WO2023182327A1 - Composition de résine photosensible positive, produit durci, dispositif d'affichage électroluminescent organique et procédé de production de produit durci - Google Patents

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

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WO2023182327A1
WO2023182327A1 PCT/JP2023/011133 JP2023011133W WO2023182327A1 WO 2023182327 A1 WO2023182327 A1 WO 2023182327A1 JP 2023011133 W JP2023011133 W JP 2023011133W WO 2023182327 A1 WO2023182327 A1 WO 2023182327A1
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photosensitive resin
positive photosensitive
resin composition
mass
group
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PCT/JP2023/011133
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English (en)
Japanese (ja)
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将 福原
早葵 原田
勇太 首藤
航 福島
一登 三好
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東レ株式会社
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Priority to CN202380023538.1A priority Critical patent/CN118749088A/zh
Publication of WO2023182327A1 publication Critical patent/WO2023182327A1/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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • 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
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices

Definitions

  • the present invention relates to a positive photosensitive resin composition, a cured product using the same, an organic EL display device equipped with the cured product, and a method for producing the cured product.
  • organic electroluminescence (hereinafter referred to as "organic EL”) display devices have been developed.
  • an organic EL display device has a driving circuit, a flattening layer, a first electrode, a pixel dividing layer, a light emitting layer, and a second electrode on a substrate, and has a gap between a first electrode and a second electrode that face each other.
  • Light can be emitted by applying a voltage or passing a current.
  • photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as the material for the flattening layer and the material for the pixel division layer.
  • photosensitive resin compositions using polyimide-based resins have high heat resistance, and produce few gas components from the cured product processed at low temperatures of about 200 to 270 degrees Celsius, making them highly reliable organic EL. It is suitably used in that a display device can be obtained (for example, see Patent Document 1).
  • pixel shrink refers to a phenomenon in which the luminance of light emitted from the edge of a pixel decreases or the pixel does not turn on.
  • photosensitive resin compositions are required to have higher sensitivity in order to shorten exposure time.
  • high-sensitivity materials have the problem of poor development adhesion, and photosensitive resin compositions are required to have better development adhesion.
  • a flexible organic EL display device has a bendable portion and/or a fixed portion in a bent state in its structure, and in this bent portion, bending stress is applied to the flattening layer and the pixel dividing layer. There is. In a flexible organic EL display device including such a bent portion, high bending resistance is required for the flattening layer material and the pixel dividing layer material.
  • siloxane resins are being considered as photosensitive resin compositions that can achieve high sensitivity (see, for example, Patent Document 2).
  • a photosensitive resin composition that can provide high bending resistance it is being considered to add a specific phenolic hydroxyl group-containing compound and a phenolic antioxidant to the photosensitive resin composition (for example, see Patent Document 3). ).
  • the present invention provides a photosensitive resin that has high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product, and is highly reliable when the cured product is used in an organic EL display device.
  • the purpose is to provide a composition.
  • the invention is as follows. [1] (A) One or more selected from the group consisting of polyimides, polyimide precursors, and copolymers thereof; (B) From the group consisting of polybenzoxazole, polybenzoxazole precursors, and copolymers thereof.
  • the content of the component (B) is 10 to 100 parts by mass based on 100 parts by mass of the component (A), A positive photosensitive resin composition, wherein the content of the component (C) is 1 to 90 parts by mass based on 100 parts by mass of the component (A).
  • the content of the component (A) is [PI] (mass)
  • the content of the component (B) is [PB] (mass)
  • the content of the component (C) is [PH] (mass).
  • [16] (1) A step of applying the positive photosensitive resin composition according to any one of [1] to [12] to a substrate to form a positive photosensitive resin film, (2) the positive photosensitive resin composition; (3) exposing the dried positive photosensitive resin film to light through a photomask; (4) developing the exposed positive photosensitive resin film; and (5) development.
  • a method for producing a cured product comprising the steps of heat-treating a positive photosensitive resin film in this order.
  • the photosensitive resin composition of the present invention has high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product, and has high reliability when the cured product is used in an organic EL display device. It is possible to provide things.
  • FIG. 1 is a cross-sectional view of an organic EL display device in which a flattening layer and a pixel dividing layer are formed.
  • FIG. 2 is a schematic diagram of a substrate of an organic EL display device.
  • the positive photosensitive resin composition of the present invention comprises at least one type selected from the group consisting of (A) polyimide, a polyimide precursor, and a copolymer thereof (hereinafter sometimes referred to as the (A) component).
  • component (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors, and copolymers thereof (hereinafter sometimes referred to as component (B)), (C) polyhydroxystyrene , and/or a copolymer of polyhydroxystyrene and polystyrene (hereinafter sometimes referred to as component (C)), (D) a quinonediazide compound, and (E) a solvent,
  • component (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors, and copolymers thereof (hereinafter sometimes referred to as component (B)), (C) polyhydroxystyrene , and/or a copolymer of polyhydroxystyrene and polystyrene (hereinafter sometimes referred to as component (C)), (D) a quinonediazide compound, and (E) a solvent,
  • component (B) is 10 to 100
  • component (B) By setting the content of component (B) to 10 to 100 parts by mass based on 100 parts by mass of component (A), a cured product with good heat resistance and bending resistance can be obtained.
  • component (C) By controlling the content of component (C) to 1 to 90 parts by mass per 100 parts by mass of component (A), the sensitivity of the resin composition is improved and development adhesion is improved.
  • the desired high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product can be achieved, and the cured product can be used in organic EL display devices. It is possible to provide a photosensitive resin composition that has high reliability over time.
  • the positive photosensitive resin composition of the present invention contains (A) one or more selected from the group consisting of polyimide, polyimide precursors, and copolymers thereof.
  • Component (A) can contain a polyimide containing a structural unit of a known polyimide, a polyimide precursor containing a structural unit of a known polyimide precursor, and a known copolymer thereof.
  • component (A) is defined as a resin having an imide bond in its main chain.
  • component (A) contains a structural unit of polyimide and/or a structural unit of polyimide precursor, a structural unit of polybenzoxazole and/or a structural unit of polybenzoxazole precursor, component (A) do.
  • component (A) has an alkali-soluble group.
  • Alkali-soluble means that a solution of the resin dissolved in ⁇ -butyrolactone is applied onto a silicon wafer, prebaked at 120°C for 4 minutes to form a prebaked film with a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m, and the prebaked film is It means that the dissolution rate determined from the decrease in film thickness when immersed in a 2.38 mass % tetramethylammonium hydroxide aqueous solution at ⁇ 1° C. for 1 minute and then rinsed with pure water is 50 nm/min or more.
  • the resin has an acidic group in its structural unit and/or at the end of its main chain.
  • acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.
  • the component (A) preferably has a fluorine atom, and when developing with an alkaline aqueous solution, imparts water repellency to the interface between the film and the base material and suppresses seepage of the alkaline aqueous solution into the interface. can.
  • the fluorine atom content of component (A) is preferably 5% by mass or more from the viewpoint of preventing the aqueous alkaline solution from seeping into the interface, and preferably 20% by mass or less from the viewpoint of solubility in the aqueous alkaline solution.
  • Component (A) is synthesized by a known method.
  • polyimide precursors in the case of polyamic acid, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature
  • polyamic acid ester for example, a method of reacting with tetracarboxylic dianhydride at low temperature.
  • the amic acid structure is partially esterified with N,N-dimethylformamide dimethyl acetal, etc., diester is obtained with tetracarboxylic dianhydride and alcohol, and then the amine and condensing agent are reacted.
  • It can be synthesized by a method of reacting in the presence of a dicarboxylic acid, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then a method of converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine.
  • polyimide it can be obtained, for example, by dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the above method by heating in a solvent or by chemical treatment with an acid or base.
  • the tetracarboxylic dianhydride used in component (A) includes 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(
  • diamine compounds used in component (A) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, , 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'-diaminobipheny
  • R 3 and R 6 each independently represent an oxygen atom, C(CF 3 ) 2 or C(CH 3 ) 2 .
  • R 4 , R 5 and R 7 to R 14 each independently represent a hydrogen atom or a hydroxyl group.
  • the main chain end of component (A) may be substituted with a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. It is preferable to seal with an end sealing agent such as.
  • monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds having at least one alkenyl group or alkynyl group are used as terminal capping agents.
  • Monoactive ester compounds can also be used.
  • the content of terminal capping agents such as monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids is 1% by mole per 100 mol% of the total of all monomer components constituting component (A). It is preferably mol% or more, more preferably 5 mol% or more. Further, from the viewpoint of obtaining a resin with good film properties, the amount is preferably 40 mol% or less, more preferably 30 mol% or less, based on the total 100 mol% of all monomer components constituting component (A). A plurality of different terminal groups may be introduced into component (A) by reacting a plurality of terminal capping agents.
  • the positive photosensitive resin composition of the present invention contains (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors, and copolymers thereof.
  • component (B) is defined as a resin that does not contain an imide bond in its main chain.
  • Component (B) may contain a polybenzoxazole containing a structural unit of a known polybenzoxazole, a polybenzoxazole precursor containing a structural unit of a known polybenzoxazole precursor, and a known copolymer thereof. can.
  • component (B) preferably has an alkali-soluble group.
  • component (B) has an acidic group in the structural unit and/or at the end of its main chain.
  • acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.
  • the component (B) preferably has a fluorine atom, and when developing with an alkaline aqueous solution, imparts water repellency to the interface between the film and the base material and suppresses seepage of the alkaline aqueous solution into the interface. can.
  • the fluorine atom content in component (B) is preferably 5% by mass or more from the viewpoint of preventing the alkaline aqueous solution from seeping into the interface, and is preferably 20% by mass or less from the viewpoint of solubility in the alkaline aqueous solution.
  • Component (B) is synthesized by a known method.
  • a polybenzoxazole precursor it can be obtained by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid.
  • methods include a method in which a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a dicarboxylic acid is added to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. Examples include dropping a solution of dichloride.
  • polybenzoxazole it can be obtained, for example, by dehydrating and ring-closing the polybenzoxazole precursor obtained by the above method by heating in a solvent or by chemical treatment with an acid or base.
  • dicarboxylic acids used in component (B) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc.
  • dicarboxylic acids used in component (B) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc.
  • trimellitic acid trimesic acid, diphenyl ethertricarboxylic acid, biphenyltricarboxylic acid, etc.
  • tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid Carboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)hexafluoropropane carboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane,
  • bisaminophenol compound used in component (B) examples include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, and 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'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4 , 4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4 ,4'-diaminobiphenyl, 2,2
  • R 3 and R 6 each independently represent an oxygen atom, C(CF 3 ) 2 or C(CH 3 ) 2 .
  • R 4 , R 5 and R 7 to R 14 each independently represent a hydrogen atom or a hydroxyl group.
  • the main chain end of component (B) may be substituted with a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. It is preferable to seal with an end sealing agent such as.
  • monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds having at least one alkenyl group or alkynyl group are used as terminal capping agents.
  • Monoactive ester compounds can also be used.
  • the content of terminal capping agents such as monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids should be 1% by mole per 100 mol% of the total of all monomer components constituting component (B). It is preferably mol% or more, more preferably 5 mol% or more. Further, from the viewpoint of obtaining a resin with good film properties, the amount is preferably 40 mol% or less, more preferably 30 mol% or less, based on the total 100 mol% of all monomer components constituting component (B). A plurality of different terminal groups may be introduced into the component (B) by reacting a plurality of terminal capping agents.
  • the content of component (B) in the positive photosensitive resin composition is 10 to 100 parts by mass based on 100 parts by mass of component (A). If the content of component (B) is less than 10 parts by mass relative to 100 parts by mass of component (A), the bending resistance decreases.
  • the content of component (B) is preferably 20 parts by mass or more. On the other hand, when the content of component (B) exceeds 100 parts by mass relative to 100 parts by mass of component (A), heat resistance decreases.
  • the content of component (B) is preferably 95 parts by mass or less per 100 parts by mass of component (A).
  • component (B) contains a resin whose main chain is a structural unit represented by formula (1).
  • the resin having the structural unit represented by (1) is improved.
  • R 1 and R 2 each independently represent a divalent to octavalent organic group having 2 to 30 carbon atoms.
  • p represents an integer from 0 to 4
  • q represents an integer from 1 to 4.
  • the positive photosensitive resin composition of the present invention contains (C) polyhydroxystyrene and/or a copolymer of polyhydroxystyrene and polystyrene.
  • C Containing polyhydroxystyrene and/or a copolymer of polyhydroxystyrene and polystyrene means containing either polyhydroxystyrene, a copolymer of polyhydroxystyrene and polystyrene, or both. means.
  • Component (C) of the present invention is synthesized by a known method.
  • component (C) As a method for producing component (C), it can be obtained by addition polymerizing a phenol derivative having an unsaturated bond.
  • phenol derivatives having unsaturated bonds include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2'-hydroxychalcone, N-hydroxyphenyl-5-norbornene-2,3-dicarboxylic acid imide, and resveratrol.
  • 4-hydroxystilbene 4-hydroxystilbene, and two or more of these may be used.
  • it may be a copolymer with a monomer containing no phenolic hydroxyl group, such as styrene. By doing so, the alkali dissolution rate of component (C) can be easily adjusted.
  • the content of component (C) is 1 to 90 parts by mass based on 100 parts by mass of component (A). When the content of component (C) is less than 1 part by mass per 100 parts by mass of component (A), sensitivity decreases.
  • the content of component (C) is preferably 3 parts by mass or more based on 100 parts by mass of component (A). On the other hand, when the content of component (C) exceeds 90 parts by mass relative to 100 parts by mass of component (A), development adhesion decreases.
  • the content of component (C) is preferably 70 parts by mass or less per 100 parts by mass of component (A).
  • the preferred weight average molecular weight of component (C) can be determined by gel permeation chromatography (GPC) in terms of polystyrene, and from the viewpoint of sensitivity, is preferably 1000 or more, more preferably 3000 or more, even more preferably 4000 or more, From the viewpoint of development adhesion, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less.
  • GPC gel permeation chromatography
  • Component (C) preferably contains polyhydroxystyrene from the viewpoint of sensitivity.
  • the content of the component (A) is [PI] (mass)
  • the content of the component (B) is [PB] (mass)
  • the content of the component (C) is [PI] (mass).
  • the mass ratio [PI]/([PB]+[PH]) is 0.5 ⁇ [PI]/([PB]+[PH]) ⁇ 5.
  • a range of 0 is preferred.
  • [PI]/([PB]+[PH]) is 0.5 or more, heat resistance can be improved.
  • [PI]/([PB]+[PH]) is more preferably 1 or more.
  • sensitivity can be improved.
  • [PI]/([PB]+[PH]) is more preferably 4 or less.
  • the relationship between [PB] and [PH] is [PB]>[PH].
  • [PB]>[PH] development adhesion can be improved.
  • the relationship between [PI], [PB] and [PH] is preferably [PI]>[PB]>[PH].
  • [PI]>[PB]>[PH] it is possible to improve the heat resistance of a cured product processed by low-temperature curing at about 200 to 270°C.
  • the mass ratio of [PB] and [PH] is preferably in the range of 1.01 ⁇ [PB]/[PH] ⁇ 55.00.
  • the mass ratio of [PB]/[PH] is more preferably 1.50 or more, and even more preferably 2.00 or more.
  • the mass ratio of [PB]/[PH] is more preferably 30.00 or less, and even more preferably 10.00 or less.
  • the positive photosensitive resin composition of the present invention contains (D) a quinonediazide compound.
  • Quinonediazide compounds include polyhydroxy compounds with quinonediazide sulfonic acid bonded to ester bonds, polyamino compounds with quinonediazide sulfonic acid bonded to sulfonamide bonds, and polyhydroxypolyamino compounds with quinonediazide sulfonic acid bonded to ester bonds and/or sulfonamide bonds. Examples include those that are combined.
  • the positive photosensitive resin composition (D) may contain two or more types of quinonediazide compounds.
  • a naphthoquinonediazide sulfonic acid ester compound can be suitably contained.
  • a naphthoquinone diazide sulfonic acid ester compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method.
  • Compounds having a phenolic hydroxyl group used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP -PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML
  • Naphthoquinone diazide sulfonic acid 4-ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure, while naphthoquinone diazide-5-sulfonic acid ester compound has absorption extending to the g-line region of a mercury lamp. suitable for g-line exposure.
  • the photosensitive resin composition of the present invention can contain both a naphthoquinonediazide-4-sulfonic acid ester compound and a naphthoquinonediazide-5-sulfonic acid ester compound, and a naphthoquinonediazide-4-sulfonyl group, It can also contain a naphthoquinonediazide sulfonic acid ester compound using a naphthoquinonediazide-5-sulfonyl group in combination, or it can contain a mixture of a naphthoquinonediazide-4-sulfonic acid ester compound and a naphthoquinonediazide-5-sulfonic acid ester compound. You can also do that.
  • the content of the quinonediazide compound (D) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the polyimide resin (A), from the viewpoint of improving sensitivity during exposure. Moreover, from the viewpoint of reducing outgas from the cured product, the amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the polyimide resin (A).
  • the positive photosensitive resin composition of the present invention contains (E) a solvent.
  • (E) By containing a solvent, it can be made into a varnish state and the coating properties can be improved.
  • the solvent (E) includes polar aprotic solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, ethylene glycol monomethyl ether, and ethylene.
  • polar aprotic solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, ethylene glycol monomethyl ether, and ethylene.
  • Glycol monoethyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Ethers such as mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, dioxane, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol, ethylene Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate
  • the solvent (E) preferably contains a polar aprotic solvent.
  • Preferred examples of the polar aprotic solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide.
  • the content of the solvent (E) is preferably such that the solid content concentration of the positive photosensitive resin composition is 3 to 30% by mass. If the solid content concentration is less than 3% by mass, coating properties will deteriorate, and the solid content concentration is more preferably 5% by mass or more. Moreover, if the content of the solvent (E) exceeds 30% by mass, the storage stability of the positive photosensitive resin composition will deteriorate, and the content of the solvent (E) is more preferably 20% by mass or less.
  • the solid content concentration refers to the concentration of components other than the (E) solvent in the positive photosensitive resin composition.
  • the content of the polar aprotic solvent is preferably 1 to 30% by mass based on 100% by mass of the solvent (E). If it is 1% by mass or more, the solubility of component (A), component (B), and component (C) can be improved, and the linearity of the pattern after development can be improved.
  • the content of the polar aprotic solvent is more preferably 3% by mass or more based on 100% by mass of the (E) solvent. Further, when the content of the polar aprotic solvent is 30% by mass or less with respect to 100% by mass of the (E) solvent, the solvent drying property during prebaking is improved and the development adhesion is improved.
  • the content of the polar aprotic solvent is more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the (E) solvent.
  • the positive photosensitive resin composition of the present invention may contain a known compound such as a thermal crosslinking agent.
  • thermal crosslinking agent examples include DML-PC, DML-PEP, DMOM-PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP, HMOM-TPPA (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Thermal crosslinking with methylol groups and/or alkoxymethyl groups such as “NIKALAC” (registered trademark) MX-270, “NIKALAC” (registered trademark) MW-100LM, (trade name, manufactured by Sanwa Chemical Co., Ltd.) agent, “Denacol” EX-850L, “Denacol” EX-201-IM (trade name, manufactured by Nagase
  • thermal crosslinking agents having oxetane groups, 1,2 -Bis(maleimido)ethane, 1,3-bis(maleimido)propane, 1,4-bis(maleimido)butane, 1,5-bis(maleimido)pentane, 1,6-bis(maleimido)hexane, 2,2 , 4-trimethyl-1,6-bis(maleimido)hexane, and other bismaleimide thermal crosslinking agents; and aromatic polyisocyanates such as 4,4'-methylenebis(phenylene isocyanate) (MDI) and tolylene diisocyanate (TDI).
  • MDI 4,4'-methylenebis(phenylene isocyanate)
  • TDI tolylene diisocyanate
  • Aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, lysine diisocyanate; isophorone diisocyanate (IPDI), 4,4'-methylene bis(cyclohexyl isocyanate) ) (H12MDI) and other alicyclic polyisocyanate thermal crosslinking agents.
  • HDI hexamethylene diisocyanate
  • trimethylene diisocyanate 1,4-tetramethylene diisocyanate
  • pentamethylene diisocyanate pentamethylene diisocyanate
  • lysine diisocyanate lysine diisocyanate
  • isophorone diisocyanate IPDI
  • H12MDI 4,4'-methylene bis(cyclohexyl isocyanate)
  • the content of the thermal crosslinking agent is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass or more with respect to 100 parts by mass of component (A). More preferred.
  • the content of the thermal crosslinking agent is 30 parts by mass or less per 100 parts by mass of component (A). is preferable, 25 parts by mass or less is more preferable, and even more preferably 20 parts by weight or less.
  • the positive photosensitive resin composition of the present invention may contain (F) a thermal acid generator.
  • the thermal acid generator is a compound that generates acid when heated, and the thermal decomposition starting temperature of the thermal acid generator is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher.
  • the thermal decomposition start temperature of the thermal acid generator (F) is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower.
  • the thermal decomposition temperature By setting the thermal decomposition temperature to 250° C. or lower, sufficient acid can be generated in the heating step.
  • the crosslinking reaction of the thermal crosslinking agent can be promoted, and as a result, unreacted crosslinkable groups remaining in the cured product can be significantly reduced. If unreacted crosslinkable groups remain in the cured product, gas components are generated during reliability tests, causing undesirable phenomena such as reduced brightness of organic EL display devices and pixel shrinkage, but gas components are generated from thermal acid generators.
  • the crosslinking promoting effect of the acid can greatly improve the reliability of the organic EL display device.
  • the thermal acid generator (F) in the positive photosensitive resin composition of the present invention only needs to have the function of generating acid when heated, and has the function of generating acid when exposed to light such as ultraviolet rays in addition to heat.
  • Compounds are also included in the definition of thermal acid generators.
  • the quinonediazide compound (D) is defined as not included in the thermal acid generator (F) even if it generates an acid upon heating.
  • the acid generated from the thermal acid generator is preferably a strong acid, such as arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. Acid, camphorsulfonic acid, etc. are preferred.
  • thermal acid generator examples include sulfonium salts and sulfonic acid esters. Two or more types of these may be contained. From the viewpoint of generating heat upon heating, the sulfonium salt preferably contains a compound selected from the group consisting of monoarylsulfonium salts and trialkylsulfonium salts.
  • thermal acid generators it is preferable to contain a thermal acid generator having a sulfonic acid ester structure since it has a high effect of improving the reliability of an organic EL display device.
  • a thermal acid generator having a sulfonic acid ester structure since it has a high effect of improving the reliability of an organic EL display device.
  • Phenyl methyl propanesulfonate, ethyl propanesulfonate, propyl propanesulfonate, butyl propanesulfonate, phenyl propanesulfonate, methyl butanesulfonate, ethyl butanesulfonate, propyl butanesulfonate, butyl butanesulfonate, butanesulfonic acid Phenyl, methyl octanesulfonate, ethyl octanesulfonate, propyl octanesulfonate, butyl octanesulfonate, phenyl octanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, p- Butyl toluenesulfonate,
  • PA-411, PA-480 (trade name, manufactured by Heraeus Co., Ltd.), and other thermal acid generators having a sulfonic acid ester structure include PAI-01, PAI-101. , PAI-106, PAI-1001, PAI-1002, PAI-1003, PAI-1004 (product name, manufactured by Midori Kagaku Co., Ltd.), SP-082, SP-601, SP-606, SP-607, SP- 612 (product name, manufactured by ADEKA Co., Ltd.), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (product name, manufactured by Heraeus Co., Ltd.) , NAI-105, NAI-106, NAI-109 (trade name, manufactured by Midori Kagaku Co., Ltd.).
  • the thermal acid generator contains a compound represented by formula (2).
  • the volatility of the (F) thermal acid generator during curing (heat treatment) decreases, and the (F) thermal acid generator during curing reduces the volatility of the (F) thermal acid generator during curing (heat treatment). Since the acid can be efficiently generated from the organic EL display and the crosslinking promoting effect is increased, the reliability of the organic EL display device can be improved.
  • the thermal acid generator (F) contains the compound represented by formula (2), its solubility in an alkaline developer tends to improve compared to when it does not contain the compound represented by formula (2). , exposure sensitivity is improved.
  • R 15 is a divalent to tetravalent group having 1 to 10 carbon atoms.
  • R 16 is each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent. , or an aryl group having 6 to 20 carbon atoms which may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an acetylene group, or a linear group having 1 to 10 carbon atoms. or a cyclic alkyl group.
  • R 15 is a divalent to tetravalent group having 1 to 6 carbon atoms which may have a substituent
  • R 16 is each independently: It is preferably a straight chain, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms which may have a substituent.
  • Examples of the compound described in formula (2) above include a compound having multiple alcoholic hydroxyl groups (sometimes referred to as a polyhydric alcohol compound), or a compound having multiple phenolic hydroxyl groups (sometimes referred to as a polyhydric phenol compound).
  • Compounds in which the alcoholic hydroxyl group or phenolic hydroxyl group of 1) are sulfonic acid esterified with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc. It will be done.
  • polyhydric alcohol compounds specific examples include methanediol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, etc. .
  • specific examples of trihydric or higher alcohol compounds include propanetriol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, pentaerythritol, and the like.
  • polyhydric phenol compounds include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, and the like.
  • the content of the compound represented by formula (2) is 20% by mass or more based on 100% by mass of the thermal acid generator (F) from the viewpoint of improving exposure sensitivity and improving the reliability of the organic EL display device. It is preferable to do so. It is more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably 100% by mass.
  • the content of the thermal acid generator is set to 1 when the total mass parts of the component (A) and the component (B) is 100 parts by mass, from the viewpoint of further improving the reliability of the organic EL display device. It is preferably at least 2 parts by mass, more preferably at least 2 parts by mass, even more preferably at least 3 parts by mass. In addition, from the viewpoint of imparting high heat resistance to the cured product, the content of the thermal acid generator (F) is 15 parts by mass when the total mass parts of the component (A) and the component (B) are 100 parts by mass. It is preferably at most 10 parts by mass, more preferably at most 8 parts by mass.
  • the positive photosensitive resin composition of the present invention can contain a colorant.
  • the colorant refers to a known organic pigment, inorganic pigment, or dye.
  • the colorant is preferably an organic pigment and/or an inorganic pigment.
  • organic pigments examples include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, copper phthalocyanine, threne pigments, benzofuranone pigments, and metal complex pigments.
  • inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, manganese violet, and cobalt violet.
  • dyes examples include azo dyes, anthraquinone dyes, fused polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, and methine or polymethine dyes.
  • the colorant is preferably black, which can block visible light over the entire wavelength range
  • the positive photosensitive resin composition is preferably mixed with organic pigments, inorganic pigments, and dyes. It is preferable to contain at least one selected colorant so that the cured product exhibits a black color.
  • the above-mentioned black organic pigment and black inorganic pigment may be included, or two or more types of organic pigments and dyes may be mixed to create a pseudo-black color. In the case of pseudo-blackening, it can be obtained by mixing two or more of the above-mentioned red, orange, yellow, purple, blue, green, and other organic pigments and dyes.
  • the positive photosensitive resin composition of the present invention itself does not necessarily have to be black, and a coloring agent that changes color during heat curing so that the cured product exhibits a black color may be used.
  • a coloring agent that contains an organic pigment and/or an inorganic pigment and exhibits a black color when cured.
  • a coloring agent that contains an organic pigment and/or dye and exhibits a black color when cured it is preferable to contain an organic pigment and a coloring agent that exhibits a black color when cured.
  • the content of the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the positive photosensitive resin composition excluding the solvent, from the viewpoint of obtaining the necessary colorability in the cured product. More preferably, the content is 15% by mass or more.
  • the amount is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the positive photosensitive resin composition excluding the solvent. .
  • the positive photosensitive resin composition contains a pigment
  • the dispersant is not particularly limited, but a polymer dispersant is preferred.
  • the polymer dispersant include a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a polyallylamine polymer dispersant, and a carbodiimide polymer dispersant.
  • a polymeric dispersant has a main chain consisting of polyamino, polyether, polyester, polyurethane, polyacrylate, etc., and has an amine, carboxylic acid, phosphoric acid, amine salt, or carboxylic acid at the side chain or main chain terminal.
  • polar groups such as acid salts and phosphates. The polar group is adsorbed onto the pigment, and the steric hindrance of the main chain polymer plays a role in stabilizing the dispersion of the pigment.
  • the dispersant can be a (polymer) dispersant that has only an amine value, a (polymer) dispersant that has only an acid value, a (polymer) dispersant that has an amine value and an acid value, or a (polymer) dispersant that has both an amine value and an acid value. Although it is classified as a (polymer) dispersant that does not have an amine value, a (polymer) dispersant that has an amine value and an acid value, and a (polymer) dispersant that has only an amine value are preferable. Molecular) dispersants are more preferred.
  • the content of the dispersant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the pigment, from the viewpoint of obtaining good dispersion stability. Further, from the viewpoint of maintaining the heat resistance of the cured product, the amount is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the pigment.
  • the positive photosensitive resin composition used in the present invention can contain an adhesion improver.
  • 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, zirconia chelating agents, titanium chelating agents, aluminum chelating agents, aromatic amine compounds Examples include compounds obtained by reacting a silicon compound with an alkoxy group-containing silicon compound.
  • adhesion improvers when developing a positive photosensitive resin film, it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO 2 , silicon nitride, or the like. Furthermore, resistance to oxygen plasma used for cleaning and UV ozone treatment can be increased.
  • the content of the adhesion improver is preferably 0.1 to 10% by mass based on the total amount of the positive photosensitive resin composition excluding the solvent.
  • the positive photosensitive resin composition used in the present invention may contain a surfactant, if necessary, for the purpose of improving wettability with the substrate.
  • a surfactant Commercially available compounds can be used as the surfactant.
  • silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray Silicone, the BYK series from BYK Chemie Japan, and Shin-Etsu Silicone.
  • fluorine-based surfactants include the KP series from Nippon Oil & Fat Corporation, the Disform series from Nippon Oil & Fats, and the TSF series from Toshiba Silicone.
  • Acrylic products include the Florado series by Asahi Glass, the Surflon (registered trademark) series, the Asahi Guard (registered trademark) series, the EF series by Shin-Akita Kasei, and the Polyfox series by Omnova Solutions.
  • surfactants made of polymers of methacrylate and/or methacrylate include, but are not limited to, the Polyflow series manufactured by Kyoeisha Chemical Co., Ltd. and the "Disparon (registered trademark)" series manufactured by Kusumoto Kasei Co., Ltd.
  • the content of the surfactant is preferably 0.001 to 1% by mass based on the total amount of the positive photosensitive resin composition excluding the solvent.
  • the positive photosensitive resin composition used in the present invention may contain a compound having a phenolic hydroxyl group, if necessary, for the purpose of supplementing the alkali developability of the photosensitive resin composition.
  • compounds having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ.
  • the resulting positive photosensitive resin composition hardly dissolves in an alkaline developer before exposure, but easily dissolves in an alkaline developer after exposure. There is less film loss due to development, and development is facilitated in a short time. Therefore, sensitivity can be easily improved.
  • the content of such a compound having a phenolic hydroxyl group is preferably 1% by mass or more and 20% by mass or less based on the total amount of the positive photosensitive resin composition excluding the solvent.
  • the positive photosensitive resin composition used in the present invention may contain inorganic particles.
  • Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, and talc.
  • the primary particle diameter of these 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 mass based on the total amount of the positive photosensitive resin composition excluding the solvent.
  • a method for producing the positive photosensitive resin composition of the present invention will be explained. For example, by dissolving component (A), component (B), component (C), (D) quinonediazide compound, (E) solvent, and if necessary, adhesion improver, surfactant, colorant, inorganic particles, etc. , a positive photosensitive resin composition can be obtained.
  • Dissolution methods include stirring and heating.
  • the heating temperature is preferably set within a range that does not impair the performance of the positive photosensitive resin composition, and is usually from room temperature to 80°C.
  • the order in which the components are dissolved is not particularly limited, and for example, a method may be used in which the compounds with the lowest solubility are dissolved in order.
  • ingredients that tend to generate bubbles during stirring and dissolution such as surfactants and some adhesion improvers, by adding them last after dissolving other ingredients, it is possible to prevent dissolution of other ingredients due to the generation of bubbles. can be prevented.
  • the obtained positive photosensitive resin composition is preferably filtered using a filtration filter to remove dust.
  • filter pore diameters include, but are not limited to, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, 0.05 ⁇ m, and 0.02 ⁇ m.
  • Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferred.
  • PP polypropylene
  • PE polyethylene
  • nylon NY
  • PTFE polytetrafluoroethylene
  • polyethylene and nylon are preferred.
  • the cured product of the present invention is a cured product obtained by curing a positive photosensitive resin composition.
  • the cured product is obtained by heat-treating a positive photosensitive resin composition.
  • a known method such as a method using a hot plate, an oven, or infrared rays can be used.
  • Preferred heat treatment conditions will be described in the below-mentioned method for producing a cured product (5) step of heat treating a developed positive photosensitive resin film.
  • the method for producing the cured product is (1) a step of applying the above-described positive photosensitive resin composition to a substrate to form a positive photosensitive resin film; (2) a step of drying the positive photosensitive resin film (prebaking step); (3) a step of exposing the dried positive photosensitive resin film to light through a photomask;
  • the method includes (4) a step of developing the exposed positive-type photosensitive resin film, and (5) a step of heat-treating the developed positive-type photosensitive resin film, in this order.
  • the positive photosensitive resin composition of the present invention is applied by spin coating, slit coating, dip coating, etc.
  • a positive photosensitive resin film of the positive photosensitive resin composition is obtained by coating by a coating method, a spray coating method, a printing method, or the like.
  • the substrate to which the positive photosensitive resin composition is applied may be pretreated with the adhesion improver described above.
  • a solution in which 0.5 to 20% by mass of the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. is used.
  • a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc.
  • examples include methods of treating the surface of the base material.
  • methods for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.
  • the applied positive photosensitive resin film is dried under reduced pressure as necessary, and then dried at 50°C or higher using a hot plate, oven, infrared rays, etc.
  • a positive photosensitive resin film is obtained by heat treatment at 180° C. for 1 minute to several hours.
  • Actinic radiation is irradiated onto the positive photosensitive resin film through a photomask having a desired pattern.
  • Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, but in the present invention, it is preferable to use I-lines (365 nm), H-lines (405 nm), and G-lines (436 nm) from a mercury lamp. .
  • a post-exposure bake may be performed.
  • effects such as improved resolution after development or increased allowable range of development conditions can be expected.
  • post-exposure baking an oven, hot plate, infrared rays, flash annealing device, laser annealing device, or the like can be used.
  • the post-exposure bake temperature is preferably 50 to 180°C, more preferably 60 to 150°C.
  • the post-exposure bake time is preferably 10 seconds to several hours. When the post-exposure bake time is within the above range, the reaction proceeds favorably and the development time may be shortened.
  • the exposed positive photosensitive resin film is developed using a developer to remove areas other than the exposed areas.
  • a developer tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl
  • alkaline compounds such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine are preferred.
  • polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination. good.
  • methods such as spray, paddle, immersion, and ultrasonic waves are possible.
  • alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may be added to distilled water for rinsing.
  • a step (5) of heat-treating the developed positive photosensitive resin film is performed. Since residual solvent and components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. Since the positive photosensitive resin composition of the present invention can form an imide ring and an oxazole ring by heat treatment, it can improve heat resistance and chemical resistance. In addition, when a thermal crosslinking agent is contained, the thermal crosslinking reaction can be advanced by heat treatment, and the heat resistance and chemical resistance can be improved. From the viewpoint of improving the heat resistance of the cured product, the heat treatment temperature is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, and particularly preferably 240°C or higher.
  • the temperature is preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 270°C or lower. In this temperature range, the temperature may be raised stepwise or continuously.
  • the heat treatment time is preferably 30 minutes or more, more preferably 45 minutes or more. Further, from the viewpoint of productivity, the time is preferably 180 minutes or less, and more preferably 120 minutes or less. Examples include a method in which heat treatment is performed at 150° C. and 250° C. for 60 minutes each, and a method in which heat treatment is performed while increasing the temperature linearly from room temperature to 250° C. over 2 hours.
  • the cured product of the present invention is preferably a cured product formed from the positive photosensitive resin composition of the present invention.
  • a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (5) are present. is detected, and the detected peak intensity ratio is 1 for the compound represented by formula (4), 0.1 to 1 for the compound represented by formula (3), and 0.1 for the compound represented by formula (5). 1 to 3.
  • R 17 to R 23 each independently represent a monovalent organic group having 1 to 30 carbon atoms which may contain a hydrogen atom or a hetero atom.
  • examples of the monovalent organic group having 1 to 30 carbon atoms that may contain a hetero atom include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. can be mentioned.
  • the alkyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the linear and branched alkyl group is usually 1 to 30, preferably 1 to 20, more preferably 1 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product.
  • the number of carbon atoms in the cyclic alkyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Examples include nonyl group and decyl group.
  • the alkenyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the linear and branched alkenyl groups is usually 2 to 30, preferably 2 to 20, more preferably 2 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product.
  • the number of carbon atoms in the cyclic alkenyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product.
  • alkenyl group examples include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, a butenyl group, a pentenyl group, a hexenyl group, a nonenyl group, and a decenyl group.
  • the alkynyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the linear and branched alkynyl group is usually 2 to 30, preferably 2 to 20, more preferably 2 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product.
  • the number of carbon atoms in the cyclic alkynyl group is usually 3 to 30, preferably 3 to 20, more preferably 3 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product.
  • Examples of the alkynyl group include ethynyl group, propynyl group, butynyl group, pentynyl group, and hexynyl group.
  • the aryl group is an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and includes a hydroxy group, the alkyl group, the alkenyl group, and the alkynyl group. Including those with functional groups.
  • the number of carbon atoms in the aryl group is usually 6 to 30, preferably 6 to 20.
  • Examples of the aryl group include phenyl group, hydroxyphenyl group, alkylphenyl group, and alkylhydroxyphenyl group. From the viewpoint of balancing high heat resistance and bending resistance of the cured product, hydroxyphenyl groups and alkylhydroxyphenyl groups are preferred.
  • alkylphenyl group examples include methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, methylethylphenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, tert-butylphenyl group. , pentylphenyl group, hexylphenyl group, cyclohexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, and the like.
  • alkylhydroxyphenyl group examples include methylhydroxyphenyl group, ethylhydroxyphenyl group, dimethylhydroxyphenyl group, propylhydroxyphenyl group, methylethylhydroxyphenyl group, propylhydroxyphenyl group, isopropylhydroxyphenyl group, butylhydroxyphenyl group, Examples include isobutylhydroxyphenyl group, tert-butylhydroxyphenyl group, pentylhydroxyphenyl group, hexylhydroxyphenyl group, cyclohexylhydroxyphenyl group, heptylhydroxyphenyl group, octylhydroxyphenyl group, nonylhydroxyphenyl group, decylhydroxyphenyl group, etc. .
  • R 2 , R 3 , and R 4 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. More preferably, it contains both an alkyl group and a hydroxyphenyl group and/or an alkylhydroxyphenyl group.
  • the compounds contained in the cured product of the present invention will be explained.
  • the compound represented by formula (3) can be obtained, for example, as a structure derived from (C) polyhydroxystyrene and/or a copolymer of polyhydroxystyrene and polystyrene, or as a residue thereof.
  • the compound represented by formula (4) can be obtained, for example, as a structure derived from (A) polyimide, a polyimide precursor, and a copolymer thereof, or as a residue thereof.
  • the compound represented by formula (5) can be obtained, for example, as a structure derived from (B) polybenzoxazole, a polybenzoxazole precursor, and a copolymer thereof, or as a residue thereof.
  • the cured product formed from the positive photosensitive resin composition of the present invention can be used in a display device including a first electrode formed on a substrate, and a second electrode provided opposite to the first electrode.
  • a display device including a first electrode formed on a substrate, and a second electrode provided opposite to the first electrode.
  • it can be used for a flattening layer of a liquid crystal display device, a flattening layer and/or a pixel division layer of an organic EL display device.
  • an organic EL display device as an example.
  • the organic EL display device of the present invention includes the cured product.
  • the substrate has a driving circuit, a planarizing layer, a first electrode, a pixel dividing layer, a light emitting layer, and a second electrode, and the planarizing layer and/or the pixel dividing layer is made of an organic material containing the cured product.
  • it is an EL display device.
  • a thin film transistor hereinafter referred to as TFT
  • TFT thin film transistor
  • a flattening layer is provided thereon to cover the unevenness, and a display element is further provided on the flattening layer.
  • the display element and the wiring are connected through contact holes formed in the planarization layer.
  • the substrate having the aforementioned drive circuit be an organic EL display device made of a resin film.
  • the organic EL display device of the present invention it is preferable that at least a part of the part including the cured product preferably has a bendable part and/or a part fixed in a bent state.
  • the radius of curvature of the bendable portion and/or the portion fixed in a bent state is preferably 0.1 mm or more, and preferably 5 mm or less. If the radius of curvature is 0.1 mm or more, bending resistance at the bent portion can be ensured, and if the radius of curvature is 5 mm or less, design properties such as narrowing of the frame can be ensured.
  • the organic EL display device of the present invention can be bent at any appropriate portion.
  • an organic EL display device may be bendable at the center like a foldable display device, or it may be bendable at the edges from the viewpoint of design and maximizing the display screen. good.
  • the organic EL display device may be bendable along its longitudinal direction, or may be bendable along its transversal direction. It is sufficient as long as a specific portion of the organic EL display device can be bent depending on the application (for example, some or all of the four corners can be bent in an oblique direction).
  • FIG. 1 shows a cross-sectional view of an example of an organic EL display device in which a flattening layer and a pixel dividing layer are formed.
  • Bottom-gate or top-gate TFTs 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 this TFT insulating layer 3.
  • a planarization layer 4 is provided on the TFT insulating layer 3 in such a manner that the wiring 2 is buried 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). Then, a pixel dividing layer 8 is formed to cover the periphery of the ITO 5.
  • the organic EL element may be of a top emission type that emits light from the side opposite to the substrate 6, or may be of a bottom emission type that extracts light from the side of the substrate 6. In this way, an active matrix type organic EL display device is obtained in which each organic EL element is connected to a TFT 1 for driving the organic EL element.
  • the TFT insulating layer 3, the flattening layer 4, and/or the pixel dividing layer 8 are formed in the step of forming a positive photosensitive resin film made of the positive photosensitive resin composition of the present invention, as described above, and in the step of forming the positive photosensitive resin composition. It can be formed by a step of exposing a resin film, a step of developing the exposed positive-type photosensitive resin film, and a step of heat-treating the developed positive-type photosensitive resin film. An organic EL display device can be obtained by a manufacturing method including these steps.
  • a cured product formed from the positive photosensitive resin composition of the present invention can be used as an insulating film or a protective film that constitutes an electronic component.
  • electronic components include active components including semiconductors such as transistors, diodes, integrated circuits (hereinafter referred to as ICs), and memories, and passive components such as resistors, capacitors, and inductors.
  • an electronic component using a semiconductor is also referred to as a semiconductor device.
  • Specific examples of cured products in electronic components include passivation films for semiconductors, surface protection films for semiconductor elements, TFTs, etc., interlayer insulating films in multilayer wiring for high-density packaging of 2 to 10 layers, insulating films for touch panel displays, and protection. Although it is suitably used for applications such as membranes, it is not limited thereto and can take various structures.
  • the surface of the substrate on which the cured product is formed can be selected as appropriate depending on the application and process, but examples include silicon, ceramics, metal, glass, epoxy resin, etc., and a plurality of these may be arranged within the same surface.
  • Examples of electronic devices having a surface protective film, interlayer insulating film, etc. on which the cured product of the present invention is disposed include MRAMs with low heat resistance. That is, the cured product of the present invention is suitable for use as a surface protective film for MRAM.
  • polymer memory Polymer Ferroelectric RAM: PFRAM
  • phase change memory Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM
  • Heat resistant compared to There is a high possibility of using new materials with low Therefore, the cured product of the present invention is also suitable for use in these surface protective films.
  • Fan-out WLP Fan-out wafer level packages
  • Fan-out WLP involves providing an extended portion around a semiconductor chip using a sealing resin such as epoxy resin, rewiring from the electrodes on the semiconductor chip to the extended portion, and mounting solder balls on the extended portion as well. This is a semiconductor package that has the required number of terminals.
  • wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material made of two or more materials: a semiconductor chip with metal wiring and a sealing resin, and the wiring is formed on the interlayer insulating film.
  • wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board.
  • an interlayer insulating film is formed on a base material made of two or more types of materials, and wiring is formed on the interlayer insulating film.
  • the cured product obtained by curing the positive photosensitive resin composition of the present invention has high adhesion to semiconductor chips with metal wiring, and also has high adhesion to sealing resins such as epoxy resins. , is suitably used as an interlayer insulating film provided on a base material made of two or more types of materials.
  • TMAH 2.38% by mass tetramethylammonium aqueous solution
  • the pattern of the obtained developed film was observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation), and the minimum required exposure amount at which the opening diameter of the contact hole reached 10 ⁇ m was determined, and this was determined as the exposure sensitivity. A value of 200 mJ/cm 2 or less was considered to be a pass. The smaller the sensitivity value is, the higher the sensitivity is, which is preferable.
  • the polyimide film substrate provided with the cured product was cut out into 10 pieces measuring 50 mm in length and 10 mm in width.
  • the cut polyimide film was stored in an air atmosphere at 100° C. for 500 hours.
  • the polyimide film substrate was bent at 180° along a 25 mm vertical line and held for 30 seconds with the cured product facing outward.
  • open the bent polyimide film substrate and observe the bent part on a 25 mm vertical line on the surface of the cured product using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation) to determine the appearance of the surface of the cured product. Changes were evaluated.
  • the bending test was conducted in the range of curvature radius of 0.1 to 2.0 mm, and the minimum radius of curvature (mm) that did not cause peeling of the cured product from the polyimide film substrate or change in appearance such as cracks on the surface of the cured product was recorded. .
  • FIG. 2 shows a schematic diagram of the substrate used.
  • a 100 nm thick ITO transparent conductive film was formed on the entire surface of a 38 ⁇ 46 mm alkali-free glass substrate 11 by sputtering and etched as a first electrode 12 .
  • an auxiliary electrode 13 was also formed at the same time.
  • the obtained substrate was ultrasonically cleaned for 10 minutes using "Semico Clean 56" (trade name, manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water.
  • a positive photosensitive resin composition (varnish) according to each of the Examples and Comparative Examples described later was applied to the entire surface of the substrate by spin coating, and prebaked for 2 minutes on a hot plate at 120°C.
  • This film was coated with a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source (a mixture of G-line, H-line, and I-line) through a photomask. After UV exposure, the film was developed with a 2.38% TMAH aqueous solution to dissolve only the exposed portion, and then rinsed with pure water. The obtained patterned substrate was cured for 60 minutes in an oven at 250° C.
  • PLA parallel light mask aligner
  • the pixel dividing layer 14 is formed such that openings each having a width of 50 ⁇ m and a length of 260 ⁇ m are 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. It was formed only in the effective area of the board. In this way, a pixel division layer with an aperture ratio of 18% was provided in the effective area of the substrate, which was a rectangle with sides of 16 mm, and the thickness of the pixel division layer was approximately 2.0 ⁇ m.
  • an organic EL layer 15 was formed by vacuum evaporation. Note that 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.
  • compound (HT-1) was deposited to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was deposited to a thickness of 50 nm as a hole transport layer.
  • a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited on the light emitting layer to a thickness of 40 nm at a doping concentration of 10%.
  • compound (ET-1) and compound (LiQ) were stacked as electron transport materials at a volume ratio of 1:1 to a thickness of 40 nm. The structure of the compound used in the organic EL layer is shown below.
  • a compound (LiQ) was deposited to a thickness of 2 nm, and then Mg and Ag were deposited to a thickness of 60 nm at a volume ratio of 1:10 to form the second electrode 16.
  • the cap-shaped glass plate was sealed using an epoxy resin adhesive in a low-humidity nitrogen atmosphere, and four light-emitting devices each having a square shape of 5 mm on a side were fabricated on one substrate. did.
  • 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 stored in an air atmosphere at 100° C., and every 100 hours, the organic EL display device was taken out and emitted by direct current driving at 10 mA/cm 2 , and the light emitting area of the light emitting pixel was measured.
  • the initial light emitting area before the reliability test is 100
  • the minimum time at which the light emitting area after the UV irradiation treatment test becomes 50 or less is defined as organic EL display device reliability (unit: hours), and reliability of 500 hours or more is considered to be a pass. did. It is preferable that the minimum time for which the light emitting area after the UV irradiation treatment test is 50 or less is longer because reliability is excellent.
  • a film was obtained by peeling off the obtained cured product with hydrofluoric acid.
  • a TGA measurement sample was prepared by packing 10 mg of the obtained single film into an Al clamp cell, and thermogravimetric measurement was performed using TGA-50 (manufactured by Shimadzu Corporation) under a nitrogen atmosphere while raising the temperature by 10°C per minute. Measurements were taken.
  • a temperature of 320°C or higher was considered to be a pass. The higher the temperature at which the weight is reduced by 5% from the weight at 200° C., the higher the heat resistance is, which is preferable.
  • TMAH 2.38% by mass tetramethylammonium aqueous solution
  • the pattern of the obtained developed film was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and 100 locations per size were observed, and the minimum closure with 90 or more patterns remaining without peeling was determined. The pattern was confirmed, and if the pattern of 10 ⁇ m or less remained without peeling off, it was judged as a pass. It is preferable that the minimum closed pattern in which 90 or more patterns remain without being peeled off is small because the development adhesion is excellent.
  • 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 mixed with 100 mL of acetone and 17 mL of propylene oxide. .4 g (0.3 mol) and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise thereto. After the dropwise addition was completed, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and dried under vacuum at 50°C.
  • BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
  • Synthesis Example 2 Synthesis of polyimide precursor (P1) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was mixed with N -Methyl-2-pyrrolidone (hereinafter referred to as NMP) was dissolved in 500 g. 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 was added thereto together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours.
  • ODPA 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride
  • NMP N -Methyl-2-pyrrolidone
  • Synthesis Example 3 Synthesis of polyimide (P2) Under a stream of dry nitrogen, 58.6 g (0.16 mol) of BAHF and 8.7 g (0.08 mol) of 3-aminophenol as an end capping agent were mixed with N-methyl-2-pyrrolidone. (NMP) was dissolved in 300 g. 62.0 g (0.20 mol) of ODPA was added thereto along with 100 g of NMP, and the mixture was stirred at 20°C for 1 hour, and then at 50°C for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while water was azeotroped with the xylene.
  • NMP N-methyl-2-pyrrolidone
  • Synthesis Example 4 Synthesis of polybenzoxazole precursor (P3) Under a stream of dry nitrogen, 41.3 g (0.16 mol) of diphenyl ether-4,4'-dicarboxylic acid and 1-hydroxy-1,2,3-benzotriazole 0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 43.2 g (0.32 mol) with 73.3 g (0.20 mol) of BAHF was dissolved in 570 g of NMP, and then reacted at 75 ° C. for 12 hours. Ta.
  • Synthesis Example 5 Synthesis of polyhydroxystyrene (P4) To a mixture of 2400 g of tetrahydrofuran and 2.56 g (0.04 mol) of sec-butyllithium as an initiator was added 105.75 g (0.04 mol) of pt-butoxystyrene. After polymerization was carried out with stirring for 3 hours, 12.82 g (0.4 mol) of methanol was added to terminate the polymerization. The reaction mixture was then poured into 3 L of methanol to purify the polymer, and the precipitated polymer was dried.
  • P4 polyhydroxystyrene
  • the obtained polymer was dissolved in 1.6 L of acetone, 2 g of concentrated hydrochloric acid was added at 60° C., and the mixture was stirred for 7 hours to deprotect pt-butoxystyrene and convert it to hydroxystyrene. After the reaction, the solution was poured into water to precipitate the polymer, and the resulting precipitate was washed three times with water and then dried in a vacuum dryer at 50°C for 24 hours to obtain the desired polyhydroxystyrene (P4). Obtained.
  • TEPIC-VL ⁇ Thermal crosslinking agent with epoxy group> TEPIC-VL; “TEPIC” (registered trademark)-VL (epoxy thermal crosslinking agent containing isocyanuric ring structure, compound shown in the chemical formula below, manufactured by Nissan Chemical Industries, Ltd.)
  • Example 20 The thermal decomposition product of the cured product of photosensitive resin composition O was analyzed by the method described in ⁇ Composition analysis by reactive pyrolysis GC/MS> above. As a result of the analysis, the structure obtained in the cured product is shown below, with a peak (1015 to 1025 seconds) assigned to the structure shown by formula (3), and a peak assigned to the structure shown by formula (4). (1335 to 1345 seconds) and a peak (1860 to 1870 seconds) assigned to the structure shown by formula (5) were obtained.
  • Substrate 2 TFT 3: TFT insulating layer 4: Wiring 5: Flattening layer 6: Contact hole 7: First electrode 8: Pixel division layer 9: Organic EL layer 10: Second electrode 11: Glass substrate 12: First electrode 13: Auxiliary electrode 14: Pixel division layer 15: Organic EL layer 16: Second electrode

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Abstract

Le but de la présente invention est de fournir une composition de résine photosensible positive qui présente une sensibilité élevée, une bonne adhérence au développement et une haute résistance à la chaleur, et ce tout en conférant une haute résistance au pliage au produit durci qu'elle permet de former, et qui permet l'obtention d'une fiabilité élevée lorsqu'un produit durci de celle-ci est utilisé dans un dispositif d'affichage électroluminescent organique. La présente invention concerne une composition de résine photosensible positive qui contient (A) une ou plusieurs substances parmi un polyimide, un précurseur de polyimide et un copolymère de ceux-ci, (B) une ou plusieurs substances parmi un polybenzoxazole, un précurseur de polybenzoxazole et un copolymère de ceux-ci, (C) un polyhydroxystyrène et/ou un copolymère d'un polyhydroxystyrène et d'un polystyrène, (D) un composé de quinonediazide et (E) un solvant. La teneur du composant (B) est de 10 parties en masse à 100 parties en masse par rapport à 100 parties en masse du composant (A) ; et la teneur du composant (C) est de 1 partie en masse à 90 parties en masse par rapport à 100 parties en masse du composant (A).
PCT/JP2023/011133 2022-03-23 2023-03-22 Composition de résine photosensible positive, produit durci, dispositif d'affichage électroluminescent organique et procédé de production de produit durci WO2023182327A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011158921A (ja) * 2004-05-07 2011-08-18 Hitachi Chemical Dupont Microsystems Ltd ポジ型感光性樹脂組成物、パターンの製造方法及び電子部品
KR20130042212A (ko) * 2011-10-18 2013-04-26 주식회사 동진쎄미켐 오엘이디용 폴리이미드 감광성 수지 조성물
WO2018159384A1 (fr) * 2017-03-03 2018-09-07 東レ株式会社 Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur
KR20220130042A (ko) * 2021-03-17 2022-09-26 주식회사 동진쎄미켐 포지티브형 감광성 수지 조성물, 절연막 및 이를 포함하는 표시장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011158921A (ja) * 2004-05-07 2011-08-18 Hitachi Chemical Dupont Microsystems Ltd ポジ型感光性樹脂組成物、パターンの製造方法及び電子部品
KR20130042212A (ko) * 2011-10-18 2013-04-26 주식회사 동진쎄미켐 오엘이디용 폴리이미드 감광성 수지 조성물
WO2018159384A1 (fr) * 2017-03-03 2018-09-07 東レ株式会社 Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur
KR20220130042A (ko) * 2021-03-17 2022-09-26 주식회사 동진쎄미켐 포지티브형 감광성 수지 조성물, 절연막 및 이를 포함하는 표시장치

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