WO2023032803A1 - Composition de résine, produit durci, dispositif d'affichage électroluminescent organique et procédé de production de produit durci - Google Patents

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

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WO2023032803A1
WO2023032803A1 PCT/JP2022/032018 JP2022032018W WO2023032803A1 WO 2023032803 A1 WO2023032803 A1 WO 2023032803A1 JP 2022032018 W JP2022032018 W JP 2022032018W WO 2023032803 A1 WO2023032803 A1 WO 2023032803A1
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resin
acid
resin composition
organic
weight
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PCT/JP2022/032018
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English (en)
Japanese (ja)
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北村友弘
山根麻央
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東レ株式会社
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Priority to KR1020247004156A priority Critical patent/KR20240051923A/ko
Priority to CN202280056956.6A priority patent/CN117858921A/zh
Priority to JP2022552149A priority patent/JPWO2023032803A1/ja
Publication of WO2023032803A1 publication Critical patent/WO2023032803A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—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
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
    • H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes

Definitions

  • the present invention relates to a resin composition, a cured product, an organic EL display device, and a method for manufacturing an organic EL display device.
  • insulating films for organic electroluminescence (hereinafter referred to as EL) elements flattening films for driving thin film transistor (hereinafter referred to as TFT) substrates of display devices using organic EL elements, wiring protection insulation for circuit substrates
  • TFT thin film transistor
  • the present invention relates to a resin composition suitable for applications such as films, on-chip microlenses for solid-state imaging devices, and flattening films for various displays and solid-state imaging devices.
  • an organic EL display device has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and a voltage is applied between the first electrode and the second electrode facing each other. can be applied to emit light.
  • resin compositions that can be patterned by ultraviolet irradiation are generally used as the material for the flattening layer and the material for the insulating layer.
  • a resin composition using a polyimide-based resin is preferably used in that it can provide a highly reliable organic EL display device because the resin composition has high heat resistance and the gas component generated from the cured product is small. ing.
  • Resin compositions using polyimide-based resins that have been proposed so far include photosensitive resin compositions obtained by mixing a polyimide precursor with a photosensitive diazoquinone compound and a phenol novolac resin (see, for example, Patent Document 1), A positive photosensitive resin composition containing a resin having a phenolic hydroxyl group in a polyimide precursor or the like, a quinonediazide compound and a solvent (see, for example, Patent Document 2).
  • the materials proposed in the above patent documents have a problem that the long-term reliability of the organic EL display device is low. Organic light-emitting materials are generally vulnerable to gas components and moisture, and exposure to these causes a decrease in emission luminance and pixel shrinkage.
  • the term "pixel shrinkage” refers to a phenomenon in which the luminance of light emitted from the edge of a pixel decreases or the pixel does not light up.
  • it is necessary to improve the durability of the organic light-emitting material itself, as well as to improve the peripheral properties such as a flattening layer covering the drive circuit and an insulating layer formed on the first electrode. It is essential to improve the water absorption and outgassing properties of the material.
  • a positive photosensitive resin composition that does not cause a decrease in emission luminance or pixel shrinkage and has excellent long-term reliability has been proposed (see, for example, Patent Document 3).
  • such a positive photosensitive resin composition has a problem that the retention rate of emission luminance is insufficient in terms of long-term reliability, and the emission area ratio of pixels decreases over a long period of time.
  • the object of the present invention is to provide a resin composition with excellent long-term reliability that does not cause a decrease in emission luminance or pixel shrinkage and does not reduce the pixel emission area ratio even over a long period of time. .
  • the resin composition of the present invention has the following constitution. i.e. (1) Alkali-soluble resin (a) and novolac-type phenolic resin (b ), wherein the content of the novolac-type phenolic resin having a molecular weight of 1,000 or less in the novolac-type phenolic resin (b) is 0.1 to 20 in the novolac-type phenolic resin (b). Resin composition in weight percent.
  • the weight-average molecular weight (Mw) of the novolak-type phenolic resin (b) is 3,000 or more and 15,000 or less, and the dispersion ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) ( The resin composition according to (1) above, wherein Mw)/(Mn) is from 1.1 to 3.5. (3) The resin composition according to (1) or (2) above, wherein the novolak-type phenolic resin (b) contains an m-cresol novolac resin. (4) The resin composition according to any one of (1) to (3), wherein the novolak-type phenolic resin (b) is 17 to 50 parts by weight per 100 parts by weight of the alkali-soluble resin (a).
  • (6) A cured product obtained by curing the resin composition according to any one of (1) to (5) above.
  • An organic EL display device having a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, wherein the planarizing layer and/or the insulating layer are (6) ).
  • the resin composition and cured product of the present invention do not cause a decrease in emission luminance or pixel shrinkage, and have excellent long-term reliability.
  • an organic EL display device with excellent long-term reliability can be provided.
  • FIG. 1 is a cross-sectional view of an example of an organic EL display device
  • FIG. It is a schematic diagram of the manufacturing procedure of the organic EL display device in the example.
  • the resin composition of the present invention contains at least one selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these and copolymers thereof, and an alkali-soluble resin (a) and a novolac type phenolic resin (b), wherein the content of the novolac-type phenolic resin having a molecular weight of 1,000 or less in the novolac-type phenolic resin (b) is 0.1 to 20% by weight.
  • the weight average molecular weight means the polystyrene-equivalent weight-average molecular weight measured by GPC (gel permeation chromatography), and the number-average molecular weight measured by GPC (gel permeation chromatography) means the polystyrene-equivalent number average molecular weight.
  • the weight-average molecular weight or number-average molecular weight of the novolak-type phenolic resin (b) is the average molecular weight as a value representative of the entire novolac-type phenolic resin (b). This is the case of describing some molecules having that molecular weight in the novolac-type phenolic resin (b).
  • the "molecular weight” is also the polystyrene-equivalent molecular weight measured by GPC (gel permeation chromatography).
  • the resin composition of the present invention comprises an alkali-soluble resin (a) (hereinafter referred to as , sometimes simply referred to as “alkali-soluble resin (a)”).
  • the term “alkali-soluble” means that a solution obtained by dissolving a resin in ⁇ -butyrolactone is coated on a silicon wafer and prebaked at 120° C. for 4 minutes to form a prebaked film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m. After immersing the pre-baked film in a 2.38% by weight tetramethylammonium hydroxide aqueous solution (hereinafter sometimes referred to as an alkaline developer) at 23 ⁇ 1 ° C. for 1 minute, the film thickness reduction when rinsing with pure water It means that the desired dissolution rate is 50 nm/min or more.
  • the alkali-soluble resin (a) used in the present invention preferably has an acidic group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility.
  • acidic groups include carboxy groups, phenolic hydroxyl groups, and sulfonic acid groups.
  • the alkali-soluble resin (a) preferably contains a fluorine atom. This is because the presence of fluorine atoms makes the surface of the pre-baked film formed water-repellent, so that it is possible to prevent the alkali developer from permeating from the surface.
  • the alkali-soluble resin (a) used in the present invention more preferably contains a polyimide, a polyimide precursor, a polybenzoxazole precursor or a copolymer thereof, and from the viewpoint of further improving sensitivity, a polyimide precursor or More preferably, it contains a polybenzoxazole precursor.
  • the polyimide precursor refers to a resin that is converted to polyimide by heat treatment or chemical treatment, and examples thereof include polyamic acid and polyamic acid ester.
  • a polybenzoxazole precursor refers to a resin that is converted to polybenzoxazole by heat treatment or chemical treatment, and includes, for example, polyhydroxyamide.
  • the polyimide described above preferably has a structural unit represented by the following general formula (1), and the polyimide precursor and the polybenzoxazole precursor preferably have a structural unit represented by the following general formula (2). In such a case, two or more of these may be contained, or a resin obtained by copolymerizing a structural unit represented by general formula (1) and a structural unit represented by general formula (2) may be used.
  • R 11 represents a 4- to 10-valent organic group having 5 to 40 carbon atoms
  • R 12 represents a di- to 8-valent organic group having 5 to 40 carbon atoms
  • R 13 and R 14 each independently represent a carboxy group, a sulfonic acid group or a hydroxyl group.
  • p and q represent integers from 0 to 6, p+q>0.
  • R 15 and R 16 represent a divalent to octavalent organic group having 5 to 40 carbon atoms.
  • R 17 and R 18 each independently represent a phenolic hydroxyl group, a sulfonic acid group or COOR 19 , and may be a single group or a mixture of different groups.
  • R 19 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • r and s represent integers from 0 to 6; However, r+s>0.
  • the polyimide, polyimide precursor, polybenzoxazole precursor or copolymer thereof preferably has 5 to 100,000 structural units represented by general formula (1) or general formula (2). Moreover, in addition to the structural unit represented by general formula (1) or general formula (2), it may have other structural units. In this case, the polyimide, polyimide precursor, polybenzoxazole precursor or copolymer thereof contains structural units represented by general formula (1) or general formula (2) in an amount of 50 mol% or more of all structural units. It is preferable to have
  • R 11 -(R 13 ) p represents an acid dianhydride residue.
  • R 11 is a tetravalent to decavalent organic group, preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.
  • acid dianhydride residues include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′- biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3 ,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methan
  • R20 represents an oxygen atom, C( CF3 ) 2 or C( CH3 ) 2 .
  • R21 and R22 represent a hydrogen atom or a hydroxyl group.
  • R 16 -(R 18 ) s represents an acid residue.
  • R 16 is a divalent to octavalent organic group having 5 to 40 carbon atoms, preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.
  • Acid residues include residues derived from dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid, trimellit residues derived from tricarboxylic acids such as acid, trimesic acid, diphenylethertricarboxylic acid, biphenyltricarboxylic acid, pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′ -biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracar
  • R20 represents an oxygen atom, C( CF3 ) 2 or C( CH3 ) 2 .
  • R21 and R22 represent a hydrogen atom or a hydroxyl group.
  • one or two carboxy groups correspond to R 18 in general formula (2). More preferably, 1 to 4 hydrogen atoms bonded to carbon atoms in the dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids exemplified above are substituted with R 18 in the general formula (2), preferably hydroxyl groups.
  • R 12 -(R 14 ) q in the general formula (1) and R 15 -(R 17 ) r in the general formula (2) represent diamine residues.
  • R 12 and R 15 are divalent to octavalent organic groups having 5 to 40 carbon atoms, and organic groups having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group are preferred.
  • Diamine residues include 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy) Benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ ether , 1,4-bis(4-aminophenoxy)benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl -4,4'-diaminobiphenyl, 3,3'-
  • Polyimides, polyimide precursors, polybenzoxazole precursors, or copolymers thereof may have two or more thereof.
  • R20 represents an oxygen atom, C( CF3 ) 2 or C( CH3 ) 2 .
  • R 21 to R 24 each independently represent a hydrogen atom or a hydroxyl group.
  • Preferred examples of monoamines having an acidic group include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene , 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-
  • acid anhydrides include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride. You may use 2 or more types of these.
  • Preferred examples of monocarboxylic acids include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene and the like. You may use 2 or more types of these.
  • acid chlorides include monoacid chloride compounds in which the carboxy group of the monocarboxylic acid is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6- Examples include monoacid chloride compounds in which only one carboxy group of dicarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is acid chlorided. You may use 2 or more types of these.
  • active ester compounds include reaction products of the monoacid chloride compounds with N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboximide. You may use 2 or more types of these.
  • the terminal blocking agent introduced into the alkali-soluble resin (a) can be easily detected by the following method.
  • a resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution, decomposed into an amine component and an acid component, which are the structural units of the resin, and subjected to gas chromatography (GC) or NMR measurement to determine the terminal
  • GC gas chromatography
  • NMR nuclear magnetic resonance
  • the encapsulant can be easily detected. It is also possible to detect the resin into which the terminal blocking agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum, and 13 C-NMR spectrum measurement.
  • PPC pyrolysis gas chromatography
  • the alkali-soluble resin (a) used in the present invention is synthesized by a known method.
  • Methods for producing polyamic acid or polyamic acid ester, which are polyimide precursors include, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, and a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol. , then a method of reacting with an amine in the presence of a condensing agent, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, followed by acid chloride of the remaining dicarboxylic acid and reaction with an amine, and the like. .
  • a method for producing polyhydroxyamide, which is a polybenzoxazole precursor includes, for example, a method of condensing a bisaminophenol compound and a dicarboxylic acid. Specifically, for example, a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisaminophenol compound thereto, a method of adding a tertiary amine such as pyridine to a solution of a bisaminophenol compound and dicarboxylic acid. A method of dropping a solution of acid dichloride and the like can be mentioned.
  • a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC)
  • DCC dicyclohexylcarbodiimide
  • a tertiary amine such as pyridine
  • Examples of methods for producing polyimide include dehydration and ring closure of the polyamic acid or polyamic acid ester obtained by the above method.
  • Methods for dehydration and ring closure include chemical treatment with an acid or base, heat treatment, and the like.
  • Examples of methods for producing polybenzoxazole include a method of dehydrating and ring-closing the polyhydroxyamide obtained by the above method.
  • Methods for dehydration and ring closure include chemical treatment with an acid or base, heat treatment, and the like.
  • Polyamideimide precursors include tricarboxylic acids, corresponding tricarboxylic acid anhydrides, and polymers of tricarboxylic acid anhydride halides and diamine compounds, preferably polymers of trimellitic anhydride chloride and aromatic diamine compounds.
  • Examples of the method for producing a polyamideimide precursor include a method of reacting a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide, etc. with a diamine compound at a low temperature.
  • Examples of methods for producing polyamideimide include a method of reacting trimellitic anhydride and an aromatic diisocyanate, and a method of dehydrating and ring-closing the polyamideimide precursor obtained by the above method.
  • Methods for dehydration and ring closure include chemical treatment with an acid or base, heat treatment, and the like.
  • the resin composition of the present invention contains a novolak-type phenolic resin (b).
  • the novolak-type phenolic resin (b) can be obtained by a known method of heterogeneously reacting phenols and aldehydes in the presence of an acid catalyst.
  • the novolac-type phenolic resin (b) used in the present invention preferably contains an m-cresol novolak resin from the viewpoint of solubility in an alkaline developer.
  • the novolac-type phenolic resin (b) is generally produced using phenols as raw materials, and m-cresol novolac resins are resins having a structure obtained by using m-cresol in phenols.
  • the weight average molecular weight (Mw) is preferably 3,000 or more and 15,000 or less, preferably 7000 or more and 13,000 or less. is more preferable. Furthermore, since it exhibits moderate solubility in an alkaline developer, good sensitivity can be obtained.
  • phenols used as raw materials for the novolac-type phenolic resin (b) used in the present invention include phenol, o-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like can be mentioned.
  • aldehydes used as raw materials for the novolak-type phenolic resin (b) used in the present invention include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde, and the like. .
  • formalin is particularly preferred. Two or more of these aldehydes may be combined.
  • the blending molar ratio (F/P) of the phenols (P) and the aldehydes (F) when producing the novolak-type phenolic resin (b) used in the present invention is preferably 0.33 to 1.20, It is more preferably 0.50 to 1.00.
  • the yield is good, and on the other hand, it is possible to prevent the dispersion ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polystyrene equivalent weight average molecular weight from becoming large.
  • the condensation reaction of phenols and aldehydes is usually carried out using an acid catalyst.
  • acid catalysts that can be used include inorganic or organic acids such as phosphoric acid, oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid, hydrochloric acid and sulfuric acid.
  • phosphoric acid is particularly preferred.
  • an aqueous solution of polyphosphoric acid such as metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, and tetraphosphoric acid can be used. Since it plays a role of forming a field for a phase separation reaction with phenols in the presence thereof, aqueous solutions such as 75% by weight phosphoric acid and 89% by weight phosphoric acid are generally preferred.
  • Organic solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, butanediol, pentanediol, ethylene glycol, propylene glycol and diethylene glycol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • Cellosolves such as , methyl cellosolve, ethyl cellosolve and butyl cellosolve, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, and cyclic ethers such as 1-4-dioxane are preferably used.
  • the amount of water in the reaction system affects the phase separation effect and production efficiency, but it is generally 40% or less on a weight basis. If the amount of water exceeds 40%, production efficiency may decrease.
  • reaction temperature between phenols and aldehydes is important for enhancing the phase separation effect, and is generally 40°C to reflux temperature, preferably 80°C to reflux temperature, more preferably reflux temperature.
  • the reaction time varies depending on, for example, the reaction temperature, raw material compounding ratio, acid catalyst compounding amount, etc., but is generally about 1 to 30 hours.
  • normal pressure is suitable, but if the heterogeneous reaction is maintained, the reaction may be carried out under increased pressure or reduced pressure.
  • the weight average molecular weight (Mw) of the novolak-type phenolic resin (b) is 3,000 or more and 15,000 or less, and the dispersion ratio (Mw)/ (Mn) is preferably 1.1 to 3.5, more preferably 1.8 to 2.8. Within this range, patterning workability of the flattening layer material and the insulating layer material by ultraviolet irradiation is excellent.
  • the content of the novolak-type phenolic resin (b) having a molecular weight of 1,000 or less is 0.1 to 20% by weight in the novolak-type phenolic resin (b). , preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. If the content of the novolak-type phenolic resin having a molecular weight of 1,000 or less exceeds 20 parts by weight in the (b) novolak-type phenolic resin, a large amount of outgassing is generated, causing deterioration in long-term reliability of the organic EL display device. On the other hand, if the content is less than 0.1% by weight, the production yield is lowered, which is not preferable.
  • the content of the novolak-type phenolic resin (b) is preferably 17-50 parts by weight, more preferably 25-40 parts by weight, relative to 100 parts by weight of the alkali-soluble resin (a).
  • the content of the novolak-type phenolic resin (b) is within the above preferred range with respect to 100 parts by weight of the alkali-soluble resin (a)
  • the sensitivity can be appropriately expressed, while the amount of outgassing is small, and the organic EL display device can be used. Less likely to cause deterioration of long-term reliability.
  • the resin composition of the present invention preferably contains a photosensitive compound (c). If the photosensitive compound (c) is contained, a resin composition having photosensitivity can be obtained, so that the exposure and development steps can be performed without applying a photoresist, and then the photoresist is removed. No need.
  • the photosensitive compound (c) include a photoacid generator (c1) and a photopolymerization initiator (c2).
  • the photoacid generator (c1) is a compound that generates an acid upon irradiation with light
  • the photopolymerization initiator (c2) is a compound that undergoes bond cleavage and/or reaction upon irradiation with light to generate radicals.
  • the content of the photosensitive compound (c) is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (a). If the content of the photosensitive compound (c) is 0.01 parts by weight or more and 100 parts by weight or less, photosensitivity can be imparted while maintaining heat resistance, chemical resistance and mechanical properties of the cured product. .
  • the photoacid generator (c1) By containing the photoacid generator (c1), an acid is generated in the light-irradiated area and the solubility of the light-irradiated area in an alkaline aqueous solution increases, so that a positive relief pattern in which the light-irradiated area dissolves can be obtained. can. Further, by containing the photoacid generator (c1) and an epoxy compound or a thermal cross-linking agent described later, the acid generated in the light-irradiated portion accelerates the cross-linking reaction of the epoxy compound and the thermal cross-linking agent, and the light-irradiated portion becomes insoluble. A negative relief pattern can be obtained.
  • radical polymerization proceeds in the light-irradiated areas, and a negative relief pattern in which the light-irradiated areas become insoluble can be obtained.
  • Examples of the photoacid generator (c1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. It is preferable to contain two or more kinds of photoacid generators (c1), and it is more preferable to contain one more kind of quinonediazide compound as an essential component, so that a highly sensitive photosensitive resin composition can be obtained.
  • a quinonediazide compound is particularly preferable as the photoacid generator (c1) from the viewpoint of light emission reliability when the cured product of the present invention, which will be described later, is used as a planarizing layer and/or an insulating layer of an organic EL display device.
  • quinonediazide compound a compound in which naphthoquinonediazide sulfonic acid is bonded to a compound having a phenolic hydroxyl group via an ester is preferable.
  • the compound having a phenolic hydroxyl group used here known compounds may be used, and those into which 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid is introduced via an ester bond are preferred. Examples can be given, but compounds other than these can also be used.
  • the affinity of the quinonediazide compound for an alkaline aqueous solution is lowered.
  • the solubility of the resin composition in the unexposed area in an alkaline aqueous solution is greatly reduced.
  • the quinonediazide sulfonyl group is converted to indenecarboxylic acid by exposure, and a high dissolution rate in an alkaline aqueous solution of the photosensitive resin composition in the exposed area can be obtained. That is, as a result, the dissolution rate ratio between the exposed area and the unexposed area of the composition can be increased, and a pattern with high resolution can be obtained.
  • a quinonediazide compound obtained by introducing 4-naphthoquinonediazide sulfonic acid through an ester bond has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • a quinonediazide compound in which 5-naphthoquinonediazide sulfonic acid is introduced via an ester bond has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure.
  • sulfonium salts phosphonium salts, diazonium salts, and iodonium salts are preferable because they moderately stabilize the acid component generated by exposure.
  • sulfonium salts are preferred.
  • a sensitizer and the like can be contained as necessary.
  • the content of the photoacid generator (c1) is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (a) from the viewpoint of increasing sensitivity.
  • the quinonediazide compound is preferably 3 to 40 parts by weight.
  • the total amount of sulfonium salt, phosphonium salt, diazonium salt and iodonium salt is preferably 0.5 to 20 parts by weight.
  • Examples of the photopolymerization initiator (c2) include benzyl ketal photopolymerization initiators, ⁇ -hydroxyketone photopolymerization initiators, ⁇ -aminoketone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and oxime esters.
  • Two or more photopolymerization initiators (c2) may be contained.
  • an ⁇ -aminoketone photopolymerization initiator it is more preferable to contain any of an ⁇ -aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and an oxime ester photopolymerization initiator.
  • ⁇ -aminoketone-based photopolymerization initiators examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, 3,6-bis(2-methyl- 2-morpholinopropionyl)-9-octyl-9H-carbazole and the like.
  • acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl)phosphine oxide.
  • oxime ester photopolymerization initiators include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxy carbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-( O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-di
  • the content of the photopolymerization initiator (c2) is 0.1 parts by weight with respect to a total of 100 parts by weight of the alkali-soluble resin (a) and the radically polymerizable compound described later, from the viewpoint of further improving sensitivity. 1 part by weight or more is preferable, and 1 part by weight or more is more preferable. On the other hand, from the viewpoint of further improving the resolution and reducing the taper angle, it is preferably 25 parts by weight or less, more preferably 15 parts by weight or less.
  • the resin composition of the present invention may further contain a radically polymerizable compound.
  • a radically polymerizable compound is a compound that has multiple ethylenically unsaturated double bonds in its molecule.
  • the radicals generated from the photopolymerization initiator (c2) described above promote radical polymerization of the radically polymerizable compound, and insolubilization of the light-irradiated portion can yield a negative pattern.
  • the photocuring of the light-irradiated portion is accelerated, and the sensitivity can be further improved.
  • the crosslink density after thermosetting is improved, the hardness of the cured product can be improved.
  • a compound having a (meth)acrylic group which facilitates the progress of radical polymerization, is preferable.
  • Compounds having two or more (meth)acrylic groups in the molecule are more preferable from the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured product.
  • the double bond equivalent of the radically polymerizable compound is preferably 80 to 400 g/mol from the viewpoint of improving the sensitivity during exposure and improving the hardness of the cured product.
  • radically polymerizable compounds include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.
  • acrylates dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[4-(3-( meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9 -bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-( meth)acryloxyphenyl)fluorene or acid-modified products thereof, ethylene oxide-modified products,
  • the content of the radically polymerizable compound is 15% by weight with respect to the total 100% by weight of the alkali-soluble resin (a) and the radically polymerizable compound, from the viewpoint of further improving the sensitivity and reducing the taper angle.
  • the above is preferable, and 30% by weight or more is more preferable.
  • it is preferably 65% by weight or less, more preferably 50% by weight or less.
  • the resin composition of the present invention may contain a thermal cross-linking agent.
  • a thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group in the molecule.
  • a thermal cross-linking agent it is possible to cross-link the alkali-soluble resin (a) or other additive components and improve the heat resistance, chemical resistance and hardness of the film after thermal curing.
  • the amount of outgassing from the cured product can be further reduced, and the long-term reliability of the organic EL display device can be improved.
  • Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMO-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, H
  • Preferred examples of compounds having at least two epoxy groups include “Epolite” (registered trademark) 40E, “Epolite” 100E, “Epolite” 200E, “Epolite” 400E, “Epolite” 70P, “Epolite” 200P, “Epolite” “400P,” Epolite” 1500NP, “Epolite” 80MF, “Epolite” 4000, “Epolite” 3002 (manufactured by Kyoeisha Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, “Denacol” EX-214L , “Denacol” EX-216L, “Denacol” EX-850L (manufactured by Nagase ChemteX Corporation), GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), “Epicort” (registered trademark) 828, "Epikote” 1002,
  • Preferable examples of compounds having at least two oxetanyl groups include Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, Ethanacol OXMA (manufactured by Ube Industries, Ltd.), and oxetaneated phenol novolak.
  • the thermal cross-linking agent may be contained in combination of two or more.
  • the content of the thermal cross-linking agent is preferably 1% by weight or more and 30% by weight or less with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent. If the content of the thermal cross-linking agent is 1% by weight or more, the chemical resistance and hardness of the cured product can be further enhanced. In addition, if the content of the thermal crosslinking agent is 30% by weight or less, the amount of outgassing from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the resin composition can be improved. Also excellent.
  • the resin composition of the present invention may contain an organic solvent. By containing an organic solvent, a varnish state can be obtained, and coatability can be improved.
  • Organic solvents include polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol.
  • polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol.
  • the content of the organic solvent is not particularly limited, it is preferably 100 to 3,000 parts by weight, more preferably 150 to 2,000 parts by weight, based on 100 parts by weight of the total resin composition excluding the organic solvent.
  • the ratio of the solvent having a boiling point of 180° C. or higher to the total amount of the organic solvent is preferably 20 parts by weight or less, more preferably 10 parts by weight or less.
  • Adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group-containing Examples thereof include compounds obtained by reacting silicon compounds.
  • the content of the adhesion improver is preferably 0.1 to 10% by weight with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent.
  • the resin composition of the present invention may contain a surfactant as necessary to improve the wettability with the substrate.
  • surfactants include SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., BYK series from BYK Chemie Japan Co., Ltd., KP series from Shin-Etsu Chemical Co., Ltd., and NOF Corporation.
  • Disform series of DIC Corporation "Megafac (registered trademark)” series of DIC Corporation, Florard series of Sumitomo 3M Limited, “Surflon (registered trademark)” series of Asahi Glass Co., Ltd., "Asahi Guard (registered trademark)” series of Asahi Glass Co., Ltd.
  • a methacrylic surfactant may be used.
  • the content of the surfactant is preferably 0.001 to 1% by weight with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent.
  • the resin composition of the present invention may contain inorganic particles.
  • Preferred specific examples of inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc.
  • the primary particle diameter of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.
  • the content of the inorganic particles is preferably 5 to 90% by weight with respect to 100% by weight of the total amount of the resin composition excluding the organic solvent.
  • the resin composition of the present invention may contain a thermal acid generator within a range that does not impair the long-term reliability of the organic EL display device.
  • the thermal acid generator generates an acid when heated to accelerate the cross-linking reaction of the thermal cross-linking agent. It promotes cyclization and can further improve the mechanical properties of the cured product.
  • the thermal decomposition initiation temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, more preferably 250°C or less.
  • no acid is generated when the resin composition of the present invention is applied to a substrate and then dried (prebaking: about 70 to 140° C.), and the final heating (curing: about 100 to 100° C.) after patterning by subsequent exposure and development. It is preferable to select one that generates an acid at 400° C.), because it can suppress a decrease in sensitivity during development.
  • the acid generated from the thermal acid generator used in the present invention is preferably a strong acid, and examples thereof include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid. and haloalkylsulfonic acids such as trifluoromethylsulfonic acid and the like are preferred. They are used as salts such as onium salts or as covalent compounds such as imidosulfonates. You may contain 2 or more types of these.
  • the content of the thermal acid generator is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, relative to 100% by weight of the total amount of the resin composition excluding the organic solvent.
  • the thermal acid generator By containing 0.01% by weight or more of the thermal acid generator, the cross-linking reaction and cyclization of the unclosed ring structure of the resin are promoted, so that the mechanical properties and chemical resistance of the cured product can be further improved. From the viewpoint of long-term reliability of the organic EL display device, it is preferably 5% by weight or less, more preferably 2% by weight or less.
  • ⁇ Method for producing resin composition> an example of a preferable manufacturing method for obtaining the resin composition of the present invention will be described.
  • the components (a) to (c) and, if necessary, a coloring agent, a thermal cross-linking agent, an organic solvent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, an inorganic particle, a thermal acid generator, etc. are dissolved.
  • a resin composition can be obtained by allowing the Dissolution methods include stirring and heating. When 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, a method of dissolving compounds in order of low solubility can be mentioned.
  • ingredients that tend to generate bubbles during stirring and dissolution such as surfactants and some adhesion improvers, by adding them at the end after dissolving the other ingredients, the other ingredients will not be dissolved due to the generation of bubbles. can be prevented.
  • the obtained resin composition is preferably filtered using a filtration filter to remove dust and particles.
  • filter pore sizes include, but are not limited to, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, 0.05 ⁇ m, 0.02 ⁇ m.
  • Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred.
  • the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
  • the resin composition can be cured by heat treatment.
  • the heat treatment may be performed by selecting a certain temperature and increasing the temperature stepwise, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, heat treatment is performed at 150° C. and 250° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used.
  • the heat treatment conditions in the present invention are preferably 300° C. or higher, more preferably 350° C. or higher, from the viewpoint of reducing the amount of outgas generated from the cured product.
  • the temperature is preferably 500° C. or lower, more preferably 450° C. or lower, from the viewpoint of imparting sufficient film toughness to the cured product.
  • the cured product of the present invention can be suitably used as a gate insulating layer or interlayer insulating layer of a thin film transistor.
  • the cured product of the present invention can be obtained by applying the resin composition to a substrate to form a resin film, drying the resin film as necessary, exposing the resin film to light, and developing the exposed resin film. and a step of heat-treating the developed resin film. Details of each step are described below.
  • the resin composition of the present invention 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 a coating film of the resin composition.
  • the slit coating method is preferably used.
  • the slit coating method is advantageous in terms of cost reduction because it can be applied with a small amount of application liquid.
  • the amount of the coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 of that for the spin coating method.
  • the slit nozzle used for coating is not particularly limited, and those marketed by multiple manufacturers can be used. Specifically, "Linear Coater" manufactured by Dainippon Screen Mfg.
  • the coating speed is generally in the range of 10 mm/sec to 400 mm/sec.
  • the film thickness of the coating film varies depending on the solid content concentration and viscosity of the resin composition, but it is usually applied so that the film thickness after drying is 0.1 to 10 ⁇ m, preferably 0.3 to 5 ⁇ m.
  • the base material to be coated with the resin composition may be pretreated with the above-described adhesion improver.
  • a solution obtained by dissolving 0.5 to 20% by weight 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, and diethyl adipate is used. and a method of treating the substrate surface.
  • Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, vapor treatment, and the like.
  • the resin composition After applying the resin composition, dry it as necessary. It is common to dry under reduced pressure together with the substrate on which the coating film is formed. For example, a substrate having a coating film formed thereon is placed on proxy pins placed in a vacuum chamber, and dried under reduced pressure by reducing the pressure in the vacuum chamber. At this time, if the substrate and the top plate of the vacuum chamber are separated from each other, a large amount of air between the substrate and the top plate of the vacuum chamber flows during drying under reduced pressure, which tends to cause unevenness. Therefore, it is preferable to adjust the proxy pin height so as to narrow the gap.
  • the distance between the substrate and the top plate of the vacuum chamber is preferably about 2-20 mm, more preferably 2-10 mm.
  • the speed of drying under reduced pressure depends on the vacuum chamber volume, the vacuum pump capacity, the diameter of the pipe between the chamber and the pump, etc.
  • the pressure in the vacuum chamber is reduced to 40 Pa after 60 seconds. set and used.
  • a general vacuum drying time is often about 30 seconds to 100 seconds, and the ultimate pressure in the vacuum chamber at the end of the vacuum drying is usually 100 Pa or less with the coated substrate in place.
  • the surface of the coating film can be kept in a non-sticky and dry state, thereby suppressing surface contamination and generation of particles during subsequent substrate transport.
  • the coating film is generally dried by heating. This step is also called pre-baking.
  • Heat drying uses a hot plate, an oven, an infrared ray, or the like.
  • a hot plate is used for drying by heating, the coating film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate.
  • Materials for proxy pins include metal materials such as aluminum and stainless steel, and synthetic resins such as polyimide resin and "Teflon" (registered trademark). .
  • the height of the proxy pin varies depending on the size of the substrate, the type of coating film, the purpose of heating, etc., but is preferably about 0.1 to 10 mm.
  • the heating temperature varies depending on the type and purpose of the coating film, and is preferably in the range of 50° C. to 180° C. for 1 minute to several hours.
  • the step of forming a pattern from the obtained resin film that is, the step of exposing the resin film and the subsequent step of developing, will be described.
  • the photosensitive resin film is irradiated with actinic rays through a mask having a desired pattern.
  • Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc.
  • the exposed portion dissolves in the developer.
  • the exposed areas are cured and rendered insoluble in the developer.
  • a desired pattern is formed by removing the exposed portion in the case of a positive type and the non-exposed portion in the case of a negative type using a developer.
  • a developer for both positive and negative types tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, Aqueous solutions of alkaline compounds such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine are preferred.
  • these alkaline aqueous solutions are added with a polar solvent such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination. good.
  • a developing method methods such as spray, puddle, immersion, and ultrasonic waves are possible.
  • alcohols such as ethanol and isopropyl alcohol
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.
  • heat treatment can remove components with low heat resistance, heat resistance and chemical resistance can be improved.
  • the resin composition of the present invention contains an alkali-soluble resin selected from polyimide precursors, polybenzoxazole precursors, copolymers thereof, or copolymers of them and polyimide
  • heat treatment Since it can form an imide ring or an oxazole ring, heat resistance and chemical resistance can be improved, and if it contains a compound having at least two alkoxymethyl groups, methylol groups, epoxy groups, or oxanyl groups, heat treatment is required.
  • the thermal cross-linking reaction can be progressed, and the heat resistance and chemical resistance can be improved.
  • a certain temperature is selected and the temperature is raised stepwise, or a certain temperature range is selected and the temperature is raised continuously for 5 minutes to 5 hours.
  • heat treatment is performed at 150° C. and 250° C. for 30 minutes each.
  • a method of linearly raising the temperature from room temperature to 300° C. over 2 hours can be used.
  • the heat treatment conditions in the present invention are preferably 300° C. or higher, more preferably 350° C. or higher, from the viewpoint of reducing the amount of outgas generated from the cured product.
  • the temperature is preferably 500° C. or lower, more preferably 450° C. or lower, from the viewpoint of imparting sufficient film toughness to the cured product.
  • the resin composition and cured product of the present invention can be used to flatten the insulating layer of an organic electroluminescence (EL) element and the driving thin film transistor (TFT) substrate of a display device using an organic EL element. It is suitable for use as a layer for protecting wiring on a circuit board, an insulating layer for protecting wiring on a circuit board, an on-chip microlens for a solid-state imaging device, and a flattening layer for various displays and solid-state imaging devices.
  • MRAM with low heat resistance polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), etc., which are promising as next-generation memories. preferred.
  • a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, for example, a display device using an LCD, ECD, ELD, or an organic electroluminescence device (Organic electroluminescence device) It can also be used as an insulating layer.
  • An organic EL display device will be described below as an example.
  • the organic EL display device of the present invention has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and the planarizing layer and/or the insulating layer are the above-described electrodes of the present invention.
  • Including hardened material Organic EL light-emitting materials are susceptible to deterioration due to moisture, and may have adverse effects such as a decrease in the area ratio of light-emitting portions to the area of light-emitting pixels. Luminescent properties are obtained.
  • a substrate made of glass, various plastics, or the like is provided with TFTs and wirings located on the sides of the TFTs and connected to the TFTs, and unevenness is covered thereon.
  • a planarization layer is thus provided, and a display element is provided on the planarization layer. The display element and the wiring are connected through a contact hole formed in the planarization layer.
  • the film thickness of the flattening layer in the organic EL display device of the present invention is preferably 1.0 to 5.0 ⁇ m, more preferably 2.0 ⁇ m or more.
  • the flatness of densely packed TFTs and wiring can be improved due to high definition.
  • the flattening layer is thickened, outgassing increases and causes deterioration of the light emission reliability of the organic EL display device.
  • the flattening layer is preferably multi-layered because TFTs and wiring can be arranged in the film thickness direction for high definition.
  • Fig. 1 shows a cross-sectional view of an example of an organic EL display device.
  • Bottom gate type or top gate type TFTs (thin film transistors) 1 are provided in a matrix on a substrate 6 , and a TFT insulating layer 3 is formed to cover the TFTs 1 .
  • a wiring 2 connected to the TFT 1 is provided on the TFT insulating layer 3 .
  • a flattening layer 4 is provided on the TFT insulating layer 3 so as to bury the wiring 2 therein.
  • a contact hole 7 reaching the wiring 2 is provided in the planarization layer 4 .
  • An ITO (transparent electrode) 5 is formed on the planarization layer 4 while being connected to the wiring 2 through the contact hole 7 .
  • the ITO 5 becomes an electrode of a display element (for example, an organic EL element).
  • An insulating layer 8 is formed so as to cover the periphery of the ITO 5 .
  • the organic EL element may be of a top emission type in which light is emitted from the side opposite to the substrate 6, or may be of a bottom emission type in which light is extracted from the substrate 6 side. In this manner, an active matrix type organic EL display device is obtained in which the TFTs 1 for driving the organic EL elements are connected to the respective organic EL elements.
  • the manufacturing method of the organic EL display device of the present invention having the TFT insulating layer 3, the planarizing layer 4 and/or the insulating layer 8 is formed from the resin composition on a substrate in the same manner as the above-described method of manufacturing the cured product. drying the resin film as necessary; exposing the resin film to light; developing the exposed resin film; and heat-treating the developed resin film.
  • the organic EL display device of the present invention can be obtained by a manufacturing method including these steps.
  • the film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under the condition of a refractive index of 1.63.
  • TMAH tetramethylammonium aqueous solution
  • the resulting pattern was observed with an FDP microscope MX61 (manufactured by Olympus Corporation) at a magnification of 20 times to measure the opening diameter of the contact hole.
  • the minimum exposure dose (mJ/cm 2 ) at which the opening diameter of the contact hole reached 10 ⁇ m was obtained and defined as the sensitivity.
  • the film thickness was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under the condition of a refractive index of 1.63.
  • the resulting pre-baked film is heated to 250° C. using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm by volume or less and a temperature increase of 5° C./min. Then, the resin composition was baked at 250° C. for 1 hour to prepare a cured product. 10 mg of the resulting cured product on a 6-inch silicon wafer was heated at 180° C. for 30 minutes using helium as a purge gas, and the desorbed components were collected on an adsorbent (Carbotrap 400) by a purge and trap method. bottom.
  • CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.
  • the amount of gas generated was calculated from a calibration curve prepared by GC-MS analysis under the same conditions as above using n-hexadecane as a standard substance.
  • FIG. 2 shows a schematic diagram of the manufacturing procedure of the organic EL display device.
  • an ITO transparent conductive film of 10 nm was formed on the entire surface of the alkali-free glass substrate 19 of 38 mm ⁇ 46 mm by sputtering, and etched as the first electrode (transparent electrode) 20 .
  • an auxiliary electrode 21 for taking out the second electrode was also formed. (Upper left figure)
  • the obtained substrate was ultrasonically cleaned for 10 minutes with Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then cleaned with ultrapure water.
  • the entire surface of the substrate was coated with a resin composition shown in Table 3, which will be described later, by spin coating, and prebaked on a hot plate at 120° C. for 2 minutes.
  • This film was exposed to UV light through a photomask, developed with a 2.38% by weight TMAH aqueous solution to dissolve unnecessary portions, and rinsed with pure water.
  • the resulting resin pattern was heat-treated at 250° C. for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.).
  • the insulating layer 22 having a width of 70 ⁇ m and a length of 260 ⁇ m is arranged at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction, and each opening exposes the first electrode. Formed only in the effective area.
  • the insulating layer 22 having an insulating layer aperture ratio of 25% was formed in the effective area of the substrate, which was a square with one side of 16 mm.
  • the thickness of the insulating layer was about 1.0 ⁇ m. (upper right figure)
  • an organic EL layer 23 including a light-emitting layer was formed by a vacuum deposition method (lower left figure).
  • the degree of vacuum during vapor deposition was 1 ⁇ 10 ⁇ 3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition.
  • 10 nm of compound (HT-1) was deposited as a hole injection layer, and 50 nm of compound (HT-2) was deposited as a hole transport layer.
  • a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm with a doping concentration of 10%.
  • the compound (ET-1) and the compound (LiQ) as electron transport materials were laminated at a volume ratio of 1:1 to a thickness of 40 nm. Structures of compounds used in the organic EL layer are shown below.
  • a compound (LiQ) LiQ
  • Mg and Ag were vapor-deposited to a thickness of 10 nm at a volume ratio of 10:1 to form a second electrode (non-transparent electrode) 24 .
  • a cap-shaped glass plate was adhered with an epoxy resin-based adhesive under a low humidity nitrogen atmosphere for sealing.
  • the film thickness referred to here is a value displayed on a crystal oscillation type film thickness monitor.
  • the produced organic EL display device was placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and irradiated with UV light having a wavelength of 365 nm and an illuminance of 0.6 mW/cm 2 .
  • the organic EL display device was driven to emit light by direct current driving at 0.625 mA, and the area ratio of the light emitting portion to the area of the light emitting pixel (pixel light emitting area ratio). was measured.
  • this evaluation method when the pixel emission area ratio after 1,000 hours has passed is 80% or more, it can be said that the long-term reliability is excellent, and when it is 90% or more, it is more preferable.
  • Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound ( ⁇ ) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was added to 100 mL of acetone and propylene. It was dissolved in 17.4 g (0.3 mol) of oxide 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 completion of the dropwise addition, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50°C.
  • BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
  • Synthesis Example 2 Synthesis of alkali-soluble resin (a-1) 44.4 g (0.10 mol) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (hereinafter referred to as 6FDA) was added to 500 g of NMP under a dry nitrogen stream. was dissolved in 4.46 g (0.05 mol) of 3-aminophenol as a terminal blocker was added together with 5 g of NMP, and reacted at 40° C. for 30 minutes.
  • 6FDA 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride
  • Synthesis Example 3 Synthesis of alkali-soluble resin (a-2) Under dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 g) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane mol), and as a terminal blocking agent, 3.27 g (0.03 mol) of 3-aminophenol was dissolved in 150 g of NMP. 3,3′,4,4′-Diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) 31.0 g (0.1 mol) was added together with NMP 50 g, stirred at 20° C. for 1 hour, and then stirred at 50° C.
  • ODPA 3,3′,4,4′-Diphenylethertetracarboxylic dianhydride
  • Synthesis Example 5 Synthesis of novolac-type phenolic resin (b-1) 100 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, and then cloudy by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 22 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 6 Synthesis of novolac-type phenolic resin (b-2) After charging 100 g of phenol, 81.9 g of 37% formalin, 1 g of oxalic acid dihydrate, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 14 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred into a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 7 Synthesis of Novolac Phenolic Resin (b-3) After charging 100 g of phenol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol, a cloudy state formed by stirring and mixing. Then, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 10 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 8 Synthesis of novolak-type phenol resin (b-4) 100 g of m-cresol, 81.9 g of 37% formalin, and 60 g of 89% phosphoric acid were charged, and then stirred and mixed to form a cloudy state. Then, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 9 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl ethyl ketone was added to dissolve the condensate, and then the stirring was stopped and the contents were transferred to a separating flask and allowed to stand. lower layer).
  • Synthesis Example 9 Synthesis of novolak-type phenolic resin (b-5) 105 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol are charged, and then cloudy by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 17 hours, after which the reaction was stopped. Next, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the contents were transferred into a separating flask and allowed to stand. The aqueous acid phase (lower layer) was allowed to separate.
  • Synthesis Example 11 Synthesis of novolak-type phenolic resin (b-7) 100 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, and then cloudy by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 24 hours, after which the reaction was stopped. Next, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the contents were transferred into a separating flask and allowed to stand. The aqueous acid phase (lower layer) was allowed to separate.
  • Synthesis Example 12 Synthesis of novolac-type phenolic resin (b-8) After charging 100 g of phenol, 81.9 g of 37% formalin, 1 g of oxalic acid dihydrate, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 12 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred into a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 13 Synthesis of novolac-type phenolic resin (b-9) After charging 100 g of phenol, 81.9 g of 37% formalin, 1 g of oxalic acid dihydrate, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 24 hours, after which the reaction was stopped. Then, while stirring and mixing, 50 g of methyl isobutyl ketone was added to dissolve the condensate, and then the stirring was stopped and the content was transferred into a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • phenol novolac resin 85 g was dissolved in a mixed solution of 50 g of methyl isobutyl ketone/350 g of methanol, 250 g of distilled water was added dropwise while stirring, and after sufficient stirring, the solution was allowed to stand to separate into a resin solution phase and an aqueous solution phase. Thereafter, the resin solution phase was taken out and the solvent was removed to obtain 45 g of phenol novolac resin (b-9), and the properties were evaluated. The results are also shown in Table 2.
  • Synthesis Example 14 Synthesis of novolak-type phenolic resin (b-10) After charging 100 g of p-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol, cloudiness formed by stirring and mixing. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 9 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 15 Synthesis of novolak-type phenolic resin (b-11) 100 g of p-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, followed by stirring and mixing to form cloudiness. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 9 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 16 Synthesis of novolac-type phenolic resin (b-12) 100 g of m-cresol, 81.9 g of 37% formalin, 60 g of 89% phosphoric acid, and 100 g of ethylene glycol were charged, followed by stirring and mixing to form cloudiness. Under these conditions, the temperature was gradually raised to the reflux temperature, and the condensation reaction was carried out at the same temperature for 8 hours, after which the reaction was stopped. Then, 50 g of methyl isobutyl ketone was added while stirring and mixing to dissolve the condensate, then the stirring was stopped and the content was transferred to a separating flask and allowed to stand. The aqueous phase (lower layer) was allowed to separate.
  • Synthesis Example 17 Synthesis of quinonediazide compound (c-1) TrisP-PA (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) 21.22 g (0.05 mol) and 5-naphthoquinonediazide sulfonyl chloride 36 under a stream of dry nitrogen. .27 g (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 inside of the system did not reach 35° C. or higher. After dropping, the mixture was stirred at 30°C for 2 hours.
  • TrisP-PA trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.
  • Example 1 10.0 g of alkali-soluble resin (a-1) and 3.5 g of m-cresol novolak resin (b-1) were added to 40 g of PGME to obtain a varnish of a resin composition. Using the obtained varnish, the outgassing of the cured product, the 5% weight loss temperature, and the long-term reliability of the organic EL display device were evaluated as described above.
  • Example 2 10.0 g of alkali-soluble resin (a-1), 3.0 g of m-cresol novolac resin (b-1), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 3 10.0 g of an alkali-soluble resin (a-2), 1.8 g of a phenol novolac resin (b-2), and 2.0 g of a quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 4 10.0 g of an alkali-soluble resin (a-3), 4.9 g of a phenol novolac resin (b-3), and 2.0 g of a quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 5 10.0 g of alkali-soluble resin (a-1), 2.5 g of m-cresol novolac resin (b-4), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 6 10.0 g of alkali-soluble resin (a-1), 3.1 g of m-cresol novolak resin (b-5), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 7 10.0 g of alkali-soluble resin (a-1), 4.2 g of m-cresol novolac resin (b-6), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 8 10.0 g of alkali-soluble resin (a-1), 2.2 g of m-cresol novolac resin (b-7), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 9 10.0 g of alkali-soluble resin (a-1), 2.2 g of m-cresol novolak resin (b-12), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative example 1 10.0 g of alkali-soluble resin (a-1) and 5.5 g of phenol novolac resin (b-8) were added to 40 g of PGME to obtain a varnish of a resin composition. Using the obtained varnish, the outgassing of the cured product, the 5% weight loss temperature, and the long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative example 2 10.0 g of an alkali-soluble resin (a-1), 5.5 g of a phenol novolac resin (b-8), and 2.0 g of a quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative example 3 10.0 g of alkali-soluble resin (a-1), 1.6 g of phenol novolac resin (b-9) and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to obtain a varnish of a positive photosensitive resin composition. rice field. Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative example 4 10.0 g of alkali-soluble resin (a-1), 5.1 g of p-cresol novolac resin (b-10), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative example 5 10.0 g of alkali-soluble resin (a-1), 5.2 g of p-cresol novolak resin (b-11), and 2.0 g of quinonediazide compound (c-1) were added to 40 g of PGME to prepare a varnish of a positive photosensitive resin composition. got Using the obtained varnish, the sensitivity, outgassing of the cured product, 5% weight loss temperature, and long-term reliability of the organic EL display device were evaluated as described above.
  • the resin composition and cured product of the present invention can be used for insulating layers of organic EL elements, flattening layers of thin TFT substrates for driving display devices using organic EL elements, wiring protection insulating layers of circuit boards, and solid-state imaging elements. It is suitably used for chip microlenses, various displays, and flattening layers for solid-state imaging devices. For example, it is suitable as a surface protective layer or an interlayer insulating layer for MRAM with low heat resistance, polymer memory (PFRAM) and phase change memory (PCRAM, OUM) that are promising as next-generation memory.
  • PFRAM polymer memory
  • PCRAM phase change memory
  • a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, for example, a display device using an LCD, ECD, ELD, or an organic electroluminescence device (Organic electroluminescence device) It can also be preferably used as an insulating layer.

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Abstract

La présente invention aborde le problème de la fourniture d'une composition de résine qui présente une excellente fiabilité à long terme, ne provoque pas de réduction d'intensité lumineuse ou de retrait de pixels, et ne génère pas un rapport de surface lumineuse de pixel réduit même sur une longue période de temps. Cette composition de résine comprend : une résine soluble dans les alcalis (a) contenant au moins un élément choisi dans le groupe constitué par des polyimides, des polybenzoxazoles, des polyamides-imides, des précurseurs de l'un quelconque de ceux-ci et des copolymères de ceux-ci ; et une résine phénolique novolaque (b), la teneur de la résine phénolique novolaque, ayant un poids moléculaire inférieur ou égal à 1 000 dans la résine phénolique novolaque (b), étant de 0,1 à 20 % en poids dans la résine phénolique novolaque (b).
PCT/JP2022/032018 2021-08-30 2022-08-25 Composition de résine, produit durci, dispositif d'affichage électroluminescent organique et procédé de production de produit durci WO2023032803A1 (fr)

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CN202280056956.6A CN117858921A (zh) 2021-08-30 2022-08-25 树脂组合物、固化物、有机el显示装置及固化物的制造方法
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58113251A (ja) * 1981-12-26 1983-07-06 Nitto Electric Ind Co Ltd 半導体封止用熱硬化性樹脂組成物
JP2005250160A (ja) * 2004-03-04 2005-09-15 Kyocera Chemical Corp ポジ型感光性樹脂組成物及びその硬化物
JP2011521295A (ja) * 2008-05-22 2011-07-21 エルジー・ケム・リミテッド ポリイミド及びノボラック樹脂を含む感光性樹脂組成物
WO2018084149A1 (fr) * 2016-11-02 2018-05-11 東レ株式会社 Composition de résine, feuille de résine, film durci, dispositif d'affichage el organique, composant électronique à semi-conducteur, dispositif à semi-conducteur et procédé de production d'un dispositif d'affichage el organique
WO2020059485A1 (fr) * 2018-09-18 2020-03-26 東レ株式会社 Composition de résine photosensible, feuille de résine, film durci, dispositif d'affichage el organique, composant électronique à semi-conducteur, dispositif à semi-conducteur et procédé de production d'un dispositif d'affichage el organique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3369344B2 (ja) 1994-01-21 2003-01-20 信越化学工業株式会社 感光性樹脂組成物
JP2013205553A (ja) 2012-03-28 2013-10-07 Toray Ind Inc ポジ型感光性樹脂組成物
WO2017159476A1 (fr) 2016-03-18 2017-09-21 東レ株式会社 Film durci et composition de résine photosensible positive

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58113251A (ja) * 1981-12-26 1983-07-06 Nitto Electric Ind Co Ltd 半導体封止用熱硬化性樹脂組成物
JP2005250160A (ja) * 2004-03-04 2005-09-15 Kyocera Chemical Corp ポジ型感光性樹脂組成物及びその硬化物
JP2011521295A (ja) * 2008-05-22 2011-07-21 エルジー・ケム・リミテッド ポリイミド及びノボラック樹脂を含む感光性樹脂組成物
WO2018084149A1 (fr) * 2016-11-02 2018-05-11 東レ株式会社 Composition de résine, feuille de résine, film durci, dispositif d'affichage el organique, composant électronique à semi-conducteur, dispositif à semi-conducteur et procédé de production d'un dispositif d'affichage el organique
WO2020059485A1 (fr) * 2018-09-18 2020-03-26 東レ株式会社 Composition de résine photosensible, feuille de résine, film durci, dispositif d'affichage el organique, composant électronique à semi-conducteur, dispositif à semi-conducteur et procédé de production d'un dispositif d'affichage el organique

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