光性向上による表示装置のコントラスト向上、および表示装置における発光素子の信頼性向上、および発光素子の低電圧駆動化の観点から、上述した画素分割層が、さらに（ＩＶ－ＤＬ）リン酸エステル構造含有化合物、ホスホン酸構造含有化合物、ホスホン酸エステル構造含有化合物、亜リン酸エステル構造含有化合物、ホスフィン酸構造含有化合物、ホスフィン酸エステル構造含有化合物、次亜リン酸エステル構造含有化合物、リン酸ベタインエステル構造含有化合物、ホスホン酸ベタイン構造含有化合物、ホスホン酸ベタインエステル構造含有化合物、亜リン酸ベタインエステル構造含有化合物、ホスフィン酸ベタイン構造含有化合物、ホスフィン酸ベタインエステル構造含有化合物および次亜リン酸ベタインエステル構造含有化合物を有する化合物からなる群より選ばれる一種類以上の化合物（以下、「（ＩＶ－ＤＬ）リン酸系構造を有する化合物」）を含有することが好ましい。 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 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”).
　（ＩＶ－ＤＬ）リン酸系構造を有する化合物は、ホスホン酸構造含有化合物、ホスホン酸エステル構造含有化合物および亜リン酸エステル構造含有化合物を有する化合物からなる群より選ばれる一種類以上の化合物を含有することがより好ましく、ホスホン酸構造含有化合物および／またはホスホン酸エステル構造含有化合物を含有することがさらに好ましい。（ＩＶ－ＤＬ）リン酸系構造を有する化合物は、上述した（Ｆ０）化合物に由来する構造を有する化合物および／または（ＦＢ）化合物に由来する構造を有する化合物であることが好ましく、上述した（Ｆ１）化合物に由来する構造を有する化合物および／または（ＦＢ１）化合物に由来する構造を有する化合物であることがより好ましい。 (IV-DL) 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. (IV-DL) 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.
　本発明の表示装置は、上述した画素分割層が、さらに（Ｄ）着色剤を含有することが好ましく、（Ｄａ）黒色剤を含有することがより好ましい。画素分割層が、（Ｄａ）黒色剤を含有することで、遮光性向上による表示装置のコントラスト向上および表示装置における発光素子の信頼性向上の効果が顕著となる。 In the display device of the present invention, the pixel division layer described above preferably further contains (D) a colorant, and more preferably contains (Da) a black agent. When 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.
　本発明の表示装置は、上述した画素分割層が、さらに（Ｄ１ａ）黒色顔料を含有することが好ましい。画素分割層は、（Ｄ１ａ）黒色顔料が上述した特定の（Ｄ１ａ－１）有機黒色顔料を含有することがより好ましく、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料を含有することがさらに好ましい。上述した画素分割層は、一般式（１６１）および一般式（１６２）のいずれかで表される構造を有する化合物、それらの幾何異性体、それらの塩、それらの幾何異性体の塩；一般式（１６４）、（１６５）および（１６６）のいずれかで表される構造を有する化合物、それらの塩；一般式（１６８）で表される構造を有する化合物、ならびにその塩、からなる群より選ばれる一種類以上の化合物を含有することも好ましい。上述した画素分割層が、一般式（１６１）および一般式（１６２）のいずれかで表される構造を有する化合物を含有することがより好ましい。 In the display device of the present invention, the pixel division layer described above preferably further contains (D1a) a black pigment. In the pixel dividing layer, 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).
　本発明の表示装置は、遮光性向上による表示装置のコントラスト向上、および表示装置における発光素子の信頼性向上の観点から、上述した画素分割層が、さらに一般式（１４１）、（１４２）、（１４３）、（１４４）、（１４５）、（１４６）および（１４７）で表される構造を有する化合物からなる群より選ばれる一種類以上の化合物を含有することが好ましい。画素分割層中の当該構造を有する化合物は、（Ｂ１）化合物に由来する構造を有する化合物であることが好ましい。 In the display device of the present invention, from the viewpoint of improving the contrast of the display device by improving the light shielding property and improving the reliability of the light-emitting element in the display device, 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).
　本発明の表示装置は、遮光性向上による表示装置のコントラスト向上、および表示装置における発光素子の信頼性向上の観点から、上述した画素分割層が、さらにフルオレン構造、ベンゾフルオレン構造、ジベンゾフルオレン構造、インデン構造、インダン構造、ベンゾインデン構造、ベンゾインダン構造、カルバゾール構造、ジベンゾフラン構造、ジベンゾチオフェン構造、ベンゾカルバゾール構造、インドール構造、インドリン構造、ベンゾインドール構造、ベンゾインドリン構造またはジフェニルスルフィド構造を有し、これらの構造にイミノ基が結合した構造、および／または、カルボニル基が結合した構造を有する化合物を含有することが好ましい。上述した画素分割層が、フルオレン構造、ベンゾフルオレン構造、ジベンゾフルオレン構造、ベンゾカルバゾール構造、インドール構造またはベンゾインドール構造を有する化合物を含有することがより好ましい。画素分割層中の当該構造を有する化合物は、（Ｃ１－１）化合物に由来する構造を有する化合物であることが好ましい。 In the display device of the present invention, from the viewpoint of improving the contrast of the display device by improving the light shielding property and improving the reliability of the light emitting element in the display device, 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. More preferably, 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.
　本発明の表示装置は、発光素子の信頼性向上の観点から、上述した画素分割層が、さらに無機粒子を含有することが好ましい。画素分割層中の無機粒子としては、上述した（Ｉ）無機粒子が好ましい。画素分割層中のシリカ粒子は、上述した（Ｉ１）シリカ粒子であることが好ましい。 In the display device of the present invention, from the viewpoint of improving the reliability of the light-emitting element, it is preferable that the above-described pixel division layer further contains inorganic particles. As 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.
　画素分割層中のシリカ粒子の一次粒子径および平均一次粒子径は５～５０ｎｍであることが好ましい。画素分割層中のシリカ粒子の一次粒子径および平均一次粒子径は、発光素子の信頼性向上の観点から、５ｎｍ以上が好ましく、７ｎｍ以上がより好ましく、１０ｎｍ以上がさらに好ましい。一方、画素分割層中のシリカ粒子の一次粒子径および平均一次粒子径は、外光反射抑制および発光素子の信頼性向上の観点から、５０ｎｍ以下が好ましく、４０ｎｍ以下がより好ましく、３０ｎｍ以下がさらに好ましく、２５ｎｍ以下がさらにより好ましく、２０ｎｍ以下が特に好ましく、１５ｎｍ以下が最も好ましい。シリカ粒子の一次粒子径とは、シリカ粒子の一次粒子における長軸径をいう。 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. Preferably, 25 nm or less is even more preferable, 20 nm or less is particularly preferable, and 15 nm or less is most preferable. The primary particle diameter of silica particles refers to the major axis diameter of primary particles of silica particles.
　画素分割層中のシリカ粒子の一次粒子径は、画素分割層を薄く割断したものを測定試料として、イオンミリング処理により研磨して平滑性を高めた断面について、ＴＥＭを用いて画素分割層の表面から深さ方向に０．２～０．８μｍの範囲に位置する箇所を倍率５０，０００倍の条件で観測した撮像を、画像解析式粒度分布測定ソフトフェア（Ｍａｃ－Ｖｉｅｗ；ＭＯＵＮＴＥＣＨ社製）を用いて測定できる。また画素分割層中のシリカ粒子の平均一次粒子径は、測定試料の断面を撮像および解析し、画素分割層中のシリカ粒子の一次粒子３０個を測定した平均値として算出できる。さらに、ＴＥＭ－ＥＤＸで観測することで粒子を構成する元素を判別でき、画素分割層中のシリカ粒子の特定が可能である。 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) is used to capture an image of a point located in the range of 0.2 to 0.8 μm in the depth direction from the observation at a magnification of 50,000 times. can be measured using Also, 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. Furthermore, by observing with TEM-EDX, it is possible to determine the elements constituting the particles, and to identify the silica particles in the pixel division layer.
　＜発光層を含む有機ＥＬ層および発光層を含む光取り出し層＞
　本発明の第二の態様の表示装置は、さらに、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層を有し、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層は、上述した第１電極上、かつ上述した第１電極および第２電極の間に形成されている。このような構成とすることで、発光画素部に相当する領域を形成できる。 <Organic EL Layer Containing Light Emitting Layer and Light Extraction Layer Containing Light Emitting 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.
　発光層を含む有機ＥＬ層における発光層とは、可視光線の波長（３８０～７８０ｎｍ）の光を発光する層である。発光層は、電子や正孔の電荷輸送機能を有するホスト材料と、発光機能を有するドーパント（ゲスト）材料とを含有することが好ましい。ドーパント材料は、ホスト材料中に０．１～１％程度の濃度で均一に分散されていることが好ましい。発光層は緻密なアモルファス性であることが好ましい。発光層を含む有機ＥＬ層は、さらに、正孔輸送層および／または電子輸送層を有することが好ましく、発光層とこれらの層の積層構造となるように有機ＥＬ層を形成することが好ましい。発光層を含む有機ＥＬ層の構成としては、例えば、（１）正孔輸送層／発光層、（２）正孔輸送層／発光層／電子輸送層または（３）発光層／電子輸送層などが挙げられる。発光層を含む有機ＥＬ層の構成については、正孔と電子の注入や輸送、発光層における発光効率などを総合的に高めるために種々検討されており、好ましい構成としては、例えば、特開平８－１０９３７３号公報に記載された有機ＥＬ素子、すなわち、少なくとも一方が透明な一対の電極間に少なくとも正孔輸送帯域を有し、前記正孔輸送帯が陽極に接する正孔輸送層と発光層に接するブロッキング層、あるいは陽極に接する正孔注入層と前記正孔注入層に接する正孔輸送層と発光層に接するブロッキング層からなる有機薄膜ＥＬ素子において、前記正孔輸送層が特定の一般式で示されるビストリフェニルアミンスチリル誘導体を含有することを特徴とする有機薄膜ＥＬ素子などが挙げられる。 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. -109373, i.e., a hole-transporting layer and a light-emitting layer having at least a hole-transporting zone between a pair of electrodes, at least one of which is transparent, and the hole-transporting zone is in contact with the anode In an organic thin-film EL device comprising a blocking layer in contact with the anode, a hole-injection layer in contact with the anode, a hole-transporting layer in contact with the hole-injection layer, and a blocking layer in contact with the light-emitting layer, the hole-transporting layer has a specific general formula: and an organic thin film EL device characterized by containing the bistriphenylamine styryl derivative shown.
　本発明の表示装置は、発光層を含む有機ＥＬ層を用いた積層構造とすることで、表示装置である有機ＥＬディスプレイを製造することができる。 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.
　一方、本発明の表示装置は、発光層を含む光取り出し層を用いた積層構造とすることで、表示装置である量子ドットディスプレイまたはマイクロＬＥＤディスプレイを製造することができる。 On the other hand, 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.
　発光層を含む光取り出し層における発光層は、発光層を含む有機ＥＬ層における発光層と別の機構により可視光線の波長（３８０～７８０ｎｍ）の光を発光する層である。発光層を含む光取り出し層とは、発光層からの発光を表示装置の光取り出し側から外部に取り出す層をいう。光取り出し層としては、単層または多層の有機層および／または無機層が好ましい。 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.
　本発明の表示装置としては、発光層を含む光取り出し層が量子ドットを含む構成である量子ドットディスプレイも好ましい。量子ドットディスプレイは、基板上に、第１電極、第２電極、画素分割層、および発光層を含む光取り出し層を有する表示装置であって、画素分割層は、第１電極の上に第１電極の一部と重なるように形成され、発光層を含む光取り出し層は、第１電極上、かつ第１電極および第２電極の間に形成された構成を有し、発光層を含む光取り出し層が量子ドットを含む構成を有する表示装置である。例えば、自発光型の量子ドットを含む層を、発光層を含む光取り出し層として配置した表示装置が挙げられる。自発光型の量子ドットを含む層の構成としては、例えば、正孔輸送層／量子ドット層／電子輸送層が挙げられる。 As the display device of the present invention, 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. For example, there is a display device in which 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.
　本発明の表示装置としては、発光層を含む光取り出し層が無機半導体を含む構成であるマイクロＬＥＤディスプレイも好ましい。マイクロＬＥＤディスプレイは、基板上に、第１電極、第２電極、画素分割層、および発光層を含む光取り出し層を有する表示装置であって、画素分割層は、第１電極の上に第１電極の一部と重なるように形成され、発光層を含む光取り出し層は、第１電極上、かつ第１電極および第２電極の間に形成された構成を有し、発光層を含む光取り出し層が無機半導体を含む構成を有する表示装置である。例えば、無機半導体である無機ＬＥＤ層を、発光層を含む光取り出し層として配置した表示装置が挙げられる。無機ＬＥＤ層としては、例えば、ＰＮ接合ＬＥＤ層が挙げられる。 As the display device of the present invention, 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. For example, there is a display device in which 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.
　本発明の表示装置において、発光層を含む有機ＥＬ層および発光層を含む光取り出し層の両方を用いる積層構造とした表示装置も好ましい。例えば、以下の（１）～（２）の表示装置が挙げられる。
（１）第１電極上に、発光層を含む有機ＥＬ層および発光層を含む光取り出し層（例えば、自発光型の量子ドットを含む層）が設けられ、発光層を含む有機ＥＬ層および発光層を含む光取り出し層の両方を光源とする表示装置。
（２）第１電極上に、発光層を含む有機ＥＬ層が光源として設けられ、発光層を含む有機ＥＬ層からの発光を、発光層を含む有機ＥＬ層上に設けられた、発光層を含む光取り出し層（例えば、量子ドットを含む層）によって色変換した後、外部に取り出す表示装置。 In the display device of the present invention, 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. For example, the following display devices (1) and (2) are listed.
(1) An organic EL layer including a light-emitting layer and a light extraction layer including a light-emitting layer (for example, a layer including self-luminous quantum dots) 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.
(2) 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. A display device in which color conversion is performed by a light extraction layer (for example, a layer containing quantum dots) and then output to the outside.
　本発明の表示装置は、第１電極上に、発光層を含む有機ＥＬ層および発光層を含む光取り出し層が、この順に形成されていることが好ましい。 In the display device of the present invention, it is preferable that 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.
　本発明の表示装置は、発光層を含む有機ＥＬ層および発光層を含む光取り出し層の両方を設けた構造として、発光層を含む光取り出し層を第１電極と第２電極の間以外の位置に有する表示装置も好ましい。例えば、以下の（３）～（５）の表示装置が挙げられる。
（３）第１電極上に、発光層を含む有機ＥＬ層が設けられ、第１電極と第２電極の間よりも光取り出し側に発光層を含む光取り出し層（例えば、量子ドットを含む層）が設けられ、発光層を含む有機ＥＬ層からの発光１およびＬＥＤなどのバックライトからの光を発光層を含む光取り出し層によって色変換させた光２、の両方を光源とする表示装置。
（４）第１電極上に、発光層を含む有機ＥＬ層が設けられ、第１電極と第２電極の間よりも光取り出し側に発光層を含む光取り出し層（例えば、量子ドットを含む層）が設けられ、発光層を含む有機ＥＬ層からの発光を、発光層を含む光取り出し層によって色変換させた光、を光源とする表示装置。
（５）第１電極上に、発光層を含む有機ＥＬ層が設けられ、第１電極と第２電極の間よりも光取り出し側に発光層を含む光取り出し層（例えば、量子ドットを含む層）が設けられ、発光層を含む有機ＥＬ層からの発光１、および、発光層を含む有機ＥＬ層からの発光を発光層を含む光取り出し層によって色変換させた光２、の両方を光源とする表示装置。 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.
(3) 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.
(4) 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.
(5) 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.
　本発明の表示装置は、発光輝度向上および発光色純度向上の観点から、さらに、量子ドットを含むカラーフィルタを有することが好ましい。量子ドットを含むカラーフィルタを有する積層構造とする場合、量子ドットを含むカラーフィルタと重畳し、かつ量子ドットを含むカラーフィルタよりも下層に位置する発光素子は、青色光を発光する有機ＥＬ発光素子、白色光を発光する有機ＥＬ発光素子、青色光を発光するＬＥＤ素子、または白色光を発光するＬＥＤ素子であることが好ましい。 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. In the case of a laminated structure having a color filter containing quantum dots, 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.
　本発明の表示装置は、複数の画素を含む画素部を有することが好ましい。本発明の表示装置は、画素分割層の開口部における、上述した第１電極上、かつ、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層が形成された箇所を画素部とすることが好ましい。画素部に相当する領域は、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層が、上述した第１電極部と接する領域に相当する。本発明の表示装置は、画素部が、カラーフィルタ層およびブラックマトリックス層の開口部と重畳することが好ましい。本発明の表示装置は、同一の基板上に、第１電極、第２電極、画素分割層、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層、封止層、カラーフィルタ層、およびブラックマトリックス層を有することが好ましい。 The display device of the present invention preferably has a pixel portion including a plurality of pixels. In the display device of the present invention, 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. In the display device of the present invention, 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.
　＜有機ＥＬディスプレイの製造プロセスの模式的断面図＞
　本発明の感光性樹脂組成物において、（Ｄ）着色剤が（Ｄａ）黒色剤を含む場合、該組成物を硬化した硬化物を、遮光性を有する画素分割層として具備する有機ＥＬディスプレイの製造プロセスの例を、図１に模式的断面図を示して説明する。まず、（工程１）ガラス基板１上に、薄膜トランジスタ（以下、「ＴＦＴ」）２を形成し、ＴＦＴ平坦化膜用の感光性材料を成膜し、フォトリソグラフィーによってパターン加工した後、熱硬化させてＴＦＴ平坦化用の硬化物３を形成する。次に、（工程２）ＴＦＴ２およびＴＦＴ平坦化用の硬化物３の上層に銀パラジウム－銅合金（以下、「ＡＰＣ」）をスパッタにより成膜し、フォトレジストを用いてエッチングによりパターン加工してＡＰＣ層を形成する。さらに、ＡＰＣ層の上層に酸化インジウムスズ（以下、「ＩＴＯ」）をスパッタにより成膜し、フォトレジストを用いたエッチングによりパターン加工し、第１電極として、ＡＰＣ層とＩＴＯ層の積層からなる反射電極４を形成する。その後、（工程３）反射電極４の上層に本発明の感光性樹脂組成物を塗布およびプリベークして、プリベーク膜５ａを形成する。次いで、（工程４）所望のパターンを有するマスク６を介して、プリベーク膜５ａに活性化学線７を照射する。次に、（工程５）露光されたプリベーク膜５ａを現像してパターン加工をした後、必要に応じてブリーチング露光およびミドルベークする。さらに、パターン加工されたプリベーク膜５ａを熱硬化させることで、遮光性を有する画素分割層として、所望のパターンを有する硬化パターン５ｂを形成する。その後、（工程６）硬化パターン５ｂの間の反射電極４の上層に、ＥＬ発光材料を、マスクを介した蒸着によって成膜して有機ＥＬ層８を形成する。さらに、有機ＥＬ層８の上層にマグネシウム－銀合金（以下、「ＭｇＡｇ」）を蒸着により成膜し、フォトレジストを用いてエッチングによりパターン加工し、第２電極として透明電極９を形成する。次に（工程７）透明電極９の上層の全面に平坦化膜用の感光性材料を成膜し、フォトリソグラフィーによってパターン加工した後、熱硬化させて平坦化用の硬化物１０を形成し、その後、硬化物１０にカバーガラス１１を接合させることで、本発明の感光性樹脂組成物の硬化物を、遮光性を有する画素分割層として具備する有機ＥＬディスプレイを得る。 <Schematic cross-sectional view of manufacturing process of organic EL display>
In the photosensitive resin composition of the present invention, when the (D) colorant contains (Da) a black agent, the cured product obtained by curing the composition is used to manufacture an organic EL display having a light-shielding pixel division layer. An example of the process will be described with reference to a schematic cross-sectional view in FIG. First, (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. Next, (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. Form the APC layer. Furthermore, a film of indium tin oxide (hereinafter referred to as “ITO”) is formed by sputtering on the upper layer of the APC layer, patterned by etching using a photoresist, and as a first electrode, a reflector composed of a lamination of the APC layer and the ITO layer is formed. An electrode 4 is formed. Thereafter, (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. Next, (step 4) the prebaked film 5a is irradiated with actinic rays 7 through a mask 6 having a desired pattern. Next, (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. Thereafter, (step 6) 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. Next (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.
　＜硬化物の製造方法＞
　本発明の感光性樹脂組成物を用いた硬化物の製造方法は、以下の（１）～（４）の工程を有することが好ましい。
（１）基板上に、本発明の感光性樹脂組成物の塗膜を成膜する工程、
（２）該感光性樹脂組成物の塗膜にフォトマスクを介して活性化学線を照射する工程、
（３）アルカリ溶液を用いて現像して、該感光性樹脂組成物のパターンを形成する工程、および、
（４）該パターンを加熱して、該感光性樹脂組成物の硬化パターンを得る工程。 <Method for producing cured product>
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.
　また、フォトマスクが、透光部および遮光部を含み、透光部と遮光部の間に透過率が透光部の値より低く、かつ透過率が遮光部の値より高い、半透光部を有するハーフトーンフォトマスクであることが好ましい。 Further, 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. is preferably a halftone photomask having
　なお、硬化物の製造方法としては、国際公開第２０１９／０８７９８５号の段落［０４５３］～段落［０４８１］に記載の各方法を適用しても構わない。 As a method for producing a cured product, each method described in paragraphs [0453] to [0481] of International Publication No. 2019/087985 may be applied.
　＜塗膜を成膜する工程＞
　本発明の硬化物の製造方法は、（１）基板上に、感光性樹脂組成物の塗膜を成膜する工程、を有する。感光性樹脂組成物を成膜する方法としては、例えば、基板上に、感光性樹脂組成物を塗布する方法、または、基板上に、感光性樹脂組成物をパターン状に塗布する方法が挙げられる。 <Step of forming a coating film>
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. .
　基板としては、例えば、ガラス上に、電極または配線として、インジウム、スズ、亜鉛、アルミニウム、およびガリウムから選ばれる一種類以上の金属を含む酸化物、金属（モリブデン、銀、銅、アルミニウム、クロム、もしくはチタンなど）またはＣＮＴ（Ｃａｒｂｏｎ　Ｎａｎｏ　Ｔｕｂｅ）が形成された基板などが用いられる。インジウム、スズ、亜鉛、アルミニウムおよびガリウムから選ばれる一種類以上の金属を含む酸化物としては、例えば、酸化インジウムスズ（ＩＴＯ）が挙げられる。 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. Examples of oxides containing one or more metals selected from indium, tin, zinc, aluminum and gallium include indium tin oxide (ITO).
　＜基板上に、感光性樹脂組成物を塗布する方法＞
　基板上に、感光性樹脂組成物を塗布する方法としては、例えば、スピンコーティング、カーテンフローコーティング、スプレーコーティングまたはスリットコーティングが挙げられる。塗布膜厚は、塗布方法、感光性樹脂組成物の固形分濃度や粘度などによって異なるが、通常は、塗布およびプリベーク後の膜厚が０．１～３０μｍであることが好ましい。 <Method of applying a photosensitive resin composition on a substrate>
Examples of methods for applying the photosensitive resin composition on the substrate 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 μm.
　基板上に、感光性樹脂組成物を塗布した後、得られた塗膜をプリベークすることが好ましい。プリベークは、オーブン、ホットプレート、赤外線、フラッシュアニール装置またはレーザーアニール装置などを使用することができる。プリベーク温度は、５０～１５０℃が好ましい。プリベーク時間は、３０秒～１０分が好ましい。また、８０℃で２分間プリベークした後、１２０℃で２分間プリベークするなど、二段またはそれ以上の多段でプリベークしても構わない。 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. Alternatively, 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.
　＜基板上に成膜した塗膜をパターン加工する方法＞
　基板上に成膜された、感光性樹脂組成物の塗膜をパターン加工する方法としては、例えば、フォトリソグラフィーにより直接パターン加工する方法またはエッチングによりパターン加工する方法が挙げられる。工程数削減およびプロセスタイム短縮の観点から、フォトリソグラフィーにより直接パターン加工する方法が好ましい。 <Method of patterning a coating film formed on a substrate>
Examples of the method of patterning the coating film of the photosensitive resin composition formed on the substrate 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.
　＜フォトマスクを介して活性化学線を照射する工程＞
　本発明の硬化物の製造方法は、（２）上述した感光性樹脂組成物の塗膜にフォトマスクを介して活性化学線を照射する工程、を有する。フォトマスクを介して活性化学線を照射する方法としては、例えば、ステッパー、スキャナー、ミラープロジェクションマスクアライナー（ＭＰＡ）、またはパラレルライトマスクアライナー（ＰＬＡ）などの露光機を用いてパターニング露光する方法が挙げられる。 <Step of irradiating actinic radiation through a photomask>
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.
　フォトマスクとしては、透光部および遮光部を含むパターンを有するフォトマスクであって、該透光部と該遮光部の間に、透過率が該透光部の値より低く、かつ透過率が該遮光部の値より高い、半透光部を有するハーフトーンフォトマスクを用いることが好ましい。ハーフトーンフォトマスクを用いて露光することで、現像後に段差形状を有するパターンを形成することができる。ネガ型の感光性組成物を用いた場合、段差形状を有するパターンにおいて、該透光部を介して活性化学線を照射した露光部から形成した箇所は厚膜部に相当し、該半透光部を介して活性化学線を照射したハーフトーン部から形成した箇所は薄膜部に相当する。 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. By exposing using a halftone photomask, a pattern having a step shape can be formed after development. When a negative photosensitive composition is used, in a pattern having a stepped shape, 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.
　活性化学線の露光波長は、１５０ｎｍ以上が好ましく、３００ｎｍ以上がより好ましい。一方、露光波長は、４５０ｎｍ以下が好ましく、４２０ｎｍ以下がより好ましい。活性化学線としては、水銀灯のｊ線（波長３１３ｎｍ）、ｉ線（波長３６５ｎｍ）、ｈ線（波長４０５ｎｍ）、もしくはｇ線（波長４３６ｎｍ）、または、ｉ線、ｈ線およびｇ線の混合線が特に好ましい。活性化学線として、ＸｅＦ（波長３５１ｎｍ）レーザー、ＸｅＣｌ（波長３０８ｎｍ）レーザー、ＫｒＦ（波長２４８ｎｍ）レーザー、またはＡｒＦ（波長１９３ｎｍ）レーザーなどを用いても構わない。活性化学線の露光量は、ｉ線照度値で、１００Ｊ／ｍ２（１０ｍＪ／ｃｍ２）～３０，０００Ｊ／ｍ２（３，０００ｍＪ／ｃｍ２）以下が好ましい。露光後の膜に対して、露光後ベークをしても構わない。露光後ベークをすることで、現像後の解像度向上、または現像条件の許容幅拡大が可能である。 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.
　＜アルカリ溶液を用いて現像して、パターンを形成する工程＞
　本発明の硬化物の製造方法は、（３）アルカリ溶液を用いて現像して、上述した感光性樹脂組成物のパターンを形成する工程、を有する。フォトマスクを介して活性化学線を照射した後、アルカリ溶液を用いて現像する方法としては、例えば、自動現像機を用いて現像する方法が挙げられる。現像方法としては、例えば、パドル現像、スプレー現像またはディップ現像が挙げられる。感光性樹脂組成物がネガ型の感光性を有する場合、未露光部が現像液で除去されたパターンを形成できる。感光性樹脂組成物がポジ型の感光性を有する場合、露光部が現像液で除去されたパターンを形成できる。 <Step of forming a pattern by developing with an alkaline solution>
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. When the photosensitive resin composition has negative photosensitivity, it is possible to form a pattern in which the unexposed areas are removed with a developer. When the photosensitive resin composition has positive photosensitivity, it is possible to form a pattern in which the exposed portion is removed with a developer.
　現像液としては、アルカリ溶液が好ましい。アルカリ溶液としては、アルカリ性を示す化合物の水溶液または有機溶液が好ましく、水溶液がより好ましい。アルカリ性を示す化合物としては、例えば、ジエタノールアミン、トリメチルアミン、トリエチルアミン、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、水酸化テトラメチルアンモニウム、または水酸化テトラエチルアンモニウムが挙げられる。現像液としては、有機溶媒を用いても構わない。現像液は、感光性樹脂組成物に対する良溶媒と貧溶媒の、両方を含有する混合溶液を用いても構わない。アルカリ溶液のアルカリ濃度は、０．０１～５質量％が好ましい。現像時間は、３０秒～１０分が好ましい。現像後、得られたパターンをリンス液で洗浄することが好ましい。リンス液としては、現像液としてアルカリ水溶液を用いた場合、水が好ましい。リンス液としては、アルコール類の水溶液、エステル類の水溶液、酸性を示す化合物の水溶液、または有機溶媒を用いても構わない。現像後、現像後露光をしても構わない。現像後露光をすることで、熱硬化後の解像度向上、熱硬化後のパターン形状制御、および熱硬化後の段差形状を有するパターン形成が可能である。また、現像後、ミドルベークをしても構わない。ミドルベークをすることで、熱硬化後の解像度向上、および熱硬化後のパターン形状制御が可能である。 An alkaline solution is preferable as the developer. As the alkaline solution, an aqueous solution or an organic solution of a compound exhibiting alkalinity is preferable, and an aqueous solution is more preferable. Examples of 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. As the rinse liquid, water is preferable when an alkaline aqueous solution is used as the developer. As the rinse liquid, an alcohol aqueous solution, an ester aqueous solution, an acidic compound aqueous solution, or an organic solvent may be used. After development, 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. In addition, 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.
　＜パターンを加熱して、硬化パターンを得る工程＞
　本発明の硬化物の製造方法は、（４）上述した感光性樹脂組成物のパターンを加熱して硬化させ、感光性樹脂組成物の硬化パターンを得る工程（以下、「（４）工程」）を有する。 <Step of heating the pattern to obtain a cured pattern>
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”). have
　熱硬化方法としては、例えば、オーブン、ホットプレート、赤外線、フラッシュアニール装置またはレーザーアニール装置を用いて加熱する方法が挙げられる。熱硬化させることで、硬化物の耐熱性を向上できるとともに、低テーパー形状のパターンを形成できる。熱硬化温度は、１５０～５００℃が好ましい。熱硬化時間は、５～３００分が好ましい。また、１５０℃で３０分間熱硬化させた後、２５０℃で３０分間熱硬化させるなど、二段またはそれ以上の多段で熱硬化させても構わない。処理雰囲気としては、例えば、空気、酸素、窒素、ヘリウム、ネオン、アルゴン、クリプトンもしくはキセノン雰囲気下、酸素を１～１０，０００ｐｐｍ（０．０００１～１質量％）含有するガス雰囲気下または真空下が挙げられる。 Examples of 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. Moreover, 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.
　以下に実施例、参考例および比較例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの範囲に限定されない。なお、以下実施例の説明または表で用いた化合物のうち略語を使用しているものについて、名称を以下に示す。
６ＦＤＡ：４，４’－ヘキサフルオロプロパン－２，２－ジイル－ビス（１，２－フタル酸無水物）
ＡＤＰ：三級アミノ基、一般式（２６）で表される構造、一般式（２９）で表される構造、およびポリオキシアルキレン構造を有する（Ｅ１）塩基性基を有する分散剤（アミン価：２０ｍｇＫＯＨ／ｇ（固形分濃度：１００質量％））
ＡＰＣ：Ａｒｇｅｎｔｕｍ－Ｐａｌｌａｄｉｕｍ－Ｃｕｐｐｅｒ（銀－パラジウム－銅合金）
ＢＡＨＦ：２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン
ＢＡＰＦ：９，９－ビス（３－アミノ－４－ヒドロキシフェニル）フルオレン
ＢＧＰＦ：９，９－ビス（４－グリシドキシフェニル）フルオレン
ＢｎＭＡ：メタクリル酸ベンジル
Ｂｋ－Ａ１１０３：一般式（１６８）で表される化合物；“ＣＨＲＯＭＯＦＩＮＥ”（登録商標）　ＢＬＡＣＫ　Ａ１１０３（大日精化工業（株）製；一次粒子径５０～１００ｎｍのアゾ系黒色顔料）
Ｂｋ－ＣＢＦ１：一般式（１６１）で表される化合物および一般式（１６２）で表される化合物の混合物；表面被覆ベンゾフラノン系黒色顔料（（ＤＣ－１）シリカ被覆層：シリカ（黒色顔料１００質量部に対して、ＳｉＯ２換算値で１０．０質量部）；（ＤＣ－２）金属酸化物被覆層：アルミナ（黒色顔料１００質量部に対して、Ａｌ２Ｏ３換算値で２．０質量部）；黒色顔料に対する被覆層の平均被覆率：９７．５％）
Ｂｋ－ＣＢＦ２：一般式（１６５）で表される化合物および一般式（１６６）で表される化合物の混合物；表面被覆ペリレン系黒色顔料（（ＤＣ－１）シリカ被覆層：シリカ＋シリカ（（ＤＣ－１）シリカ被覆層が二層；黒色顔料１００質量部に対して、ＳｉＯ２換算値で３．０＋７．０質量部）；黒色顔料に対する被覆層の平均被覆率：８４．５％）
Ｂｋ－ＦＫ４２８０：一般式（１６５）で表される化合物および一般式（１６６）で表される化合物の混合物；“ＬＵＭＯＧＥＮ”（登録商標）ＢＬＡＣＫ　ＦＫ４２８０（ＢＡＳＦ社製；一次粒子径５０～１００ｎｍのペリレン系黒色顔料）
Ｂｋ－Ｓ００８４：一般式（１６４）で表される化合物；“ＰＡＬＩＯＧＥＮ”（登録商標）　ＢＬＡＣＫ　Ｓ００８４（ＢＡＳＦ社製；一次粒子径５０～１００ｎｍのペリレン系黒色顔料）
Ｂｋ－Ｓ０１００ＣＦ：一般式（１６１）で表される化合物および一般式（１６２）で表される化合物の混合物；“ＩＲＧＡＰＨＯＲ”（登録商標）　ＢＬＡＣＫ　Ｓ０１００ＣＦ（ＢＡＳＦ社製；一次粒子径４０～８０ｎｍのベンゾフラノン系黒色顔料）
ＣＨＴＡ：シクロヘキサン－１，２，４－トリカルボン酸－１，２－無水物
ｃｙＥｐｏＴＭＳ：２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン
ＥＤＭ：ジエチレングリコールエチルメチルエーテル
ＥＭＧ－１０１５：イソシアヌル酸構造を含み、さらに脂環式構造を有するトリイソシアネート化合物に由来する構造単位を有するポリアミドイミド（ＤＩＣ（株）製；酸当量：３８０ｇ／ｍｏｌ）
ＥＱＧ－１１７０：イソシアヌル酸構造を含み、さらに脂環式構造を有するトリイソシアネート化合物に由来する構造単位を有し、さらにエチレン性不飽和二重結合基を有するポリアミドイミド（ＤＩＣ（株）製；酸当量：３９０ｇ／ｍｏｌ、二重結合当量：６１０ｇ／ｍｏｌ）
ＧＭＡ：メタクリル酸グリシジル
ＨＡＤ：ホルムアルデヒド
ＨＳＴ：４－ヒドロキシスチレン
ＩＴＯ：酸化インジウムスズ
ＫＢＭ－５０３：３－メタクリロイルオキシプロピルトリメトキシシラン（信越化学工業社製）
ＭＡＡ：メタクリル酸
ＭＡＰ：ｍ－アミノフェノール
ＭＢＡ：３－メトキシ－ｎ－ブチルアセテート
ＭＣＳ：ｍ－クレゾール
ＭＥＫ：メチルエチルケトン
ＭＥＫ－ＳＴ－４０：メチルエチルケトンを分散溶媒に用いたシリカ粒子分散液（日産化学社製）
ＭＥＫ－ＳＴ－Ｌ：メチルエチルケトンを分散溶媒に用いたシリカ粒子分散液（日産化学社製）
ＭｅＴＭＳ：メチルトリメトキシシラン
ＭｇＡｇ：Ｍａｇｎｅｓｉｕｍ－Ａｒｇｅｎｔｕｍ（マグネシウム－銀合金）
ＭＯＩ：２－メタクリロキシエチルイソシアネート
ＭＯＰ：４－メトキシフェノール
ＮＡ：５－ノルボルネン－２，３－ジカルボン酸無水物
ＮＣ－３５００：ビフェニル骨格、ベンゼン骨格、および２つのエポキシ基を含む構造単位を有するエポキシ樹脂（日本化薬（株）製）
ＯＤＢ－ＨＢＴ：ビス（４－カルボキシフェニル）エーテルと、１－ヒドロキシ－１，２，３－ベンゾトリアゾールとを反応させて得られたジカルボン酸誘導体の混合物
ＯＤＰＡ：オキシジフタル酸二無水物
Ｐ．Ｂ．６０：Ｃ．Ｉ．ピグメントブルー６０（インダントロン系青色顔料）
Ｐ．Ｒ．１７９：Ｃ．Ｉ．ピグメントレッド１７９（ペリレン系赤色顔料）
Ｐ．Ｙ．１９２：Ｃ．Ｉ．ピグメントイエロー１９２（イミダゾロン系黄色顔料）
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＰＨＡ：フタル酸無水物
ＰｈＴＭＳ：フェニルトリメトキシシラン
ＳｉＤＡ：１，３－ビス（３－アミノプロピル）テトラメチルジシロキサン
ＳＴＲ：スチレン
ＴＣＤＭ：メタクリル酸トリシクロ［５．２．１．０２，６］デカン－８－イル；メチロール－トリシクロデカンメタクリレート
ＴＨＰＨＡ：１，２，３，６－テトラヒドロフタル酸無水物
ＴＭＡＣ：無水トリメリット酸クロリド
ＴＭＡＨ：水酸化テトラメチルアンモニウム
ＴＭＭ－ＴＡＺ：２，４，６－トリス［Ｎ，Ｎ－ビス（メトキシメチル）アミノ］－１，３，５－トリアジン
ＴＭＯＳ：テトラメトキシシラン
ＴＭＳ－ＩＣＡ：１，３，５－トリス（３－トリメトキシシリルプロピル）イソシアヌル酸
ＴＭＳ－ＴＡＺ：２，４，６－トリス［（３－トリメトキシシリルプロピル）アミノ］－１，３，５－トリアジン
ＺＣＲ－１５６９Ｈ：ビフェニル骨格およびベンゼン骨格を含む構造単位を有する酸変性エポキシ樹脂（日本化薬（株）製；酸当量：５７０ｇ／ｍｏｌ、二重結合当量：５００ｇ／ｍｏｌ）。 EXAMPLES The present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples below, but the present invention is not limited to these scopes. Among the compounds used in the description of the examples and the tables below, the names of the compounds for which abbreviations are used are shown below.
6FDA: 4,4'-hexafluoropropane-2,2-diyl-bis(1,2-phthalic anhydride)
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" (registered trademark) BLACK A1103 (manufactured by Dainichiseika Kogyo Co., Ltd.; azo black pigment)
Bk-CBF1: a mixture of a compound represented by the general formula (161) and a compound represented by the general formula (162); surface-coated benzofuranone-based black pigment ((DC-1) silica coating layer: silica (black pigment 100 mass (DC- 2 ) Metal oxide coating layer: alumina (2.0 parts by mass in terms of Al 2 O 3 with respect to 100 parts by mass of black pigment part); average coverage of the coating layer with respect to the black pigment: 97.5%)
Bk-CBF2: a mixture of a compound represented by the general formula (165) and a compound represented by the general formula (166); surface-coated perylene-based black pigment ((DC-1) silica coating layer: silica + silica ((DC -1) Two layers of silica coating layers; 3.0 + 7.0 parts by mass in terms of SiO 2 with respect to 100 parts by mass of black pigment); Average coverage of coating layer with respect to black pigment: 84.5%)
Bk-FK4280: a mixture of a compound represented by the general formula (165) and a compound represented by the general formula (166); black pigment)
Bk-S0084: compound represented by the general formula (164); "PALIOGEN" (registered trademark) BLACK S0084 (manufactured by BASF; perylene-based black pigment having a primary particle size of 50 to 100 nm)
Bk-S0100CF: a mixture of the compound represented by the general formula (161) and the compound represented by the general formula (162); "IRGAPHOR" (registered trademark) BLACK S0100CF (manufactured by BASF; black pigment)
CHTA: cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane EDM: diethylene glycol ethyl methyl ether EMG-1015: contains isocyanuric acid structure Furthermore, a polyamideimide having a structural unit derived from a triisocyanate compound having an alicyclic structure (manufactured by DIC Corporation; acid equivalent: 380 g / mol)
EQG-1170: Polyamideimide containing an isocyanuric acid structure, further having a structural unit derived from a triisocyanate compound having an alicyclic structure, and having an ethylenically unsaturated double bond group (manufactured by DIC Corporation; acid equivalent weight: 390 g/mol, double bond equivalent weight: 610 g/mol)
GMA: glycidyl methacrylate HAD: formaldehyde HST: 4-hydroxystyrene ITO: indium tin oxide KBM-503: 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
MAA: methacrylic acid MAP: m-aminophenol MBA: 3-methoxy-n-butyl acetate MCS: m-cresol MEK: methyl ethyl ketone MEK-ST-40: silica particle dispersion using methyl ethyl ketone as a dispersion solvent (Nissan Chemical Co., Ltd. )
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. B. 60: C.I. I. Pigment Blue 60 (indanthron blue pigment)
P. R. 179:C. I. Pigment Red 179 (perylene red pigment)
P. Y. 192:C. I. Pigment Yellow 192 (imidazolone yellow pigment)
PGMEA: propylene glycol monomethyl ether acetate PHA: phthalic anhydride PhTMS: phenyltrimethoxysilane SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane STR: styrene TCDM: tricyclo methacrylate [5.2.1 .0 2,6 ]decane-8-yl; methylol-tricyclodecane methacrylate THPHA: 1,2,3,6-tetrahydrophthalic anhydride TMAC: trimellitic anhydride chloride TMAH: tetramethylammonium hydroxide TMM-TAZ : 2,4,6-tris[N,N-bis(methoxymethyl)amino]-1,3,5-triazine TMOS: tetramethoxysilane TMS-ICA: 1,3,5-tris(3-trimethoxysilyl Propyl)isocyanuric acid TMS-TAZ: 2,4,6-tris[(3-trimethoxysilylpropyl)amino]-1,3,5-triazine ZCR-1569H: an acid having a structural unit containing a biphenyl skeleton and a benzene skeleton Modified epoxy resin (manufactured by Nippon Kayaku Co., Ltd.; acid equivalent: 570 g/mol, double bond equivalent: 500 g/mol).
　＜各樹脂の合成（合成例１～２８）＞
　（Ａ）アルカリ可溶性樹脂として、表１－１～表１－２に示すモノマーの種類および共重合比率で合成例１～２８の樹脂を合成した。各樹脂は以下のとおり、適宜モノマーとなる単量体化合物や共重合比率を変更して、公知の方法により合成するか市販の樹脂を用いた。合成例１～２８で得られた各樹脂のモノマー組成および各特性を、まとめて表１－１～表１－２に示す。 <Synthesis of each resin (synthesis examples 1 to 28)>
(A) As alkali-soluble resins, resins of Synthesis Examples 1 to 28 were synthesized using the monomer types and copolymerization ratios shown in Tables 1-1 and 1-2. Each resin was synthesized by a known method or a commercially available resin by appropriately changing the monomer compound and copolymerization ratio as shown below. The monomer composition and properties of each resin obtained in Synthesis Examples 1-28 are summarized in Tables 1-1 and 1-2.
　合成例１、２および４～１１（ＰＩ－１，ＰＩ－２，ＰＩ－４，ＰＩ－５，ＰＩ－６，ＰＩ－７，ＰＩ－８，ＰＩ－９，ＰＩ－１０およびＰＩ－１１）は、国際公開第２０１７／０５７２８１号の段落［０５４４］の合成例１に記載の方法によりそれぞれ合成した。
合成例１３および１４の（ＰＩＰ－１）および（ＰＩＰ－２）は、国際公開第２０１７／０５７２８１号の段落［０５４８］の合成例１５に記載の方法によりそれぞれ合成した。
合成例１５の（ＰＢ－１）は、国際公開第２０１７／０５７２８１号の段落［０５４６］の合成例１２に記載の方法によりそれぞれ合成した。
合成例２０～２２の（ＰＳ－１）、（ＰＳ－２）および（ＰＳ－３）は、国際公開第２０１７／０５７２８１号の段落［０５５３］の合成例３０に記載の方法によりそれぞれ合成した。
合成例２３の（ＣＲ－１）は、国際公開第２０１７／０５７２８１号の段落［０５６３］の合成例４５に記載の方法によりそれぞれ合成した。
合成例３および１２の（ＰＩ－３）および（ＰＩ－１２）は、国際公開第２０１７／１５９８７６号の段落［０７２６］の合成例６に記載の方法によりそれぞれ合成した。
合成例２４の（ＡＥ－２）は、国際公開第２０１７／１５９８７６号の段落［０７４４］の合成例２５に記載の方法によりそれぞれ合成した。
合成例２５の（ＡＣ－１）は、国際公開第２０１７／１５９８７６号の段落［０７３９］の合成例２０に記載の方法によりそれぞれ合成した。
合成例２６および２７の（ＰＲ－１）および（ＰＲ－２）は、国際公開第２０１７／１５９８７６号の段落［０７４０］の合成例２１に記載の方法によりそれぞれ合成した。
合成例２８の（ＰＨＳ－１）は、国際公開第２０１７／１５９８７６号の段落［０７４２］の合成例２３に記載の方法によりそれぞれ合成した。
合成例１６の（ＰＢＰ－１）は、国際公開第２０１７／０５７１４３号の段落［０１６１］の合成例９に記載の方法によりそれぞれ合成した。
合成例１７および１８の（ＰＡＩ－１）および（ＰＡＩ－２）は、国際公開第２０１８／１５９３８４号の段落［０１６０］の合成例９に記載の方法によりそれぞれ合成した。
合成例１９の（ＰＡＩ－３）は、国際公開第２０１０／１０７０４５号の段落［００５５］の合成例１に記載の方法によりそれぞれ合成した。 Synthesis Examples 1, 2 and 4 to 11 (PI-1, PI-2, PI-4, PI-5, PI-6, PI-7, PI-8, PI-9, PI-10 and PI-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.
(PS-1), (PS-2) and (PS-3) of Synthesis Examples 20 to 22 were synthesized by the method described in Synthesis Example 30 of paragraph [0553] of WO 2017/057281.
(CR-1) of Synthesis Example 23 was synthesized by the method described in Synthesis Example 45 of paragraph [0563] of WO 2017/057281.
(PI-3) and (PI-12) of Synthesis Examples 3 and 12 were synthesized by the method described in Synthesis Example 6 of paragraph [0726] of WO 2017/159876, respectively.
(AE-2) of Synthesis Example 24 was synthesized by the method described in Synthesis Example 25 of paragraph [0744] of WO 2017/159876.
(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.
(PAI-1) and (PAI-2) of Synthesis Examples 17 and 18 were synthesized by the method described in Synthesis Example 9 of paragraph [0160] of WO 2018/159384, respectively.
(PAI-3) of Synthesis Example 19 was synthesized by the method described in Synthesis Example 1 of paragraph [0055] of WO 2010/107045.
　なお、合成例３、１２および１８は、国際公開第２０１７／１５９８７６号に記載の方法に基づき、エチレン性不飽和二重結合基を導入した。
合成例２５は、国際公開第２０１７／１５９８７６号の段落［０７３９］の合成例２０に記載の方法に基づき、エチレン性不飽和二重結合基を導入した。
合成例２４において、エポキシ基を有するＮＣ－３５００に対して、不飽和カルボン酸を反応させており、ＮＣ－３５００由来のエポキシ基に対して全て開環付加させた。
合成例２５において（ＡＣ－１）の合成に際し、エポキシ基を有するＧＭＡを反応させており、ＧＭＡのエポキシ基を全て開環付加させた。 In Synthesis Examples 3, 12 and 18, an ethylenically unsaturated double bond group was introduced based on the method described in WO 2017/159876.
In 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.
In Synthesis Example 24, 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.
When 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.
　ポリアミドイミド（ＰＡＩ－４）および（ＰＡＩ－５）は、市販のＥＭＧ－１０１５およびＥＱＧ－１１７０をそれぞれ使用した。
酸変性エポキシ樹脂（ＡＥ－１）としては、市販のＺＣＲ－１５６９Ｈを使用した。 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).
　合成例１１で使用したトリアジン構造を有するジアミン（ＰＢＡ－ＴＡＺ）、および、合成例１９で使用したイソシアヌル酸構造を有するトリイソシアネート化合物（ＩＰＴＣ－ＩＣＡ）としては、市販の原料を使用した。これらジアミンおよびトリイソシアネート化合物の構造を以下に示す。 As the diamine (PBA-TAZ) having a triazine structure used in Synthesis Example 11 and the triisocyanate compound (IPTC-ICA) having an isocyanuric acid structure used in Synthesis Example 19, commercially available raw materials were used. The structures of these diamine and triisocyanate compounds are shown below.
　合成例２１で使用したイソシアヌル酸構造を有するオルガノシランである１，３，５－トリス（３－トリメトキシシリルプロピル）イソシアヌル酸（ＴＭＳ－ＩＣＡ）および合成例２２で使用したトリアジン構造を有するオルガノシランである２，４，６－トリス［（３－トリメトキシシリルプロピル）アミノ］－１，３，５－トリアジン（ＴＭＳ－ＴＡＺ）としては、市販の原料を使用した。 1,3,5-tris(3-trimethoxysilylpropyl)isocyanuric acid (TMS-ICA) which is an organosilane having an isocyanuric acid structure used in Synthesis Example 21 and an organosilane having a triazine structure used in Synthesis Example 22 As 2,4,6-tris[(3-trimethoxysilylpropyl)amino]-1,3,5-triazine (TMS-TAZ), a commercially available raw material was used.
　合成例２７で使用したトリアジン構造を有するビスアルコキシメチル化合物である２，４，６－トリス［Ｎ，Ｎ－ビス（メトキシメチル）アミノ］－１，３，５－トリアジン（ＴＭＭ－ＴＡＺ）としては、市販の原料を使用した。 As the bisalkoxymethyl compound having a triazine structure used in Synthesis Example 27, 2,4,6-tris[N,N-bis(methoxymethyl)amino]-1,3,5-triazine (TMM-TAZ) , using commercially available raw materials.
　合成例１３および１４で使用した以下に示す構造のヒドロキシ基含有ジアミン（ＨＡ）は、国際公開第２０１６／０５６４５１号の段落［０３７４］～段落［０３７６］における、合成例１に記載の合成方法に基づき、公知の方法により合成した。 The hydroxy group-containing diamine (HA) 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.
　合成例４、６、７、１２、および１４で使用したイソシアヌル酸構造を有するジアミンまたはトリアミン（ＢＡ－ＩＣＡ）、（ＴＡ－ＩＣＡ）、および（ＢＡＨ－ＩＣＡ）は、国際公開第２０２０／１９６７６４号の段落［０１３１］～段落［０１３３］に記載の合成方法に基づき、公知の方法により合成した。合成例５および８で使用したイソシアヌル酸構造を有するジアミン（ＢＡＥ－ＩＣＡ）、および（ＢＡＨＥ－ＩＣＡ）は、国際公開第２０２０／１９６７６４号の段落［０１３６］～段落［０１３８］に記載の合成方法に基づき、公知の方法により合成した。これらジアミンおよびトリアミンの構造を以下に示す。 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.
　合成例１０で使用したトリアジン構造を有するジアミン（ＢＡ－ＴＡＺ）は、公知の方法により合成した。このジアミンの構造を以下に示す。 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.
　合成例９で使用したイソシアヌル酸構造を有するトリアミン（ＩＰＴＡ－ＩＣＡ）は、市販の原料のトリイソシアネート化合物（ＩＰＴＣ－ＩＣＡ）から公知の方法により合成した。これらトリアミンおよびトリイソシアネート化合物の構造を以下に示す。 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.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
　＜各顔料分散液の調製（調製例１～７）＞
　顔料分散液として、表２－１に示す組成で、国際公開第２０１９／０８７９８５号の段落［０５０６］に記載の方法に基づき、調製例１～７の顔料分散液を調製した。調製例１～７で得られた各分散液の組成および各特性を、まとめて表２－１に示す。 <Preparation of each pigment dispersion (Preparation Examples 1 to 7)>
As pigment dispersions, pigment dispersions of Preparation Examples 1 to 7 were prepared according to the method described in paragraph [0506] of WO 2019/087985 with the composition shown in Table 2-1. The composition and properties of each dispersion obtained in Preparation Examples 1 to 7 are summarized in Table 2-1.
　なお、調製例６で使用した表面被覆ベンゾフラノン系黒色顔料（Ｂｋ－ＣＢＦ１）は、国際公開第２０１９／０８７９８５号の段落［０５０３］～段落［０５０５］における、被覆例１に記載の合成方法に基づき、公知の方法により合成した。調製例７で使用した表面被覆ペリレン系黒色顔料（Ｂｋ－ＣＰＲ１）は、国際公開第２０１８／０３８０８３号の段落［０１８６］～段落［０１８８］および段落［０１９１］における、実施例１８に記載の合成方法に基づき、公知の方法により合成した。また、調製例１～７で使用したポリアルキレンアミン系－ポリオキシアルキレンエーテル系分散剤（ＡＤＰ）は、一般式（２６）で表される構造、一般式（２９）で表される構造、およびポリオキシアルキレン構造を有する（Ｅ１）塩基性基を有する顔料分散剤である。調製例１～７で使用したＡＤＰは、特開２０２０－０７０３５２号公報の段落［０１３８］～段落［０１４１］における、合成例２に記載の方法に基づき、公知の方法により合成した。 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. Further, the 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.
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　合成例２９　シリカ粒子（ＳＰ－１）分散液の合成
　三口フラスコに、溶剤としてＭＥＫを１０４．５ｇ、ナトリウム元素を含有するシリカ粒子分散液としてＭＥＫ－ＳＴ－４０を１４２．５ｇ、重合禁止剤としてＭＯＰを０．０１ｇ秤量して添加して混合し、１０分間攪拌した後、液温を５０℃に昇温した。次いで、表面修飾剤として、３．０ｇのＫＢＭ－５０３を５０．０ｇのＭＥＫに溶解させた溶液を１０分間かけて滴下した。滴下終了後、５０℃で２時間攪拌して表面修飾剤を脱水縮合させた。反応後、反応溶液を室温に冷却し、シリカ粒子（ＳＰ－１）分散液を得た。得られたシリカ粒子（ＳＰ－１）は、ラジカル重合性基としてメタクリロイル基を含む表面修飾基を有する。 Synthesis Example 29 Synthesis of Silica Particle (SP-1) Dispersion In a three-necked flask, 104.5 g of MEK as a solvent, 142.5 g of MEK-ST-40 as a silica particle dispersion containing sodium element, and 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. Then, as a surface modifier, 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. 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.
　シリカ粒子として、合成例１５で得られたシリカ粒子分散液および市販のシリカ粒子分散液の組成および各特性を、まとめて表２－２に示す。なおシリカ粒子（ＳＰ－２）分散液は、市販のシリカ粒子分散液であるＭＥＫ－ＳＴ－４０を使用した。シリカ粒子（ＳＰ－３）分散液は、市販のシリカ粒子分散液であるＭＥＫ－ＳＴ－Ｌを使用した。 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. As the silica particle (SP-2) dispersion, MEK-ST-40, which is a commercially available silica particle dispersion, was used. As the silica particle (SP-3) dispersion, MEK-ST-L, which is a commercially available silica particle dispersion, was used.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　＜各実施例、参考例および比較例における評価方法＞
　各実施例、参考例および比較例における評価方法を以下に示す。 <Evaluation method in each example, reference example and comparative example>
Evaluation methods in each example, reference example and comparative example are shown below.
　（１）樹脂の重量平均分子量
　ＧＰＣ分析装置（ＨＬＣ－８２２０；東ソー（株）製）を用い、流動層としてテトラヒドロフランまたはＮ－メチル－２－ピロリドンを用いて、ＪＩＳ　Ｋ　７２５２－３（２００８）に基づき、常温付近で測定してポリスチレン換算の重量平均分子量を求めた。 (1) Weight average molecular weight of resin Using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation), using tetrahydrofuran or N-methyl-2-pyrrolidone as a fluidized bed, according to JIS K 7252-3 (2008). Based on this, the polystyrene-equivalent weight-average molecular weight was obtained by measuring at around room temperature.
　（２）酸当量、メチロール当量
　電位差自動滴定装置（ＡＴ－５１０；京都電子工業（株）製）を用い、滴定試薬として０．１ｍｏｌ／Ｌの水酸化ナトリウム／エタノール溶液、滴定溶剤としてキシレン／Ｎ，Ｎ－ジメチルホルムアミド＝１／１（質量比）を用いて、ＪＩＳ　Ｋ　２５０１（２００３）に基づき、電位差滴定法により、酸価（単位はｍｇＫＯＨ／ｇ）を求めた。測定した酸価の値から、酸当量（単位はｇ／ｍｏｌ）を算出した。なお、メチロール当量は、メチロール基をアセチル化した試料を調製し、同様に電位差滴定法によって測定したメチロール価から、メチロール当量（単位はｇ／ｍｏｌ）を算出した。 (2) Acid equivalent, methylol equivalent Using a potentiometric automatic titrator (AT-510; manufactured by Kyoto Electronics Industry Co., Ltd.), 0.1 mol / L sodium hydroxide / ethanol solution as a titration reagent, xylene / N as a titration solvent , N-dimethylformamide = 1/1 (mass ratio), the acid value (unit: mgKOH/g) was determined by potentiometric titration according to JIS K 2501 (2003). The acid equivalent (unit: g/mol) was calculated from the measured acid value. The methylol equivalent (unit: g/mol) was calculated from the methylol value similarly measured by potentiometric titration after preparing a sample in which the methylol group was acetylated.
　（３）二重結合当量
　電位差自動滴定装置（ＡＴ－５１０；京都電子工業（株）製）を用い、ヨウ素供給源として一塩化ヨウ素溶液（三塩化ヨウ素＝７．９ｇ、ヨウ素＝８．９ｇ、酢酸＝１，０００ｍＬの混合溶液）、未反応ヨウ素の捕捉水溶液として１００ｇ／Ｌのヨウ化カリウム水溶液、滴定試薬として０．１ｍｏｌ／Ｌのチオ硫酸ナトリウム水溶液を用いて、ＪＩＳ　Ｋ　００７０：１９９２「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価および不けん化物の試験方法」の「第６項よう素価」に記載の方法に基づき、ウィイス法により、樹脂のヨウ素価を測定した。測定したヨウ素価（単位はｇＩ／１００ｇ）の値から、二重結合当量（単位はｇ／ｍｏｌ）を算出した。 (3) Double bond equivalent Using a potentiometric automatic titrator (AT-510; manufactured by Kyoto Electronics Industry Co., Ltd.), an iodine monochloride solution (iodine trichloride = 7.9 g, iodine = 8.9 g, Acetic acid = 1,000 mL mixed solution), 100 g / L potassium iodide aqueous solution as an aqueous solution for capturing unreacted iodine, and 0.1 mol / L sodium thiosulfate aqueous solution as a titrant. Test method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of product”, the iodine value of the resin is measured by the Wiiss method based on the method described in “Item 6 Iodine value”. It was measured. The double bond equivalent (unit: g/mol) was calculated from the measured iodine value (unit: gI/100 g).
　（４）顔料の数平均粒子径
　ゼータ電位・粒子径・分子量測定装置（ゼータサイザーナノＺＳ；シスメックス（株）製）を用い、希釈溶媒としてＰＧＭＥＡを用いて、顔料分散液を１．０×１０－５～４０体積％の濃度に希釈し、希釈溶媒の屈折率をＰＧＭＥＡの屈折率に、測定対象の屈折率を１．６に設定して、波長６３３ｎｍのレーザー光を照射して顔料分散液中の顔料の数平均粒子径を測定した。 (4) Number average particle size of pigment Using a zeta potential/particle size/molecular weight measuring device (Zetasizer Nano ZS; manufactured by Sysmex Corporation), using PGMEA as a dilution solvent, a pigment dispersion liquid of 1.0 × 10 -5 Dilute to a concentration of 40% by volume, set the refractive index of the diluted solvent to the refractive index of PGMEA, set the refractive index of the measurement target to 1.6, and irradiate the pigment dispersion with a laser beam of wavelength 633 nm. The number average particle size of the pigment inside was measured.
　（５）基板の前処理
　ガラス板上に、ＡＰＣ（銀／パラジウム／銅＝９８．０７／０．８７／１．０６（質量比））をスパッタにより１００ｎｍ成膜し、さらに、ＡＰＣ層の上層に、ＩＴＯをスパッタにより１０ｎｍ成膜したガラス基板（ジオマテック（株）製；以下、「ＩＴＯ／Ａｇ基板」）は、卓上型光表面処理装置（ＰＬ１６－１１０；セン特殊光源（株）製）を用いて、１００秒間ＵＶ－Ｏ３洗浄処理をして使用した。テンパックスガラス基板（ＡＧＣテクノグラス社製）は、前処理をせずに使用した。 (5) Substrate pretreatment On a glass plate, APC (silver/palladium/copper = 98.07/0.87/1.06 (mass ratio)) was deposited to a thickness of 100 nm by sputtering, and then an upper layer of the APC layer. Then, 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.
　（６）膜厚測定
　表面粗さ・輪郭形状測定機（ＳＵＲＦＣＯＭ１４００Ｄ；（株）東京精密製）を用いて、測定倍率を１０，０００倍、測定長さを１．０ｍｍ、測定速度を０．３０ｍｍ／ｓとして、膜厚を測定した。 (6) Film thickness measurement Using a surface roughness/contour shape measuring machine (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the measurement magnification is 10,000 times, the measurement length is 1.0 mm, and the measurement speed is 0.30 mm. /s, the film thickness was measured.
　（７）現像残渣
　下記、実施例１記載の方法で、感光性樹脂組成物の現像後膜を作製した。ＦＰＤ／ＬＳＩ検査顕微鏡（ＯＰＴＩＰＨＯＴ－３００；（株）ニコン製）を用いて、作製した現像後膜の解像パターンを観察した。現像残渣の指標として、２０μｍのライン・アンド・スペースパターンにおいて、開口部に相当するパターンの残渣の有無を観察した。下記のように判定し、残渣の存在面積が２０％以下となる、Ａ＋、Ａ、Ｂ＋、Ｂ、Ｃ＋およびＣを合格とした。残渣の存在面積が小さいほど良好であり、残渣の存在面積が３％以下となる、Ａ＋およびＡは特に優秀である。
Ａ＋：残渣無し
Ａ：残渣の存在面積が３％以下
Ｂ＋：残渣の存在面積が３％を超え、かつ６％以下
Ｂ：残渣の存在面積が６％を超え、かつ１０％以下
Ｃ＋：残渣の存在面積が１０％を超え、かつ１５％以下
Ｃ：残渣の存在面積が１５％を超え、かつ２０％以下
Ｄ：残渣の存在面積が２０％を超え、かつ５０％以下
Ｅ：残渣の存在面積が５０％を超え、かつ１００％以下。 (7) Development residue 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 μm. 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.
A + : No residue A : Residue existing area is 3% or less B + : Residue existing area is more than 3% and 6% or less B : Residue existing area is more than 6% and 10% or less C + : Residue existing area exceeds 10% and 15% or less C: Residue existing area exceeds 15% and 20% or less D: Residue existing area exceeds 20% and 50% or less E: Residue is more than 50% and 100% or less.
　（８）パターン寸法バラツキ
　下記、実施例１記載の方法で、ＩＴＯ／Ａｇ基板上に感光性樹脂組成物のプリベーク膜を４．４μｍの膜厚で成膜した。両面アライメント片面露光装置（マスクアライナー　ＰＥＭ－６Ｍ；ユニオン光学（株）製）を用いて、ハーフトーン特性評価用のハーフトーンフォトマスクを介して、露光量を変えて超高圧水銀灯のｉ線（波長３６５ｎｍ）、ｈ線（波長４０５ｎｍ）、およびｇ線（波長４３６ｎｍ）でプリベーク膜をパターニング露光した後、フォトリソ用小型現像装置（ＡＤ－１２００；滝沢産業（株）製）を用いて現像して組成物の現像後膜を作製した。パターン寸法バラツキ評価に用いたハーフトーンフォトマスクの、透光部、遮光部、および半透光部の配置、ならびに、寸法の概略図を、図３に示す。ハーフトーンフォトマスクは、透光部Ｔ、遮光部Ｓ、および半透光部Ｈを有する。透光部Ｔはライン形状であり、遮光部Ｓは四角形形状である。透光部Ｔが半透光部Ｈに隣接しており、かつ遮光部Ｔが半透光部Ｈに隣接しており、遮光部Ｓが隣接する半透光部Ｈに囲まれている。幅３０μｍおよび長さ６０μｍの遮光部Ｓが、幅方向にピッチ９０μｍおよび長さ方向にピッチ１５０μｍで配置されている。半透光部Ｈと透光部Ｔは、幅３０μｍの遮光部Ｓと遮光部Ｓとの間の６０μｍ（ピッチ９０μｍ－幅３０μｍ＝６０μｍ）の間隙に、幅２０μｍの透光部Ｔが配置されているとともに、遮光部Ｓに隣接する幅２０μｍの半透光部Ｈが透光部の両側に配置されている。また、長さ６０μｍの遮光部Ｓと遮光部Ｓとの間の９０μｍ（ピッチ１５０μｍ－長さ６０μｍ＝９０μｍ）の間隙に、幅３０μｍの透光部Ｔが配置されているとともに、遮光部Ｓに隣接する幅３０μｍの半透光部Ｈが透光部の両側に配置されている。 (8) Variation in Pattern Dimension A pre-baked film of a photosensitive resin composition was formed on an ITO/Ag substrate to a thickness of 4.4 μm by the method described in Example 1 below. Using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.), the exposure amount is changed through a halftone photomask for evaluating halftone characteristics, and the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm), and then developed using a compact developing device for photolithography (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) to compose. A film was prepared after development of the product. 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, and 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 μm and a length of 60 μm are arranged at a pitch of 90 μm in the width direction and a pitch of 150 μm in the length direction. As for the semi-transparent portion H and the transparent portion T, the transparent portion T having a width of 20 μm is arranged in a gap of 60 μm (pitch 90 μm−width 30 μm=60 μm) between the light shielding portions S each having a width of 30 μm. In addition, a semi-transparent portion H having a width of 20 μm adjacent to the light-shielding portion S is arranged on both sides of the light-transmitting portion. In addition, a light transmitting portion T having a width of 30 μm is arranged in a gap of 90 μm (pitch 150 μm−length 60 μm=90 μm) between the light shielding portions S each having a length of 60 μm. Adjacent semi-transparent portions H having a width of 30 μm are arranged on both sides of the transparent portion.
　ＦＰＤ／ＬＳＩ検査顕微鏡（ＯＰＴＩＰＨＯＴ－３００；（株）ニコン製）を用いて、作製した段差形状を有する現像後膜の解像パターンを観察した。ハーフトーン露光部である半透光部から形成された薄膜部は、ハーフトーンフォトマスクの透過率（％ＴＨＴ）％が、透光部の透過率（％ＴＦＴ）の２０％、２５％または３０％となる箇所に対応する現像後膜の部分を観察した。段差形状を有する現像後膜の解像パターンにおいて、ハーフトーンフォトマスクにおける幅３０μｍの遮光部に対応する現像後膜の開口パターンの開口寸法（ＣＤＤＥＶ）μｍを測長した。なお、ハーフトーン露光部である半透光部の露光量は、半透光部から形成された薄膜部の現像後の膜厚が、２．０μｍとなる露光量とした。同様の方法で、同一基板の面内で４点の開口パターンの開口寸法（ＣＤＤＥＶ）μｍを測長した。パターン寸法バラツキの指標として、４点の開口パターンの開口寸法（ＣＤＤＥＶ）μｍの標準偏差σを算出した。下記のように判定し、標準偏差σが０．７５以下となる、Ａ＋、Ａ、Ｂ＋、Ｂ、Ｃ＋およびＣを合格とした。標準偏差σが小さいほど良好であり、標準偏差σが０．３０以下となる、Ａ＋およびＡは特に優秀である。
Ａ＋：標準偏差σが０．２５以下
Ａ：標準偏差σが０．２５を超え、かつ０．３０以下
Ｂ＋：標準偏差σが０．３０を超え、かつ０．４０以下
Ｂ：標準偏差σが０．４０を超え、かつ０．５０以下
Ｃ＋：標準偏差σが０．５０を超え、かつ０．６３以下
Ｃ：標準偏差σが０．６３を超え、かつ０．７５以下
Ｄ：標準偏差σが０．７５を超え、かつ１．００以下
Ｅ：標準偏差σが１．００を超過。 Using an FPD/LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolution pattern of the developed film having a step shape was observed. In the thin film portion formed from the semi-transparent portion which is the halftone exposure portion, the transmittance (%T HT )% of the halftone photomask is 20% or 25% of the transmittance (%T FT ) of the light-transmitting portion. Alternatively, the portion of the film after development corresponding to the 30% was observed. In the resolution pattern of the film after development having a stepped shape, the opening dimension (CD DEV ) μm of the opening pattern of the film after development corresponding to the light shielding portion with a width of 30 μm 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 μm. By the same method, the opening dimension (CD DEV ) μm of the opening pattern at four points within the plane of the same substrate was measured. As an index of pattern dimension variation, the standard deviation σ of the aperture dimension (CD DEV ) μm of the aperture pattern at four points was calculated. A + , A, B + , B, C + and C with a standard deviation σ of 0.75 or less were evaluated as follows. A smaller standard deviation σ is better, and A + and A with a standard deviation σ of 0.30 or less are particularly excellent.
A + : standard deviation σ is 0.25 or less A: standard deviation σ is greater than 0.25 and 0.30 or less B + : standard deviation σ is greater than 0.30 and 0.40 or less B: standard deviation σ greater than 0.40 and 0.50 or less C + : standard deviation σ greater than 0.50 and 0.63 or less C: standard deviation σ greater than 0.63 and 0.75 or less D: Standard deviation σ exceeds 0.75 and is 1.00 or less E: Standard deviation σ exceeds 1.00.
　（９）ハーフトーン特性
　下記、実施例１記載の方法で、ＩＴＯ／Ａｇ基板上に感光性樹脂組成物のプリベーク膜を５μｍの膜厚で成膜し、両面アライメント片面露光装置（マスクアライナー　ＰＥＭ－６Ｍ；ユニオン光学（株）製）を用いて、ハーフトーン特性評価用のハーフトーンフォトマスクを介して、露光量を変えて超高圧水銀灯のｉ線（波長３６５ｎｍ）、ｈ線（波長４０５ｎｍ）およびｇ線（波長４３６ｎｍ）でパターニング露光し、フォトリソ用小型現像装置（ＡＤ－１２００；滝沢産業（株）製）を用いて現像して組成物の現像後膜を作製した。ハーフトーンフォトマスクとしては、透光部、遮光部および透光部と遮光部の間に半透光部を有し、半透光部の透過率（％ＴＨＴ）％がそれぞれ、透光部の透過率（％ＴＦＴ）の２０％、２５％、３０％、３５％、４０％または５０％である箇所を有するフォトマスクを用いた。透光部と半透光部は隣接しており、半透光部と遮光部は隣接している。ハーフトーンフォトマスクの一例として、透光部、遮光部および半透光部の配置、ならびに、寸法の一例を、図２に示す。幅１０μｍの遮光部Ｓが、幅方向にピッチ４５μｍで配置されている。半透光部Ｈと透光部Ｔは、幅１０μｍの遮光部Ｓと遮光部Ｓとの間の３５μｍ（ピッチ４５μｍ－幅１０μｍ＝３５μｍ）の間隙に、幅１５μｍの透光部Ｔが配置されているとともに、遮光部Ｓに隣接する幅１０μｍの半透光部Ｈが透光部の両側に配置されている。 (9) Halftone characteristics A pre-baked film of a photosensitive resin composition is formed on an ITO/Ag substrate with a thickness of 5 μm by the method described in Example 1 below, and a double-sided alignment single-sided exposure apparatus (mask aligner PEM- 6M; manufactured by Union Optical Co., Ltd.), through a halftone photomask for halftone characteristic evaluation, changing the exposure amount to i-line (wavelength 365 nm), h-line (wavelength 405 nm) and h line of ultra-high pressure mercury lamp Patterning exposure was performed with g-line (wavelength 436 nm), and development was performed using a compact developing device for photolithography (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) to prepare a film after development of the composition. 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. As an example of a halftone photomask, 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 μm are arranged at a pitch of 45 μm in the width direction. As for the semi-transparent portion H and the transparent portion T, the transparent portion T having a width of 15 μm is arranged in a gap of 35 μm (pitch 45 μm−width 10 μm=35 μm) between the light shielding portions S each having a width of 10 μm. In addition, a semi-transparent portion H having a width of 10 μm adjacent to the light-shielding portion S is arranged on both sides of the light-transmitting portion.
　作製した段差形状を有する現像後膜の解像パターンについて、透光部から形成された厚膜部の現像後の膜厚（ＴＦＴ）μｍを測定した。ハーフトーン露光部である半透光部から形成された薄膜部は、ハーフトーンフォトマスクの透過率の異なる箇所の現像後の膜厚（ＴＨＴ）μｍを測定し、現像後に残膜した薄膜部の最小膜厚（ＴＨＴ／ｍｉｎ）μｍを求めた。ハーフトーン特性の指標として、最大段差膜厚（（ＴＦＴ）－（ＴＨＴ／ｍｉｎ））μｍを算出した。下記のように判定し、最大段差膜厚が０．４μｍ以上となる、Ａ＋、Ａ、Ｂ＋、Ｂ、Ｃ＋およびＣを合格とした。最大段差膜厚が大きいほど良好であり、最大段差膜厚が２．０μｍ以上となる、Ａ＋およびＡが特に優秀である。
Ａ＋：最大段差膜厚が２．５μｍ以上
Ａ：最大段差膜厚が２．０μｍ以上、かつ２．５μｍ未満
Ｂ＋：最大段差膜厚が１．５μｍ以上、かつ２．０μｍ未満
Ｂ：最大段差膜厚が１．０μｍ以上、かつ１．５μｍ未満
Ｃ＋：最大段差膜厚が０．７μｍ以上、かつ１．０μｍ未満
Ｃ：最大段差膜厚が０．４μｍ以上、かつ０．７μｍ未満
Ｄ：最大段差膜厚が０．１μｍ以上、かつ０．４μｍ未満
Ｅ：最大段差膜厚が０．１μｍ未満、または現像後に残膜せず測定不能。 With respect to the resolution pattern of the formed film after development having a stepped shape, the film thickness (T FT ) μm after development of the thick film portion formed from the light-transmitting portion was measured. For the thin film portion formed from the semi-transparent portion, which is the halftone exposed portion, the film thickness (T HT ) μm 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 ) μm was obtained. As an index of halftone characteristics, the maximum step thickness ((T FT )−(T HT/min )) μm was calculated. A + , A, B + , B, C + and C having a maximum step thickness of 0.4 μm 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 μm or more, are particularly excellent.
A + : Maximum step thickness is 2.5 μm or more A: Maximum step thickness is 2.0 μm or more and less than 2.5 μm B + : Maximum step thickness is 1.5 μm or more and less than 2.0 μm B: Maximum Step thickness is 1.0 μm or more and less than 1.5 μm C + : Maximum step thickness is 0.7 μm or more and less than 1.0 μm C: Maximum step thickness is 0.4 μm or more and less than 0.7 μm D : The maximum step thickness is 0.1 μm or more and less than 0.4 μm E: The maximum step thickness is less than 0.1 μm, or no film remains after development and cannot be measured.
　（１０）遮光性（光学濃度値（以下、「ＯＤ値」））
　下記、実施例１記載の方法で、テンパックスガラス基板上に感光性樹脂組成物の硬化物を作製した。透過濃度計（Ｘ－Ｒｉｔｅ　３６１Ｔ（Ｖ）；Ｘ－Ｒｉｔｅ社製）を用いて、作製した硬化物の面内３箇所における入射光強度（Ｉ０）および透過光強度（Ｉ）をそれぞれ測定した。遮光性の指標として、膜厚１μｍ当たりのＯＤ値を下記式により算出し、面内３箇所におけるＯＤ値の平均値を算出した。
ＯＤ値＝ｌｏｇ１０（Ｉ０／Ｉ）。 (10) Light shielding property (optical density value (hereinafter referred to as “OD value”))
A cured product of the photosensitive resin composition was prepared on a Tempax glass substrate by the method described in Example 1 below. Using a transmission densitometer (X-Rite 361T (V); manufactured by X-Rite), the incident light intensity (I 0 ) and transmitted light intensity (I) were measured at three points in the plane of the prepared cured product. . As an index of the light-shielding property, the OD value per 1 μm film thickness was calculated by the following formula, and the average value of the OD values at three points in the plane was calculated.
OD value = log10 ( I0 /I).
　（１１）発光素子の発光特性（電流密度－電圧特性、および信頼性）
　＜有機ＥＬディスプレイの作製方法＞
　図４に、使用した基板の概略図を示す。まず、３８×４６ｍｍの無アルカリガラス基板４７に、非透明導電性金属層としてＡＰＣ（銀／パラジウム／銅＝９８．０７／０．８７／１．０６（質量比））をスパッタにより１００ｎｍ成膜し、エッチングによりパターン加工してＡＰＣ層を形成した。さらに、ＡＰＣ層の上層に透明導電性酸化膜層としてアモルファス性のＩＴＯをスパッタにより１０ｎｍ成膜し、エッチングによりパターン加工し、第１電極４８としてＡＰＣ層とＩＴＯ層の積層からなる反射電極を形成した。このとき、第２電極を取り出すため補助電極４９も同時に形成した（図４（工程１））。得られた基板を“セミコクリーン”（登録商標）５６（フルウチ化学（株）製）を用いて１０分間超音波洗浄した後、超純水で洗浄した。次に、この基板上に、感光性樹脂組成物を実施例１に記載された方法で塗布およびプリベークし、プリベーク膜を作製した。プリベーク膜を、所定のパターンを有するフォトマスクを介してパターンニング露光し、現像およびリンスした後、加熱して熱硬化させた。以上の方法で、幅７０μｍおよび長さ２６０μｍの開口部が、幅方向にピッチ１５５μｍおよび長さ方向にピッチ４６５μｍで配置され、それぞれの開口部が第１電極を露出せしめる形状の画素分割層５０を、基板有効エリアに限定して形成した（図４（工程２））。なお、この開口部が、最終的に有機ＥＬディスプレイの発光画素となる。また、基板有効エリアは、１６ｍｍ四方であり、画素分割層５０の厚さは、約１．０μｍで形成した。 (11) Light-Emitting Characteristics of Light-Emitting Element (Current Density-Voltage Characteristics and Reliability)
<Method for producing organic EL display>
FIG. 4 shows a schematic diagram of the substrate used. First, APC (silver/palladium/copper = 98.07/0.87/1.06 (mass ratio)) was formed as a non-transparent conductive metal layer to a thickness of 100 nm on a non-alkali glass substrate 47 of 38 x 46 mm by sputtering. Then, pattern processing was performed by etching to form an APC layer. Further, 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. At this time, 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. Next, 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. By the above method, the pixel division layer 50 having a width of 70 μm and a length of 260 μm is arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm 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 μm.
　次に、第１電極４８、補助電極４９および画素分割層５０を形成した基板を用いて、有機ＥＬディスプレイの作製を行った。前処理として、窒素プラズマ処理を行った後、真空蒸着法により、画素分割層５０の開口部に発光層を含む有機ＥＬ層５１を形成した（図４（工程３））。なお、蒸着時の真空度は、１×１０－３Ｐａ以下であり、蒸着中は蒸着源に対して基板を回転させた。 Next, using the substrate on which the first electrode 48, the auxiliary electrode 49 and the pixel dividing layer 50 were formed, an organic EL display was manufactured. After performing nitrogen plasma treatment as a pretreatment, 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.
　なお、有機ＥＬ層５１としては、まず、正孔注入層として、化合物（ＨＴ－１）を１０ｎｍ蒸着し、さらに正孔輸送層として、化合物（ＨＴ－２）を５０ｎｍ蒸着した。次に、発光層として、ホスト材料である化合物（ＧＨ－１）とドーパント材料である化合物（ＧＤ－１）を、ドープ濃度が１０％になるように４０ｎｍの厚さに蒸着した。その後、電子輸送層として、化合物（ＥＴ－１）と化合物（ＬｉＱ）を、体積比１：１で４０ｎｍの厚さに積層した。なお、有機ＥＬ層で用いた化合物（ＨＴ－１）、（ＨＴ－２）、（ＧＨ－１）、（ＧＤ－１）、（ＥＴ－１）および（ＬｉＱ）の構造を以下の化学式以下に示す。 As the organic EL layer 51, first, 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. Next, as a light-emitting 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%. After that, as an electron transport layer, 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.
　次に、有機ＥＬ層５１の上に、化合物（ＬｉＱ）を２ｎｍ蒸着した後、ＭｇＡｇ（マグネシウム／銀＝１０／１（体積比））を１０ｎｍ蒸着して、第２電極５２として透明電極を形成した（図４（工程４））。その後、低湿窒素雰囲気下、エポキシ樹脂系接着剤を用いて、キャップ状ガラス板を接着することで封止をした。このようにして、１枚の基板上に５ｍｍ四方のトップエミッション型有機ＥＬディスプレイを４つ作製した。なお、上記でいう膜厚は、水晶発振式膜厚モニター表示値である。 Next, after vapor-depositing a compound (LiQ) to a thickness of 2 nm on the organic EL layer 51, MgAg (magnesium/silver=10/1 (volume ratio)) was vapor-deposited to a thickness of 10 nm to form a transparent electrode as the second electrode 52. (Fig. 4 (step 4)). After that, in a low-humidity nitrogen atmosphere, a cap-shaped glass plate was adhered using an epoxy resin-based adhesive for sealing. Thus, four 5 mm square top emission type organic EL displays were produced on one substrate. Incidentally, the film thickness referred to above is a value displayed by a crystal oscillation type film thickness monitor.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　＜電流密度－電圧特性評価＞
　上述した方法で作製した有機ＥＬディスプレイを、低電圧側から順次電圧値を変え、電流密度が３０ｍＡ／ｃｍ２となるまで直流駆動にて発光させた。低電圧側から順次電圧値を変えた場合における電圧値および電流密度をプロットし、電流密度－電圧特性の指標として、電流密度が１０ｍＡ／ｃｍ２となる駆動電圧を求めた。下記のように判定し、駆動電圧が４．５Ｖ以下となる、Ａ＋、Ａ、Ｂ＋、Ｂ、Ｃ＋およびＣを合格とした。駆動電圧が小さいほど良好であり、駆動電圧が３．５Ｖ以下となる、Ａ＋およびＡが特に優秀である。
Ａ＋：駆動電圧が３．２Ｖ以下
Ａ：駆動電圧が３．２Ｖを超え、かつ３．５Ｖ以下
Ｂ＋：駆動電圧が３．５Ｖを超え、かつ３．７Ｖ以下
Ｂ：駆動電圧が３．７Ｖを超え、かつ４．０Ｖ以下
Ｃ＋：駆動電圧が４．０Ｖを超え、かつ４．２Ｖ以下
Ｃ：駆動電圧が４．２Ｖを超え、かつ４．５Ｖ以下
Ｄ：駆動電圧が４．５Ｖを超え、かつ５．５Ｖ以下
Ｅ：駆動電圧が５．５Ｖを超過、または測定不能。 <Current density-voltage characteristic evaluation>
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.
A + : Drive voltage is 3.2 V or less A: Drive voltage is over 3.2 V and 3.5 V or less B + : Drive voltage is over 3.5 V and 3.7 V or less B: Drive voltage is 3.5 V or less Exceeding 7 V and 4.0 V or less C + : Drive voltage exceeding 4.0 V and 4.2 V or less C: Driving voltage exceeding 4.2 V and 4.5 V or less D: Driving voltage of 4.5 V and less than or equal to 5.5 V E: Drive voltage exceeds 5.5 V or cannot be measured.
　＜信頼性評価＞
　上述した方法で作製した有機ＥＬディスプレイを、１０ｍＡ／ｃｍ２で直流駆動にて発光させ、非発光領域や輝度ムラなどの発光不良がないかを観察した。また、耐久性試験として、有機ＥＬディスプレイを８０℃で５００時間保持した。耐久性試験後、有機ＥＬディスプレイを１０ｍＡ／ｃｍ２で直流駆動にて発光させて発光特性に変化がないかを観察し、耐久性試験前の発光領域面積を１００％とした場合における、耐久性試験後の発光領域面積を測定した。下記のように判定し、発光領域面積が８０％以上となる、Ａ＋、Ａ、Ｂ＋、Ｂ、Ｃ＋およびＣを合格とした。発光領域面積が大きいほど良好であり、発光領域面積が９７％以上となる、Ａ＋およびＡが優秀である。
Ａ＋：発光領域面積が１００％
Ａ：発光領域面積が９７％以上、かつ１００％未満
Ｂ＋：発光領域面積が９４％以上、かつ９７％未満
Ｂ：発光領域面積が９０％以上、かつ９４％未満
Ｃ＋：発光領域面積が８５％以上、かつ９０％未満
Ｃ：発光領域面積が８０％以上、かつ８５％未満
Ｄ：発光領域面積が６０％以上、かつ８０％未満
Ｅ：発光領域面積が６０％未満。 <Reliability evaluation>
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. The larger the light-emitting area, the better, and A + and A, where the light-emitting area is 97% or more, are excellent.
A + : Emission region area is 100%
A: Light-emitting region area is 97% or more and less than 100% B + : Light-emitting region area is 94% or more and less than 97% B: Light-emitting region area is 90% or more and less than 94% C + : Light-emitting region area is 85% or more and less than 90% C: Emissive area of 80% or more and less than 85% D: Emission area of 60% or more and less than 80% E: Emission area of less than 60%.
　＜各実施例、参考例および比較例で使用した化合物＞
　各実施例、参考例および比較例で使用した（Ｆ１）化合物、（ＦＢ１）化合物、（ＦＣ１）化合物および（ＦＴ）化合物の一覧と物性値を、まとめて表２－３～表２－４に示す。（ＦＢ１）化合物である（ｆｂ－１）の組成比についても、表２－４に示す。 <Compounds used in Examples, Reference Examples and Comparative Examples>
The list and physical properties of the (F1) compound, (FB1) compound, (FC1) compound and (FT) compound used in each example, reference example and comparative example are summarized in Tables 2-3 to 2-4. show. The composition ratio of (fb-1), which is the (FB1) compound, is also shown in Table 2-4.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　各合成例で得られた樹脂ならびに各実施例、参考例および比較例で使用した樹脂について、各樹脂はそれぞれ以下の構造単位を有する。 Regarding the resins obtained in each synthesis example and the resins used in each example, reference example and comparative example, each resin has the following structural units.
　ポリイミド（ＰＩ－１）～（ＰＩ－３）は、一般式（１）で表される構造単位を有する。なお（ＰＩ－３）は、エチレン性不飽和二重結合基も有する。 Polyimides (PI-1) to (PI-3) have structural units represented by general formula (1). (PI-3) also has an ethylenically unsaturated double bond group.
　ポリイミド（ＰＩ－４）～（ＰＩ－９）および（ＰＩ－１２）は、一般式（１）で表される構造単位および一般式（２１）で表される構造単位を有する。なお（ＰＩ－１２）は、エチレン性不飽和二重結合基も有する。 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.
　ポリイミド（ＰＩ－１０）および（ＰＩ－１１）は、一般式（１）で表される構造単位および一般式（２２）で表される構造単位を有する。 Polyimides (PI-10) and (PI-11) have a structural unit represented by general formula (1) and a structural unit represented by general formula (22).
　ポリイミド前駆体（ＰＩＰ－１）は、一般式（３）で表される構造単位を有する。なお（ＰＩＰ－１）における、アミド酸構造単位、アミド酸エステル構造単位、アミド酸アミド構造単位、およびイミド閉環構造単位の含有比率の合計に占める、アミド酸エステル構造単位の含有比率は６５ｍｏｌ％であり、アミド酸構造単位の含有比率は２５ｍｏｌ％であり、イミド閉環構造単位の含有比率は１０ｍｏｌ％である。 The polyimide precursor (PIP-1) has a structural unit represented by general formula (3). In (PIP-1), 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%, and the content ratio of the imide ring-closing structural unit is 10 mol%.
　ポリイミド前駆体（ＰＩＰ－２）は、一般式（３）で表される構造単位および一般式（２１）で表される構造単位を有する。なお（ＰＩＰ－２）における、アミド酸構造単位、アミド酸エステル構造単位、アミド酸アミド構造単位、およびイミド閉環構造単位の含有比率の合計に占める、アミド酸エステル構造単位の含有比率は６５ｍｏｌ％であり、アミド酸構造単位の含有比率は２５ｍｏｌ％であり、イミド閉環構造単位の含有比率は１０ｍｏｌ％である。 The polyimide precursor (PIP-2) has a structural unit represented by general formula (3) and a structural unit represented by general formula (21). In (PIP-2), 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%, and the content ratio of the imide ring-closing structural unit is 10 mol%.
　ポリベンゾオキサゾール（ＰＢ－１）は、す一般式（２）で表される構造単位を有する。 Polybenzoxazole (PB-1) has a structural unit represented by general formula (2).
　ポリベンゾオキサゾール前駆体（ＰＢＰ－１）は、一般式（４）で表される構造単位を有する。 The polybenzoxazole precursor (PBP-1) has a structural unit represented by general formula (4).
　ポリアミドイミド（ＰＡＩ－１）および（ＰＡＩ－２）は、一般式（５）で表される構造単位を有する。なお（ＰＡＩ－２）は、エチレン性不飽和二重結合基も有する。 Polyamideimides (PAI-1) and (PAI-2) have structural units represented by general formula (5). (PAI-2) also has an ethylenically unsaturated double bond group.
　ポリアミドイミド（ＰＡＩ－３）、（ＰＡＩ－４）および（ＰＡＩ－５）は、一般式（５）で表される構造単位および一般式（２１）で表される構造単位を有する。なお（ＰＡＩ－５）は、エチレン性不飽和二重結合基も有する。 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.
　ポリシロキサン（ＰＳ－１）は、一般式（８）で表される構造単位および一般式（９）で表される構造単位を有する。 Polysiloxane (PS-1) has a structural unit represented by general formula (8) and a structural unit represented by general formula (9).
　ポリシロキサン（ＰＳ－２）および（ＰＳ－３）は、一般式（８）で表される構造単位、一般式（９）で表される構造単位および（ＡＸ）樹脂の環状構造単位を有する。 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.
　多環側鎖含有樹脂（ＣＲ－１）は、一般式（４４）で表される構造を含む一般式（４１）で表される構造単位を有する。なお（ＣＲ－１）は、エチレン性不飽和二重結合基も有する。 The polycyclic side chain-containing resin (CR-1) 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.
　酸変性エポキシ樹脂（ＡＥ－１）および（ＡＥ－２）は、一般式（６６）で表される構造を含む一般式（６１）で表される構造単位を有する。なお（ＡＥ－１）および（ＡＥ－２）は、エチレン性不飽和二重結合基も有する。 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.
　アクリル樹脂（ＡＣ－１）は、一般式（８１）で表される構造単位および一般式（８２）で表される構造単位を有する。なお（ＡＣ－１）は、エチレン性不飽和二重結合基も有する。 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.
　フェノール樹脂（ＰＲ－１）は、一般式（３６）で表される構造単位を有する。 The phenolic resin (PR-1) has a structural unit represented by general formula (36).
　フェノール樹脂（ＰＲ－２）は、一般式（３６）で表される構造単位および（ＡＸ）樹脂の環状構造単位を有する。 The phenolic resin (PR-2) has a structural unit represented by the general formula (36) and a cyclic structural unit of the (AX) resin.
　ポリヒドロキシスチレン（ＰＨＳ－１）は、一般式（９１）で表される構造単位を有する。 Polyhydroxystyrene (PHS-1) has a structural unit represented by general formula (91).
　各実施例、参考例および比較例における略語に対応する名称を以下に示す。
（ｄ－１）：Ｂｋ－Ｓ０１００ＣＦ
（ｄ－２）：Ｂｋ－Ｓ００８４
（ｄ－３）：Ｂｋ－ＦＫ４２８０
（ｄ－４）：Ｂｋ－Ａ１１０３
（ｄ－５）：Ｐ．Ｒ．１７９／Ｐ．Ｙ．１９２／Ｐ．Ｂ．６０の混合物
（ｄ－６）：Ｂｋ－ＣＢＦ１
（ｄ－７）：Ｂｋ－ＣＢＦ２
（ｅ－１）：ＡＤＰ
（Ｃｌ－１）塩化シクロプロピルメチル
（Ｃｌ－２）塩化テトラブチルアンモニウム
（Ｂｒ－１）臭化ベンジル
（Ｓ－１）ｐ－トルエンチオール
（Ｓ－２）ジメチルスルホキシド
（Ｐ－１）トリフェニルホスフィン。 Names corresponding to abbreviations in Examples, Reference Examples and Comparative Examples are shown below.
(d-1): Bk-S0100CF
(d-2): Bk-S0084
(d-3): Bk-FK4280
(d-4): Bk-A1103
(d-5): P.I. R. 179/P. Y. 192/P. B. 60 mixture (d-6): Bk-CBF1
(d-7): 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 .
　また、各実施例、参考例および比較例で使用した化合物として、（ｂ－１）～（ｂ－６）、（ｃ－１）～（ｃ－４）、（ｇ－１）～（ｇ－１５）、（ｆ－１）～（ｆ－２）、（ｆｔ－１）、（ｈ－１）および（ＮＱＤ－１）の構造を以下の化学式に示す。 Further, as compounds used in Examples, Reference Examples and Comparative Examples, (b-1) to (b-6), (c-1) to (c-4), (g-1) to (g- 15), (f-1) to (f-2), (ft-1), (h-1) and (NQD-1) are shown in the chemical formulas below.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　＜実施例１＞
　表３－１に記載の組成にて、感光性樹脂組成物（組成物１）を調製した。まず、表３－１に記載の組成のうち、（Ｄ）着色剤および（Ｅ）分散剤以外の成分を含む調合液を調製した後、該調合液と上述の顔料分散液の調製例１で調整した顔料分散液（Ｂｋ－１）とを、得られた組成物が表３－１に記載の組成になるように混合して、組成物１を調製した。さらに溶剤として、ＰＧＭＥＡ／ＥＤＭ／ＭＢＡ＝６０／２０／２０（質量比）を用いて、組成物の固形分濃度が１５質量％となるように調製した。なお、得られた組成物は、０．４５μｍφのフィルターで濾過して使用した。 <Example 1>
A photosensitive resin composition (composition 1) was prepared with the composition shown in Table 3-1. First, of the compositions shown in Table 3-1, after preparing a preparation containing components other than (D) the colorant and (E) the dispersant, the preparation and the above pigment dispersion in Preparation Example 1 Composition 1 was prepared by mixing the prepared pigment dispersion (Bk-1) so that the resulting composition had the composition shown in Table 3-1. Furthermore, PGMEA/EDM/MBA = 60/20/20 (mass ratio) was used as a solvent to prepare a composition having a solid content concentration of 15 mass%. The resulting composition was filtered through a 0.45 μmφ filter before use.
　＜組成物の硬化物の作製＞
　調製した組成物１を、ＩＴＯ／Ａｇ基板上にスピンコーター（ＭＳ－Ａ１００；ミカサ社製）を用いて任意の回転数でスピンコーティングにより塗布した後、ブザーホットプレート（ＨＰＤ－３０００ＢＺＮ；アズワン（株）製）を用いて１２０℃で１２０秒間プリベークし、膜厚約１．８μｍのプリベーク膜を作製した。作製したプリベーク膜を、フォトリソ用小型現像装置（ＡＤ－１２００；滝沢産業（株）製）を用いて、２．３８質量％ＴＭＡＨ水溶液でスプレー現像し、プリベーク膜（未露光部）が完全に溶解するのに要する時間（Ｂｒｅａｋｉｎｇ　Ｐｏｉｎｔ；以下、「ＢＰ」）を測定した。 <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 μm. 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.
　上述の方法と同様にプリベーク膜を作製し、作製したプリベーク膜を、両面アライメント片面露光装置（マスクアライナー　ＰＥＭ－６Ｍ；ユニオン光学（株）製）を用いて、感度測定用のグレースケールマスク（ＭＤＲＭ　ＭＯＤＥＬ　４０００－５－ＦＳ；Ｏｐｔｏ－Ｌｉｎｅ　Ｉｎｔｅｒｎａｔｉｏｎａｌ社製）を介して、超高圧水銀灯のｉ線（波長３６５ｎｍ）、ｈ線（波長４０５ｎｍ）およびｇ線（波長４３６ｎｍ）でパターニング露光した。露光量は、２０μｍのライン・アンド・スペースパターンにおいて、開口部に相当するスペースパターンを１８μｍの寸法幅にて形成できる露光量（ｉ線照度計の値）とした。露光後、フォトリソ用小型現像装置（ＡＤ－１２００；滝沢産業（株）製）を用いて、２．３８質量％ＴＭＡＨ水溶液で現像し、水で３０秒間リンスして組成物１の現像後膜を作製した。現像時間は、ＢＰ＋２０秒とした。現像後、高温イナートガスオーブン（ＩＮＨ－９ＣＤ－Ｓ；光洋サーモシステム（株）製）を用いて、２５０℃で熱硬化させ、膜厚約１．２μｍの組成物１の硬化物を作製した。熱硬化条件としては、窒素雰囲気下、２５０℃で６０分間熱硬化させた。 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 μm in a 20 μm line-and-space pattern. 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 μm. As for the heat curing conditions, heat curing was performed at 250° C. for 60 minutes in a nitrogen atmosphere.
　核磁気共鳴分光分析、赤外分光分析、および飛行時間型二次イオン質量分析などの方法で得られた硬化物を分析し、硬化物中に含まれる樹脂の構造単位および化合物の構造を分析した。上述の方法で組成物１を硬化した硬化物は、以下の樹脂および化合物を含有することを確認した。すなわち、組成物１を硬化した硬化物は、組成物１が含有する各構成成分に由来する構造を有する化合物を含有する。
（Ｘ－ＤＬ）樹脂：一般式（２１）で表される構造単位を有する樹脂。
（Ｉ－ＤＬ）樹脂：一般式（１）で表される構造単位を有する樹脂。
（ＩＩ－ＤＬ）樹脂：一般式（２４）で表される構造単位を有する樹脂。
（ＩＩＩ－ＤＬ）樹脂：一般式（３６）で表される構造単位を有する樹脂。
（ＩＶ－ＤＬ）リン酸系構造：ホスホン酸エステル構造を有する化合物。
（Ｂ１）化合物に由来する構造：一般式（１４１）で表される構造を有する化合物。
（Ｃ１－１）化合物に由来する構造：ベンゾカルバゾール構造を有する化合物。
（Ｄ１ａ）黒色顔料：（Ｄ１ａ－１ａ）一般式（１６１）で表される構造を有するベンゾフラノン系黒色顔料。 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).
(C1-1) A structure derived from a compound: a compound having a benzocarbazole structure.
(D1a) Black pigment: (D1a-1a) A benzofuranone-based black pigment having a structure represented by general formula (161).
　＜実施例２～８３および比較例１～５＞
　実施例１と同様に、組成物２～８８を表３－１～表１０に記載の組成にて調製した。表３－１～表１０において括弧内の数値は各成分の固形分の質量部を示す。 <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.
　得られた各組成物を用いて、実施例１と同様に、基板上に組成物を成膜して感光特性、硬化物特性および発光特性の評価を行った。これらの評価結果を、まとめて表３－１～表１０に示す。なお、比較しやすくするため、表３－２、表４、表５、表６および表９には実施例１の組成および評価結果、表７には実施例１、１４および１６の組成および評価結果ならびに表１０には実施例１および１６～１９の組成および評価結果をそれぞれ記載した。 Using each of the obtained compositions, a film of the composition was formed on a substrate in the same manner as in Example 1, and the photosensitive characteristics, cured product characteristics, and luminescence characteristics were evaluated. These evaluation results are collectively shown in Tables 3-1 to 10. For ease of comparison, Tables 3-2, 4, 5, 6 and 9 show the composition and evaluation results of Example 1, and Table 7 shows the composition and evaluation of Examples 1, 14 and 16. The results and Table 10 describe the compositions and evaluation results of Examples 1 and 16-19, respectively.
　表３－１および表３－２において、（Ａ）アルカリ可溶性樹脂として（ＡＸ）樹脂、（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂からなる群より選ばれる一種類以上の樹脂を変えた組成物にて、各種特性の評価をした。
表４において、（Ｆ）化合物および／または（Ｈ）化合物を変えた組成物にて、各種特性の評価をした。
表５において、（Ｇ）化合物を変えた組成物について、各種特性の評価をした。
表６において、（Ｂ）化合物、（Ｃ）感光剤および（Ｃ１－１）化合物からなる群より選ばれる一種類以上の化合物を変えた組成物について、各種特性の評価をした。
表７において、（Ｄ１ａ）黒色顔料の種類を変えた組成物について、各種特性の評価をした。なお実施例６９～７０は、（Ｄ）着色剤および（Ｅ）分散剤を含有しない組成物について、各種特性の評価をした。また実施例７１～７２はポジ型の感光性を有し、（Ｄ）着色剤および（Ｅ）分散剤の含有有無を変えた組成物について、各種特性の評価をした。
表８において、塩素元素、臭素元素、硫黄元素、またはリン元素を含む添加剤を変えた組成物について、各種特性の評価をした。なお表８に、塩素元素、臭素元素、硫黄元素、またはリン元素の含有量を記載した。
表９において、（Ｉ）無機粒子を変えた組成物について、各種特性の評価をした。
表１０において、比較例１～５は（ＡＸ）樹脂を含有しない組成物について、各種特性の評価をした。 In Tables 3-1 and 3-2, 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.
In Table 4, various properties were evaluated for compositions in which the (F) compound and/or the (H) compound were changed.
In Table 5, various properties were evaluated for the compositions in which the (G) compound was changed.
In 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.
In Table 7, (D1a) compositions with different types of black pigments were evaluated for various properties. In Examples 69 to 70, various properties were evaluated for compositions containing no (D) colorant and (E) dispersant. In 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.
In 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.
In Table 9, (I) compositions with different inorganic particles were evaluated for various properties.
In Table 10, Comparative Examples 1 to 5 evaluated various properties of compositions containing no (AX) resin.
　なおポジ型の感光性を有する組成物を用いた場合の現像時間は６０秒、９０秒、または１２０秒とし、感度測定用のグレースケールマスク（ＭＤＲＭ　ＭＯＤＥＬ　４０００－５－ＦＳ；Ｏｐｔｏ－Ｌｉｎｅ　Ｉｎｔｅｒｎａｔｉｏｎａｌ社製）を用いて露光した際に、２０μｍのライン・アンド・スペースパターンにおいて、開口部に相当するスペースパターンを１８μｍの寸法幅にて形成できる最適露光量（ｉ線照度計の値）を求めた。またポジ型の感光性を有する組成物を用いた場合、熱硬化条件としては、窒素雰囲気下、２００℃で６０分間熱硬化させた。 When a positive photosensitive composition is used, 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 μm in a line and space pattern of 20 μm was determined. . When a positive photosensitive composition was used, the heat curing conditions were such that the composition was heat cured at 200° C. for 60 minutes in a nitrogen atmosphere.
　塩素元素、臭素元素、硫黄元素、またはリン元素の含有量は、燃焼イオンクロマトグラフィーによって測定した。組成物を分析装置の燃焼管内で燃焼および分解させ、発生したガスを吸収液に吸収後、吸収液の一部をイオンクロマトグラフィーにより分析した。
＜燃焼・吸収条件＞
システム：ＡＱＦ－２１００Ｈ、ＧＡ－２１０（三菱化学社製）
電気炉温度：Ｉｎｌｅｔ　９００℃，　Ｏｕｔｌｅｔ　１０００℃
ガス：Ａｒ／Ｏ２　２００ｍＬ／ｍｉｎ，　Ｏ２　４００ｍＬ／ｍｉｎ
吸収液：Ｈ２Ｏ２　０．１％
吸収液量：５ｍＬ
＜イオンクロマトグラフィー・アニオン分析条件＞
システム：ＩＣＳ１６００（ＤＩＯＮＥＸ社製）
移動相：２．７ｍｍｏｌ／Ｌ　Ｎａ２ＣＯ３，　０．３ｍｍｏｌ／Ｌ　ＮａＨＣＯ３
流速：１．５０ｍＬ／ｍｉｎ
検出器：電気伝導度検出器
注入量：１００μＬ。 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.
<Combustion/absorption conditions>
System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation)
Electric furnace temperature: Inlet 900°C, Outlet 1000°C
Gas: Ar/O2 200 mL/min, O2 400 mL/min
Absorption liquid: H2O2 0.1 %
Absorbing liquid volume: 5mL
<Conditions for ion chromatography/anion analysis>
System: ICS1600 (manufactured by DIONEX)
Mobile phase: 2.7 mmol/L Na2CO3 , 0.3 mmol/L NaHCO3
Flow rate: 1.50 mL/min
Detector: Conductivity detector Injection volume: 100 μL.
　各実施例および比較例の元素含有量を以下に記載する。元素含有量の記載が無いものは、当該元素が検出されなかったことを示す。実施例１～３６、４０～５５、５７、５９～６５、６７、６８および比較例１～４の、リン元素含有量は７２ｐｐｍであった。実施例３７のリン元素含有量は３９ｐｐｍであった。実施例３８のリン元素含有量は１９ｐｐｍであった。実施例３９のリン元素含有量は１３５ｐｐｍであった。実施例５６のリン元素含有量は７２ｐｐｍであり、硫黄元素含有量は５９８ｐｐｍであった。実施例５８のリン元素含有量は７０ｐｐｍであり、硫黄元素含有量は１１４ｐｐｍであった。実施例６６のリン元素含有量は５７ｐｐｍであった。実施例６９および７０のリン元素含有量は２１９ｐｐｍであった。実施例７１の硫黄元素含有量は４４９ｐｐｍであった。実施例７２の硫黄元素含有量は６３２ｐｐｍであった。 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.
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000051
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
　１　ガラス基板
　２　ＴＦＴ
　３　ＴＦＴ平坦化用の硬化物
　４　反射電極
　５ａ　プリベーク膜
　５ｂ　硬化パターン
　６　マスク
　７　活性化学線
　８，５１　有機ＥＬ層
　９　透明電極
　１０　平坦化用の硬化物
　１１　カバーガラス
　Ｓ　遮光部
　Ｔ　透光部
　Ｈ　半透光部
　４７　無アルカリガラス基板
　４８　第１電極
　４９　補助電極
　５０　画素分割層
　５２　第２電極 1 glass substrate 2 TFT
3 TFT planarization cured product 4 reflective electrode 5a pre-baked film 5b curing pattern 6 mask 7 actinic radiation 8, 51 organic EL layer 9 transparent electrode 10 planarization cured product 11 cover glass S light shielding part T translucent part H Translucent portion 47 Non-alkali glass substrate 48 First electrode 49 Auxiliary electrode 50 Pixel division layer 52 Second electrode

Claims (20)

  1. 　（Ａ）アルカリ可溶性樹脂および（Ｃ）感光剤を含有する感光性樹脂組成物であって、
    　前記（Ａ）アルカリ可溶性樹脂が、少なくとも以下の（ＡＸ）樹脂を含み、さらに以下の（Ａ１）樹脂、（Ａ２）樹脂および（Ａ３）樹脂からなる群より選ばれる一種類以上の樹脂を含有する感光性樹脂組成物：
    （ＡＸ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂；
    （Ａ１）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂；
    （Ａ２）樹脂：エチレン性不飽和二重結合基を有する樹脂；
    （Ａ３）樹脂：フェノール性水酸基を有する樹脂。     (A) an alkali-soluble resin and (C) a photosensitive resin composition containing a photosensitive agent,
    The (A) alkali-soluble resin contains at least the following (AX) resin, and further contains one or more resins selected from the group consisting of the following (A1) resin, (A2) resin and (A3) resin. Photosensitive resin composition:
    (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.
  2. 　前記（Ａ）アルカリ可溶性樹脂が、前記（Ａ１）樹脂および／または前記（Ａ３）樹脂を含有する請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin contains the (A1) resin and/or the (A3) resin.
  3. 　前記（Ａ）アルカリ可溶性樹脂が、前記（Ａ１）樹脂および／または前記（Ａ３）樹脂を含有し、さらに前記（Ａ２）樹脂を含有する請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin contains the (A1) resin and/or the (A3) resin, and further contains the (A2) resin.
  4. 　前記（Ａ）アルカリ可溶性樹脂が、前記（Ａ１）樹脂を含み、
    　前記（Ａ１）樹脂が、以下の（Ａ１－１）樹脂、（Ａ１－２）樹脂、（Ａ１－３）樹脂、（Ａ１－４）樹脂、（Ａ１－５）樹脂および（Ａ１－６）樹脂からなる群より選ばれる一種類以上の樹脂を含有する請求項１～３のいずれかに記載の感光性樹脂組成物：
    （Ａ１－１）樹脂：ポリイミド；
    （Ａ１－２）樹脂：ポリイミド前駆体；
    （Ａ１－３）樹脂：ポリベンゾオキサゾール；
    （Ａ１－４）樹脂：ポリベンゾオキサゾール前駆体；
    （Ａ１－５）樹脂：ポリアミドイミド；
    （Ａ１－６）樹脂：ポリシロキサン。     The (A) alkali-soluble resin contains the (A1) resin,
    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 The photosensitive resin composition according to any one of claims 1 to 3, containing one or more resins selected from the group consisting of:
    (A1-1) resin: polyimide;
    (A1-2) resin: polyimide precursor;
    (A1-3) resin: polybenzoxazole;
    (A1-4) resin: polybenzoxazole precursor;
    (A1-5) resin: polyamideimide;
    (A1-6) Resin: Polysiloxane.
  5. 　さらに、（Ｄ１ａ－１）有機黒色顔料および／または（Ｄ１ａ－３）二色以上の着色顔料混合物を含有し、
    　前記（Ｄ１ａ－１）有機黒色顔料が、（Ｄ１ａ－１ａ）ベンゾフラノン系黒色顔料、（Ｄ１ａ－１ｂ）ペリレン系黒色顔料および（Ｄ１ａ－１ｃ）アゾ系黒色顔料からなる群より選ばれる一種類以上の顔料を含み、
    　前記（Ｄ１ａ－３）二色以上の着色顔料混合物が、赤、橙、黄、緑、青および紫色の顔料からなる群より選ばれる二色以上の顔料を含む請求項１～４のいずれかに記載の感光性樹脂組成物。     Further, (D1a-1) contains an organic black pigment and/or (D1a-3) a mixture of two or more colored pigments,
    The (D1a-1) organic black pigment is one or more types 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. contains pigments,
    Any one of claims 1 to 4, wherein (D1a-3) a mixture of two or more color pigments contains two or more color pigments selected from the group consisting of red, orange, yellow, green, blue and violet pigments. The photosensitive resin composition described.
  6. 　前記（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、
    　該イソシアヌル酸構造および／またはトリアジン構造を含む構造単位が、脂肪族構造、脂環式構造および芳香族構造からなる群より選ばれる一種類以上の構造を有する有機基を、少なくとも２つ有する請求項２～５のいずれかに記載の感光性樹脂組成物。     The (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 triazine structure has at least two organic groups having one or more structures selected from the group consisting of an aliphatic structure, an alicyclic structure and an aromatic structure. 6. The photosensitive resin composition according to any one of 2 to 5.
  7. 　前記（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、
    　イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する請求項２～６のいずれかに記載の感光性樹脂組成物。     The (AX) resin has a structural unit containing an isocyanuric acid structure and/or a triazine structure, and
    7. The photosensitive resin composition according to any one of claims 2 to 6, 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.
  8. 　前記（ＡＸ）樹脂が、イソシアヌル酸構造および／またはトリアジン構造を含む構造単位を有し、かつ、
    　以下の（ＡＸ－１）樹脂、（ＡＸ－２）樹脂、（ＡＸ－３）樹脂、（ＡＸ－４）樹脂、（ＡＸ－５）樹脂および（ＡＸ－６）樹脂からなる群より選ばれる一種類以上の樹脂を含有する請求項２～７のいずれかに記載の感光性樹脂組成物：
    （ＡＸ－１）樹脂：窒素環含有ポリイミド；
    （ＡＸ－２）樹脂：窒素環含有ポリイミド前駆体；
    （ＡＸ－３）樹脂：窒素環含有ポリベンゾオキサゾール；
    （ＡＸ－４）樹脂：窒素環含有ポリベンゾオキサゾール前駆体；
    （ＡＸ－５）樹脂：窒素環含有ポリアミドイミド；
    （ＡＸ－６）樹脂：窒素環含有ポリシロキサン。     The (AX) resin has a structural unit containing an isocyanuric acid structure and/or a triazine structure, and
    One selected from the group consisting of the following (AX-1) resin, (AX-2) resin, (AX-3) resin, (AX-4) resin, (AX-5) resin and (AX-6) resin The photosensitive resin composition according to any one of claims 2 to 7, which contains more than one kind of resin:
    (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.
  9. 　前記（ＡＸ）樹脂が、イソシアヌル酸構造を含む構造単位を有する請求項７または８に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 7 or 8, wherein the (AX) resin has a structural unit containing an isocyanuric acid structure.
  10. 　さらに、（Ｉ）無機粒子を含有し、
    　該（Ｉ）無機粒子が、（Ｉ１）シリカ粒子を含有する、請求項１～９のいずれかに記載の感光性組成物。     Furthermore, (I) contains inorganic particles,
    10. The photosensitive composition according to any one of claims 1 to 9, wherein the (I) inorganic particles contain (I1) silica particles.
  11. 　前記感光性樹脂組成物が、ハロゲン元素を含む成分、硫黄元素を含む成分、およびリン元素を含む成分からなる群より選ばれる一種類以上の成分を含有し、かつ、下記（１）～（３）の条件を１つ以上満たす、請求項１～１０のいずれかに記載の感光性樹脂組成物：
    （１）該感光性樹脂組成物中に占めるハロゲン元素の含有量が０．０１～１００ｐｐｍ；
    （２）該感光性樹脂組成物中に占める硫黄元素の含有量が０．０１～１００ｐｐｍ；
    （３）該感光性樹脂組成物中に占めるリン元素の含有量が０．０１～１００ｐｐｍ。     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 following (1) to (3) ) satisfying one or more conditions, the photosensitive resin composition according to any one of claims 1 to 10:
    (1) the content of halogen elements in the photosensitive resin composition is 0.01 to 100 ppm;
    (2) the sulfur element content in the photosensitive resin composition is 0.01 to 100 ppm;
    (3) The content of elemental phosphorus in the photosensitive resin composition is 0.01 to 100 ppm.
  12. 　さらに、以下の（Ｆ０）化合物および／または（ＦＢ）化合物を含有する請求項１～１１のいずれかに記載の感光性樹脂組成物：
    （Ｆ０）化合物：リン原子を含む酸性基および／またはリン原子を含む酸性基の塩を有する化合物；
    （ＦＢ）化合物：リン原子を含むベタイン構造を有する化合物。     The photosensitive resin composition according to any one of claims 1 to 11, further comprising 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;
    (FB) compound: a compound having a betaine structure containing a phosphorus atom.
  13. 　前記（Ｃ）感光剤が、（Ｃ１）光重合開始剤を含み、
    　前記（Ｃ１）光重合開始剤が、（Ｃ１－１）オキシムエステル系化合物を含有し、
    　前記（Ｃ１－１）オキシムエステル系化合物が、ニトロ基、ナフチルカルボニル構造、トリメチルベンゾイル構造、チオフェニルカルボニル構造、フリルカルボニル構造および少なくとも２つのオキシムエステル構造からなる群より選ばれる一種類以上の構造を有する請求項１～１２のいずれかに記載の感光性樹脂組成物。     The (C) photosensitive agent contains (C1) a photopolymerization initiator,
    The (C1) photopolymerization initiator contains (C1-1) an oxime ester compound,
    The (C1-1) oxime ester 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 and at least two oxime ester structures. The photosensitive resin composition according to any one of claims 1 to 12.
  14. 　前記（Ａ）アルカリ可溶性樹脂が、以下の（ＡＸｂ）樹脂を含有する請求項１～１３のいずれかに記載の感光性樹脂組成物：
    （ＡＸｂ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、さらにエチレン性不飽和二重結合基を有する樹脂。     The photosensitive resin composition according to any one of claims 1 to 13, wherein the (A) alkali-soluble resin contains the following (AXb) resin:
    (AXb) 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.
  15. 　前記（Ａ）アルカリ可溶性樹脂が、以下の（ＡＸｂ）樹脂および（ＡＸａ）樹脂を含有する請求項１～１３のいずれかに記載の感光性樹脂組成物：
    （ＡＸｂ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、さらにエチレン性不飽和二重結合基を有する樹脂；
    （ＡＸａ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有し、かつエチレン性不飽和二重結合基を有しない樹脂。     The photosensitive resin composition according to any one of claims 1 to 13, wherein the (A) alkali-soluble resin contains the following (AXb) resin and (AXa) resin:
    (AXb) 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;
    (AXa) resin: a resin having a structural unit containing a cyclic structure having at least three nitrogen atoms and having no ethylenically unsaturated double bond group.
  16. 　さらに、（Ｂ１）疎水性骨格含有ラジカル重合性化合物を含有し、
    　前記（Ｂ１）疎水性骨格含有ラジカル重合性化合物が、以下の（Ｉ－ｂ１）構造および（ＩＩ－ｂ１）構造を有し、（ＩＩ－ｂ１）構造を少なくとも２つ有する請求項１～１５のいずれかに記載の感光性樹脂組成物：
    （Ｉ－ｂ１）構造：フルオレン構造、インダン構造、縮合多環脂環式構造、インドリノン構造、およびイソインドリノン構造からなる群より選ばれる一種類以上の構造を含む構造；
    （ＩＩ－ｂ１）構造：エチレン性不飽和二重結合基を有する有機基。     Furthermore, (B1) contains a hydrophobic skeleton-containing radically polymerizable compound,
    Claims 1 to 15, wherein the (B1) hydrophobic skeleton-containing radically polymerizable compound has the following (I-b1) structure and (II-b1) structure, and has at least two (II-b1) structures: The photosensitive resin composition according to any one of:
    (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: an organic group having an ethylenically unsaturated double bond group.
  17. 　さらに、以下の（Ｇ２）化合物および／または（Ｇ３）化合物を含有し、
    　架橋性基が、アルコキシアルキル基、ヒドロキシアルキル基、エポキシ基、オキセタニル基、ビニル基およびアリル基からなる群より選ばれる一種類以上の基を含む請求項１～１６のいずれかに記載の感光性樹脂組成物：
    （Ｇ２）化合物：少なくとも２つのフェノール性水酸基、および少なくとも２つの架橋性基を有する化合物；
    （Ｇ３）化合物：窒素原子を少なくとも２つ有する環状構造、および少なくとも２つの架橋性基を有する化合物。     Furthermore, containing the following (G2) compound and / or (G3) compound,
    The photosensitive material according to any one of claims 1 to 16, wherein the crosslinkable group contains one or more groups selected from the group consisting of alkoxyalkyl groups, hydroxyalkyl groups, epoxy groups, oxetanyl groups, vinyl groups and allyl groups. Resin composition:
    (G2) compounds: compounds having at least two phenolic hydroxyl groups and at least two crosslinkable groups;
    (G3) Compound: a compound having a cyclic structure having at least two nitrogen atoms and at least two crosslinkable groups.
  18. 　請求項１～１７のいずれかに記載の感光性樹脂組成物を硬化した硬化物。 A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 17.
  19. 　硬化物の製造方法であって、
    　（１）基板上に、請求項１～１７のいずれかに記載の感光性樹脂組成物の塗膜を成膜する工程、
    　（２）前記感光性樹脂組成物の塗膜にフォトマスクを介して活性化学線を照射する工程、
    　（３）アルカリ溶液を用いて現像し、前記感光性樹脂組成物のパターンを形成する工程および
    　（４）前記パターンを加熱して、前記感光性樹脂組成物の硬化パターンを得る工程、を有する硬化物の製造方法。     A method for producing a cured product,
    (1) forming a coating film of the photosensitive resin composition according to any one of claims 1 to 17 on a substrate;
    (2) a step of irradiating the coating film of the photosensitive resin composition with actinic radiation through a photomask;
    (3) developing with an alkaline solution to form a pattern of the photosensitive resin composition; and (4) heating the pattern to obtain a cured pattern of the photosensitive resin composition. A method of making things.
  20. 　基板、第１電極、第２電極および画素分割層を少なくとも有し、
    　さらに、発光層を含む有機ＥＬ層および／または発光層を含む光取り出し層を有する表示装置であって、
    　前記画素分割層は、前記第１電極の上に第１電極の一部と重なるように形成され、
    　前記発光層を含む有機ＥＬ層および／または前記発光層を含む光取り出し層は、前記第１電極上、かつ前記第１電極および前記第２電極の間に形成され、
    　前記画素分割層が、少なくとも以下の（Ｘ－ＤＬ）樹脂を有し、
    　さらに以下の（Ｉ－ＤＬ）樹脂、（ＩＩ－ＤＬ）樹脂および（ＩＩＩ－ＤＬ）樹脂からなる群より選ばれる一種類以上の樹脂を有する表示装置：
    （Ｘ－ＤＬ）樹脂：窒素原子を少なくとも３つ有する環状構造を含む構造単位を有する樹脂；
    （Ｉ－ＤＬ）樹脂：イミド構造、アミド構造、オキサゾール構造およびシロキサン構造からなる群より選ばれる一種類以上の構造を含む構造単位を有する樹脂；
    （ＩＩ－ＤＬ）樹脂：一般式（２４）で表される構造単位を有する樹脂；
    （ＩＩＩ－ＤＬ）樹脂：フェノール樹脂、ポリヒドロキシスチレン、フェノール基変性エポキシ樹脂およびフェノール基変性アクリル樹脂からなる群より選ばれる一種類以上の樹脂；
    Figure JPOXMLDOC01-appb-C000001
     一般式（２４）において、Ｒ６７～Ｒ６９は、それぞれ独立して、水素原子または炭素数１～６のアルキル基を表す；ａは０または１である；＊１は樹脂中の結合点を表す。     having at least a substrate, a first electrode, a second electrode and a pixel dividing 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,
    A display device further comprising one or more resins selected from the group consisting of the following (I-DL) resins, (II-DL) resins and (III-DL) resins:
    (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;
    Figure JPOXMLDOC01-appb-C000001
     In general formula (24), 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 ; show.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009092952A (en) * 2007-10-09 2009-04-30 Toppan Printing Co Ltd Photosensitive colored composition, color filter using the same, and liquid crystal display device
JP2016191905A (en) * 2015-03-30 2016-11-10 東京応化工業株式会社 Photosensitive resin composition, pattern forming method, cured film, insulation film, color filter, and display device
WO2018159384A1 (en) * 2017-03-03 2018-09-07 東レ株式会社 Resin composition, resin sheet, curing pattern, and semiconductor electronic component or semiconductor device
JP2020070352A (en) * 2018-10-31 2020-05-07 東レ株式会社 Pigment dispersion, negative photosensitive composition, and cured product

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009092952A (en) * 2007-10-09 2009-04-30 Toppan Printing Co Ltd Photosensitive colored composition, color filter using the same, and liquid crystal display device
JP2016191905A (en) * 2015-03-30 2016-11-10 東京応化工業株式会社 Photosensitive resin composition, pattern forming method, cured film, insulation film, color filter, and display device
WO2018159384A1 (en) * 2017-03-03 2018-09-07 東レ株式会社 Resin composition, resin sheet, curing pattern, and semiconductor electronic component or semiconductor device
JP2020070352A (en) * 2018-10-31 2020-05-07 東レ株式会社 Pigment dispersion, negative photosensitive composition, and cured product

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