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WO2020075592A1 - 感光性樹脂組成物、硬化膜、および該硬化膜を用いた表示装置 - Google Patents

感光性樹脂組成物、硬化膜、および該硬化膜を用いた表示装置 Download PDF

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Publication number
WO2020075592A1
WO2020075592A1 PCT/JP2019/038927 JP2019038927W WO2020075592A1 WO 2020075592 A1 WO2020075592 A1 WO 2020075592A1 JP 2019038927 W JP2019038927 W JP 2019038927W WO 2020075592 A1 WO2020075592 A1 WO 2020075592A1
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WIPO (PCT)
Prior art keywords
photosensitive resin
group
resin composition
partition
general formula
Prior art date
Application number
PCT/JP2019/038927
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English (en)
French (fr)
Japanese (ja)
Inventor
有本真治
大西啓之
亀本聡
三好一登
Original Assignee
東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2019554953A priority Critical patent/JP7352176B2/ja
Priority to CN201980064350.5A priority patent/CN112889002B/zh
Priority to KR1020217009063A priority patent/KR102699266B1/ko
Publication of WO2020075592A1 publication Critical patent/WO2020075592A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • 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
    • 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

Definitions

  • the present invention relates to a photosensitive resin composition, a cured film, and a display device using the cured film.
  • organic EL organic electroluminescence
  • an organic EL light emitting device has a drive circuit, a flattening layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate, and between a first electrode and a second electrode facing each other, Light can be emitted by applying a voltage.
  • a photosensitive resin composition that can be patterned by ultraviolet irradiation is generally used as the material for the flattening 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 gas component generated from the cured film, and thus can provide a highly durable organic EL display device. It is preferably used because it is possible (Patent Document 1).
  • Patent Document 2 a method of developing a liquid repellency by subjecting the upper surface of the partition pattern on the substrate to fluorination treatment by plasma irradiation has been studied.
  • a method of forming partition walls with a photosensitive resin composition to which a compound having liquid repellency is added is being studied.
  • a resist composition containing a specific fluorine-based polymer Patent Document 3
  • a photosensitive resin composition containing a fluorine-containing compound having a silane compound and a novolac type phenol resin as main components Patent Document 4
  • Patent Document 4 a photosensitive resin composition containing a fluorine-containing compound having a silane compound and a novolac type phenol resin as main components
  • JP-A-2002-91343 Japanese Patent No. 4612773 Japanese Patent Laid-Open No. 2012-220860 Japanese Patent No. 6098635
  • the demand for high durability such as a longer driving life of the organic EL light emitting element is becoming stricter year by year, and even after the durability test under acceleration conditions such as high temperature, high humidity, and light irradiation, the light emitting element can be used as a light emitting element. Performance maintenance is required.
  • Patent Document 2 has a problem in that the liquid repellent component adheres to the openings between the partition walls due to the fluorination treatment, resulting in insufficient ink wettability of the openings.
  • Patent Documents 3 and 4 have sufficient liquid repellency and can form a pattern as a photosensitive resin composition, but since the resin as the main component uses a phenol compound, Degassing components from the resin composition forming the partition wall pattern are liable to cause display defects, resulting in a problem that the driving life of the organic EL element is significantly impaired.
  • the present invention aims to solve the problems associated with the conventional techniques as described above, and to provide a photosensitive resin composition having excellent ink wettability at the openings and having a cured film having sufficient liquid repellency. To do.
  • Another object of the present invention is to provide a display device which comprises a cured film of the photosensitive resin composition, has few display defects, and has high durability against subsequent heat treatment.
  • the first aspect of the photosensitive resin composition of the present invention is a photosensitive resin composition containing a liquid repellent material (A) having at least an amide group or a urethane group, an alkali-soluble resin (B), and a photosensitizer (E).
  • the alkali-soluble resin (B) contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof.
  • the first aspect of the cured film of the present invention comprises the cured product of the first aspect of the photosensitive resin composition of the present invention.
  • the first aspect of the display device of the present invention is a display device having a grid-shaped partition formed on a substrate, and the partition includes the first aspect of the cured film of the present invention.
  • the first aspect of the method for producing a substrate with a partition of the present invention has the following steps (1) to (4) in this order.
  • a step of applying the first aspect of the photosensitive resin composition of the present invention on a substrate having a first electrode to form a photosensitive resin film (2)
  • a step of exposing the photosensitive resin film (3)
  • Step of developing exposed photosensitive resin film (4) Step of forming partition by heat treatment of developed photosensitive resin film.
  • the first aspect of the method for manufacturing a display device of the present invention has the following steps (5) to (6) in this order. (5) In a partition-attached substrate having a partition containing the cured product of the first aspect of the photosensitive resin composition of the present invention, a functional ink is applied by inkjet to a region surrounded by the partition to form a functional layer. Forming step (6) A step of forming a second electrode on the functional layer.
  • the present invention can provide a display device that includes a cured film of the photosensitive resin composition, has few display defects, and has high durability against subsequent heat treatment.
  • the first aspect of the photosensitive resin composition of the present invention is a photosensitive resin composition containing a liquid repellent material (A) having at least an amide group or a urethane group, an alkali-soluble resin (B), and a photosensitizer (E).
  • the alkali-soluble resin (B) contains at least one alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof.
  • the first embodiment of the photosensitive resin composition of the present invention contains a liquid repellent material (A) having at least an amide group or a urethane group in order to impart liquid repellency to the surface of the cured film.
  • a liquid repellent material (A) having at least an amide group or a urethane group is referred to as "component (A)” or "liquid repellent material (A)”. May be called.
  • the component (A) having an amide group or a urethane group improves the compatibility with the alkali-soluble resin (B) described below, reduces defects such as cissing, and improves the film thickness uniformity of the cured film.
  • the alkali-soluble resin (B) is selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof. Since it contains at least one kind of alkali-soluble resin, it is possible to remarkably improve the compatibility.
  • the liquid repellent material (A) having at least an amide group or a urethane group preferably contains a compound having a structural unit represented by the following general formula (1) or general formula (11).
  • R 1 , R 2 and R 3 represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.
  • R 18 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 19 represents an aliphatic group having 1 to 6 carbon atoms
  • A represents a urethane group of the following (A-1) or (A-2).
  • the compound having the structural unit represented by the general formula (1) or the general formula (11) is represented by, for example, a (meth) acrylamide monomer represented by the following general formula (3) or the following general formula (12). It can be obtained by (co) polymerizing a (meth) acrylate monomer.
  • R 1 , R 2 and R 3 represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.
  • R 18 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 19 represents an aliphatic group having 1 to 6 carbon atoms
  • A represents a urethane group represented by the following formula (A-1) or (A-2).
  • Preferred examples of the (meth) acrylamide monomer represented by the general formula (3) include N, N-dimethylacrylamide and N, N-diethylacrylamide.
  • the total of the structural units represented by the general formula (1) or the general formula (11) is the whole structural unit constituting the liquid repellent material (A). Is preferably 15 mol% or more, and more preferably 30 mol% or more. Further, in order to further improve the liquid repellency, it is preferably 85 mol% or less, more preferably 70 mol% or less.
  • the liquid repellent material (A) having at least an amide group or a urethane group preferably contains a compound having a urethane group from the viewpoint of improving alkali solubility. It is more preferable to contain a compound having a structural unit represented by the general formula (11).
  • the liquid repellent material (A) having at least an amide group or a urethane group preferably contains a compound having a structural unit represented by the general formula (2) or a structure represented by the general formula (13).
  • a structural unit represented by the general formula (2) or the structure represented by the general formula (13) it is possible to easily impart liquid repellency to the surface of the cured film.
  • R 4 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 5 represents an aliphatic group having 1 to 6 carbon atoms
  • R 6 represents a peroxy group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.
  • X is selected from the following structural formulas (a) to (e), all X may have the same structure, or a plurality of structures may exist randomly or in a block form. . m is an integer of 1 to 100 representing the number of repeating units.
  • the compound having the structural unit represented by the general formula (2) or the structure represented by the general formula (13) is, for example, the (meth) acrylate monomer represented by the general formula (4), or the general formula (13). It can be obtained by (co) polymerizing a monomer having a structure represented by
  • R 4 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 5 represents an aliphatic group having 1 to 6 carbon atoms
  • R 6 represents a peroxy group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.
  • Preferred examples of the (meth) acrylate monomer having a perfluoroalkyl group represented by the general formula (4) include 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl (meth ) Acrylate and the like.
  • Preferred examples of the monomer having the structure represented by the general formula (13) include monomers having the following structures.
  • the liquid repellent material (A) having at least an amide group or a urethane group is represented by the general formula (13) from the viewpoint of further improving the alkali solubility. It is preferable to contain a compound having a structure. By further improving the alkali solubility, residues in the openings are reduced during alkali development, so that the wettability of the functional ink applied to the openings can be further improved. As a result, it is possible to improve the film thickness uniformity of the functional layer formed of the functional ink, reduce display defects in the display device, and improve durability.
  • the liquid repellent material (A) having at least an amide group or a urethane group contains a urethane group and a compound having a structure represented by the general formula (13).
  • the alkali solubility of the component (A) is likely to be further improved.
  • the first aspect of the photosensitive resin composition of the present invention more preferably contains a compound having a structural unit represented by the general formula (11) and a structure represented by the general formula (13).
  • a liquid repellent which is a compound having a urethane group and a structure represented by the general formula (13), and containing a structural unit represented by the general formula (11) and a compound having a structure represented by the general formula (13).
  • "Megafuck (registered trademark)" RS-72-K, RS-72-A, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 ( DIC Corporation).
  • the liquid repellent material (A) having at least an amide group or a urethane group preferably further has an epoxy group. Having an epoxy group facilitates polycondensation with the alkali-soluble resin (B) to further improve the durability of the light emitting device. It is more preferable that the component (A) further has a structural unit represented by the general formula (5).
  • the component (A) having the structural unit represented by the general formula (5) is obtained by copolymerizing, for example, an epoxy group-containing (meth) acrylate monomer represented by the general formula (6) as one of the copolymerization components. Can be obtained at
  • R 7 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 8 represents an epoxy group-containing monovalent organic group having 2 to 16 carbon atoms.
  • Preferred examples of the epoxy group-containing (meth) acrylate monomer represented by the general formula (6) include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE), and 4-hydroxybutyl metallylate glycidyl ether. , Acrylates having an alicyclic epoxy group, and metalylates having an alicyclic epoxy group.
  • the structural unit represented by the general formula (5) is preferably 10 mol% or more, and more preferably 20 mol% or more of the entire structural units constituting the liquid repellent material (A).
  • the cured film of the photosensitive resin composition is formed, it is polycondensed with the alkali-soluble resin (B) to form a cured film having high heat resistance.
  • the heat resistance is increased and the durability of the display device is improved.
  • it is preferably 50 mol% or less, more preferably 40 mol% or less.
  • the liquid repellent material (A) having at least an amide group or a urethane group may be a copolymer obtained by copolymerizing different functional group-substituted (meth) acrylic monomers. Further, by copolymerizing different functional group-substituted (meth) acrylic monomers, it is possible to easily balance the liquid repellency and the solubility.
  • hydroxyl group-containing (meth) acrylates for example, hydroxyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylamides, alkoxy group-containing (meth) acrylates, blocked isocyanate group-containing (meth) acrylates, phenoxy group-containing (meth) acrylates, alkyl (meth) Examples thereof include acrylates and vinyl group-containing compounds.
  • hydroxyl group-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate.
  • hydroxyl group-containing (meth) acrylamides examples include N-hydroxymethyl acrylamide.
  • Examples of (meth) acrylates having an alkoxy group include 3-methacryloxypropylmethyldimethoxysilane.
  • blocked isocyanate group-containing (meth) acrylates examples include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM: Showa Denko KK; registered trademark). Can be mentioned.
  • phenoxy group-containing (meth) acrylates examples include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate.
  • Alkyl (meth) acrylates are unsubstituted or substituted with at least one of an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring and a heterocycle, or an acid anhydride is cleaved and added to a hydroxy group.
  • an amino group a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring and a heterocycle, or an acid anhydride is cleaved and added to a hydroxy group.
  • alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, such as a diluting monomer, for example, an alkyl acrylate.
  • vinyl group-containing compounds examples include n-butyl vinyl ether and the like.
  • the compound contained in the liquid repellent material (A) having at least an amide group or a urethane group is usually a (co) polymer.
  • the (co) polymer as a compound contained in the liquid repellent (A) can be obtained by a known polymerization method.
  • the (co) polymer may be obtained by ionic polymerization such as radical polymerization or anionic polymerization. Further, it may be any of a random copolymer, a block copolymer, a graft (co) polymer, and an alternating copolymer.
  • the radical (co) polymerization method is taken as an example.
  • the component (A) can be obtained by random copolymerization in the presence of a radical polymerization initiator and, if necessary, a chain transfer agent.
  • radical polymerization initiator for example, tert-butylperoxy-2-ethylhexanoate can be used.
  • chain transfer agent for example, dodecyl mercaptan can be used.
  • solvent for example, an inert solvent such as cyclohexanone can be used.
  • the weight average molecular weight of the liquid repellent material (A) having at least an amide group or a urethane group is preferably in the range of 1,500 to 50,000. When the molecular weight is within this range, it can be more easily dissolved in the solvent used for the photosensitive resin composition. Further, when the molecular weight is within this range, the defoaming property of the photosensitive resin composition solution tends to be high.
  • the liquid repellent material (A) having at least an amide group or a urethane group is 0.% from the viewpoint that the resulting cured film easily exhibits liquid repellency with respect to 100 parts by mass of the alkali-soluble resin (B).
  • the amount is preferably 1 part by mass or more, and more preferably 0.3 part by mass or more. Further, from the viewpoint that liquid repellency is less likely to occur in the pixel and high durability is easily obtained, the amount is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
  • the first embodiment of the photosensitive resin composition of the present invention contains an alkali-soluble resin (B) (hereinafter sometimes referred to as component (B)).
  • the alkali-soluble resin means a resin having a dissolution rate defined below of 50 nm / min or more. Specifically, a resin solution of ⁇ -butyrolactone is applied on a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m.
  • the alkali-soluble resin (B) may have an alkali-soluble group in the structural unit of the resin and / or at the main chain end thereof in order to impart alkali solubility.
  • the alkali-soluble group refers to a functional group that increases the solubility in an alkaline solution by interacting with or reacting with an alkali, and specific examples thereof include an acidic group.
  • Examples of preferable alkali-soluble groups include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.
  • the alkali-soluble resin (B) in the first aspect of the present invention contains at least one kind of alkali-soluble resin selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof. .
  • alkali-soluble resins may be used alone, or a plurality of alkali-soluble resins may be used in combination. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgas at a high temperature of 200 ° C. or higher after heat treatment is reduced, and the durability of the display device can be improved.
  • Preferred embodiments of polyimide, polybenzoxazole, polyamideimide, precursors thereof and copolymers thereof used as the alkali-soluble resin (B) are described in the second section of the photosensitive resin composition of the present invention described later. It is as described for the alkali-soluble resin (BI) in the embodiment.
  • the first embodiment of the photosensitive resin composition of the present invention may be further referred to as at least one resin (C) selected from the group consisting of a phenol resin and a polyhydroxystyrene resin (hereinafter referred to as a component (C)). ) Is preferably contained. These resins have a function as a compatibilizer, and by mixing them, the compatibility of the components (A) and (B) is further improved, and the solubility of each component in the developing solution is stabilized. This contributes to the improvement of the straightness of the pattern. As a result, display defects of the display device are expected to be reduced.
  • the inclusion of the component (C) can reduce the amount of film slippage in the developing step. It has the effect of facilitating retention on the surface and can improve the process margin for obtaining good liquid repellency.
  • the photosensitive resin composition of the present invention at least one resin selected from the group consisting of the phenol resin and the polyhydroxystyrene resin with respect to 100 parts by mass of the alkali-soluble resin (B).
  • the sum of (C) is preferably 10 to 100 parts by mass.
  • the total amount of the component (C) is 10 parts by mass or more. It is preferably 30 parts by mass or more.
  • the amount is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.
  • Preferable embodiments of the at least one resin (C) selected from the group consisting of a phenol resin and a polyhydroxystyrene resin are the phenol resin and polyhydroxystyrene in the second embodiment of the photosensitive resin composition of the present invention described later. It is as described for any one or more of the resins (CI).
  • the first aspect of the photosensitive resin composition of the present invention preferably further contains a thermal crosslinking agent (D).
  • a thermal crosslinking agent (D) By containing the thermal crosslinking agent (D), the durability of the display device can be more easily improved. Suitable aspects and the like of the thermal crosslinking agent (D) are as described for the thermal crosslinking agent (DI) in the second aspect of the photosensitive resin composition of the present invention described below.
  • the first aspect of the photosensitive resin composition of the present invention contains a photosensitizer (E).
  • the photosensitive agent (E) may be a negative type which is cured by light or a positive type which is solubilized by light.
  • the photosensitive agent (E) may preferably contain (e-1) a polymerizable unsaturated compound and a photopolymerization initiator, or (e-2) a quinonediazide compound.
  • the positive type is preferable from the viewpoint of forming the step-shaped partition wall to be processed later by one-time photolithography by halftone processing. Suitable aspects and the like of the photosensitizer (E) are as described for the photosensitizer (EI) in the second aspect of the photosensitive resin composition of the present invention described later.
  • the first aspect of the photosensitive resin composition of the present invention preferably further contains a colorant (F).
  • a colorant (F) include known organic pigments, inorganic pigments or dyes that are commonly used in the field of electronic information materials.
  • the colorant (F) is preferably an organic pigment and / or an inorganic pigment. Suitable aspects and the like of the colorant (F) are as described for the colorant (FI) in the second aspect of the photosensitive resin composition of the present invention described later.
  • the first aspect of the photosensitive resin composition of the present invention preferably contains an organic solvent (G).
  • the organic solvent (G) include compounds of ethers, acetates, esters, ketones, aromatic hydrocarbons, amides or alcohols. Suitable aspects and the like of the organic solvent (G) are as described for the organic solvent (GI) in the second aspect of the photosensitive resin composition of the present invention described later.
  • the first aspect of the photosensitive resin composition of the present invention may contain an adhesion improver. Suitable aspects of the adhesion improver and the like are as described for the adhesion agent in the second aspect of the photosensitive resin composition of the present invention described below.
  • the first aspect of the photosensitive resin composition of the present invention can be obtained, for example, by dissolving the components (A) to the colorant (F) in the organic solvent (G).
  • the dissolution method include stirring and heating.
  • the heating temperature is preferably set in a range that does not impair the performance of the resin composition, and is usually 20 ° C. to 80 ° C.
  • the order of dissolving each component is not particularly limited, and for example, there is a method of sequentially dissolving the compounds having a low solubility.
  • the obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dust and particles.
  • a filtration filter to remove dust and particles.
  • Suitable aspects of the filtration filter and the like are as described for the filtration filter in the second aspect of the photosensitive resin composition of the present invention described below.
  • the first aspect of the cured film of the present invention comprises the cured product of the first aspect of the photosensitive resin composition of the present invention.
  • the description of the method for producing the first aspect of the cured film of the present invention corresponds to the method for producing the cured film of the second aspect of the photosensitive resin composition of the present invention described below.
  • the first aspect of the cured film of the present invention can be used for electronic parts such as organic EL display devices, semiconductor devices, and multilayer wiring boards.
  • a partition of an organic EL element, a flattening layer of a substrate with a drive circuit of a display device using the organic EL element, an interlayer insulating film between rewirings of a semiconductor device or a semiconductor component, a semiconductor passivation film, a semiconductor element It is suitable for use in various applications such as a protective film, an interlayer insulating film for multi-layer wiring for high-density mounting, a wiring protective insulating layer for a circuit board, an on-chip microlens for a solid-state image sensor and various display / solid-state image sensor flattening layers.
  • Examples of the electronic device having the surface protective film, the interlayer insulating film, and the like on which the first aspect of the cured film of the present invention is arranged include a magnetoresistive memory (hereinafter, referred to as MRAM) having low heat resistance. That is, the first aspect of the cured film of the present invention is suitable for a surface protective film of MRAM.
  • a display device including a first electrode formed on a substrate and a second electrode provided so as to face the first electrode specifically, for example, a display such as an LCD, an ECD, an ELD, and an organic EL. It can be used as a partition wall or an insulating layer of a device.
  • the first aspect of the cured film of the present invention has good liquid repellency and prevents the ink applied by the inkjet method from penetrating into adjacent pixels, thereby reducing the occurrence of display defects. Furthermore, in the first aspect of the cured film of the present invention, since the amount of outgas at a high temperature is small, at least one kind selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material is used for the functional layer. It can be suitably used for an organic EL display device including the above.
  • the contact angle of the surface of the cured film when propylene glycol monomethyl ether acetate is dropped by the sessile drop method is 30 ° or more in accordance with JIS-R3258. It is preferably 40 ° or more.
  • the contact angle on the surface of the cured film increases, for example, when the content of the liquid repellent material (A) having at least an amide group or a urethane group increases, and decreases when the content of the liquid repellent material (A) decreases. Therefore, for example, the content can be adjusted to the above range by adjusting the content of the liquid repellent material (A) having at least an amide group or a urethane group.
  • a first aspect of the display device of the present invention is a display device having a lattice-shaped partition formed on a substrate, and the partition includes the first aspect of the cured film of the present invention.
  • the first aspect of the cured film of the present invention it is possible to reduce the occurrence of display defects in the display device. Further, the amount of outgas at a high temperature of 200 ° C. or higher after heat treatment is reduced, and the durability of the display device can be improved.
  • the first aspect of the cured film of the present invention has good liquid repellency, so that the ink applied by the ink jet method inside the pixels surrounded by the grid-shaped partition walls penetrates into the adjacent pixels. By preventing this, the occurrence of display defects is reduced.
  • the grid-like partition formed on the substrate is a first partition having a trapezoidal transverse cross section that is cut perpendicularly to the length direction of the partition and the surface of the substrate.
  • the width of the bottom surface of the part is B, it is preferable that the relationship of A> B is satisfied.
  • FIG. 1 shows an example of a schematic view of a cross section obtained by cutting a lattice-shaped partition wall formed on a substrate perpendicularly to the length direction of the partition wall and the surface of the substrate.
  • the partition wall is formed on the substrate 8 having the first electrode 2.
  • the partition wall has a step shape having a first partition wall portion 9 and a second partition wall portion 10 having a trapezoidal transverse cross section, and satisfies the relationship of A> B.
  • a functional layer is formed by applying a functional ink by ink jet in a region (pixel) surrounded by a grid-like partition formed on a substrate, the functional ink is applied after the functional ink is applied.
  • the solvent contained in is dried to form a functional layer. Since the ink droplets are dried near the partition walls, the viscosity of the ink near the partition walls tends to increase as the drying progresses. Therefore, it is known that the film thickness of the functional layer is thicker at the end portion than at the central portion. In the case of an organic EL display device, this causes a problem that the brightness is different between the central part and the peripheral part of the pixel.
  • the functional layer end portion having a large film thickness is changed to the first partition portion. It can be formed on the upper surface. That is, it is possible to form a shape in which the end portion of the functional layer is located on the side surface of the second partition wall portion on the surface cut in the direction perpendicular to the substrate. With such a structure, the end portion of the functional layer having a large film thickness is made non-luminous by the first partition wall portion, and only the area where the functional layer has a uniform film thickness can emit light.
  • the functional layer 11 and the end 12 of the functional layer are shown in an example of a schematic cross-sectional view of the partition wall in FIG. 1.
  • the partition wall thickness is preferably 0.5 to 5.0 ⁇ m. When it is 0.5 ⁇ m or more, the functional ink can be easily retained in the pixel. From the viewpoint of facilitating the processing of the photosensitive resin composition by photolithography, the partition wall thickness is preferably 5.0 ⁇ m or less. Further, the film thickness of the first partition wall portion is preferably 0.1 to 1.0 ⁇ m. When the film thickness of the first partition is 0.1 ⁇ m or more, the insulation required for the partition can be maintained. When the thickness of the first partition wall is 1.0 ⁇ m or less, the functional layer end portion having a large film thickness can be formed on the first partition wall. In the first aspect of the display device of the present invention, the partition wall has a thickness of 0.5 to 5.0 ⁇ m, and the first partition wall has a thickness of 0.1 to 1.0 ⁇ m. , And more preferable.
  • the first partition wall portion and the second partition wall portion are formed of a cured film of the same material.
  • the “same material” means one made of the same photosensitive resin composition.
  • the step shape can be easily formed by one-time photolithography by the half-exposure that is performed later.
  • a functional layer in a region surrounded by the partition walls of the display device.
  • a colored layer for coloring transmitted light by forming a colored layer for coloring transmitted light and arranging a plurality of colored layers having different colors for each pixel, it can be used as a color filter.
  • it can be used as an organic EL display device by forming an organic EL light emitting layer containing at least one selected from an organic EL light emitting material, a hole injecting material, and a hole transporting material.
  • an end portion of the functional layer is located on a side surface of the second partition portion in a transverse section cut perpendicularly to a length direction of the partition wall and a surface of the substrate. It is preferable. If the end of the functional layer is located on the side surface of the second partition, the end of the functional layer having a large film thickness is made non-luminous by the first partition, and the functional layer has a uniform film thickness. Only the light can be emitted. As a result, it is possible to solve the problem that the brightness is different between the central portion and the end portion of the pixel.
  • the functional layer of the display device includes at least one selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material.
  • the organic EL light emitting layer can be formed by including at least one selected from the group consisting of an organic EL light emitting material, a hole injecting material, and a hole transporting material in the functional layer.
  • a first aspect of the organic EL display device of the present invention has a drive circuit, a flattening layer, a first electrode, a partition wall, an organic EL light emitting layer and a second electrode on a substrate, and the partition wall is cured by the present invention. It comprises the first aspect of the membrane.
  • a TFT such as a glass or a resin film is provided on a substrate, and a wiring located on a side portion of the TFT and connected to the TFT is provided on the TFT.
  • the flattening layer is provided, and the display element is provided over the flattening layer.
  • the display element and the wiring are connected through a contact hole formed in the flattening layer.
  • the partition wall By using the first aspect of the cured film of the present invention for the partition wall, it has liquid repellency and prevents the ejection liquid used in the inkjet method from entering into the adjacent pixels, so that the occurrence of display defects occurs. It is possible to obtain an organic EL display device which is small and has excellent durability.
  • a first aspect of the method of manufacturing a substrate with a partition of the present invention has the following steps (1) to (4) in this order.
  • a step of applying the first aspect of the photosensitive resin composition of the present invention onto a substrate having a first electrode to form a photosensitive resin film (2)
  • a step of exposing the photosensitive resin film (3) Step of developing exposed photosensitive resin film (4) Step of forming partition by heat treatment of developed photosensitive resin film.
  • Examples of methods for applying the photosensitive resin composition to the substrate having the first electrode include spin coating method, slit coating method, dip coating method, spray coating method, and printing method.
  • the substrate on which the photosensitive resin composition is coated may be pretreated with the adhesion improver described above.
  • a solution prepared by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate is used.
  • a method of treating the surface of the base material can be mentioned.
  • Examples of the method for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment and the like.
  • the applied photosensitive resin film is dried under reduced pressure if necessary, and then heat-treated at 50 ° C to 180 ° C for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like.
  • a dried photosensitive resin film can be obtained by applying.
  • actinic rays through a photomask having a desired pattern on the photosensitive resin film.
  • the actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays.
  • baking may be performed after exposure. By performing post-exposure bake, effects such as improvement in resolution after development and increase in the allowable range of development conditions can be expected.
  • the post-exposure bake an oven, a hot plate, infrared rays, a flash annealing device, a laser annealing device, or the like can be used.
  • the post-exposure bake temperature is preferably 50 to 180 ° C, more preferably 60 to 150 ° C.
  • the post-exposure bake time is preferably 10 seconds to several hours. If the post-exposure bake time is within the above range, the reaction may proceed favorably and the developing time may be shortened in some cases.
  • the "half exposure" is a step shape having a first partition wall section having a trapezoidal cross section and a second partition section having a trapezoidal cross section above the first partition section.
  • Half-exposure refers to the process of leaving the exposed portion of the photosensitive resin film underlying the photosensitive resin film to some extent when development is completed. In other words, it refers to a process of performing exposure so that the first partition of the photosensitive resin film is not exposed to light.
  • the exposed photosensitive resin film is developed using a developing solution, and parts other than the exposed part are removed.
  • a developing solution tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl
  • Aqueous solutions of compounds showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred.
  • a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone or dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination of several kinds. Good.
  • a method such as spraying, paddle, dipping, and ultrasonic wave can be used.
  • rinse treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to distilled water.
  • a cured film is obtained by the heat treatment process of the developed photosensitive resin film.
  • the cured film of the photosensitive resin composition can be suitably used for the partition walls of the organic EL display device. Since the residual solvent and the components having low heat resistance can be removed by the heat treatment, heat resistance and chemical resistance can be improved.
  • a thermal crosslinking agent (D) is contained, the thermal crosslinking reaction can be promoted by heat treatment, and heat resistance and chemical resistance can be improved.
  • This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and gradually increasing the temperature or by selecting a certain temperature range and continuously increasing the temperature. As an example, there is a method of performing heat treatment at 150 ° C. and 250 ° C. for 30 minutes each.
  • the heat treatment condition in the present invention is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, further preferably 230 ° C. or higher, particularly preferably 250 ° C. or higher.
  • the heat treatment condition is preferably 400 ° C. or lower, more preferably 350 ° C. or lower, still more preferably 300 ° C. or lower.
  • the first aspect of the method for manufacturing a display device of the present invention has the following steps (5) to (6) in this order. (5) In a partition-attached substrate having a partition containing the cured product of the first aspect of the photosensitive resin composition of the present invention, a functional ink is applied by inkjet to a region surrounded by the partition to form a functional layer. Forming step (6) A step of forming a second electrode on the functional layer.
  • a functional ink is applied by inkjet to a region surrounded by the partition to function.
  • the step of forming a layer will be described.
  • the functional layer is formed by applying the functional ink with an ink jet in the area (pixel) surrounded by the lattice-shaped partition wall formed on the substrate.
  • a composition containing at least one selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material is dropped into a pixel as a functional ink and dried.
  • the organic EL light emitting layer can be formed.
  • the second electrode is formed so as to cover the entire partition and functional layer.
  • Examples of the method for forming the second electrode include a sputtering method and a vapor deposition method.
  • the first embodiment of the method for manufacturing a display device of the present invention preferably has the following steps (1) to (6) in this order.
  • a step of applying the first aspect of the photosensitive resin composition of the present invention on a substrate having a first electrode to form a photosensitive resin film (2)
  • a step of exposing the photosensitive resin film (3)
  • Step of developing exposed photosensitive resin film (4)
  • Step of forming partition wall by heat treatment of developed photosensitive resin film (5)
  • the second embodiment of the photosensitive resin composition of the present invention is a compound (AI) having a structural unit represented by at least the general formula (1) and the general formula (2) (hereinafter, compound (AI)). ) And an alkali-soluble resin (BI) selected from polyimide, polybenzoxazole, polyamideimide, a precursor of any of them, and a copolymer thereof.
  • AI general formula (1)
  • BI alkali-soluble resin
  • the photosensitive resin composition in the second embodiment of the photosensitive resin composition of the present invention may be referred to as photosensitive resin composition (I).
  • R 1 , R 2 and R 3 represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.
  • R 4 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 5 represents an aliphatic group having 1 to 6 carbon atoms
  • R 6 represents a peroxy group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.
  • the compound (AI) is obtained by copolymerizing at least a (meth) acrylamide monomer represented by the general formula (3) and a (meth) acrylate monomer having a perfluoro group represented by the general formula (4). It is a liquid repellent material that is compatible with the photosensitive resin composition (I) and is added for imparting liquid repellency to the surface of the cured film.
  • R 1 , R 2 and R 3 represent a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms, and may be the same or different.
  • R 4 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 5 represents an aliphatic group having 1 to 6 carbon atoms
  • R 6 represents a peroxy group having 3 to 6 carbon atoms. Represents a fluoroalkyl group.
  • Preferred examples of the (meth) acrylamide monomer represented by the general formula (3) include N, N-dimethylacrylamide and N, N-diethylacrylamide. Further, preferable examples of the (meth) acrylate monomer having a perfluoro group represented by the general formula (4) include 2- (perfluorobutyl) ethyl (meth) acrylate and 2- (perfluorohexyl) ethyl ( (Meth) acrylate, etc. are mentioned.
  • the compound (AI) has a structural unit represented by the general formula (1), which is obtained by copolymerizing the (meth) acrylamide monomer represented by the general formula (3).
  • the structural unit represented by the general formula (1) has the effects of improving compatibility with the alkali-soluble resin (B) described later, reducing defects such as cissing, and improving the film thickness uniformity of the cured film. As a result, display defects of the organic EL display device are reduced.
  • the structural unit represented by the general formula (1) is preferably 35 mol% or more, and further 40 mol% of the total structural units constituting the compound (AI).
  • the molar ratio is at least%, and is the highest in the plural structural units constituting the compound (AI). Further, in order to impart liquid repellency, it is preferably 85 mol% or less, more preferably 70 mol% or less.
  • the compound (AI) is generally used for the purpose of further polycondensing with the alkali-soluble resin (B) when forming a cured film of the photosensitive resin composition (I) to further improve durability as a light emitting device. It is preferable to have a structural unit represented by the formula (5), and it is more preferable to use a copolymer represented by the general formula (6) that is copolymerized with an epoxy group-containing (meth) acrylate monomer.
  • R 7 represents a hydrogen atom or a monovalent organic group having 1 to 4 carbon atoms
  • R 8 represents an epoxy group-containing monovalent organic group having 2 to 16 carbon atoms.
  • Preferred examples of the epoxy group-containing (meth) acrylate monomer represented by the general formula (6) include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE), and acrylate having an alicyclic epoxy group. Examples include monomers.
  • the structural unit represented by the general formula (5) has a molar ratio equal to or higher than that of the structural unit represented by the general formula (2), a cured film of the photosensitive resin composition (I) can be obtained.
  • the structural unit represented by the general formula (5) has a molar ratio equal to or higher than that of the structural unit represented by the general formula (2), a cured film of the photosensitive resin composition (I) can be obtained.
  • it polycondenses with the alkali-soluble resin (B) to form a cured film with high heat resistance, and the cured film of the photosensitive resin composition (I) has increased heat resistance, and durability of the organic EL display device. Is more preferable because it is improved.
  • the compound (AI) may be a copolymer obtained by copolymerizing different functional group-substituted (meth) acrylic monomers for the purpose of balancing liquid repellency and solubility.
  • examples thereof include acrylates and vinyl group-containing compounds.
  • Examples of the hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate.
  • Examples of the hydroxyl group-containing (meth) acrylamides include N-hydroxymethyl acrylamide.
  • Examples of the (meth) acrylates having an alkoxy group include 3-methacryloxypropylmethyldimethoxysilane.
  • Examples of the blocked isocyanate group-containing (meth) acrylates include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM: Showa Denko KK; registered trademark). Can be mentioned.
  • phenoxy group-containing (meth) acrylates examples include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate.
  • Alkyl (meth) acrylates are unsubstituted or substituted with at least one of an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring and a heterocycle, or an acid anhydride is cleaved and added to a hydroxy group.
  • an amino group a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring and a heterocycle, or an acid anhydride is cleaved and added to a hydroxy group.
  • alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, such as a diluting monomer, for example, an alkyl acrylate.
  • vinyl group-containing compounds examples include n-butyl vinyl ether and the like.
  • the copolymer of compound (AI) may be obtained by ionic polymerization such as radical polymerization or anionic polymerization, and can be obtained by a known polymerization method. Further, it may be any of a random copolymer, a block copolymer and a graft copolymer, and may be an alternating copolymer.
  • the radical polymerization method is taken as an example.
  • the compound (AI) can be obtained by random copolymerization in the presence of a radical polymerization initiator and, if necessary, a chain transfer agent.
  • radical polymerization initiator for example, tert-butylperoxy-2-ethylhexanoate can be used, and as the chain transfer agent, for example, dodecyl mercaptan can be used.
  • chain transfer agent for example, dodecyl mercaptan can be used.
  • solvent for example, an inert solvent such as cyclohexanone can be used.
  • the weight average molecular weight of the compound (AI) is preferably in the range of 1,500 to 50,000, and if the weight average molecular weight is within this range, it can be easily dissolved in the solvent used in the photosensitive resin composition (I). And the defoaming property of the photosensitive resin composition solution is high.
  • the compound (AI) is based on 100 parts by mass of an alkali-soluble resin (B) selected from polyimide, polybenzoxazole or polyamideimide, a precursor of any of them, and a copolymer thereof described below.
  • an alkali-soluble resin (B) selected from polyimide, polybenzoxazole or polyamideimide, a precursor of any of them, and a copolymer thereof described below.
  • the resulting cured film sufficiently exhibits liquid repellency, it is preferably 0.1 part by mass or more, and more preferably 0.3 part by mass or more.
  • liquid repellency is not generated in the pixel and high durability is obtained, it is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
  • the appropriate addition amount of the compound (AI) can be determined by using the contact angle when propylene glycol monomethyl ether acetate is dropped onto the surface of the cured film of the photosensitive resin composition (I). According to JIS-R3258, it is preferable that the contact angle when measured by the sessile drop method is 40 ° or more.
  • the photosensitive resin composition (I) is an alkali-soluble resin (BI) selected from polyimide, polybenzoxazole, polyamideimide, a precursor of any of them, and a copolymer thereof (hereinafter, referred to as (BI)). Sometimes called a component)). Further, it may contain two or more kinds selected from polyimide, polybenzoxazole, polyamideimide and a precursor of any of them, or may contain a copolymer having two or more kinds of these repeating units.
  • BI alkali-soluble resin
  • Alkali-soluble in the second embodiment of the photosensitive resin composition of the present invention means that a solution of resin in ⁇ -butyrolactone is applied on a silicon wafer and prebaked at 120 ° C. for 4 minutes to obtain a film thickness of 10 ⁇ m ⁇ 0. It is determined from the decrease in film thickness when a prebaked film having a thickness of 0.5 ⁇ m is formed, and the prebaked film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ⁇ 1 ° C. for 1 minute and rinsed with pure water. It means that the dissolution rate is 50 nm / min or more.
  • the polyimide can be obtained, for example, by reacting tetracarboxylic acid or tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. with a diamine or diisocyanate compound, trimethylsilylated diamine, etc.
  • the polyimide has a tetracarboxylic acid residue and a diamine residue.
  • the polyimide can be obtained, for example, by subjecting a polyamic acid, which is one of the polyimide precursors obtained by reacting a tetracarboxylic dianhydride and a diamine, to a dehydration ring closure by heat treatment.
  • a solvent that is azeotropic with water such as m-xylene
  • a solvent that is azeotropic with water such as m-xylene
  • a dehydration condensing agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a base such as triethylamine as a ring-closing catalyst
  • a weakly acidic carboxylic acid compound and performing dehydration ring closure by heat treatment at a low temperature of 100 ° C. or lower.
  • Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol compound with dicarboxylic acid or dicarboxylic acid chloride, dicarboxylic acid active ester, or the like. Polybenzoxazole has a dicarboxylic acid residue and a bisaminophenol residue. Further, polybenzoxazole can be obtained, for example, by subjecting polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound and a dicarboxylic acid, to dehydration ring closure by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc. and performing a dehydration ring closure by a chemical treatment.
  • the polyimide precursor examples include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.
  • the polyamic acid can be obtained by reacting a tetracarboxylic acid or a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride or the like with a diamine or a diisocyanate compound and a trimethylsilylated diamine.
  • the polyimide can be obtained, for example, by subjecting the polyamic acid obtained by the above method to dehydration ring closure by heating or chemical treatment with an acid or a base.
  • the polybenzoxazole precursor may include polyhydroxyamide.
  • polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid or dicarboxylic acid chloride, dicarboxylic acid active ester and the like.
  • Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing the polyhydroxyamide obtained by the above method by heating or by chemical treatment with phosphoric anhydride, a base, a carbodiimide compound, or the like.
  • the polyamideimide precursor can be obtained, for example, by reacting a dicarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide or the like with a diamine or diisocyanate.
  • Polyamideimide can be obtained, for example, by subjecting the precursor obtained by the above method to dehydration ring closure by heating or chemical treatment with acid or base.
  • the copolymer of polyimide, polybenzoxazole, and polyamideimide may be any of block copolymerization, random copolymerization, alternating copolymerization, graft copolymerization, or a combination thereof.
  • a block copolymer can be obtained by reacting polyhydroxyamide with tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride, or the like.
  • dehydration ring closure can be carried out by heating or chemical treatment with acid or base.
  • the component (BI) preferably has a structural unit represented by any of the general formulas (7) to (10), more preferably a structural unit represented by (10). Two or more kinds of resins having these structural units may be contained, or two or more kinds of structural units may be copolymerized.
  • the resin as the component (BI) preferably contains 3 to 1000, and more preferably 20 to 200, the structural unit represented by any one of formulas (7) to (10) in the molecule.
  • R 9 and R 12 are tetravalent organic groups
  • R 10 , R 11 and R 14 are divalent organic groups
  • R 13 is a trivalent organic group
  • R 15 is A divalent to tetravalent organic group
  • R 16 represents a divalent to divalent organic group
  • R 17 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • p represents an integer of 0 to 2 and q represents an integer of 0 to 10.
  • n represents an integer of 0 to 2.
  • R 9 to R 16 have an aromatic ring and / or an aliphatic ring.
  • R 9 is a tetracarboxylic acid derivative residue
  • R 11 is a dicarboxylic acid derivative residue
  • R 13 is a tricarboxylic acid derivative residue
  • R 15 is di-, tri- or tetra- Represents a carboxylic acid derivative residue.
  • Examples of the acid component constituting R 9 , R 11 , R 13 , R 15 (COOR 17 ) n (OH) p include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid and bis (carboxyphenyl) hexa.
  • one or two carboxyl groups of tricarboxylic acid and tetracarboxylic acid correspond to the COOR 15 group.
  • These acid components can be used as they are, or as acid anhydrides, active esters and the like. Moreover, you may use combining these 2 or more types of acid components.
  • R 10 , R 12 , R 14 and R 16 represent diamine derivative residues.
  • Examples of the diamine component constituting R 10 , R 12 , R 14 and R 16 (OH) q include bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (3-amino-4-hydroxyphenyl).
  • alicyclic diamines such as cyclohexyldiamine, methylenebiscyclohexylamine and the like can be mentioned. These diamines can be used as they are or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components. In applications where heat resistance is required, it is preferable to use the aromatic diamine in an amount of 50 mol% or more based on the whole diamine.
  • R 9 to R 16 in the general formulas (7) to (10) may contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group, etc. in the skeleton.
  • a resin having an appropriate amount of a phenolic hydroxyl group, a sulfonic acid group or a thiol group By using a resin having an appropriate amount of a phenolic hydroxyl group, a sulfonic acid group or a thiol group, a positive photosensitive resin composition having an appropriate alkali solubility is obtained.
  • the fluorine atom imparts water repellency to the surface of the film at the time of alkali development, and can prevent bleeding from the surface.
  • the content of fluorine atoms in the component (BI) is preferably 10% by mass or more in order to sufficiently obtain the effect of preventing the soaking into the interface, and is preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.
  • the resin of the component (BI) has a main chain terminal such as known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to seal with an end-capping agent.
  • the introduction ratio of the monoamine used as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50 mol%, based on all amine components. It is not more than mol%.
  • the introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% with respect to the diamine component. It is above, preferably 100 mol% or less, particularly preferably 90 mol% or less.
  • a plurality of different end groups may be introduced by reacting a plurality of end capping agents.
  • the number of repeating structural units is preferably 3 or more and 200 or less.
  • the number of repeating structural units is preferably 10 or more and 1000 or less. Within this range, a thick film can be easily formed.
  • the component (BI) may be composed of only the structural unit represented by any of the general formulas (7) to (10), or may be a copolymer or a mixture with another structural unit. It may be. In that case, it is preferable that the structural unit represented by any one of the general formulas (7) to (10) is contained in an amount of 10% by mass or more, and more preferably 30% by mass or more based on the entire resin.
  • the type and amount of the structural unit used for copolymerization or mixing can be selected within a range that does not impair the mechanical properties of the thin film obtained by the final heat treatment.
  • the photosensitive resin composition (I) further contains at least one resin (CI) of phenol resin or polyhydroxystyrene resin (hereinafter sometimes referred to as "CI component").
  • CI component phenol resin or polyhydroxystyrene resin
  • these resins have a function as a compatibilizing agent, and by mixing these, the compatibility of the compounds (AI) and (BI) components is further improved, and the solubility of each component in the developing solution is improved. Contributes to stabilization and improves the straightness of the pattern. As a result, it is expected to reduce display defects of the organic EL display device.
  • the photosensitive agent (EI) to be post-processed is a positive type, it is possible to reduce the amount of film slippage in the developing step by containing the component (CI), and thus the compound (AI) is added. It has the effect of retaining the film surface after development, and can improve the process margin for obtaining good liquid repellency.
  • the phenol resin includes novolac phenol resin and resole phenol resin, which are obtained by polycondensing various phenols alone or a mixture of plural kinds thereof with aldehydes such as formalin by a known method.
  • phenols constituting the novolac phenol resin and the resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol and 2,5-dimethyl.
  • aldehydes examples include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like, and these can be used alone or as a mixture of two or more.
  • polyhydroxystyrene resin it is also possible to use a homopolymer of vinylphenol or a copolymer with styrene.
  • the weight average molecular weight of the phenol resin or polyhydroxystyrene resin is 2,000 to 20,000, preferably 3,000 to 10,000, in terms of polystyrene by GPC (gel permeation chromatography). Within this range, a resin composition having a high concentration and a low viscosity can be obtained.
  • the total content of the phenol resin and the polyhydroxystyrene resin in the photosensitive resin composition (I) is 100 parts by mass of the component (BI), and the total amount of the compound (AI) and the component (BI) is From the viewpoint of improving the compatibility and improving the straightness of the pattern and reducing display defects of the organic EL display device, the amount is preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. Further, for the purpose of not lowering the durability of the cured film of the photosensitive resin composition, it is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less.
  • the photosensitive resin composition (I) preferably further contains a thermal crosslinking agent (DI) for the purpose of easily obtaining a cured film.
  • the thermal crosslinking agent refers to a compound having at least two thermoreactive functional groups in the molecule, such as a methylol group, an alkoxymethyl group, an epoxy group, and an oxetanyl group.
  • the thermal cross-linking agent (DI) can cross-link the component (BI) or other additive components to enhance the durability of the cured film.
  • Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include, for example, 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- PE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX -290, NIKALAC MX-280
  • VG3101L (trade name, manufactured by Printec Co., Ltd.), "Tepic” (registered trademark) S, "Tepic” G, “Tepic” P (these product names, Nissan Chemical Co., Ltd.
  • the (DI) thermal crosslinking agent one having a phenolic hydroxyl group in one molecule and a methylol group and / or an alkoxymethyl group at both ortho positions of the phenolic hydroxyl group is preferable.
  • the methylol group and / or alkoxymethyl group is adjacent to the phenolic hydroxyl group, the durability of the cured film can be further enhanced.
  • the alkoxymethyl group include, but are not limited to, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.
  • the content of the (DI) thermal crosslinking agent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more, with respect to 100 parts by mass of the (BI) alkali-soluble resin. . Further, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less.
  • the content of the (DI) thermal crosslinking agent is 5 parts by mass or more, the heat resistance of the cured film is improved, and when it is 50 parts by mass or less, the elongation reduction of the cured film can be prevented.
  • the photosensitive resin composition (I) preferably contains a photosensitizer (EI).
  • the photosensitizer (EI) may be a negative type that is hardened by light or a positive type that is solubilized by light.
  • (E-1) a polymerizable unsaturated compound and a photopolymerization initiator, or (e-2) a quinonediazide compound Can be preferably contained.
  • Examples of the polymerizable unsaturated compound in (e-1) include unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group, methacryloyl group and / or unsaturated triple bond functional groups such as propargyl group.
  • unsaturated double bond functional groups such as vinyl group, allyl group, acryloyl group, methacryloyl group and / or unsaturated triple bond functional groups such as propargyl group.
  • compounds having a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable from the viewpoint of polymerizability.
  • the number of functional groups contained therein is preferably 1 to 4 from the viewpoint of stability, and each does not have to be the same group.
  • the compound referred to herein preferably has a molecular weight of 30 to 800.
  • the compatibility with the polymer and the reactive diluent is good. Specifically, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate.
  • the photopolymerization initiator in (e-1) means one that initiates polymerization mainly by generating radicals when irradiated with light in the ultraviolet to visible light range.
  • a known photopolymerization initiator selected from an acetophenone derivative, a benzophenone derivative, a benzoin ether derivative, and a xanthone derivative is preferable from the viewpoint that a general-purpose light source can be used and the rapid curing property.
  • photopolymerization initiators examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexylphenylketone, Isobutyl benzoin ether, benzoin methyl ether, thioxanthone, isopropyl thioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 and the like, but not limited thereto.
  • Examples of the quinonediazide compound (e-2) include a polyhydroxy compound in which a sulfonic acid of quinonediazide is ester-bonded, a polyamino compound in which a sulfonic acid of quinonediazide is sulfonamide-bonded, and a polyhydroxypolyamino compound in which a sulfonic acid of quinonediazide is ester.
  • Known compounds such as those having a bond and / or a sulfonamide bond can be used.
  • quinonediazide a positive type photosensitive resin composition that is sensitive to general ultraviolet rays i line (wavelength 365 nm), h line (wavelength 405 nm), and g line (wavelength 436 nm) of a mercury lamp is prepared. Obtainable.
  • Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP.
  • TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (these are trade names, manufactured by Honshu Kagaku Kogyo), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), 2,6- Dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene Bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Although such a novolak resin include, but are not limited
  • Polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl. Examples include, but are not limited to, sulfides.
  • examples of the polyhydroxy polyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3′-dihydroxybenzidine.
  • the (e-2) quinonediazide compound contains a phenol compound and an ester with a 5-naphthoquinonediazidesulfonyl group. This makes it possible to obtain high sensitivity and higher resolution in i-line exposure.
  • the content of the (e-2) quinonediazide compound is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin of the component (BI).
  • the photosensitive resin composition (I) can contain a colorant (FI).
  • the colorant (FI) refers to a known organic pigment, inorganic pigment or dye that is commonly used in the field of electronic information materials.
  • the colorant (FI) is preferably an organic pigment and / or an inorganic pigment.
  • organic pigment examples include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine or metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone and anthraquinone.
  • Anthraquinone pigments such as pyrimidine, flavantron, anthantrone, indanthrone, pyrantrone or violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments , Quinophthalone pigments, slene pigments, benzofuranone pigments, or metal complex pigments.
  • the inorganic pigment for example, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermillion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt.
  • examples include green, cobalt chrome green, Victoria green, ultramarine blue, navy blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet or cobalt violet.
  • the dye examples include azo dye, anthraquinone dye, condensed polycyclic aromatic carbonyl dye, indigoid dye, carbonium dye, phthalocyanine dye, methine or polymethine dye.
  • red pigments examples include Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217, 220, 223, 224. 226, 227, 228, 240 or 254 (numerical values are color indexes (hereinafter, "CI" numbers)).
  • orange pigments examples include Pigment Orange 13, 36, 38, 43, 51, 55, 59, 61, 64, 65 or 71 (all numerical values are CI numbers).
  • yellow pigments examples include Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168 or 185 (numerical values are all CI numbers).
  • Examples of purple pigments include Pigment Violet 19, 23, 29, 30, 32, 37, 40 or 50 (all numerical values are CI numbers).
  • examples of blue pigments include Pigment Blue 15, 15: 3, 15: 4, 15: 6, 22, 60, and 64 (numerical values are all CI numbers).
  • examples of green pigments include Pigment Green 7, 10, 36, and 58 (all numerical values are CI numbers).
  • black pigments include black organic pigments and black inorganic pigments.
  • black organic pigments include carbon black, benzofuranone black pigments (described in International Publication No. 2010/081624), perylene black pigments, aniline black pigments, or anthraquinone black pigments.
  • benzofuranone-based black pigments or perylene-based black pigments are particularly preferable in that a negative photosensitive resin composition having higher sensitivity can be obtained.
  • Benzofuranone black pigments and perylene black pigments have a relatively high transmittance in the ultraviolet region while realizing a high light-shielding property with a low transmittance in the visible region, which allows the chemical reaction during exposure to proceed efficiently. is there.
  • the benzofuranone black pigment and the perylene black pigment may be contained together.
  • the black inorganic pigment for example, graphite, or fine particles of metal such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver, oxides, complex oxides, sulfides, nitrides or Examples thereof include oxynitride, and carbon black or titanium nitride having high light-shielding property is preferable.
  • dyes examples include Sumilan, Lanyl (registered trademark) series (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Orasol (registered trademark), Oracet (registered trademark), Filamid (registered trademark), Irgasperse (registered trademark).
  • Zapon, Neozapon, Neptune Acidol series (all manufactured by BASF Corp.), Kayaset (registered trademark), Kayakalan (registered trademark) series (all manufactured by Nippon Kayaku Co., Ltd.), and Valifast ( (Registered trademark) Colors series (manufactured by Orient Chemical Industries, Ltd.), Savinyl, Sandoplast, Polysynththren (registered trademark), Lanasyn (registered trademark) series (all of which are manufactured by Clariant Japan Co., Ltd.) Aizen (registered trademark), Spiron (registered trademark) series (all of which are manufactured by Hodogaya Chemical Co., Ltd.), functional dyes (manufactured by Yamada Chemical Co., Ltd.), Plast Color, Oil Color series (Arimoto Kagaku) Industrial Co., Ltd. etc. can be mentioned.
  • the color of the colorant is preferably black which can block visible light over the entire wavelength range, and at least one selected from organic pigments, inorganic pigments and dyes is used.
  • a colorant that exhibits a black color when formed into a cured film may be used.
  • the above-mentioned black organic pigment and black inorganic pigment may be used, or pseudo blackening may be performed by mixing two or more kinds of organic pigments and dyes. In the case of pseudo blackening, it can be obtained by mixing two or more kinds of the above-mentioned organic pigments and dyes such as red, orange, yellow, purple, blue and green.
  • the photosensitive resin composition (I) itself does not necessarily have to be black, and a colorant that causes the cured film to show black due to a change in color during heat curing may be used.
  • a colorant that contains an organic pigment and / or an inorganic pigment and exhibits a black color when formed into a cured film it is preferable to use a colorant that contains an organic pigment and / or dye and that exhibits a black color when formed into a cured film. That is, it is preferable to use a colorant that contains an organic pigment and exhibits a black color when formed into a cured film, from the viewpoint that both high heat resistance and insulation can be achieved at the same time.
  • the content of the colorant (FI) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more with respect to 100 parts by mass of the component (BI). It is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less.
  • the content of the colorant is 10 parts by mass or more, the coloring property required for the cured film is obtained, and when it is 300 parts by mass or less, the storage stability becomes good.
  • the photosensitive resin composition (I) preferably contains a dispersant.
  • the colorant can be uniformly and stably dispersed in the resin composition.
  • the dispersant is not particularly limited, but a polymer dispersant is preferable.
  • the polymer dispersant include a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a polyallylamine polymer dispersant, and a carbodiimide dispersant.
  • the polymer dispersant has a main chain made of polyamino, polyether, polyester, polyurethane, polyacrylate, etc., and has an amine, a carboxylic acid, a phosphoric acid, an amine salt, or a carboxylic acid at a side chain or main chain end. It refers to a polymer compound having a polar group such as acid salt and phosphate. The polar group is adsorbed on the pigment, and the steric hindrance of the main chain polymer serves to stabilize the dispersion of the pigment.
  • the dispersant is a (polymer) dispersant having only an amine value, a (polymer) dispersant having only an acid value, a (polymer) dispersant having an amine value and an acid value, or both an amine value and an acid value. Although it is classified as a dispersant having no (polymer), a dispersant having a amine value and an acid value (polymer) or a dispersant having only an amine value is preferable, and having only an amine value (high). More preferred are (molecular) dispersants.
  • polymer dispersant having only an amine value examples include, for example, DISPERBYK (registered trademark) 102, 160, 161, 162, 2163, 164, 2164, 166, 167, 168, 2000, 2050, 2150, 2155. 9075, 9077, BYK-LP N6919, BYK-LP N21116 or BYK-LP N21234 (all manufactured by Big Chemie), EFKA (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300.
  • DISPERBYK registered trademark
  • 102 160, 161, 162, 2163, 164, 2164, 166, 167, 168, 2000, 2050, 2150, 2155. 9075, 9077, BYK-LP N6919, BYK-LP N21116 or BYK-LP N21234 (all manufactured by Big Chemie)
  • EFKA registered trademark
  • the ratio of the dispersant to the colorant is preferably 1% by mass or more and more preferably 3% by mass or more in order to improve the dispersion stability while maintaining the heat resistance. Moreover, 100 mass% or less is preferable, and 50 mass% or less is more preferable.
  • the photosensitive resin composition (I) preferably contains an organic solvent (GI).
  • organic solvent examples include compounds of ethers, acetates, esters, ketones, aromatic hydrocarbons, amides or alcohols.
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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 , Dipropylene glycol monomethyl ether, Propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-
  • a pigment When a pigment is used as the colorant (FI), it is preferable to use an acetate compound as the organic solvent (GI) in order to stabilize the dispersion of the pigment.
  • the proportion of the acetate compound in all the organic solvents (GI) contained in the photosensitive resin composition (I) is preferably 50% by mass or more, more preferably 70% by mass or more. Moreover, 100 mass% or less is preferable, and 90 mass% or less is more preferable.
  • the amount of the solvent used is not particularly limited as it varies depending on the required film thickness and the coating method adopted, but is preferably 50 to 2000 parts by mass relative to 100 parts by mass of the resin of the component (BI). It is particularly preferably 100 to 1500 parts by mass.
  • the photosensitive resin composition (I) contains a surfactant, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl for the purpose of improving the wettability with a substrate as necessary. It may also contain ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane.
  • esters such as ethyl lactate or propylene glycol monomethyl ether acetate
  • alcohols such as ethanol, cyclohexanone
  • methyl for the purpose of improving the wettability with a substrate as necessary.
  • ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane.
  • the photosensitive resin composition (I) may contain an adhesion improver.
  • Adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Containing silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy groups Examples thereof include compounds obtained by reacting a silicon compound.
  • the adhesion to the underlying substrate such as a silicon wafer, ITO, SiO2, or silicon nitride can be enhanced when developing the photosensitive resin film.
  • resistance to oxygen plasma and UV ozone treatment used for cleaning and the like can be enhanced.
  • the content of the adhesion improver is preferably 0.1 part by mass or more, and more preferably 0.3 part by mass or more, relative to 100 parts by mass of the component (BI). Further, it is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
  • the photosensitive resin composition (I) may optionally contain a surfactant for the purpose of improving the wettability with the substrate.
  • a surfactant for the purpose of improving the wettability with the substrate.
  • a surfactant a commercially available compound can be used.
  • the silicone-based surfactant SH series, SD series, ST series of Toray Dow Corning Silicone, BYK series of Big Chemie Japan, Shin-Etsu Silicone are used.
  • the fluorine-based surfactant include "Megafuck (registered trademark)" series by Dainippon Ink and Chemicals, Fluorard series by Sumitomo 3M, and Asahi Glass Co., Ltd.
  • the content of the surfactant is preferably 0.001 part by mass or more, and more preferably 0.002 part by mass or more, relative to 100 parts by mass of the component (BI). Further, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.
  • the photosensitive resin composition (I) can be obtained by dissolving the components (AI) to (EI) in the organic solvent (GI).
  • the dissolution method include stirring and heating.
  • the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually room temperature to 80 ° C.
  • the order of dissolving each component is not particularly limited, and for example, there is a method of sequentially dissolving the compounds having a low solubility.
  • the obtained photosensitive resin composition (I) is preferably filtered using a filtration filter to remove dust and particles.
  • the filter pore size includes, for example, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, and 0.05 ⁇ m, but is not limited thereto.
  • Examples of the material of the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and it is preferable to filter using polyethylene or nylon.
  • the method of manufacturing the cured film is (1) A step of applying the photosensitive resin composition (I) to a substrate to form a photosensitive resin film, (2) Pre-baking step of drying the photosensitive resin film, (3) An exposure step of irradiating the dried photosensitive resin film with actinic radiation through a photomask, The process includes (4) a developing step of developing the exposed photosensitive resin film and (5) a step of heating the developed photosensitive resin film to form a cured film in this order.
  • the photosensitive resin composition (I) is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method or the like to obtain the photosensitive resin composition (I).
  • a spin coating method a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method or the like.
  • the substrate on which the photosensitive resin composition (I) is coated may be pretreated with the adhesion improver described above.
  • a solution prepared by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate is used.
  • a method of treating the surface of the base material can be mentioned. Examples of the method for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment and the like.
  • the applied photosensitive resin film is subjected to a reduced-pressure drying treatment if necessary, and then, using a hot plate, an oven, an infrared ray, etc., in a range of 50 ° C to 180 ° C. Heat treatment is performed for a few minutes to several hours to obtain a dried photosensitive resin film.
  • Actinic rays are irradiated on the photosensitive resin film through a photomask having a desired pattern.
  • the actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays.
  • baking may be performed after exposure. By performing post-exposure bake, effects such as improvement in resolution after development and increase in the allowable range of development conditions can be expected.
  • the post-exposure bake an oven, a hot plate, infrared rays, a flash annealing device, a laser annealing device, or the like can be used.
  • the post-exposure bake temperature is preferably 50 to 180 ° C, more preferably 60 to 150 ° C.
  • the post-exposure bake time is preferably 10 seconds to several hours. If the post-exposure bake time is within the above range, the reaction may proceed favorably and the developing time may be shortened in some cases.
  • the exposed photosensitive resin film is developed using a developing solution, and parts other than the exposed part are removed.
  • a developing solution tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl
  • Aqueous solutions of compounds showing alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred.
  • a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone or dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination of several kinds. Good.
  • a method such as spraying, paddle, dipping, and ultrasonic wave can be used.
  • rinse treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to distilled water.
  • a cured film is obtained by the heat treatment process of the developed photosensitive resin film. Since the residual solvent and the components having low heat resistance can be removed by the heat treatment, heat resistance and chemical resistance can be improved. Further, when the heat-crosslinking agent (DI) is contained, the heat-crosslinking reaction can be promoted by heat treatment, and heat resistance and chemical resistance can be improved.
  • This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and gradually increasing the temperature or by selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 150 ° C. and 250 ° C. for 30 minutes each. Alternatively, a method of linearly increasing the temperature from room temperature to 300 ° C. over 2 hours may be used.
  • the heat treatment condition in the present invention is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, further preferably 230 ° C. or higher, particularly preferably 250 ° C. or higher.
  • the heat treatment condition is preferably 400 ° C. or lower, more preferably 350 ° C. or lower, still more preferably 300 ° C. or lower.
  • the photosensitive sheet is defined as a sheet obtained by coating the releasable substrate with the photosensitive resin composition (I) and drying it.
  • the photosensitive sheet can be obtained by coating the photosensitive resin composition (I) on a support film made of polyethylene terephthalate, which is a releasable substrate, and drying the composition.
  • Thermocompression bonding can be performed by hot pressing, thermal laminating, thermal vacuum laminating, or the like.
  • the bonding temperature is preferably 40 ° C. or higher in terms of adhesion to the substrate and embedding property.
  • the laminating temperature is preferably 140 ° C. or lower in order to prevent the photosensitive sheet from being hardened at the time of laminating and reducing the resolution of pattern formation in the exposure / developing process.
  • the photosensitive resin film obtained by sticking the photosensitive sheet to the substrate follows the steps of exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heating and curing. To form a cured film.
  • the cured film obtained by curing the photosensitive resin composition (I) or the photosensitive sheet (hereinafter, sometimes referred to as the second aspect of the cured film of the present invention) is used for organic EL display devices, semiconductor devices, multilayer wiring boards and the like. It can be used for electronic parts.
  • an insulating layer of an organic EL element a flattening layer of a substrate with a drive circuit of a display device using the organic EL element, an interlayer insulating film between rewirings of a semiconductor device or a semiconductor component, a semiconductor passivation film, a semiconductor Suitable for use as device protection film, interlayer insulation film for multi-layer wiring for high-density mounting, circuit board wiring protection insulation layer, on-chip microlens of solid-state image sensor, flattening layer for various displays and solid-state image sensor, etc.
  • the electronic device having a surface protective film, an interlayer insulating film, or the like on which the second aspect of the cured film of the present invention is arranged include MRAM having low heat resistance.
  • the second aspect of the cured film of the present invention is suitable for a surface protective film of MRAM.
  • a display device including a first electrode formed on a substrate and a second electrode provided so as to face the first electrode, specifically, for example, a display such as an LCD, an ECD, an ELD, and an organic EL. It can be used as an insulating layer of a device.
  • the organic EL display device will be described as an example.
  • An organic EL display device having a cured film of a photosensitive resin composition (I) has a drive circuit, a flattening layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate.
  • the layer comprises the second aspect of the cured film of the present invention.
  • a TFT such as a glass or a resin film is provided on a substrate, and a wiring located on a side portion of the TFT and connected to the TFT is provided on the TFT.
  • the flattening layer is provided, and the display element is provided over the flattening layer.
  • the display element and the wiring are connected through a contact hole formed in the flattening layer.
  • the organic EL display device having the cured film of the photosensitive resin composition (I) is preferably used when a manufacturing method in which at least a part of pixels surrounded by the cured film is formed by an inkjet method is used. To be done.
  • the cured film obtained by curing the photosensitive resin composition (I) or the photosensitive resin sheet it has liquid repellency and prevents the ejection liquid used in the inkjet method from entering into adjacent pixels.
  • the molecular weights of (b1) to (b4) used in the examples were measured using the above-mentioned GPC device with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent, and the number average in terms of polystyrene.
  • NMP N-methyl-2-pyrrolidone
  • the measurement result of the PGMEA contact angle on the cured film was judged as follows, and the contact angle was 60 ° or more (A +), the contact angle was 50 ° or more and less than 60 ° (A), and the contact angle was 40 ° or more and 50 °. Less than (B) is excellent, contact angle is 30 ° or more and less than 40 ° (C) is good, and contact angle is less than 30 ° (D) is bad.
  • B Contact angle is 40 ° or more and less than 50 °
  • C Contact angle is 30 ° or more and less than 40 °
  • D Contact angle is less than 30 °.
  • the organic EL display device manufactured by the method described later was driven to emit light by direct current drive at 10 mA / cm 2 and observed for a display defect such as a non-light emitting region at the center of the pixel. Then, the display defect occurrence rate was calculated from the number of 20 organic EL display devices that normally emit light.
  • the display defect occurrence rate is 30% or more and less than 40% (C)
  • the display defect occurrence rate is 20% or more and less than 30% (B)
  • the display defect occurrence rate is less than 20%.
  • a and A + were considered excellent.
  • a + Display defect occurrence rate of 0% or more and less than 10%
  • D Display defect occurrence rate is 40% or more and less than 70%
  • E Display defect occurrence rate is 70% or more and less than 100% (6)
  • Durability evaluation The organic EL display device manufactured by the method described below was tested at 80 ° C.
  • Synthesis Example 1 Compound (AI) and liquid repellent material (A) are synthesized in a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and 100 parts by mass of cyclohexanone. In addition, the temperature was raised to 110 ° C. under a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110 ° C., and the monomer mixed solution shown in Table 1 was dropped at a constant rate over 2 hours by a dropping funnel to prepare each monomer solution. After completion of the dropping, the monomer solution was heated to 115 ° C. and reacted for 2 hours to obtain copolymers (a1) to (a9).
  • DMAA N, N-dimethylacrylamide
  • FAMAC-6 2- (perfluorohexyl) ethyl methacrylate
  • GMA Glycidyl methacrylate
  • Karenz MOI-BM 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate
  • Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) 18.3 g (0.05 mol) of acetone 100 mL, propylene oxide 17 It was dissolved in 0.4 g (0.3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After the dropping was completed, the reaction was carried out at ⁇ 15 ° C. for 4 hours and then the temperature was returned to room temperature. The precipitated white solid was filtered off and dried in vacuum at 50 ° C.
  • BAHF 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • Synthesis Example 3 Synthesis of alkali-soluble resin (b1) 62.0 g (0.20 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dianhydride (hereinafter referred to as ODPA) was dried under a dry nitrogen stream.
  • ODPA 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dianhydride
  • NMP -Methyl-2-pyrrolidone
  • the solution was poured into 5 L of water to collect a white precipitate.
  • the precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 24 hours to obtain the target polyimide (b2).
  • the number average molecular weight of the polyimide (b2) was 8200.
  • the precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 24 hours to obtain a target polybenzoxazole (PBO) precursor (b3).
  • the number average molecular weight of the PBO precursor (b3) was 8500.
  • Synthesis Example 7 Synthesis of phenol resin (c1) 108.0 g (1.00 mol) of m-cresol, 75.5 g of 37% by mass aqueous formaldehyde solution (0.93 mol of formaldehyde), oxalic acid dihydrate under a dry nitrogen stream. After charging 0.63 g (0.005 mol) and 264 g of methyl isobutyl ketone, the mixture was immersed in an oil bath and the polycondensation reaction was carried out for 4 hours while refluxing the reaction solution. After that, the temperature of the oil bath was raised over 3 hours, and then the pressure inside the flask was reduced to 4.0 kPa to 6.7 kPa to remove volatile components, and the dissolved resin was cooled to room temperature. Thus, a novolac type phenol resin (c1) was obtained. From GPC, the weight average molecular weight was 3,500.
  • Synthesis Example 8 Synthesis of quinonediazide compound (e2) 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g of 5-naphthoquinonediazidesulfonyl acid chloride under a dry nitrogen stream. (0.135 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not exceed 35 ° C. After dropping, the mixture was stirred at 30 ° C. for 2 hours.
  • TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
  • HMOM-TPHAP a compound having a phenolic hydroxyl group and having a substituent having a molecular weight of 40 or more at both ortho positions of the phenolic hydroxyl group, represented by the following chemical formula, manufactured by Honshu Chemical Industry Co., Ltd.
  • VG3101L a compound represented by the following chemical formula, manufactured by Printec Co., Ltd.).
  • PGMEA Propylene glycol monomethyl ether acetate PGME; Propylene glycol monomethyl ether GBL; ⁇ -butyrolactone.
  • FIG. 2 shows a schematic diagram of a substrate used for evaluation.
  • an ITO transparent conductive film 10 nm was formed on the entire surface of a non-alkali glass plate 1 by a sputtering method on a 38 ⁇ 46 mm non-alkali glass plate 1 and etched as a first electrode 2. Further, the auxiliary electrode 3 was also formed at the same time to take out the second electrode.
  • the obtained substrate was ultrasonically cleaned with "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, washed with ultrapure water, and dried to obtain a substrate.
  • "Semicoclean" registered trademark
  • the components were mixed under a yellow light at the compounding ratios shown in Tables 2 and 3, and sufficiently stirred at room temperature to dissolve them. Then, the obtained solution was filtered with a filter having a pore size of 1 ⁇ m to obtain photosensitive resin compositions W1 to W34. The resulting photosensitive resin composition was applied onto this substrate by spin coating, prebaked on a hot plate at 120 ° C. for 4 minutes to form a dry coating film, and then a photomask having a predetermined pattern.
  • openings having a width of 70 ⁇ m and a length of 260 ⁇ m are arranged on the substrate at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction.
  • the barrier rib pattern 5 having a shape in which each opening exposes the first electrode was formed.
  • the partition pattern 4 in which an opening is arranged at one place in the center, and the substrate on which the partition pattern 5 was formed were subjected to a nitrogen atmosphere in a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) at 250 ° C. (3)
  • the contact angle was evaluated using a substrate having a partition wall pattern 4 in which one opening was arranged at the center and was cured by heating for 1 hour. The results are shown in Tables 4 and 5.
  • an ink of a compound (HT-1) using methyl benzoate as a solvent was used as a hole injecting layer.
  • a device (Litex 142 manufactured by ULVAC)
  • the ink was dropped onto a region surrounded by partition walls, and (4) the ink wettability of the opening was evaluated. Then, it baked at 200 degreeC and formed the positive hole injection layer.
  • a compound (HT-2) using 4-methoxytoluene as a solvent was dropped into a region surrounded by partition walls using an inkjet device, and then baked at 190 ° C.
  • a transport layer was formed. Further, as a light emitting layer, a mixture of compound (GH-1) and compound (GD-1) using 4-methoxytoluene as a solvent was dropped into a region surrounded by partition walls using an inkjet device, and then 130 ° C. Was fired to form a light emitting layer. Then, the compound (ET-1) and the compound (LiQ) as electron transporting materials were sequentially laminated at a volume ratio of 1: 1 by a vacuum vapor deposition method to form an organic EL layer 6. Next, after compound (LiQ) was vapor-deposited to 2 nm, Mg and Ag were vapor-deposited to 10 nm at a volume ratio of 10: 1 to form a second electrode 7. Finally, a cap-shaped glass plate was adhered and sealed using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to fabricate four 5 mm square light-emitting devices on one substrate.
  • the organic EL display device produced by the above method was driven to emit light at 10 mA / cm 2 by direct current drive, and (5) display defect occurrence rate was evaluated. Further, the sample was kept at 80 ° C. for 100 hours, and was again made to emit light by direct current driving at 10 mA / cm 2 , and it was confirmed whether or not the light emission characteristics were changed. (6) The results of durability evaluation are shown in Tables 4 and 5. Show.
  • the organic EL light emitting element has a high durability in which the occurrence of display defects is small and the performance as the light emitting element is maintained even after the durability test under the acceleration condition.
  • FIG. 2 shows a schematic diagram of a substrate used for evaluation.
  • an ITO transparent conductive film 10 nm was formed on the entire surface of a non-alkali glass plate 1 by a sputtering method on a 38 ⁇ 46 mm non-alkali glass plate 1 and etched as a first electrode 2. Further, the auxiliary electrode 3 was also formed at the same time to take out the second electrode.
  • the obtained substrate was ultrasonically cleaned with "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, washed with ultrapure water, and dried to obtain a substrate.
  • "Semicoclean" registered trademark
  • the photosensitive resin composition W21 was applied onto this substrate by a spin coating method, and pre-baked on a hot plate at 120 ° C. for 4 minutes to form a dry coating film. Then, patterning exposure was performed through a photomask having a predetermined pattern. At this time, due to the “half exposure”, a step shape having a first partition wall section having a trapezoidal cross section and a second partition section having a trapezoidal cross section above the first partition section is formed.
  • the width of the upper surface of the first partition wall section is A and the width of the bottom surface of the second partition wall section is B in the plane cut in the vertical direction, exposure is performed so that a step shape satisfying the relation of A> B is obtained. I went.
  • the ink of the compound (HT-1) using methyl benzoate as a solvent was used as a hole injection layer by using an inkjet device (Litex 142 manufactured by ULVAC). It dripped in the area surrounded by. At this time, the presence or absence of ink leakage to the outside of the opening was confirmed and evaluated as follows.
  • the hole injection layer end is on the side surface of the second partition.
  • the edge portion of the hole injection layer is on the side surface of the first partition wall portion.
  • a compound (HT-2) using 4-methoxytoluene as a solvent was dropped onto the other substrate in a region surrounded by partition walls using an inkjet device, and then at 190 ° C. Firing was performed to form a hole transport layer.
  • a mixture of compound (GH-1) and compound (GD-1) using 4-methoxytoluene as a solvent was dropped into a region surrounded by partition walls using an inkjet device, and then 130 ° C. was fired to form a light emitting layer.
  • the compound (ET-1) and the compound (LiQ) as electron transporting materials were sequentially laminated at a volume ratio of 1: 1 by a vacuum vapor deposition method to form an organic EL layer 6.
  • Mg and Ag were vapor-deposited to 10 nm at a volume ratio of 10: 1 to form a second electrode 7.
  • a cap-shaped glass plate was adhered and sealed using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to fabricate four 5 mm square light-emitting devices on one substrate.
  • the organic EL display device manufactured by the above method was driven to emit light at 10 mA / cm 2 by direct current drive, the central portion and the outer peripheral portion of the pixel were compared, and the presence or absence of uneven brightness in the pixel was observed and evaluated.

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WO2022181351A1 (ja) * 2021-02-24 2022-09-01 東レ株式会社 積層体、表示装置、および表示装置の製造方法
WO2023032821A1 (ja) * 2021-08-31 2023-03-09 富士フイルム株式会社 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス
JP2023538470A (ja) * 2021-07-27 2023-09-08 チーリン オーレッド オプティカル アンド エレクトロニック マテリアルズ カンパニー リミテッド 樹脂組成物、樹脂フィルム、および表示装置
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JP2023538470A (ja) * 2021-07-27 2023-09-08 チーリン オーレッド オプティカル アンド エレクトロニック マテリアルズ カンパニー リミテッド 樹脂組成物、樹脂フィルム、および表示装置
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