WO2020059485A1 - 感光性樹脂組成物、樹脂シート、硬化膜、有機ｅｌ表示装置、半導体電子部品、半導体装置、および有機ｅｌ表示装置の製造方法 - Google Patents

感光性樹脂組成物、樹脂シート、硬化膜、有機ｅｌ表示装置、半導体電子部品、半導体装置、および有機ｅｌ表示装置の製造方法 Download PDF

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Publication number
WO2020059485A1
WO2020059485A1 PCT/JP2019/034699 JP2019034699W WO2020059485A1 WO 2020059485 A1 WO2020059485 A1 WO 2020059485A1 JP 2019034699 W JP2019034699 W JP 2019034699W WO 2020059485 A1 WO2020059485 A1 WO 2020059485A1
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Prior art keywords
photosensitive resin
resin composition
organic
display device
compound
Prior art date
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Ceased
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PCT/JP2019/034699
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English (en)
French (fr)
Japanese (ja)
Inventor
小森悠佑
三好一登
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Toray Industries Inc
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Toray Industries Inc
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Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP2019548752A priority Critical patent/JP7272268B2/ja
Priority to CN201980057501.4A priority patent/CN112654927B/zh
Priority to US17/273,401 priority patent/US11852973B2/en
Priority to KR1020217005335A priority patent/KR102687870B1/ko
Publication of WO2020059485A1 publication Critical patent/WO2020059485A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • G03F7/022—Quinonediazides
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/0387—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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • H05B33/02—Details
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a photosensitive resin composition containing an alkali-soluble resin, a phenol resin having a halogen atom, and a photosensitive compound.
  • organic EL organic electroluminescence
  • an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and a voltage is applied between the opposing first and second electrodes. Can be emitted by applying.
  • a photosensitive resin composition that can be patterned by ultraviolet irradiation is generally used as the material for the planarizing layer and the material for the insulating layer.
  • a photosensitive resin composition using a polyimide-based or polybenzoxazole-based resin has high heat resistance of the resin and a small amount of gas components generated from a cured film, so that a highly reliable organic EL display device can be provided. It is suitably used because it can be used (for example, see Patent Document 1).
  • the flexible organic EL display device has a bendable portion and / or a portion fixed in a bent state on the structure, and a bending stress is applied to the flattening layer and the insulating layer in the bent portion. .
  • a flexible organic EL display device including such a bent portion high bending resistance is required for the material for the planarizing layer and the material for the insulating layer.
  • development of a photosensitive resin composition capable of patterning with high sensitivity and obtaining a cured film having high bending resistance has been strongly desired.
  • a method has been proposed in which a resin composition containing a novolak resin using bisphenol A, a polyamide resin, and an o-quinonediazide compound (see, for example, Patent Document 3).
  • an object of the present invention is to provide a photosensitive resin composition having high sensitivity, high bending resistance of a cured film, and high long-term reliability when the cured film is used for an organic EL display device.
  • the present invention is a photosensitive resin composition containing an alkali-soluble resin (a), a phenol resin having a halogen atom (b), and a photosensitive compound (c).
  • the photosensitive resin composition of the present invention can provide a photosensitive resin composition having high sensitivity, high bending resistance of a cured film, and high long-term reliability when the cured film is used in an organic EL display device.
  • FIG. 5 is a schematic view illustrating an example of a method for manufacturing a semiconductor device having bumps. It is a schematic diagram of a manufacturing procedure of an organic EL display device in an example. It is the schematic of the bending resistance evaluation in an Example.
  • the photosensitive resin composition of the present invention has an alkali-soluble resin (a), a phenol resin having a halogen atom (b), and a photosensitive compound (c).
  • the photosensitive resin composition of the present invention contains an alkali-soluble resin (a).
  • alkali-soluble means that a solution obtained by dissolving a resin in ⁇ -butyrolactone is coated on a silicon wafer, and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m. After the film is immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ⁇ 1 ° C. for 1 minute, and then rinsed with pure water, the dissolution rate determined from the decrease in film thickness is 50 nm / min or more.
  • the alkali-soluble resin (a) in the present invention has a hydroxyl group and / or an acidic group in the structural unit of the resin and / or at the terminal of its main chain in order to impart alkali solubility.
  • the acidic group include a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group.
  • the alkali-soluble resin (a) preferably has a fluorine atom in order to impart water repellency.
  • alkali-soluble resin (a) in the present invention examples include polyimide, a polyimide precursor, a polybenzoxazole precursor, a polyamideimide, a polyamideimide precursor, a polyamide, a polymer of a radical polymerizable monomer having an acidic group, and a phenol resin. But not limited thereto. Two or more of these resins may be contained.
  • these alkali-soluble resins (a) the long-term reliability when a cured film described later is used for an organic EL display device because of its high development adhesion, excellent heat resistance, and low outgas amount at high temperatures.
  • polyimide refers to a resin that is converted into polyimide by heat treatment or chemical treatment, and examples thereof include polyamic acid and polyamic acid ester.
  • polybenzoxazole precursor refers to a resin that is converted into polybenzoxazole by heat treatment or chemical treatment, and includes, for example, polyhydroxyamide.
  • polyimide precursor and polybenzoxazole precursor have a structural unit represented by the following general formula (3)
  • polyimide has a structural unit represented by the following general formula (4). Two or more of these may be contained, or a resin obtained by copolymerizing the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) may be contained.
  • X represents a divalent to octavalent organic group
  • Y represents a divalent to 11-valent organic group
  • R 11 and R 13 represent a hydroxyl group or a sulfonic acid group, and each may be single or different.
  • R 12 and R 14 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • t, u and w represent an integer of 0 to 3
  • v represents an integer of 0 to 6.
  • E represents a 4- to 10-valent organic group
  • G represents a 2- to 8-valent organic group.
  • R 15 and R 16 represent a carboxy group, a sulfonic group or a hydroxyl group.
  • a plurality of R 15 and R 16 may be the same or different.
  • x and y each independently represent an integer of 0 to 6. However, x + y> 0.
  • the polyimide, the polyimide precursor, the polybenzoxazole precursor or a copolymer thereof preferably has 5 to 100,000 structural units represented by the general formula (3) or (4). Further, in addition to the structural unit represented by the general formula (3) or (4), it may have another structural unit. In this case, it is preferable that the structural unit represented by the general formula (3) or (4) has 50 mol% or more of all the structural units.
  • X (R 11 ) t (COOR 12 ) u represents an acid residue.
  • X is a divalent to octavalent organic group, and among them, an organic group having an aromatic ring or a cycloaliphatic group and having 5 to 40 carbon atoms is preferable.
  • Examples of the acid include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid, trimellitic acid, trimesic acid, and diphenyl ether tricarboxylic acid.
  • dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid, trimellitic acid, trimesic acid, and diphenyl ether tricarboxylic acid.
  • Tricarboxylic acids such as biphenyltricarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3 3'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 2,2', 3,3'-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxy Phenyl) hexafluoropropane, 2, -Bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3 , 4-Dicarboxyphenyl) methane
  • R 20 represents an oxygen atom, C (CF 3 ) 2 or C (CH 3 ) 2 .
  • R 21 and R 22 each independently represent a hydrogen atom or a hydroxyl group.
  • the above acids in the case of tricarboxylic acid or tetracarboxylic acid, one or two carboxy groups correspond to (COOR 12 ) in the general formula (3). These acids may be used as they are, or may be used as acid anhydrides, active esters, or active amides.
  • the active ester is, for example, an N-hydroxysuccinimide ester compound obtained by reacting a carboxyl group of an acid with N-hydroxysuccinimide.
  • the active amide is, for example, a reaction of a carboxyl group of an acid with N, N′-carbonyldiimidazole. N-acylimidazole compounds obtained by the above method.
  • E (R 15 ) x represents a residue of an acid dianhydride.
  • E is a tetravalent to pentavalent organic group, and among them, an organic group having an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms is preferable.
  • the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarbox
  • R 20 represents an oxygen atom, C (CF 3 ) 2 or C (CH 3 ) 2 .
  • R 21 and R 22 each independently represent a hydrogen atom or a hydroxyl group.
  • Y (R 13 ) v (COOR 14 ) w in the general formula (3) and G (R 16 ) y in the general formula (4) represent a diamine residue.
  • Y is a divalent to divalent organic group
  • G is a divalent to octavalent organic group, and among them, an organic group having an aromatic ring or a cycloaliphatic group and having 5 to 40 carbon atoms is preferable.
  • diamine examples include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis (4-amino Phenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis @ 4- (4-aminophenoxy) phenyl ⁇ Ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3 ′ -Dimethyl-4,4'-diaminobiphenyl, 3,3'
  • R 20 represents an oxygen atom, C (CF 3 ) 2 or C (CH 3 ) 2 .
  • R 21 to R 24 each independently represent a hydrogen atom or a hydroxyl group.
  • These diamines may be used as they are or used as, for example, a diisocyanate compound obtained by reacting an amino group of a diamine with phosgene or a trimethylsilylated diamine obtained by reacting, for example, an amino group of a diamine with chlorotrimethylsilane. You may.
  • Preferred examples of the monoamine having an acidic group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, and 3-amino-4. Examples thereof include 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used.
  • Preferred examples of the acid anhydride include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and the like. Two or more of these may be used.
  • Preferred examples of the monocarboxylic acid include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, and the like. Two or more of these may be used.
  • Preferred examples of the acid chloride include a monoacid chloride compound in which the carboxy group of the monocarboxylic acid is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, and 1,6-dicarboxylic acid.
  • Monoacid chloride compounds in which only one carboxy group of dicarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene are acid-chloridated are exemplified. Two or more of these may be used.
  • Preferred examples of the active ester compound include a reaction product of the above monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these may be used.
  • the alkali-soluble resin (a) in the present invention is synthesized by a known method.
  • Examples of a method for producing a polyamic acid as a polyimide precursor include a method in which a tetracarboxylic dianhydride and a diamine compound are reacted in a solvent at a low temperature.
  • a method for producing a polyamic acid ester which is also a polyimide precursor in addition to the above-mentioned method of reacting a polyamic acid with an esterifying agent, a diester is obtained with a tetracarboxylic dianhydride and an alcohol, and then a condensing agent Reaction with an amine in a solvent in the presence of
  • a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, the remaining dicarboxylic acid is converted into an acid chloride, and the resulting compound is reacted with an amine in a solvent may be used.
  • the esterifying agent is not particularly limited, and a known method can be applied. However, N, N-dimethylformamide dialkyl acetal is preferable because the obtained resin is easily purified.
  • Examples of the method for producing polyhydroxyamide, which is a polybenzoxazole precursor include a method in which a bisaminophenol compound and a dicarboxylic acid are subjected to a condensation reaction in a solvent. Specifically, for example, a method in which a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto. A method of dropping a solution of dicarboxylic acid dichloride into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added, and the like can be given.
  • a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC)
  • Examples of the method for producing the polyimide include a method in which the polyamic acid or polyamic acid ester obtained by the above-described method is dehydrated and ring-closed in a solvent.
  • Examples of the dehydration ring closure method include chemical treatment with an acid or a base, heat treatment, and the like.
  • Examples of the method for producing polybenzoxazole include a method in which the polyhydroxyamide obtained by the above-mentioned method is dehydrated and ring-closed in a solvent.
  • Examples of the dehydration ring closure method include chemical treatment with an acid or a base, heat treatment, and the like.
  • Examples of the polyamideimide precursor include tricarboxylic acid, a corresponding tricarboxylic anhydride, and a polymer of a tricarboxylic anhydride halide and a diamine compound, and a polymer of trimellitic anhydride chloride and an aromatic diamine compound is preferable.
  • Examples of the method for producing the polyamideimide precursor include a method in which a dicarboxylic acid is reacted with a tricarboxylic acid, a corresponding tricarboxylic anhydride, or a tricarboxylic anhydride halide in a solvent at a low temperature.
  • Examples of the method for producing polyamideimide include a method in which trimellitic anhydride and an aromatic diisocyanate are reacted in a solvent, a method in which the polyamideimide precursor obtained by the above-described method is dehydrated and ring-closed in a solvent, and the like.
  • Examples of the dehydration ring closure method include chemical treatment with an acid or a base, heat treatment, and the like.
  • the polymerization solvent is not particularly limited, and alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate, isobutyl acetate, and the like, methyl isobutyl ketone, methyl propyl ketone, and the like Ketones, butyl alcohol, alcohols such as isobutyl alcohol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, Gamma-butyrolactone, N-methyl-2-pyro Don, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N, N-di
  • the photosensitive resin composition of the present invention contains a phenol resin (b) having a halogen atom (hereinafter sometimes simply referred to as “phenol resin (b)”).
  • phenol resin (b) a phenol resin having a halogen atom
  • halogen atom substitution form examples include a halogen atom, a halo (cyclo) alkyl group or a haloaryl group, and a combination thereof.
  • the halo (cyclo) alkyl group represents an alkyl group and a cycloalkyl group at least partially halogenated
  • the haloaryl group represents an aryl group at least partially halogenated.
  • Examples of the haloalkyl group include a trihalomethyl group and a pentahaloethyl group.
  • the haloaryl group examples include a dihalophenyl group and a pentahalophenyl group.
  • the substituent having a halogen atom is a divalent or higher valent group
  • the remaining bond forms a bond with an arbitrary atom or substituent
  • the bond of the phenol resin (b) is further bonded through a further substituent. It may be linked to the main chain.
  • the halogen atom of the phenol resin (b) having a halogen atom preferably contains a fluorine atom.
  • the phenol resin examples include a novolak resin and a resol resin.A method of polycondensing various phenols alone or a mixture thereof with an aldehyde such as formalin, or a polycondensation of a phenol with a methylol compound and a phenol. Obtained by the following method.
  • the phenol resin having a halogen atom in the present invention can be obtained by using a phenol having a halogen atom.
  • phenols having a halogen atom include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 2,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6- Tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, perfluoro-1-naphthol, perfluoro-2-naphthol, 2-chlorophenol, 3-chloro Phenol, 4-chlorophenol, 2,4-dichloroph Phenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-t
  • the aldehydes used for polycondensation with a novolak resin or a resole resin include, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, alone or as a mixture thereof. Can be used.
  • the phenolic methylol compound is obtained by converting the above-mentioned phenols to methylol with formaldehyde or the like, and has at least one or more methylol groups in the molecule.
  • the phenol resin (b) used in the present invention may contain a structure derived from another phenol in addition to the phenol having a halogen atom, as long as the above-mentioned properties are not deteriorated.
  • a structure derived from another phenol it has 50 to 100 mol% of a structural unit derived from a phenol having a halogen atom as a repeating unit based on 100 mol% of all the repeating units of the phenol resin (b). Is preferred. With such a range, the long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device can be improved.
  • phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6 -Dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5 -Trimethylphenol, methylenebisphenol, methylenebis-p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m- Methoxyphenol, p-methoxyphenol, -Butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-iso
  • the phenolic resin (b) has the general formula (1) and / or the general formula (1) from the viewpoint of further improving long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device. It preferably has a structural unit represented by the formula (2).
  • the general formulas (1) and / or (2) represent structural units of a phenol resin derived from bisphenols.
  • A represents a divalent substituent having a halogen atom.
  • R 1 , R 2 , R 5 and R 6 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, a methylol group or an alkoxymethyl group.
  • R 3 , R 4 , R 7 and R 8 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms.
  • p represents an integer of 0 to 2
  • q represents an integer of 0 to 4
  • r and s represent an integer of 0 to 3.
  • the A for example, -CF 2 -, - CCl 2 -, - CBr 2 -, - CI 2 -, - C (CF 3) 2 -, - C (CCl 3) 2 -, - C (CBr 3) And divalent substituents such as 2-and -C (CI 3 ) 2- .
  • those containing a fluorine atom are preferred, and -C (CF 3 ) 2 -is more preferred.
  • Examples of the phenol resin having the structural unit represented by the general formula (1) and / or the general formula (2) include a novolak resin and a resol resin, and various bisphenols may be used alone or a mixture thereof may be used, such as formalin. Obtained by polycondensation with aldehydes.
  • the resin having the structural unit represented by the general formula (1) and / or the general formula (2) can be obtained by using a bisphenol having a halogen atom.
  • bisphenols having a halogen atom include bisphenol AF, 2,2-bis (4-hydroxyphenyl) hexachloropropane, 2,2-bis (4-hydroxyphenyl) hexabromopropane, and 2,2-bis (4-hydroxyphenyl) hexaiodopropane, which can be used alone or as a mixture thereof.
  • the aldehydes used for polycondensation with a novolak resin or a resole resin include, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, alone or as a mixture thereof. Can be used.
  • the phenol resin (b) used in the present invention may have a structure other than the structural unit represented by the general formula (1) and / or the general formula (2). ),
  • the structural unit represented by the general formula (1) and / or the general formula (2) is preferably 50 mol% or more as a repeating unit based on 100 mol% of all the repeating units.
  • the long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device can be further improved. It is more preferably at least 80 mol%, particularly preferably at least 100 mol%.
  • the phenol resin (b) has a weight average molecular weight (Mw) of 500 or more in terms of polystyrene.
  • Mw is preferably 50,000 or less, more preferably 10,000 or less.
  • the content of the phenolic resin (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the alkali-soluble resin (a) from the viewpoint of improving long-term reliability.
  • the amount is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less.
  • the photosensitive resin composition of the present invention contains a photosensitive compound (c).
  • the photosensitive compound (c) include a photoacid generator (c1) and a photopolymerization initiator (c2).
  • the photoacid generator (c1) is a compound that generates an acid upon irradiation with light
  • the photopolymerization initiator (c2) is a compound that generates a radical by cleaving and / or reacting upon exposure to light.
  • the content of the photosensitive compound (c) is preferably 25 to 100 parts by mass based on 100 parts by mass of the total of the alkali-soluble resin (a) and the resin (b).
  • the photoacid generator (c1) By containing the photoacid generator (c1), an acid is generated in the light-irradiated part, so that the solubility of the light-irradiated part in an aqueous alkali solution is increased, and a positive relief pattern in which the light-irradiated part is dissolved can be obtained. it can. Further, by containing the photoacid generator (c1) and an epoxy compound or a thermal crosslinking agent described later, the acid generated in the light-irradiated portion promotes a crosslinking reaction of the epoxy compound and the thermal crosslinking agent, and the light-irradiated portion becomes insoluble. A negative relief pattern can be obtained.
  • Examples of the photoacid generator (c1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like. It is preferable to contain two or more photoacid generators, and a highly sensitive photosensitive resin composition can be obtained. From the viewpoint of long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device, a quinonediazide compound is particularly preferred as the photoacid generator (c1).
  • Examples of the quinonediazide compound include: a polyhydroxy compound in which sulfonic acid of quinonediazide is bound by an ester; a polyamino compound in which a sulfonic acid of quinonediazide is bound by a sulfonamide; An amide bond and the like can be mentioned. It is preferable that 50 mol% or more of all the functional groups of the polyhydroxy compound and the polyamino compound are substituted with sulfonic acid of quinonediazide.
  • both a 5-naphthoquinonediazidosulfonyl group and a 4-naphthoquinonediazidosulfonyl group are preferably used.
  • the same molecule may contain a naphthoquinonediazidosulfonyl ester compound having a 4-naphthoquinonediazidosulfonyl group or a 5-naphthoquinonediazidosulfonyl group, or a compound containing a 4-naphthoquinonediazidosulfonylester compound and a 5-naphthoquinonediazidosulfonylester compound. You may.
  • the 4-naphthoquinonediazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the absorption of the 5-naphthoquinonediazidosulfonyl ester compound extends to the g-line region of a mercury lamp, and is suitable for g-line exposure.
  • a 4-naphthoquinonediazidosulfonyl ester compound or a 5-naphthoquinonediazidosulfonylester compound depending on the wavelength to be exposed but it is preferable to include a 4-naphthoquinonediazidosulfonylester compound from the viewpoint of increasing sensitivity.
  • a 5-naphthoquinonediazidosulfonyl ester compound is preferable from the viewpoint of long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device.
  • a 4-naphthoquinonediazidosulfonyl ester compound can be suitably used.
  • the quinonediazide compound can be synthesized from a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound by an arbitrary esterification reaction. By using these quinonediazide compounds, resolution, sensitivity, and residual film ratio are further improved.
  • the photoacid generators (c1) sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts are preferable because acid components generated by exposure can be appropriately stabilized. Among them, sulfonium salts are preferred. Further, a sensitizer and the like can be contained as needed.
  • the content of the photoacid generator (c1) is 0.1 parts by mass or more based on 100 parts by mass of the alkali-soluble resin (a) and the phenol resin (b) in total from the viewpoint of increasing the sensitivity. It is preferably at least 10 parts by mass, more preferably at least 25 parts by mass. From the viewpoint of further improving the chemical resistance of the cured film, the amount is preferably 100 parts by mass or less. From the viewpoint of improving long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device, the content of the photoacid generator (c1) is preferably small. However, in the present invention, since the long-term reliability can be improved by containing the phenol resin (b) having a halogen atom described above, the content of the photoacid generator (c1) is increased for higher sensitivity. Can be increased.
  • Examples of the photopolymerization initiator (c2) include benzyl ketal photopolymerization initiator, ⁇ -hydroxyketone photopolymerization initiator, ⁇ -aminoketone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, oxime ester Photopolymerization initiator, acridine photopolymerization initiator, titanocene photopolymerization initiator, benzophenone photopolymerization initiator, acetophenone photopolymerization initiator, aromatic ketoester photopolymerization initiator, benzoate ester photopolymerization start Agents and the like. Two or more photopolymerization initiators (c2) may be contained.
  • ⁇ -aminoketone-based photopolymerization initiators acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are more preferable.
  • Examples of the ⁇ -aminoketone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one, 3,6-bis (2-methyl- 2-morpholinopropionyl) -9-octyl-9H-carbazole and the like.
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl) phosphine oxide and the like.
  • Examples of the oxime ester-based photopolymerization initiator include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime and 1-phenylbutane-1,2-dione-2- (O-methoxy Carbonyl) oxime, 1,3-diphenylpropane-1,2,3-trione-2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- ( O-benzoyl) oxime, 1- [4- [4- (carboxyphenyl) thio] phenyl] propane-1,2-dione-2- (O-acetyl) oxime, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyl) oxime, 1- [9-eth
  • the content of the photopolymerization initiator (c2) is from 100 parts by mass of the alkali-soluble resin (a), the phenol resin (b), and the radical polymerizable compound described below in total from the viewpoint of increasing the sensitivity. , 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more.
  • the amount is preferably 50 parts by mass or less. From the viewpoint of improving long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device, the smaller the content of the photoacid generator (c2), the better.
  • the long-term reliability can be improved by containing the phenol resin (b) having a halogen atom described above, the content of the photoacid generator (c2) is increased for higher sensitivity. Can be increased.
  • the photosensitive resin composition of the present invention may further contain a radical polymerizable compound.
  • the radical polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bonds in a molecule.
  • radical polymerization of the radically polymerizable compound proceeds by radicals generated from the above-mentioned photopolymerization initiator (c2), and the light-irradiated portion becomes insoluble, whereby a negative pattern can be obtained.
  • c2 photopolymerization initiator
  • photo-curing of the light-irradiated portion is promoted, and the sensitivity can be further improved.
  • the crosslink density after heat curing is improved, the hardness of the cured film can be improved.
  • radical polymerizable compound a compound having a (meth) acryl group, in which radical polymerization easily proceeds, is preferable.
  • a compound having two or more (meth) acryl groups in the molecule is more preferable from the viewpoints of improving the sensitivity at the time of exposure and the hardness of the cured film.
  • the double bond equivalent of the radical polymerizable compound is preferably from 80 to 400 g / mol from the viewpoint of improving the sensitivity at the time of exposure and the hardness of the cured film.
  • radical polymerizable compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, 2,2-bis [4- (3- ( (Meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 1,3,5-tris ((meth) acryloxyethyl) isocyanuric acid, 1,3-bis ((meth) (Acryl)
  • the content of the radical polymerizable compound is preferably from the viewpoint of further improving the sensitivity and reducing the taper angle by adding the total of the alkali-soluble resin (a) and the radical polymerizable compound to 100 parts by mass.
  • the amount is preferably at least 15 parts by mass, more preferably at least 30 parts by mass.
  • the amount is preferably 65 parts by mass or less, more preferably 50 parts by mass or less.
  • the photosensitive resin composition of the present invention may further contain a thermal crosslinking agent (d).
  • the thermal crosslinking agent (d) refers to a compound having at least two thermally reactive functional groups such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group in a molecule.
  • the alkali-soluble resin (a) or other additional components can be crosslinked to improve the heat resistance, chemical resistance and bending resistance of the film after heat curing.
  • Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, MOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA,
  • Preferred examples of the compound having at least two epoxy groups include “Epolite” (registered trademark) 40E, “Epolite” 100E, “Epolite” 200E, “Epolite” 400E, “Epolite” 70P, “Epolite” 200P, and “Epolite”.
  • Preferred examples of the compound having at least two oxetanyl groups include, for example, etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (all manufactured by Ube Industries, Ltd.), and oxetanated phenol novolak.
  • the thermal crosslinking agent (d) may contain two or more kinds in combination.
  • the content of the thermal crosslinking agent (d) is preferably 1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the total amount of the resin composition excluding the solvent.
  • the content of the thermal crosslinking agent (d) is at least 1 part by mass, the chemical resistance and bending resistance of the cured film can be further increased.
  • the content of the thermal crosslinking agent (d) is 30 parts by mass or less, the amount of outgas from the cured film can be further reduced, and the long-term reliability of the organic EL display device can be further increased. Excellent storage stability.
  • the photosensitive resin composition of the present invention may further contain a solvent.
  • the varnish By containing the solvent, the varnish can be made into a varnish, and the applicability can be improved.
  • the solvent examples include polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether.
  • polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether.
  • Ethyl ether diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Propylene glycol mono-n-butyl ether, dip Ethers such as pyrene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran and dioxane Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone
  • the content of the solvent is not particularly limited, but is preferably from 100 to 3,000 parts by mass, more preferably from 150 to 2,000 parts by mass, based on 100 parts by mass of the photosensitive resin composition excluding the solvent.
  • the proportion of the solvent having a boiling point of 180 ° C. or higher relative to the total amount of the solvent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
  • the photosensitive resin composition of the present invention may further contain an adhesion improver.
  • adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agent such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agent, aluminum chelating agent, aromatic amine compound and containing alkoxy group Examples include compounds obtained by reacting a silicon compound.
  • adhesion improvers Two or more of these may be contained.
  • a base material such as a silicon wafer, ITO, SiO 2 , or silicon nitride when a resin film is developed. Further, resistance to oxygen plasma and UV ozone treatment used for cleaning or the like can be increased.
  • the content of the adhesion improver is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the resin composition excluding the solvent.
  • the photosensitive resin composition of the present invention may further contain a surfactant, if necessary, to improve the wettability with the substrate.
  • a surfactant examples include SH series, SD series, ST series of Dow Corning Toray Co., Ltd., BYK series of Big Chemie Japan, KP series of Shin-Etsu Chemical Co., Ltd., and NOF Corporation.
  • the content of the surfactant is preferably 0.001 to 1 part by mass based on 100 parts by mass of the total amount of the resin composition excluding the solvent.
  • a phenol compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500 may be contained.
  • phenol compounds having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP- EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisPHAP, TrisP-PA TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis 5X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP, (
  • the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer when exposed, so Film loss is small and development is facilitated in a short time. Therefore, the sensitivity is easily improved.
  • a phenolic compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500 further contains an electron. It preferably has a withdrawing group.
  • the term “electron-withdrawing group” refers to a substituent constant ⁇ p 0 value defined in Chemical Handbook Basic Edition, Revised 5th Edition, II-379 to II-380 (edited by The Chemical Society of Japan, published by Maruzen Co., Ltd.). Is a group that is positive.
  • a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group, a sulfinyl group, a halo (cyclo) alkyl group or a haloaryl group, and Combinations can be given.
  • the halo (cyclo) alkyl group represents an alkyl group and a cycloalkyl group at least partially halogenated
  • the haloaryl group represents an aryl group at least partially halogenated.
  • phenol compound (e) having an electron-withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500 include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, and 2,4-difluorophenol.
  • bisphenols are preferred as the phenol compound (e) having an electron withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500.
  • examples of bisphenols include bisphenol AF, bisphenol S, 2,2'-dihydroxybenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, and 2,3,4-trihydroxybenzophenone. , 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and the like.
  • the content of such a phenolic compound having a phenolic hydroxyl group having a molecular weight of 100 or more and less than 500 is preferably 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the alkali-soluble resin (a).
  • the alkali developability of the photosensitive resin composition can be improved while maintaining high heat resistance.
  • the photosensitive resin composition of the present invention may further contain inorganic particles.
  • Preferred specific examples of the inorganic particles include, for example, silicon oxide, titanium oxide, barium titanate, alumina, and talc.
  • the primary particle diameter of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.
  • the content of the inorganic particles is preferably 5 to 90 parts by mass based on 100 parts by mass of the total amount of the resin composition excluding the solvent.
  • the photosensitive resin composition of the present invention may further contain a thermal acid generator as long as long-term reliability of the organic EL display device is not impaired.
  • the thermal acid generator generates an acid by heating to accelerate the crosslinking reaction of the thermal crosslinking agent, and when the resin of the component (a) has an unclosed imide ring structure or oxazole ring structure, these compounds are used. Cyclization can be promoted, and the mechanical properties of the cured film can be further improved.
  • the thermal decomposition temperature of the thermal acid generator used in the present invention is preferably from 50 ° C to 270 ° C, and more preferably 250 ° C or less. Further, when the resin composition of the present invention is applied to a substrate and dried (pre-baked: about 70 to 140 ° C.), no acid is generated, and the final heating (curing: about 100 to 100) after patterning by subsequent exposure and development. (400 ° C.) is preferred because it can suppress the decrease in sensitivity during development.
  • the acid generated from the thermal acid generator used in the present invention is preferably a strong acid, for example, arylsulfonic acid such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid.
  • alkyl halosulfonic acids such as trifluoromethylsulfonic acid. They are used as salts such as onium salts or as covalent compounds such as imidosulfonates. Two or more of these may be contained.
  • the content of the thermal acid generator is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the resin composition excluding the solvent.
  • the thermal acid generator is contained in an amount of 0.01 part by mass or more, the crosslinking reaction and the cyclization of the unring-closed structure of the resin are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • the amount is preferably 5 parts by mass or less, more preferably 2 parts by mass or less.
  • a method for producing the photosensitive resin composition of the present invention will be described.
  • an alkali-soluble resin (a), a phenol resin (b), and a photosensitive compound (c) and if necessary, a radical polymerizable compound, a thermal crosslinking agent, a solvent, an adhesion improver, a surfactant, and a molecular weight of 100 or more and less than 500
  • a photosensitive resin composition can be obtained.
  • stirring and heating can be mentioned.
  • the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C.
  • the order of dissolving each component is not particularly limited, and for example, a method of sequentially dissolving the compounds with low solubility may be mentioned.
  • poor dissolution of other components due to the generation of air bubbles can be achieved by adding the last component after dissolving the other components. Can be prevented.
  • the obtained photosensitive resin composition is filtered using a filter to remove dust and particles.
  • the filter pore size includes, for example, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, 0.05 ⁇ m, 0.02 ⁇ m, etc., but is not limited thereto.
  • Examples of the material of the filtration filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable.
  • the photosensitive resin sheet of the present invention is formed using the photosensitive resin composition.
  • the sheet of the present invention can be obtained, for example, by applying the above-described photosensitive resin composition on a peelable substrate such as polyethylene terephthalate to obtain a coating film of the photosensitive resin composition, and drying the film. . Further, a protective film may be laminated.
  • the coating method examples include a spin coating method, a slit coating method, a dip coating method, a spray coating method, and a printing method.
  • the slit coating method is preferable because the coating can be performed with a small amount of the coating liquid, which is advantageous for cost reduction.
  • the amount of the coating solution required for the slit coating method is, for example, about 1/5 to 1/10 as compared with the spin coating method.
  • the slit nozzle used for coating include “Linear Coater” manufactured by Dainippon Screen Mfg. Co., Ltd., “Spinless” manufactured by Tokyo Ohka Kogyo Co., Ltd., “TS Coater” manufactured by Toray Engineering Co., Ltd., Chugai Furnace Co., Ltd.
  • the coating speed is generally in the range of 10 mm / sec to 400 mm / sec.
  • the thickness of the applied film varies depending on the solid content concentration and viscosity of the resin composition, but is usually applied so that the thickness after drying is 0.1 to 10 ⁇ m, preferably 0.3 to 5 ⁇ m.
  • the substrate on which the photosensitive resin composition is to be coated may be pretreated with the above-described adhesion improver in advance.
  • an adhesion improver is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate in an amount of 0.5 to 20% by mass.
  • a method of treating the surface of the base material using the dissolved solution may be used. Examples of the method for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.
  • a reduced pressure drying treatment as needed, and heat and dry the coated film.
  • This step is also called prebaking. Drying uses a hot plate, oven, infrared rays, and the like.
  • a hot plate When a hot plate is used, the coating film is heated directly on the plate or on a jig such as a proxy pin provided on the plate.
  • the material of the proxy pin include a metal material such as aluminum and stainless steel, and a synthetic resin such as a polyimide resin and “Teflon” (registered trademark). Any material can be used as long as it has heat resistance.
  • the height of the proxy pin varies depending on the size of the base material, the type of the coating film, the purpose of heating, and the like, but is preferably about 0.1 to 10 mm.
  • the heating temperature and heating time vary depending on the type and purpose of the coating film, but the heating temperature is preferably from 50 ° C. to 180 ° C., and the heating time is preferably from 1 minute to several hours.
  • the photosensitive resin sheet can form a pattern.
  • a desired pattern can be formed by irradiating the photosensitive resin sheet with a mask having a desired pattern by irradiating it with actinic radiation and developing the same.
  • Actinic radiation used for exposure includes ultraviolet light, visible light, electron beam, X-ray and the like.
  • the exposed part dissolves in the developer.
  • the exposed portion is hardened and becomes insoluble in a developer.
  • a desired pattern is formed by removing the exposed portion in the case of a positive type and the non-exposed portion in the case of a negative type with a developing solution.
  • a developing solution tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethanol
  • An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine is preferred.
  • a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide, and an alcohol such as methanol, ethanol, and isopropanol are added to these alkaline aqueous solutions.
  • Ethyl lactate, esters such as propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone.
  • Examples of the developing system include a system such as spray, paddle, immersion, and ultrasonic wave.
  • the pattern formed by development is rinsed with distilled water.
  • Alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water and rinsed.
  • the cured film of the present invention can be obtained by curing the photosensitive resin sheet or the photosensitive resin composition.
  • the photosensitive resin composition or the photosensitive resin sheet of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof or a copolymer thereof with polyimide
  • the imide is cured by heating. Since a ring and an oxazole ring are formed, heat resistance and chemical resistance can be further improved.
  • the heat curing temperature is preferably 180 ° C or higher, more preferably 200 ° C or higher, further preferably 230 ° C or higher, and particularly preferably 250 ° C or higher, from the viewpoint of further reducing the amount of outgas generated from the cured film.
  • the temperature is preferably 500 ° C or less, more preferably 450 ° C or less. In this temperature range, the temperature may be increased stepwise or continuously.
  • the heat curing time is preferably 30 minutes or more from the viewpoint of further reducing the outgas amount. Also, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or less. For example, a method of performing heat treatment at 150 ° C. and 250 ° C. for 30 minutes each, and a method of performing heat treatment while linearly increasing the temperature from room temperature to 300 ° C. over 2 hours, and the like can be given.
  • the photosensitive resin composition, the photosensitive resin sheet and the cured film of the present invention are used for a surface protective layer and an interlayer insulating layer of a semiconductor element, an insulating layer of an organic electroluminescence (EL) element, and an organic EL element.
  • MRAM with low heat resistance polymer memory (Polymer Ferroelectric RAM: PFRAM) which is promising as a next-generation memory, and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM) are suitable as surface protective layers and interlayer insulating layers.
  • PFRAM Polymer Ferroelectric RAM
  • OUM Phase Change memory
  • a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode for example, an LCD, an ECD, an ELD, and an organic electroluminescent element is used. It can also be used for an insulating layer of a conventional display device (organic electroluminescent device), etc.
  • organic EL display device, a semiconductor device, and a semiconductor electronic component will be described as examples.
  • Organic light-emitting materials are generally susceptible to gas components and moisture, and exposure to these materials causes a reduction in light emission luminance and pixel shrinkage.
  • the pixel shrink refers to a phenomenon in which the light emission luminance is reduced from the edge of the pixel or the pixel is turned off.
  • Long-term reliability can be improved by including the cured film of the present invention as a flattening layer and / or an insulating layer of an organic EL display device.
  • the insulating layer is adjacent to the organic light emitting material, it has a greater effect on long-term reliability than the flattening layer, and in order to obtain an organic EL display device with high long-term reliability, at least the cured film of the present invention is included in the insulating layer. Is preferred.
  • an active matrix type display device As an example, it has a TFT on a substrate such as glass or various plastics, and a wiring located on the side of the TFT and connected to the TFT, and covers irregularities thereon. Thus, a flattening layer is provided, and a display element is provided on the flattening layer. The display element and the wiring are connected via a contact hole formed in the flattening layer. Particularly, in recent years, the flexibility of the organic EL display device has become mainstream, and it is preferable that the substrate having the above-described drive circuit is an organic EL display device including a resin film.
  • the cured film obtained by curing the photosensitive resin composition or the photosensitive sheet of the present invention is used as an insulating layer and a flattening layer of such a flexible display, it is particularly preferably used because of excellent bending resistance.
  • polyimide is particularly preferred as the resin film.
  • the thickness is preferably 1.0 to 5.0 ⁇ m, more preferably 2.0 ⁇ m or more.
  • the flattening layer is preferably a multilayer. The number of layers is, for example, 2 to 5 layers.
  • the organic EL display device of the present invention preferably has at least a part where the cured film is provided and a part which can be bent and / or a part which is fixed in a bent state.
  • a cured film obtained by curing the photosensitive resin composition or the photosensitive resin sheet of the present invention an organic EL display device having excellent bending resistance can be obtained.
  • the radius of curvature of the bendable portion and / or the portion fixed in a bent state is preferably 0.1 mm or more, and more preferably 5 mm or less. If the radius of curvature is 0.1 mm or more, the bending resistance at the bent portion can be secured, and if it is 5 mm or less, design properties such as narrowing of the frame can be secured.
  • the organic EL display device of the present invention can be bent at any appropriate portion.
  • the organic EL display device may be bendable at a central portion like a foldable display device, or may be bendable at an end portion from the viewpoint of maximizing design and a display screen. Good.
  • the organic EL display device may be bendable along its longitudinal direction or may be bendable along its short direction. It suffices if the specific portion of the organic EL display device is bendable (for example, some or all of the four corners can be bent in an oblique direction) depending on the application.
  • FIG. 1 shows a cross-sectional view of an example of a TFT substrate.
  • a bottom-gate or top-gate TFT (thin film transistor) 1 is provided in a matrix on a substrate 6, and a TFT insulating layer 3 is formed so as to cover the TFT 1.
  • the wiring 2 connected to the TFT 1 is provided on the TFT insulating layer 3.
  • a flattening layer 4 is provided on the TFT insulating layer 3 so as to bury the wiring 2.
  • the planarization layer 4 is provided with a contact hole 7 reaching the wiring 2.
  • an ITO (transparent electrode) 5 is formed on the flattening layer 4 while being connected to the wiring 2 via the contact hole 7.
  • the ITO 5 serves as an electrode of a display element (for example, an organic EL element). Then, an insulating layer 8 is formed so as to cover the periphery of the ITO 5.
  • the organic EL element may be a top emission type that emits light emitted from the side opposite to the substrate 6 or a bottom emission type that emits light from the substrate 6 side.
  • an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the same is obtained.
  • the TFT insulating layer 3, the flattening layer 4, and / or the insulating layer 8 are used to form a photosensitive resin film made of a photosensitive resin composition or a photosensitive resin sheet of the present invention.
  • An organic EL display device can be obtained by a manufacturing method including these steps.
  • the cured film of the present invention can be suitably used as an interlayer insulating layer and / or a surface protective layer in a semiconductor electronic component and a semiconductor device having an electrode, a metal wiring, an interlayer insulating layer and / or a surface protective layer on a substrate. .
  • the cured film of the present invention can be included in at least a part of the interlayer insulating layer and / or the surface protective layer. Since the cured film of the present invention has excellent mechanical properties, the stress from the sealing resin can be reduced even at the time of mounting, the damage of the low-k layer can be suppressed, and a highly reliable semiconductor device can be provided.
  • FIG. 2 shows an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having a bump.
  • an Al pad 10 for input / output and a passivation layer 11 having a via hole are formed on a silicon wafer 9, an Al pad 10 for input / output and a passivation layer 11 having a via hole are formed. Further, an insulating layer 12 is formed on the passivation layer 11, a metal layer 13 made of Cr, Ti or the like is formed so as to be connected to the Al pad 10, and a metal wiring made of Al, Cu, or the like is formed by electrolytic plating or the like. 14 are formed. By etching the metal layer 13 located around the solder bumps 18, the pads are insulated. A barrier metal 16 and a solder bump 18 are formed on the insulated pad. When processing the insulating film 15, scribe lines 17 are formed.
  • FIG. 3 shows an example of a method for manufacturing a semiconductor device having bumps.
  • the resin composition of the present invention is applied on the silicon wafer 9 on which the Al pad 10 and the passivation layer 11 are formed, and a photolithography step is performed to form a patterned insulating layer 12.
  • the metal layer 13 is formed by a sputtering method.
  • a metal wiring 14 is formed on the metal layer 13 by plating.
  • the resin composition of the present invention is applied, and in the step 3d, a pattern of the insulating layer 15 is formed through a photolithography step.
  • the resin composition forming the insulating layer 15 is processed into a thick film at the scribe line 17.
  • Wiring (so-called rewiring) can be further formed on the insulating layer 15.
  • the above steps are repeated to form a multilayer wiring structure in which the rewiring of two or more layers is separated by the interlayer insulating layer composed of the cured film of the present invention. can do.
  • a barrier metal 16 is formed, and in a step 3f, a solder bump 18 is formed.
  • dicing is performed along the last scribe line 17 and cut into chips to obtain a semiconductor device having bumps.
  • TMAH tetramethylammonium
  • polyimide film substrates 25 each having a cured film were cut into a size of 50 mm long ⁇ 10 mm wide.
  • the polyimide film substrate 25 was held for 30 seconds in a state where the surface of the cured film 26 was turned outside and the polyimide film substrate 25 was bent at 180 ° on a line of 25 mm in length.
  • open the folded polyimide film substrate observe the bent portion on the 25 mm vertical line of the cured film surface using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and observe the appearance of the cured film surface. The change was evaluated.
  • the bending test was performed with a radius of curvature in the range of 0.1 to 1.0 mm, and the minimum radius of curvature that did not cause appearance change such as cracking on the cured film surface or peeling of the cured film from the polyimide film substrate was recorded.
  • FIG. 4 is a schematic view of a procedure for manufacturing an organic EL display device.
  • a 10-nm ITO transparent conductive film was formed on the entire surface of a non-alkali glass substrate 19 of 38 mm ⁇ 46 mm by a sputtering method, and was etched as a first electrode (transparent electrode) 20.
  • an auxiliary electrode 21 for taking out the second electrode was formed.
  • the obtained substrate was subjected to ultrasonic cleaning with Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes and then with ultrapure water.
  • the photosensitive resin composition shown in Table 1 was applied to the entire surface of the substrate by spin coating, and was prebaked on a hot plate at 120 ° C. for 2 minutes. After this film was exposed to UV through a photomask, it was developed with a 2.38% by mass TMAH aqueous solution to dissolve unnecessary portions and rinsed with pure water.
  • the obtained resin pattern was heat-treated at 250 ° C. for 1 hour in a nitrogen atmosphere using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.).
  • the opening 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 the insulating layer 22 is formed such that each opening exposes the first electrode. It was formed only in the effective area. In this way, an insulating layer having an insulating layer aperture ratio of 25% was formed in a substrate effective area having a square shape with one side of 16 mm. The thickness of the insulating layer was about 1.0 ⁇ m.
  • an organic EL layer 23 including a light emitting layer was formed by a vacuum evaporation method. Note that the degree of vacuum at the time of evaporation was 1 ⁇ 10 ⁇ 3 Pa or less, and the substrate was rotated with respect to the evaporation source during evaporation.
  • a compound (HT-1) was deposited to a thickness of 10 nm as a hole injection layer, and a compound (HT-2) was 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 deposited on the light emitting layer to a thickness of 40 nm so that the doping concentration was 10%.
  • the compound (ET-1) and the compound (LiQ) were stacked as electron transporting materials at a volume ratio of 1: 1 to a thickness of 40 nm.
  • the structure of the compound used in the organic EL layer is shown below.
  • a cap-shaped glass plate is bonded by using an epoxy resin-based adhesive in a low-humidity nitrogen atmosphere to seal it, and a top emission type organic EL having a square shape of 5 mm on a single substrate is formed on one substrate.
  • the film thickness referred to here is a value displayed on a crystal oscillation type film thickness monitor.
  • the produced organic EL display device was placed on a hot plate heated to 80 ° C. with the light emitting surface facing upward, and irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW / cm 2 .
  • the organic EL display device emits light by DC driving of 0.625 mA, and the area ratio of the light emitting portion to the area of the light emitting pixel (pixel light emitting area ratio) is measured. did. If the pixel light emitting area ratio after 1000 hours has passed by this evaluation method is 80% or more, it can be said that the long-term reliability is excellent, and 90% or more is more preferable.
  • Synthesis Example 1 Synthesis of hydroxyl-containing diamine compound ( ⁇ ) 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was added to 100 mL of acetone, It was dissolved in 17.4 g (0.3 mol) of propylene oxide and cooled to -15 ° C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the reaction was carried out at ⁇ 15 ° C. for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and dried at 50 ° C. in vacuo.
  • BAHF 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • Synthesis Example 2 Synthesis of quinonediazide compound (c-1) Under dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidosulfonyl chloride 36 .27 g (0.135 mol) were dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35 ° C. or higher. After the addition, the mixture was stirred at 30 ° C. for 2 hours.
  • TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
  • Synthesis Example 3 Synthesis of quinonediazide compound (c-2) 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 4-naphthoquinonediazidosulfonyl chloride 36 in a stream of dry nitrogen .27 g (0.135 mol) were dissolved in 450 g of 1,4-dioxane and brought to room temperature.
  • 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35 ° C. or higher. After the dropwise addition, the mixture was stirred at 30 ° C. for 2 hours.
  • Synthesis Example 4 Synthesis of alkali-soluble resin (a-1) 31.0 g (0.10 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) under a stream of dry nitrogen was dissolved in 500 g of NMP.
  • ODPA 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride
  • SiDA 1,3-bis (3-aminopropyl) tetramethyldisiloxane
  • MAP 3-aminophenol
  • NMP N-dimethylformamide diethyl acetal 32
  • a solution obtained by diluting 0.39 g (0.22 mol) with 50 g of NMP was added dropwise over 10 minutes, and the mixture was stirred for 3 hours at 50 ° C.
  • the solution was cooled to room temperature, and the solution was added to 3 L of water.
  • the precipitate was collected by filtration, washed with water three times, and dried in a vacuum drier at 80 ° C. for 24 hours to obtain a polyimide precursor (a-1) as an alkali-soluble resin.
  • Synthesis Example 5 Synthesis of Alkali-Soluble Resin (a-2) Under dry nitrogen flow, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, and 3.27 g (0.2%) of MAP as a terminal blocking agent. 03 mol) was dissolved in 150 g of NMP. To this, 31.0 g (0.1 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was added together with 50 g of NMP, stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. Stirred at C for 4 hours.
  • ODPA 4,4′-diphenylethertetracarboxylic dianhydride
  • a solution dissolved in 25 g was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued at ⁇ 15 ° C. for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80 ° C. for 24 hours to obtain a polybenzoxazole precursor (a-3) as an alkali-soluble resin.
  • Synthesis Example 7 Synthesis of Alkali-Soluble Resin (a-4) In a 500 ml flask, 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). 150 g). Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate were added, and the mixture was stirred at room temperature for a while, and the atmosphere in the flask was replaced with nitrogen.
  • PGMEA propylene glycol monomethyl ether acetate
  • the mixture was heated and stirred at 5 ° C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 ° C. for 4 hours, and an acrylic resin (a- The solution of 4) was obtained.
  • the solid content concentration of the obtained acrylic resin solution was 43% by weight.
  • Synthesis Example 8 Synthesis of phenol resin (b-1) having a halogen atom Under dry nitrogen flow, 672 g (2.0 mol) of bisphenol AF and 96 g (1.6 mol) of a 50% by weight aqueous formaldehyde solution were dissolved in 250 g of methyl isobutyl ketone. While cooling to 30 ° C. or lower, 2.5 g of p-toluenesulfonic acid was added, followed by stirring at 100 ° C. for 4 hours. After completion of the stirring, 5.3 g of a 10% aqueous solution of NaOH was added to neutralize, and then washed with 750 g of pure water to remove neutralized salts. Then, the mixture was heated to 160 ° C.
  • Synthesis Example 9 Synthesis of phenol resin (b-2) having halogen atom Instead of 672 g (2.0 mol) of bisphenol AF, 537 g (1.6 mol) of bisphenol AF and 43 g (0.4 mol) of m-cresol were used. Except that in the same manner as in Synthesis Example 8, bisphenol AF / cresol novolak resin (b-2) was obtained. The weight average molecular weight of (b-2) was 1200.
  • Synthesis Example 10 Synthesis of phenol resin (b-3) having a halogen atom Instead of 672 g (2.0 mol) of bisphenol AF, 336 g (1.0 mol) of bisphenol AF and 108 g (1.0 mol) of m-cresol were used. Except that in the same manner as in Synthesis Example 8, bisphenol AF / cresol novolak resin (b-3) was obtained. The weight average molecular weight of (b-3) was 1,100.
  • Synthesis Example 11 Synthesis of phenol resin (b-4) having halogen atom Instead of 672 g (2.0 mol) of bisphenol AF, 134 g (0.4 mol) of bisphenol AF and 173 g (1.6 mol) of m-cresol were used. Except that in the same manner as in Synthesis Example 8, bisphenol AF / cresol novolak resin (b-4) was obtained. The weight average molecular weight of (b-4) was 1,000.
  • Synthesis Example 12 Synthesis of phenol resin (b-5) having halogen atom Same as Synthesis Example 8 except that 170 g (1.6 mol) of benzaldehyde was used instead of 96 g (1.6 mol) of a 50% by weight aqueous solution of formaldehyde. As a result, a novolak resin (b-5) of bisphenol AF was obtained. The weight average molecular weight of (b-5) was 1,400.
  • Synthesis Example 13 Synthesis of phenol resin (b-6) having halogen atom Bisphenol AF was placed in a four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer. 672 g (2.0 mol) and 240 g (4.0 mol) of a 50% by weight aqueous solution of formaldehyde are dissolved in 250 g of methyl isobutyl ketone, 6.4 g of trimethylamine is added while cooling to 30 ° C. or lower, and the mixture is stirred at 100 ° C. for 2 hours. did. After completion of the stirring, 4 parts of oxalic acid was added, and the mixture was dried under reduced pressure at 100 ° C. and 400 mmHg for 2 hours to obtain a resole resin (b-6) of bisphenol AF. The weight average molecular weight of (b-6) was 900.
  • Synthesis Example 14 Synthesis of phenol resin (b-8) having a halogen atom Instead of using 672 g (2.0 mol) of bisphenol AF, 537 g (1.6 mol) of bisphenol AF and 100 g (0.4 mol) of bisphenol S were used. A novolak resin (b-8) of bisphenol AF / bisphenol S was obtained in the same manner as in Synthesis Example 8. The weight average molecular weight of (b-8) was 1,300.
  • Synthesis Example 15 Synthesis of phenol resin (b-9) having a halogen atom Except that bisphenol AF 537 g (1.6 mol) and bisphenol A 91 g (0.4 mol) were used instead of bisphenol AF 672 g (2.0 mol).
  • a novolak resin (b-9) of bisphenol AF / bisphenol A was obtained in the same manner as in Synthesis Example 8.
  • the weight average molecular weight of (b-9) was 1200.
  • Example 1 8.0 g of the alkali-soluble resin (a-1), 2.0 g of the phenol resin (b-1), and 2.0 g of the quinonediazide compound (c-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. . Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 2 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.0 g of the phenol resin (b-1) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 3 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.0 g of the phenol resin (b-1) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 4 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 2.0 g of the phenol resin (b-4) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 5 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.0 g of the phenol resin (b-5) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 6 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.0 g of the phenol resin (b-6) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 7 Instead of 8.0 g of the alkali-soluble resin (a-1) and 2.0 g of the phenol resin (b-1), 9.5 g of the alkali-soluble resin (a-1) and 0.5 g of the phenol resin (b-1) were used.
  • a varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except for the above. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 8 Instead of 8.0 g of the alkali-soluble resin (a-1) and 2.0 g of the phenol resin (b-1), 9.0 g of the alkali-soluble resin (a-1) and 1.0 g of the phenol resin (b-1) were used.
  • a varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except for the above. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 9 Instead of 8.0 g of the alkali-soluble resin (a-1) and 2.0 g of the phenol resin (b-1), 5.0 g of the alkali-soluble resin (a-1) and 5.0 g of the phenol resin (b-1) were used.
  • a varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except for the above. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 10 Instead of 8.0 g of the alkali-soluble resin (a-1) and 2.0 g of the phenol resin (b-1), 3.0 g of the alkali-soluble resin (a-1) and 7.0 g of the phenol resin (b-1) were used.
  • a varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except for the above. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 11 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 2.0 g of the quinonediazide compound (c-1) was used instead of 2.0 g of the quinonediazide compound (c-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 12 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 4.0 g of the quinonediazide compound (c-1) was changed to 4.0 g. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 13 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 11 except that 4.0 g of the quinonediazide compound (c-2) was changed to 4.0 g. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 14 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 8.0 g of the alkali-soluble resin (a-1) was used instead of 8.0 g of the alkali-soluble resin (a-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 15 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 8.0 g of the alkali-soluble resin (a-1) was used instead of 8.0 g of the alkali-soluble resin (a-1). Using the obtained varnish, the sensitivity, the bending resistance and the long-term reliability of the organic EL display device were evaluated as described above.
  • Example 16 Positive-type photosensitization was performed in the same manner as in Example 1, except that 8.0 g of the alkali-soluble resin (a-1) was used instead of 8.0 g of the alkali-soluble resin (a-4) solution (8.0 g of resin solid content). A varnish of a conductive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 17 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 2.0 g of the thermal crosslinking agent (d-1) was added. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 18 Positive photosensitive resin was prepared in the same manner as in Example 1 except that 2.0 g of WPAG-336 (trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used instead of 2.0 g of the quinonediazide compound (c-1). A varnish of the composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • WPAG-336 trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • Example 19 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 1.0 g of a phenol compound (e-1) having an electron-withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500 was added.
  • a phenol compound (e-1) having an electron-withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500 was added.
  • Example 20 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1 except that 1.0 g of a phenol compound (e-2) having an electron-withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500 was added.
  • a phenol compound (e-2) having an electron-withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500 was added.
  • e-2 a phenol compound having an electron-withdrawing group and a phenolic hydroxyl group and having a molecular weight of 100 or more and less than 500 was added.
  • Example 21 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.0 g of the phenol resin (b-8) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 22 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 2.0 g of the phenol resin (b-9) was used instead of 2.0 g of the phenol resin (b-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 1 A varnish of a positive photosensitive resin composition was obtained in addition to 10.0 g of the alkali-soluble resin (a-1), 2.0 g of the quinonediazide compound (c-1) and 30 g of GBL. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 2 Positive was carried out in the same manner as in Comparative Example 1 except that 8.0 g of the alkali-soluble resin (a-1) and 2.0 g of the phenol resin (b'-1) were used instead of 10.0 g of the alkali-soluble resin (a-1). A varnish of the photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 3 Positive was performed in the same manner as in Comparative Example 1 except that 8.0 g of the alkali-soluble resin (a-1) and 2.0 g of the phenol resin (b'-2) were used instead of 10.0 g of the alkali-soluble resin (a-1). A varnish of the photosensitive resin composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 4 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 1, except that 2.0 g of the quinonediazide compound (c-2) was used instead of 2.0 g of the quinonediazide compound (c-1). Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 5 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 1, except that 2.0 g of the quinonediazide compound (c-1) was changed to 4.0 g. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 6 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Comparative Example 4, except that 2.0 g of the quinonediazide compound (c-2) was changed to 4.0 g. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 7 Positive photosensitive resin was prepared in the same manner as in Comparative Example 1 except that 2.0 g of WPAG-336 (trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used instead of 2.0 g of the quinonediazide compound (c-1). A varnish of the composition was obtained. Using the obtained varnish, the sensitivity, bending resistance, and long-term reliability of the organic EL display device were evaluated as described above.
  • WPAG-336 trade name, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • Tables 1 and 2 show the compositions and evaluation results of the examples and comparative examples.
  • TFT thin film transistor
  • Wiring 3 TFT insulating layer 4: Flattening layer 5: ITO (transparent electrode) 6: substrate 7: contact hole 8: insulating layer 9: silicon wafer 10: Al pad 11: passivation layer 12: insulating layer 13: metal (Cr, Ti, etc.) layer 14: metal wiring (Al, Cu, etc.) 15: insulating layer 16: barrier metal 17: scribe line 18: solder bump 19: alkali-free glass substrate 20: first electrode (transparent electrode) 21: auxiliary electrode 22: insulating layer 23: organic EL layer 24: second electrode (non-transparent electrode) 25: polyimide film substrate 26: cured film

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