WO2020184326A1 - 感光性樹脂組成物、感光性樹脂シート、硬化膜、硬化膜の製造方法、有機ｅｌ表示装置、および電子部品 - Google Patents

感光性樹脂組成物、感光性樹脂シート、硬化膜、硬化膜の製造方法、有機ｅｌ表示装置、および電子部品 Download PDF

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WO2020184326A1
WO2020184326A1 PCT/JP2020/009104 JP2020009104W WO2020184326A1 WO 2020184326 A1 WO2020184326 A1 WO 2020184326A1 JP 2020009104 W JP2020009104 W JP 2020009104W WO 2020184326 A1 WO2020184326 A1 WO 2020184326A1
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photosensitive resin
resin composition
compound
film
cured film
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English (en)
French (fr)
Japanese (ja)
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小森悠佑
鷲見岳
三好一登
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2020513935A priority Critical patent/JP7517149B2/ja
Priority to KR1020217027813A priority patent/KR102813261B1/ko
Priority to CN202080018551.4A priority patent/CN113544585B/zh
Priority to US17/436,941 priority patent/US11953830B2/en
Publication of WO2020184326A1 publication Critical patent/WO2020184326A1/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] 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
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • 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
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
    • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
    • H10W20/48—Insulating materials thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching

Definitions

  • the present invention relates to a photosensitive resin composition that can be suitably used for a flattening layer and an insulating layer of an organic EL display device, an interlayer insulating layer of an electronic component, a surface protective layer, and the like.
  • an organic EL display device has a drive circuit, a flattening layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate, and a voltage is applied between the first electrode and the second electrode facing each other. Can be emitted by applying.
  • a photosensitive resin composition that can be patterned by ultraviolet irradiation is generally used.
  • the photosensitive resin composition using a polyimide-based resin is preferable in that it can provide a highly reliable organic EL display device because the heat resistance of the resin is high and the gas component generated from the cured film is small. It is used.
  • polyimide is obtained by thermally dehydrating and ring-closing the coating film of its precursor to obtain a thin film having excellent heat resistance and mechanical properties. In that case, high temperature firing of 300 ° C. or higher is usually required.
  • a white OLED (Organic Light Emitting Diode) + color filter type organic EL display device has a low heat resistance of the color filter, so that a low temperature curing process is required in a subsequent step.
  • polyimide and polybenzoxazole are widely used as a surface protective layer and an interlayer insulating layer of a semiconductor device.
  • MRAM Magneticoresistive Random Access Memory
  • Magnetoresistive Random Memory which is promising as a next-generation memory
  • sealing resin are vulnerable to high temperatures. Therefore, in order to use it as an insulating layer, a flattening layer, and a protective layer of such an element, the imidization rate is good even when it is cured by firing at a low temperature of 200 ° C. or lower, and a conventional material is used at a high temperature of about 300 ° C. There is a demand for a polyimide resin that can obtain properties comparable to those when fired in.
  • negative photosensitive including a polyimide precursor having a weight average molecular weight of 3000 or more and less than 16000 and a carboxy group of polyamic acid substituted in a specific structure and a photopolymerization initiator.
  • the resin composition is disclosed (see Patent Document 1).
  • the strong bases 1,4-diazabicyclo [2.2.2] octane and 1,8-diazabicyclo [ A technique for adding a catalytic amount of 5.4.0] -7-undecene to a polyamic acid solution (see Non-Patent Document 1) is also disclosed. According to the method of using a strong acid or a strong base as an imidization accelerator as described above, a polyimide having a high imidization rate can be obtained at a temperature of 200 ° C. or lower.
  • the present invention is a photosensitive resin composition having a good imidization rate even when fired at a temperature of 200 ° C. or lower, high pattern processability, and high long-term reliability when a cured film is used in an organic EL display device.
  • the challenge is to provide.
  • the photosensitive resin composition of the present invention contains a polyimide precursor (a), a phenol compound (b) having an electron-attracting group, and a photosensitive compound (c), and the polyimide is contained.
  • Precursor (a) has residues derived from diamine with an ionization potential of less than 7.1 eV.
  • the photosensitive resin composition of the present invention has a good imidization rate even when fired at a temperature of 200 ° C. or lower, has high pattern processability, and has high long-term reliability when a cured film is used in an organic EL display device. ..
  • the photosensitive resin composition of the present invention contains a polyimide precursor (a), a phenol compound (b) having an electron-attracting group, and a photosensitive compound (c), and the polyimide precursor (a) is ionized. It has residues derived from diamines with a potential of less than 7.1 eV.
  • the photosensitive resin composition of the present invention contains a polyimide precursor (a).
  • the polyimide precursor (a) has a residue derived from a diamine having an ionization potential of less than 7.1 eV.
  • a cured film having a high imidization rate can be obtained even when fired at a temperature of 200 ° C. or lower.
  • long-term reliability can be improved when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device.
  • the polyimide precursor refers to a resin that is converted into polyimide by heat treatment or chemical treatment. Examples of the polyimide precursor include polyamic acid and polyamic acid ester.
  • the polyimide precursor preferably has alkali solubility.
  • Alkali-soluble in the present invention means that a solution of the polyimide precursor (a) dissolved in ⁇ -butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to obtain a prebaked film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m.
  • the prebake film was formed, immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ⁇ 1 ° C. for 1 minute, and then rinsed with pure water to reduce the film thickness to obtain a dissolution rate of 50 nm / min. That is all.
  • the polyimide precursor (a) in the present invention preferably has a hydroxyl group and / or an acidic group in the structural unit of the polyimide precursor (a) and / or at the end of the main chain thereof.
  • the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group and the like.
  • the polyimide precursor (a) preferably has a fluorine atom. By having a fluorine atom, water repellency can be imparted to the cured film.
  • the polyimide precursor (a) in the present invention preferably has a structural unit represented by the following general formula (3).
  • X represents a 4- to 7-valent organic group and Y represents a 2- to 11-valent organic group.
  • R 11 and R 13 each independently represent a hydroxyl group or a sulfonic acid group, and each of them may be a single group or a mixture of different groups.
  • R 12 and R 14 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • t and w each independently represent an integer of 0 to 3, and v represents an integer of 0 to 6.
  • the polyimide precursor (a) preferably has 5 to 100,000 structural units represented by the general formula (3). Further, the polyimide precursor (a) may have other structural units in addition to the structural units represented by the general formula (3). In this case, the polyimide precursor (a) preferably has the structural unit represented by the general formula (3) in an amount of 50 mol% or more of the total structural units.
  • X (R 11 ) t (COOR 12 ) 2 represents an acid residue.
  • X is a 4- to 7-valent organic group, and more preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group.
  • Examples of the acid include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid.
  • an aliphatic tetracarboxylic acid such as butanetetracarboxylic acid, or a tetracarboxylic acid such as an aliphatic tetracarboxylic acid containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid.
  • a tetracarboxylic acid such as an aliphatic tetracarboxylic acid containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid.
  • R 20 represents an oxygen atom, C (CF 3 ) 2 or C (CH 3 ) 2 .
  • R 21 and R 22 independently represent a hydrogen atom or a hydroxyl group, respectively.
  • two carboxy groups correspond to (COOR 12 ) 2 in the general formula (3).
  • These acids may be used as they are, or may be used as an acid anhydride, an active ester, or an active amide.
  • an active ester for example, an N-hydroxysuccinimide ester compound obtained by reacting a carboxyl group of an acid with N-hydroxysuccinimide, and as an active amide, for example, a carboxyl group of an acid is reacted with N, N'-carbonyldiimidazole.
  • acid dianhydride examples include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic.
  • 1,2,3,4-cyclopentanetetracarboxylic dianhydride etc.
  • examples thereof include aliphatic tetracarboxylic dianhydride containing a cyclic aliphatic group. Two or more of these may be used.
  • R 20 represents an oxygen atom, C (CF 3 ) 2 or C (CH 3 ) 2 .
  • R 21 and R 22 independently represent a hydrogen atom or a hydroxyl group, respectively.
  • Y (R 13 ) v (COOR 14 ) w in the above general formula (3) represents a diamine residue.
  • Y is a 2- to 11-valent organic group.
  • the polyimide precursor (a) in the present invention has a residue derived from a diamine having an ionization potential (hereinafter, may be referred to as “Ip”) of less than 7.1 eV.
  • the polyimide precursor (a) having a residue derived from a diamine having an ionization potential of less than 7.1 eV a cured film showing a high imidization rate can be obtained even when calcined at a temperature of 200 ° C. or lower.
  • the mechanism that can be achieved is not clear, but it can be estimated, for example, as follows. That is, the imidization reaction of the polyimide precursor (a) proceeds by nucleophilically attacking the carbonyl carbon of the residue derived from acid dianhydride by the nitrogen atom of the residue derived from diamine.
  • a polyimide precursor having a low ionization potential that is, a residue derived from an electron-rich diamine, has a high nucleophilic force of a nitrogen atom. Therefore, it can be estimated that the reactivity of the imidization reaction is high and a cured film having a high imidization rate can be obtained even at a temperature of 200 ° C. or lower.
  • Diamines with an ionization potential of less than 7.1 eV include 2,7-diaminofluorene (Ip6.48 eV, literature value), o-tolidine (Ip6.58 eV, literature value), benzidine (Ip6.73eV, literature value), 4 , 4'-diaminodiphenyl ether (Ip6.78eV, literature value), 1,4-bis (4-aminophenoxy) benzene (Ip6.80eV, literature value), 2,2-bis [4- (4-aminophenoxy) Phenyl] propane (Ip6.84eV, calculated value), 9,9-bis (4-aminophenyl) fluorene (Ip6.88eV, literature value), 4,4'-diaminodiphenylmethane (Ip6.94eV, literature value), p.
  • the ionization potential is preferably less than 7.0 eV, more preferably 6.9 eV, and even more preferably 6.8 eV from the viewpoint that a high imidization rate can be more easily achieved even when firing at a temperature of 200 ° C. or lower.
  • the lower limit of the ionization potential is not particularly limited, but is about 6.0 eV.
  • the residue derived from the diamine having an ionization potential of less than 7.1 eV has an ether bond.
  • diamines having an ionization potential of less than 7.1 eV are 4,4'-diaminodiphenyl ether (Ip6.78 eV, literature value), 1,4-bis (4-aminophenoxy) benzene (Ip6.80 eV, literature value), and the like.
  • the polyimide precursor (a) used in the present invention contains diamine residues having an ionization potential of 7.1 eV or more in addition to diamine residues having an ionization potential of less than 7.1 eV, as long as the above-mentioned characteristics are not deteriorated. It may be contained.
  • a diamine residue having an ionization potential of 7.1 eV or more is contained, a residue derived from a diamine having an ionization potential of less than 7.1 eV is contained in 100 mol% of the diamine residues constituting the polyimide precursor (a).
  • the amount is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, from the viewpoint that a high imidization rate can be more easily achieved even when fired at a temperature of 200 ° C. or lower. Further, from the viewpoint of further improving the sensitivity, 50 mol% or less is preferable, and 40 mol% or less is further preferable.
  • diamines having an ionization potential of 7.1 eV or more examples include 3,3'-diaminodiphenyl ether (Ip7.12 eV, literature value) and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (Ip7.
  • diamines may be used as they are, or may be used as a diisocyanate compound obtained by reacting an amino group of a diamine with phosgene, or as a trimethylsilylated diamine obtained by reacting an amino group of a diamine with chlorotrimethylsilane. You may. Further, by sealing the ends of these resins with a monoamine having an acidic group, an acid anhydride, an acid chloride, a monocarboxylic acid, or an active ester compound, a resin having an acidic group at the end of the main chain can be obtained. ..
  • Preferred examples of monoamines having an acidic group are 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4, Examples thereof include 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.
  • the acid anhydride examples include phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride and the like. Two or more of these may be used.
  • Preferred examples of the monocarboxylic acid include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, and the like. Two or more of these may be used.
  • the acid chloride include a monoacid chloride compound in which the carboxy group of the monocarboxylic acid is acid chlorided, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-.
  • Examples thereof include a monoacid chloride compound in which only one carboxy group of dicarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chlorided. Two or more of these may be used.
  • the active ester compound include a reaction product of the monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide. Two or more of these may be used.
  • the polyimide precursor (a) in the present invention can be synthesized by a known method.
  • Examples of the method for producing a polyamic acid as a polyimide precursor include a method in which a tetracarboxylic dianhydride and a diamine compound are reacted in a solvent at a low temperature.
  • a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then a condensing agent is obtained.
  • Examples include a method of reacting an amine with an alcohol in the presence of an amine, a method of obtaining a diester with a tetracarboxylic acid dianhydride and an alcohol, and then acid chlorideizing the remaining dicarboxylic acid and reacting the amine with a solvent. Be done.
  • the esterifying agent is not particularly limited, and a known method can be applied, but N, N-dimethylformamide dialkyl acetal is preferable because the obtained resin can be easily purified.
  • the polymerization solvent is not particularly limited, and alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate and isobutyl acetate, methyl isobutyl ketone, methyl propyl ketone and the like.
  • Ketones butyl alcohol, alcohols such as isobutyl alcohol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, Gamma butyrolactone, N-methyl-2-pyrrolidone, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, propylene glycol monomethyl ether acetate, N, N- Dimethylisobutyric acid amide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, N, N-dimethyl
  • the photosensitive resin composition of the present invention contains a phenol compound (b) having an electron-attracting group (hereinafter, may be simply referred to as "phenol compound (b)").
  • phenol compound (b) By containing the above-mentioned polyimide precursor (a) and phenol compound (b), a cured film having a high imidization rate can be obtained even when fired at a temperature of 200 ° C. or lower, and the curing of the present invention described later can be obtained. It is possible to improve the long-term reliability when the film is used as a flattening layer and / or an insulating layer of an organic EL display device.
  • An electron-attracting group is a positive value of Hammett's substituent constant ⁇ p 0 defined in the 5th revised edition of the Chemical Society of Japan, II-379 to II-380 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.). It is a substituent.
  • the phenol compound (b) having an electron-attracting group has an electron-attracting group in the molecule, so that the acidity of the phenolic hydroxyl group becomes high and acts as an acid catalyst to act as an acid catalyst of the polyimide precursor (a). Imidization can be promoted.
  • the electron-attracting group examples include a sulfonyl group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid amide group, a sulfonic acid imide group, a carboxyl group, a carbonyl group, a carboxylic acid ester group, a cyano group, and a halogen group.
  • Examples thereof include a trifluoromethyl group and a nitro group, but the group is not limited to these, and any known electron-attracting group may be used.
  • a carbonyl group, a trifluoromethyl group, a halogen group and a sulfonyl group are preferable, and a trifluoromethyl group and a sulfonyl group are particularly preferable, from the viewpoint of further promoting the imidization of the polyimide precursor (a).
  • the phenol compound (b) is a compound (b1) having a phenolic hydroxyl group having an acid dissociation constant (pKa) of 11.0 or less, which is obtained by quantum chemical calculation based on the density functional theory. ) Is preferably contained.
  • pKa ⁇ 0 the sulfonic acid compound known as an imidization accelerator
  • imidization is not promoted in the solvent drying step (prebaking) of the photosensitive resin composition described later, and pattern processing is performed.
  • the effect of promoting imidization can be enhanced in the subsequent firing step of the photosensitive resin film.
  • the lower limit of pKa is not particularly limited, but is about 1.0.
  • the acid dissociation constant (pKa) is the reciprocal of the acid dissociation constant, and in the case of multi-stage dissociation, the first-stage dissociation constant (that is, pKa1) is adopted. Further, as the acid dissociation constant (pKa) in the present invention, the acid dissociation constant calculated by quantum chemical calculation based on the density functional theory (DFT method) is adopted. For such quantum chemistry calculations, use an electronic computer, Gaussian09, functional B3LYP, basis set 6-311G (d) (structural optimization calculation), 6-311 ++ G (d, p). Use the value calculated using (energy calculation and vibration analysis).
  • DFT method density functional theory
  • thermodynamic quantity shown in the reaction scheme of the acid dissociation reaction (proton dissociation reaction) of the acid (formula: acid represented by HA) shown in FIG. 1 is calculated.
  • HA represents an acid
  • a ⁇ represents an acid ion
  • H + represents a hydrogen ion (proton).
  • the formula: HA (aq) ⁇ H + (aq) + A ⁇ (aq) shows the dissociation reaction of protons in water
  • the formula: HA (g) ⁇ H + (g) + A ⁇ (g). ) Indicates the dissociation reaction of protons in the gas phase.
  • the free energy G 0 gas (HA) of Gibbs in the gas phase of HA was obtained using Gaussian 09, and then the free energy difference ⁇ G * solve of Gibbs in the gas phase of HA and in water by the SMD solvation model. Calculate (HA).
  • a - sought after, A - of the free energy G 0 gas of Gibbs in the gas phase (A) - of the free energy difference ⁇ G * solv in the gas phase and the water of the Gibbs - the (A) calculate.
  • pKa is calculated based on the formulas (1) to (4).
  • H + of free energy G 0 gas of Gibbs (H +) is -6.275kcal / mol
  • a free energy difference of H + in the gas phase and the water of Gibbs ⁇ G * solv (H +) is - It is 1112.5 kJ / mol
  • T absolute temperature
  • the phenol compound (b) contains the compound (b2) represented by the general formula (1).
  • A represents a divalent group selected from the group consisting of each structure represented by the general formula (2), a and b each independently represent an integer of 0 to 3, and a + b is. It is an integer of 2-4.
  • R 1 and R 2 represent monovalent organic groups having 1 to 20 carbon atoms, which are independently substituted with halogen atoms or halogen atoms, respectively.
  • the compound (b2) represented by the general formula (1) has high heat resistance and has two or more phenolic hydroxyl groups
  • the cured film of the present invention described later can be used as a flattening layer and / or insulation of an organic EL display device. The effect of improving long-term reliability when layered can be further enhanced.
  • the content of the phenol compound (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the polyimide precursor (a). By setting it in such a range, it becomes easy to achieve a high imidization ratio even when firing at a temperature of 200 ° C. or lower.
  • the content of the phenol compound (b) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less. Within such a range, it is possible to easily suppress a decrease in the residual film ratio after alkaline development.
  • the photosensitive resin composition of the present invention contains the photosensitive compound (c).
  • the photosensitive compound (c) include a photoacid generator (c1) and a photopolymerization initiator (c2).
  • the photoacid generator (c1) is a compound that generates an acid upon light irradiation
  • the photopolymerization initiator (c2) is a compound that undergoes bond cleavage and / or reaction upon exposure to generate radicals.
  • the photoacid generator (c1) By containing the photoacid generator (c1), acid is generated in the light irradiation part, the solubility of the light irradiation part in the alkaline aqueous solution is increased, and a positive relief pattern in which the light irradiation part is dissolved can be obtained. it can. Further, by containing the photoacid generator (c1) and the epoxy compound or the heat cross-linking agent described later, the acid generated in the light irradiation part promotes the cross-linking reaction of the epoxy compound and the heat cross-linking agent, and the light irradiation part becomes insoluble. It is possible to obtain a negative type relief pattern.
  • radical polymerization proceeds in the light irradiation part, and a negative type relief pattern in which the light irradiation part is insolubilized can be obtained.
  • Examples of the photoacid generator (c1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like. It is preferable to contain two or more kinds of photoacid generators, and when two or more kinds are contained, a more sensitive photosensitive resin composition can be obtained.
  • a quinonediazide compound is particularly preferable as the photoacid generator (c1) from the viewpoint of long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device.
  • the quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and / or sulfone.
  • Examples thereof include amide-bonded compounds. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are replaced with quinonediazide sulfonic acid.
  • any of 5-naphthoquinone diazidosulfonyl group and 4-naphthoquinone diazidosulfonyl group is preferably used.
  • a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. You may.
  • the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed but it is preferable to include a 4-naphthoquinone diazidosulfonyl ester compound from the viewpoint of increasing sensitivity.
  • a 5-naphthoquinonediazide sulfonyl ester compound is preferable from the viewpoint of long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device.
  • a 4-naphthoquinonediazide sulfonyl ester compound is preferably used. Can be done.
  • the quinone diazide compound can be synthesized from a compound having a phenolic hydroxyl group and a quinone diazido sulfonic acid compound by an arbitrary esterification reaction. By using these quinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
  • sulfonium salts phosphonium salts, diazonium salts, and iodonium salts are preferable because they appropriately stabilize the acid component generated by exposure.
  • the sulfonium salt is preferable.
  • a sensitizer or the like can be contained as needed.
  • the content of the photoacid generator (c1) when used is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the polyimide precursor (a) from the viewpoint of increasing sensitivity. It is 10 parts by mass or more, more preferably 25 parts by mass or more. From the viewpoint of further improving the chemical resistance of the cured film, 100 parts by mass or less is preferable. From the viewpoint of improving long-term reliability when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device, it is preferable that the content of the photoacid generator (c1) is small.
  • the photoacid generator (c1) is used to increase the sensitivity.
  • Content can be increased.
  • Examples of the photopolymerization initiator (c2) include a benzyl ketal-based photopolymerization initiator, an ⁇ -hydroxyketone-based photopolymerization initiator, an ⁇ -aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester.
  • Initiators of photopolymerization aclysin-based photopolymerization initiators, titanosen-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, benzoic acid ester-based photopolymerization initiators Agents and the like can be mentioned. Two or more kinds of photopolymerization initiators (c2) may be contained.
  • an ⁇ -aminoketone-based photopolymerization initiator an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator are further preferable.
  • Examples of the ⁇ -aminoketone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4).
  • -Morphorinophenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butane-1-one, 3,6-bis (2-methyl-) 2-morpholinopropionyl) -9-octyl-9H-carbazole and the like can be mentioned.
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). )-(2,4,4-trimethylpentyl) phosphine oxide and the like.
  • oxime ester-based photopolymerization initiator examples include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime and 1-phenylbutane-1,2-dione-2- (O-methoxy).
  • the content thereof is 0. From the viewpoint of increasing sensitivity, the content is 0. With respect to 100 parts by mass in total of the polyimide precursor (a) and the radically polymerizable compound described later. It is preferably 1 part by mass or more, more preferably 1 part by mass or more, and further preferably 10 parts by mass or more. On the other hand, from the viewpoint of further improving the resolution and reducing the taper angle, 50 parts by mass or less is preferable.
  • the content of the photopolymerization initiator (c2) is small.
  • the photopolymerization initiator (c2) is used to increase the sensitivity. ) Content can be increased.
  • the photosensitive resin composition of the present invention preferably further contains a coloring material (d).
  • a coloring material By containing the colorant (d), the light having a wavelength absorbed by the colorant (d) is shielded from the light transmitted through the film of the photosensitive resin composition or the light reflected from the film of the photosensitive resin composition. It is possible to impart light-shielding properties. By imparting light-shielding properties, when the cured film of the present invention described later is used as a flattening layer and / or an insulating layer of an organic EL display device, deterioration, malfunction, leakage current, etc. due to light intrusion into the TFT are prevented. be able to. Further, it is possible to suppress the reflection of external light from the wiring and the TFT, and improve the contrast between the light emitting area and the non-light emitting area.
  • the coloring material (d) it is preferable to use a dye (d1) and / or a pigment (d2). At least one kind of coloring material (d) may be contained, for example, a method using one kind of dye or an organic pigment, a method using a mixture of two or more kinds of dyes or pigments, and one or more kinds of dyes and one kind or more. Examples thereof include a method of using the above pigments in combination.
  • those having an absorption maximum at 400 to 750 nm are preferably selected.
  • the dye (d1) is preferable as the colorant (d) in the present invention.
  • the pigment (d2) is preferable from the viewpoint of suppressing fading of the colorant in the heat curing step of the photosensitive resin composition or the photosensitive resin sheet of the present invention, which will be described later.
  • the dye (d1) can also be preferably used.
  • the coloring material (d) contains a dye (d1-1) and / or a pigment (d2-1) having an absorption maximum in the range of (d-1) wavelength of 400 nm or more and less than 490 nm. It is preferable to contain it.
  • a dye (d1-1) and / or a pigment (d2-1) having an absorption maximum in the range of (d-1) wavelength of 400 nm or more and less than 490 nm. It is preferable to contain it.
  • d-1 component a dye (d1-1) and / or a pigment (d2-1) having an absorption maximum in the range of (d-1) wavelength of 400 nm or more and less than 490 nm. It is preferable to contain it.
  • (d-1) component, (d1-1) component, and (d2-1) component respectively.
  • the dye (d1-1) used as the component (d-1) is soluble in an organic solvent that dissolves the polyimide precursor (a) from the viewpoints of storage stability, curing, and fading during light irradiation. Moreover, a dye that is compatible with the resin and a dye having high heat resistance and light resistance are preferable. Since the component (d1-1) has an absorption maximum in the wavelength range of 400 nm or more and less than 490 nm, examples thereof include yellow dyes and orange dyes. Examples of the type of dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes and direct dyes.
  • Examples of the skeleton structure of the dye include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, and xanthene-based.
  • anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based are preferable from the viewpoint of solubility in organic solvents and heat resistance.
  • each of these dyes may be used alone or as a metal-containing complex salt system.
  • the pigment (d2-1) used as the component (d-1) is preferably a pigment having high heat resistance and light resistance from the viewpoint of fading during curing and light irradiation.
  • organic pigments used for these are shown by Color Index (CI) numbers.
  • yellow pigments include Pigment Yellow 83, 117, 129, 138, 139, 150, 180 and the like.
  • orange pigments include Pigment Orange 38, 43, 64, 71, 72 and the like. In addition, pigments other than these can also be used.
  • the content of the component (d-1) when used in the present invention is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass with respect to 100 parts by mass of the polyimide precursor (a). In particular, 1 to 200 parts by mass is preferable.
  • the content of the component (d-1) is 0.1 parts by mass or more, light of the corresponding wavelength can be absorbed. Further, by setting the amount to 300 parts by mass or less, it is possible to absorb light of a corresponding wavelength while maintaining the adhesion strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.
  • the organic pigment used as the component (d2-1) may be one that has been subjected to surface treatment such as rosin treatment, acidic group treatment, and basic group treatment, if necessary. In some cases, it can be used together with a dispersant.
  • the dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants.
  • the colorant (d) used in the photosensitive resin composition of the present invention contains a dye (d1-2) and / or a pigment (d2-2) having an absorption maximum in the range of (d-2) wavelength of 490 nm or more and less than 580 nm. It is preferable to contain it.
  • a (d-2) component a (d1-2) component, and a (d2-2) component, respectively.
  • the dye used as the component (d1-2) is soluble in an organic solvent that dissolves the polyimide precursor (a) and is compatible with the resin from the viewpoints of storage stability, curing, and fading during light irradiation. Dissolvable dyes and dyes with high heat resistance and light resistance are preferable. Since the component (d1-2) has an absorption maximum in the wavelength range of 490 nm or more and less than 580 nm, examples thereof include red dyes and purple dyes. Examples of the type of dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes and direct dyes.
  • Examples of the skeleton structure of the dye include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, and xanthene-based.
  • anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based are preferable from the viewpoint of solubility in organic solvents and heat resistance.
  • each of these dyes may be used alone or as a metal-containing complex salt system.
  • the pigment (d2-2) used as the component (d-2) is preferably a pigment having high heat resistance and light resistance from the viewpoint of fading during curing and light irradiation.
  • organic pigments used for these are shown by Color Index (CI) numbers.
  • red pigments include Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 and the like.
  • purple pigments include Pigment Violet 19, 23, 29, 32, 33, 36, 37, 38 and the like. In addition, pigments other than these can also be used.
  • the content of the component (d-2) when used in the present invention is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass with respect to 100 parts by mass of the polyimide precursor (a). In particular, 1 to 200 parts by mass is preferable.
  • the content of the component (d-2) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass with respect to 100 parts by mass of the polyimide precursor (a). In particular, 1 to 200 parts by mass is preferable.
  • the organic pigment used as the component (d2-2) may be a pigment that has been subjected to surface treatment such as rosin treatment, acidic group treatment, and basic group treatment, if necessary. In some cases, it can be used together with a dispersant.
  • the dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants.
  • the colorant (d) used in the photosensitive resin composition of the present invention is a dye (d1-3) and / or a pigment (d2-3) having an absorption maximum in the range of (d-3) wavelength of 580 nm or more and less than 800 nm. It is preferable to contain it.
  • the dye (d1-3) used as the component (d-3) is soluble in an organic solvent that dissolves the polyimide precursor (a) from the viewpoints of storage stability, curing, and fading during light irradiation. Moreover, a dye that is compatible with the resin and a dye having high heat resistance and light resistance are preferable. Since the component (d1-3) has an absorption maximum in the wavelength range of 580 nm or more and less than 800 nm, examples thereof include blue dyes and green dyes. Examples of the type of dye include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes and direct dyes.
  • Examples of the skeleton structure of the dye include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, and xanthene-based.
  • anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based are preferable from the viewpoint of solubility in organic solvents and heat resistance.
  • each of these dyes may be used alone or as a metal-containing complex salt system.
  • the pigment (d2-3) used as the component (d-3) is preferably a pigment having high heat resistance and light resistance from the viewpoint of fading during curing and light irradiation.
  • organic pigments used for these are shown by Color Index (CI) numbers.
  • blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64 and the like.
  • green pigments include Pigment Green 7, 10, 36, 47, 58 and the like.
  • pigments other than these can also be used.
  • the content of the component (d-3) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, particularly preferably 0.2 to 200 parts by mass with respect to 100 parts by mass of the polyimide precursor (a). 1 to 200 parts by mass is preferable.
  • the content of the component (d-3) is 0.1 parts by mass or more, light of the corresponding wavelength can be absorbed. Further, by setting the amount to 300 parts by mass or less, it is possible to absorb light of a corresponding wavelength while maintaining the adhesion strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.
  • the organic pigment used as the component (d2-3) may be one that has been subjected to surface treatment such as rosin treatment, acidic group treatment, and basic group treatment, if necessary. In some cases, it can be used together with a dispersant.
  • the dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants.
  • Blackening is possible by using the component (d-1), the component (d-2), and the component (d-3) in combination.
  • Blackening can be expressed by an optical density (OD value), and the OD value is preferably 0.3 or more, more preferably 0.6 or more, and further preferably 1.0 or more.
  • the photosensitive resin composition of the present invention may further contain a thermochromic compound.
  • the thermochromic compound is a thermochromic compound that develops color by heat treatment and has an absorption maximum at 350 nm or more and 700 nm or less, more preferably color by heat treatment and has an absorption maximum at 350 nm or more and 500 nm or less. It is a compound.
  • the thermochromic compound in place of the above-mentioned component (d-1) or in combination with the component (d-1), the absorption of the photosensitive resin composition in the exposure wavelength region of 350 to 450 nm is suppressed. , The decrease in sensitivity can be suppressed.
  • the thermochromic compound is preferably a compound that develops color at a temperature higher than 120 ° C., and more preferably a thermochromic compound that develops color at a temperature higher than 180 ° C.
  • the higher the color development temperature of the thermochromic compound the better the heat resistance under high temperature conditions, and the less the color fades due to long-term irradiation with ultraviolet light and visible light, and the better the light resistance.
  • thermochromic compound may be a general heat-sensitive dye or a pressure-sensitive dye, or may be another compound.
  • thermochromic compounds include those that develop color by changing their chemical structure and charge state due to the action of acidic groups coexisting in the system during heat treatment, or thermal oxidation reactions due to the presence of oxygen in the air. Examples include those that cause color development.
  • thermochromic compound examples include triarylmethane skeleton, diarylmethane skeleton, fluorane skeleton, bislactone skeleton, phthalide skeleton, xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenothiazine skeleton, phenoxazine skeleton, and spiropyran skeleton. Be done. Of these, a triarylmethane skeleton is preferable because it has a high thermal color development temperature and excellent heat resistance.
  • triarylmethane skeleton examples include 2,4', 4''-methyridentrisphenol, 4,4', 4''-methyridentrisphenol, 4,4'-[(4-hydroxyphenyl). Methylene] bis (benzeneamine), 4,4'-[(4-aminophenyl) methylene] bisphenol, 4,4'-[(4-aminophenyl) methylene] bis [3,5-dimethylphenol], 4, 4'-[(2-Hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,4'-[(2) -Hydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2 -Ethoxyphenol, 4,4'-[(4-hydroxyphenyl
  • the hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinone diazide compound by ester-bonding a sulfonic acid of naphthoquinone diazide to the compound.
  • the content of the thermally chromogenic compound is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyimide precursor (a).
  • the content of the thermochromic compound is 5 parts by mass or more, the transmittance of the cured film in the ultraviolet visible light region can be reduced. Further, if it is 80 parts by mass or less, the heat resistance and strength of the cured film can be maintained and the water absorption rate can be reduced.
  • the photosensitive resin composition in the present invention may contain a resin other than the polyimide precursor (a).
  • the resin (a) other than the polyimide precursor (a) examples include polyimide, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, a polymer of a radically polymerizable monomer having an acidic group, and a phenol resin.
  • these resins are preferably alkali-soluble, and may contain two or more of these resins.
  • high development adhesion, excellent heat resistance, and a small amount of outgas at high temperatures provide high long-term reliability when the cured film described later is used in an organic EL display device.
  • Polyimides, polybenzoxazole precursors or copolymers thereof are more preferred.
  • the polybenzoxazole precursor refers to a resin that is converted to polybenzoxazole by heat treatment or chemical treatment, and examples thereof include polyhydroxyamide.
  • the photosensitive resin composition of the present invention may further contain a radically polymerizable compound.
  • the radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bonds in the molecule.
  • radical polymerization of the radically polymerizable compound proceeds by the radicals generated from the above-mentioned photopolymerization initiator (c2), and the light-irradiated portion is insolubilized, so that a negative pattern can be obtained.
  • the photocuring of the light-irradiated portion is promoted, and the sensitivity can be further improved.
  • the crosslink density after thermosetting is improved, the hardness of the cured film can be improved.
  • a compound having a (meth) acrylic group which facilitates radical polymerization, is preferable. From the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured film, a compound having two or more (meth) acrylic groups in the molecule is more preferable.
  • 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 film.
  • Examples of the radically polymerizable compound include trimethylol propanetri (meth) acrylate, ditrimethylol propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
  • the content of the radically polymerizable compound is 100 parts by mass in total of the polyimide precursor (a) and the radically polymerizable compound from the viewpoint of further improving the sensitivity and reducing the taper angle.
  • 15 parts by mass or more is preferable, and 30 parts by mass or more is more preferable.
  • 65 parts by mass or less is preferable, and 50 parts by mass or less is more preferable.
  • the photosensitive resin composition of the present invention may further contain a thermal cross-linking agent.
  • the thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group.
  • an epoxy group and an oxetanyl group are used.
  • a thermal cross-linking agent that does not contain the above is preferable. This is because when the photosensitive resin composition of the present invention contains a thermal cross-linking agent that reacts with a phenolic hydroxyl group such as an epoxy group and an oxetanyl group, the phenolic hydroxyl group of the phenol compound (b) reacts with the thermal cross-linking agent. It is presumed that the effect of the invention is reduced.
  • Preferred examples of compounds having at least two alkoxymethyl or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, H
  • Preferred examples of compounds having at least two epoxy groups are “Epolite” (registered trademark) 40E, "Epolite” 100E, “Epolite” 200E, “Epolite” 400E, "Epolite” 70P, “Epolite” 200P, “Epolite”.
  • the compound having at least two oxetanyl groups include, for example, Ethanacole EHO, Ethanacole OXBP, Ethanacole OXTP, Ethanacole OXMA (all manufactured by Ube Industries, Ltd.), oxetaneized phenol novolac and the like.
  • the thermal cross-linking agent may be contained in combination of two or more.
  • the content is preferably 1% by mass or more and 30% by mass or less in 100% by mass of the total amount of the photosensitive resin composition excluding the solvent.
  • the content of the thermal cross-linking agent is 1 part by mass or more, the chemical resistance and bending resistance of the cured film can be further enhanced.
  • the content of the thermal cross-linking agent is 30 parts by mass or less, the amount of outgas from the cured film can be further reduced, the long-term reliability of the organic EL display device can be further enhanced, and the photosensitive resin composition can be stored. It also has excellent stability.
  • the photosensitive resin composition of the present invention may further contain a solvent. By containing a solvent, it can be made into a varnish state, and the coatability can be improved.
  • the solvent examples include polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol mono.
  • polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol mono.
  • Ethyl ether diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Propropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Ethers such as monoethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone
  • the content when the solvent is contained is not particularly limited, but is preferably 100 to 3000 parts by mass, more preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.
  • the ratio of the solvent having a boiling point of 180 ° C. or higher to 100% by mass of the total amount of the solvent is preferably 20% by mass or less, and more preferably 10% by mass or less.
  • the photosensitive resin composition of the present invention may further contain an adhesion improver.
  • Adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Contains silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy groups.
  • Examples thereof include a compound obtained by reacting a silicon compound. Two or more of these may be contained.
  • these adhesion improvers it is possible to improve the development adhesion with a base substrate such as a silicon wafer, indium tin oxide (ITO), SiO 2 , or silicon nitride when developing a resin film. ..
  • a base substrate such as a silicon wafer, indium tin oxide (ITO), SiO 2 , or silicon nitride
  • ITO indium tin oxide
  • SiO 2 silicon nitride
  • resistance to oxygen plasma and UV ozone treatment used for cleaning and the like can be enhanced.
  • the adhesion improver is contained, the content is preferably 0.01 to 10% by mass in 100% by mass of the total amount of the photosensitive resin composition excluding the solvent.
  • the photosensitive resin composition of the present invention may further contain a surfactant, if necessary, and can improve the wettability with the substrate.
  • surfactants include SH series, SD series, ST series of Toray Dow Corning Co., Ltd., BYK series of Big Chemy Japan Co., Ltd., KP series of Shin-Etsu Chemical Co., Ltd., and NOF Corporation. Disform series, DIC Co., Ltd. "Mega Fuck (registered trademark)" series, Sumitomo 3M Co., Ltd. Florard series, Asahi Glass Co., Ltd.
  • the content is preferably 0.001 to 1% by mass in 100% by mass of the total amount of the photosensitive resin composition excluding the solvent.
  • the photosensitive resin composition of the present invention may further contain inorganic particles.
  • Preferred specific examples of the inorganic particles include, for example, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like.
  • the primary particle size of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.
  • the content is preferably 5 to 90% by mass in 100% by mass of the total amount of the photosensitive resin composition excluding the solvent.
  • a method for producing the photosensitive resin composition of the present invention will be described.
  • a polyimide precursor (a), a phenol compound (b) and a photosensitive compound (c), and if necessary, a coloring material (d), a thermochromic compound, a radically polymerizable compound, a thermal cross-linking agent, a solvent, and adhesion improvement for example, a polyimide precursor (a), a phenol compound (b) and a photosensitive compound (c), and if necessary, a coloring material (d), a thermochromic compound, a radically polymerizable compound, a thermal cross-linking agent, a solvent, and adhesion improvement.
  • the photosensitive resin composition of the present invention can be obtained by dissolving an agent, a surfactant, inorganic particles and the like.
  • Examples of the melting method include stirring and heating.
  • the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C.
  • the dissolution order of each component is not particularly limited, and examples thereof include a method of sequentially dissolving compounds having low solubility.
  • components that tend to generate bubbles during stirring and dissolution such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.
  • the obtained photosensitive resin composition is filtered using a filtration filter to remove dust and particles.
  • the filter pore diameter includes, for example, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, 0.05 ⁇ m, 0.02 ⁇ m, and the like, but is not limited thereto.
  • Examples of the material of the filtration filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Of these, polyethylene and nylon are preferable.
  • the photosensitive resin sheet of the present invention is a photosensitive resin sheet formed from the photosensitive resin composition of the present invention.
  • the photosensitive resin sheet of the present invention can be obtained by applying and drying the photosensitive resin composition of the present invention on a peelable substrate such as polyethylene terephthalate.
  • the photosensitive resin film can be obtained by applying the photosensitive resin composition of the present invention to obtain a coating film of the photosensitive resin composition and drying it. Further, the photosensitive resin sheet may be used as a photosensitive resin film.
  • Examples of the method for applying the photosensitive resin composition of the present invention include a spin coating method, a slit coating method, a dip coating method, a spray coating method, and a printing method.
  • the slit coating method is preferable because it can be applied with a small amount of coating liquid and is advantageous in cost reduction.
  • the amount of the coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 as compared with the spin coating method.
  • Examples of slit nozzles used for coating include "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, viscosity, etc. of the resin composition, but 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 which the photosensitive resin composition is applied may be pretreated with the above-mentioned adhesion improving agent in advance.
  • the adhesion improver is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass.
  • a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass.
  • examples thereof include a method of treating the surface of the base material using the dissolved solution.
  • the method for treating the surface of the base material include a spin coating method, a slit die
  • the vacuum drying rate depends on the volume of the vacuum chamber, the capacity of the vacuum pump, the diameter of the pipe between the chamber and the pump, etc., but for example, the conditions under which the inside of the vacuum chamber is depressurized to 40 Pa after 60 seconds have passed without the coating substrate. It is preferable to set to.
  • the general vacuum drying time is often about 30 seconds to 100 seconds, and the pressure reached in the vacuum chamber at the end of vacuum drying is usually 100 Pa or less with the coated substrate. By setting the ultimate pressure to 100 Pa or less, it is possible to reduce the stickiness of the coating film surface to a dry state, and thereby it is possible to suppress surface contamination and generation of particles in the subsequent substrate transfer.
  • the coating film It is common to heat-dry the coating film after coating or drying under reduced pressure. This process is also called prebaking.
  • a hot plate When a hot plate is used, the coating film is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate.
  • the heating time is preferably 1 minute to several hours.
  • the heating temperature varies depending on the type and purpose of the coating film, but is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of promoting solvent drying during prebaking. On the other hand, from the viewpoint of reducing the progress of imidization during prebaking, the temperature is preferably 150 ° C.
  • the photosensitive resin composition in the present invention suppresses the progress of imidization at the time of prebaking, but is fired at a temperature of 200 ° C. or lower. Even in this case, a cured film having a high imidization rate can be obtained.
  • the photosensitive resin film and the photosensitive resin sheet can form a pattern.
  • a desired pattern can be formed by exposing and developing a photosensitive resin film and a photosensitive resin sheet by irradiating them with chemical rays through a mask having a desired pattern.
  • Examples of chemical beams used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays.
  • the exposed part dissolves in the developer.
  • the exposed portion is cured and insolubilized in a developing solution.
  • the developing solution includes tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, and dimethyl.
  • An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone and dimethylacrylamide, alcohols such as methanol, ethanol and isopropanol are added.
  • Classes, 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 in an amount of one or more.
  • Examples of the developing method include spray, paddle, immersion, ultrasonic and the like.
  • Alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.
  • the cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention.
  • the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention contains a polyimide precursor and forms an imide ring by heat curing, heat resistance and chemical resistance can be further improved.
  • the cured film of the present invention is suitable for, for example, a flattening layer and / or an insulating layer in an organic EL display device having a drive circuit, a flattening layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate. Can be used for.
  • the cured film of the present invention can be suitably used, for example, as an interlayer insulating layer and / or a surface protective layer in an electronic component having an electrode, a metal wiring, an interlayer insulating layer and / or a surface protective layer on a substrate. ..
  • the first aspect of the method for producing a cured film of the present invention is a step of forming a photosensitive resin film composed of the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention on a substrate, the photosensitive resin. It includes a step of exposing the film, a step of developing the exposed photosensitive resin film, and a step of heat-treating the developed photosensitive resin film at 200 ° C. or lower.
  • a second aspect of the method for producing a cured film of the present invention is a step of forming a photosensitive resin film composed of the photosensitive resin composition of the present invention or the photosensitive resin sheet of the present invention on a substrate, the photosensitive resin. It includes a step of exposing the film, a step of developing the exposed photosensitive resin film, and a step of heat-treating the developed photosensitive resin film in an atmosphere having an oxygen concentration of 1% or more. In the present invention, the oxygen concentration represents the volume concentration.
  • the step of forming the photosensitive resin film the step of exposing the photosensitive resin film, and the step of developing the exposed photosensitive resin film in the method for producing a cured film of the present invention
  • the above ⁇ photosensitive resin film, photosensitive It is as described in the item of resin sheet>.
  • the first aspect of the method for producing a cured film of the present invention includes a step of heat-treating a photosensitive resin film at 200 ° C. or lower.
  • a photosensitive resin film By containing the polyimide precursor (a) and the phenol compound (b) in the photosensitive resin composition of the present invention, a cured film having a high imidization rate can be obtained even when heat-treated at 200 ° C. or lower.
  • the heat treatment is preferably performed at 200 ° C. or lower from the viewpoint of more easily suppressing the fading of the colorant (d).
  • the temperature in the heat treatment step may be raised stepwise or continuously.
  • the atmosphere at the time of heat curing further reduces the amount of outgas generated from the cured film, and a long period of time when the cured film is used as a flattening layer and / or an insulating layer of an organic EL display device.
  • An inert gas atmosphere is preferable from the viewpoint of increasing reliability. Specific examples of the inert gas include nitrogen and argon.
  • the oxygen concentration in the atmosphere of the inert gas is preferably 5% or less, more preferably 1% or less, further preferably 0.5% or less, and 0.01%. The following are particularly preferred.
  • the heating time in the heat treatment step is preferably 30 minutes or more from the viewpoint of further reducing the amount of outgas.
  • the heating time represents the holding time at the maximum temperature reached in the heat treatment step. Further, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or less.
  • the heat treatment method include a method of heat treatment at 200 ° C. for 30 minutes, a method of heat treatment at 150 ° C. and 200 ° C. for 30 minutes each, and a method of heat treatment while linearly raising the temperature from room temperature to 200 ° C. for 2 hours. How to do it.
  • the second aspect of the method for producing a cured film of the present invention includes a step of heat-treating the developed photosensitive resin film in an atmosphere having an oxygen concentration of 1% or more.
  • the photosensitive resin composition of the present invention has long-term reliability when the cured film is used as a flattening layer and / or an insulating layer of an organic EL display device. Since the properties can be improved, it can be suitably heat-cured even at an oxygen concentration of 1% or more.
  • the temperature in the heat treatment step is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, and 230 ° C. or higher, from the viewpoint of further reducing the amount of outgas generated from the cured film. ° C. or higher is more preferable, and 250 ° C. or higher is particularly preferable.
  • the temperature is preferably 500 ° C. or lower, more preferably 450 ° C. or lower.
  • the heat treatment step is performed from the viewpoint of easily suppressing the fading of the colorant (d).
  • the temperature is preferably 230 ° C. or lower, more preferably 200 ° C. or lower.
  • the heating time in the heat treatment step is preferably 30 minutes or more from the viewpoint of further reducing the amount of outgas. Further, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or less.
  • the heat treatment method include a method of heat treatment at 250 ° C. for 30 minutes, a method of heat treatment at 150 ° C. and 250 ° C. for 30 minutes each, and a method of heat treatment while linearly raising the temperature from room temperature to 300 ° C. for 2 hours. How to do it.
  • the photosensitive resin composition, the photosensitive resin sheet and the cured film of the present invention use a surface protective layer or an interlayer insulating layer of a semiconductor element, an insulating layer of an organic electroluminescence (hereinafter referred to as EL) element, and an organic EL element.
  • EL organic electroluminescence
  • TFT Thin Film Transistor
  • a surface protective layer or an interlayer insulating layer such as an MRAM having low heat resistance
  • PFRAM polymer memory
  • PCRAM phase change memory
  • OUM Ovonics Unified Memory
  • a display device including a first electrode formed on the substrate and a second electrode provided so as to face the first electrode, for example, a display device using an LCD, ECD, ELD, or an organic electroluminescent element. It can also be used for an insulating layer such as (organic electroluminescent device).
  • an organic EL display device, a semiconductor device, and a semiconductor electronic component will be described as an example.
  • the organic EL display device of the present invention is an organic EL display device having a drive circuit, a flattening layer, a first electrode, an insulating layer, a light emitting layer and a second electrode on a substrate, and is a flattening layer and / or insulation.
  • the layer has the cured film of the present invention.
  • Organic luminescent materials are generally vulnerable to gas components and moisture, and exposure to these causes a decrease in emission brightness and pixel shrinkage.
  • the pixel shrink refers to a phenomenon in which the emission brightness decreases or the light is not turned on from the end of the pixel.
  • the organic EL display device of the present invention can improve long-term reliability by including the cured film of the present invention in the flattening layer and / or the insulating layer of the organic EL display device.
  • the insulating layer is adjacent to the organic light emitting material, it has a greater effect on long-term reliability than the flattening layer. Therefore, in order to obtain an organic EL display device having high long-term reliability, it is preferable that at least the insulating layer contains the cured film of the present invention.
  • an active matrix type display device As an example, it has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass or various plastics, and covers unevenness on the TFT.
  • the flattening layer is provided, and the display element is further provided on the flattening layer.
  • the display element and the wiring are connected via a contact hole formed in the flattening layer.
  • the substrate having the above-mentioned drive circuit is an organic EL display device containing a resin film.
  • the photosensitive resin composition of the present invention or a cured film obtained by curing a photosensitive sheet is used as an insulating layer or a flattening layer of such a flexible display, it is particularly preferably used because it has excellent bending resistance.
  • Polyimide is particularly preferable as the resin film from the viewpoint of improving the adhesion of the photosensitive resin composition of the present invention or the photosensitive sheet to the cured film.
  • the film thickness is preferably 1.0 to 5.0 ⁇ m, more preferably 2.0 ⁇ m or more.
  • the flattening layer By setting the flattening layer within the above range, it is possible to improve the flatness of dense TFTs and wiring by increasing the definition.
  • the flattening layer is thickened, outgas is increased, which causes a decrease in long-term reliability of the organic EL display device.
  • the cured film of the present invention can improve long-term reliability even when the film is thickened. it can.
  • the flattening layer is preferably multi-layered, and more preferably the flattening layer is composed of 2 to 5 layers.
  • FIG. 2 shows a cross-sectional view of an example of the TFT substrate.
  • Bottom gate type or top gate type TFTs (thin film transistors) 1 are provided in a matrix on the substrate 6, and the TFT insulating layer 3 is formed so as to cover the TFT 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 in a state where the wiring 2 is embedded.
  • the flattening layer 4 is provided with a contact hole 7 that reaches the wiring 2.
  • ITO (transparent electrode) 5 is formed on the flattening layer 4 in a state of being connected to the wiring 2 through the contact hole 7.
  • ITO5 serves as an electrode for a display element (for example, an organic EL element).
  • the insulating layer 8 is formed so as to cover the peripheral edge of the ITO 5.
  • the organic EL element may be a top emission type that emits emitted light from the side opposite to the substrate 6, or a bottom emission type that emits light from the substrate 6 side. In this way, an active matrix type organic EL display device in which a TFT 1 for driving the organic EL element is connected to each organic EL element can be obtained.
  • the TFT insulating layer 3, the flattening layer 4, and / or the insulating layer 8 is a step of forming a photosensitive resin film made of the photosensitive resin composition or the photosensitive resin sheet of the present invention, the photosensitive resin film. It can be formed by a step of exposing the exposed photosensitive resin film, a step of developing the exposed photosensitive resin film, and a step of heat-treating the developed photosensitive resin film. An organic EL display device can be obtained from a manufacturing method having these steps.
  • the electronic component of the present invention is an electronic component having an electrode and a metal wiring on a substrate and further having an interlayer insulating layer and / or a surface protective layer, and at least of the interlayer insulating layer and / or the surface protective layer. It has a cured film of the present invention in part.
  • electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (hereinafter, ICs), and memories, and passive components such as resistors, capacitors, and inductors.
  • active components having semiconductors such as transistors, diodes, integrated circuits (hereinafter, ICs), and memories
  • passive components such as resistors, capacitors, and inductors.
  • semiconductor devices may be referred to as semiconductor devices.
  • the cured film in electronic components include a passivation film for semiconductors, a surface protective film for semiconductor elements, TFTs, etc., an interlayer insulating film for 2 to 10 layers of multilayer wiring for high-density mounting, an insulating film for touch panel displays, and protection.
  • a passivation film for semiconductors a surface protective film for semiconductor elements, TFTs, etc.
  • an interlayer insulating film for 2 to 10 layers of multilayer wiring for high-density mounting an insulating film for touch panel displays, and protection.
  • Membranes and the like can be mentioned, but are not limited to these, and various structures can be taken.
  • the cured film of the present invention since the cured film of the present invention has excellent mechanical properties, stress from the sealing resin can be relaxed even during mounting, damage to the low-k layer is suppressed, and a highly reliable semiconductor is used. Equipment can be provided.
  • FIG. 3 shows an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having bumps.
  • a passivation layer 11 having an Al pad 10 for input / output and a via hole is formed on the silicon wafer 9. Further, an insulating layer 12 is formed on the passivation layer 11, a metal layer 13 made of Cr, Ti, etc. is formed so as to be connected to the Al pad 10, and a metal wiring made of Al, Cu, etc. is formed by electroplating or the like. 14 is formed.
  • the pads are insulated from each other by etching the metal layer 13 located around the solder bump 18.
  • a barrier metal 16 and a solder bump 18 are formed on the insulated pad.
  • a scribe line 17 is formed when the insulating film 15 is processed.
  • FIG. 4 shows an example of a method for manufacturing a semiconductor device having bumps.
  • the photosensitive resin composition of the present invention is applied onto the silicon wafer 9 on which the Al pad 10 and the passivation layer 11 are formed, and the patterned insulating layer 12 is formed through the photolithography step.
  • the metal layer 13 is formed by the sputtering method.
  • the metal wiring 14 is formed on the metal layer 13 by a plating method.
  • the photosensitive resin composition of the present invention is applied, and in the step 3d, the pattern of the insulating layer 15 is formed through the photolithography step.
  • the resin composition constituting the insulating layer 15 is thickened on the scribe line 17. Further wiring (so-called rewiring) can be formed on the insulating layer 15.
  • rewiring can be formed on the insulating layer 15.
  • the above steps are repeated to form a multi-layer wiring structure in which the rewiring of two or more layers is separated by an interlayer insulating layer made of the cured film of the present invention. can do.
  • the barrier metal 16 is formed in the step 3e, and the solder bump 18 is formed in the step 3f.
  • the semiconductor device having bumps can be obtained by dicing along the last scribe line 17 and cutting each chip.
  • the obtained prebake film was cut into three pieces, the first was untreated, and the second was oxygen at 200 ° C. using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.). Heat-treated for 1 hour in a nitrogen atmosphere with a concentration of 0.01%, and third, heat-treated at 250 ° C. for 1 hour in a nitrogen atmosphere with an oxygen concentration of 0.01%, photosensitive resin composition prebake film, 200. Cured films at ° C and 250 ° C were prepared.
  • An infrared absorption spectrum of the obtained prebaked film and the cured film at 200 ° C. and 250 ° C. was obtained by the ATR method using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation). Based on the formula (5), assuming that the cured film after heating at 250 ° C. for 1 hour has an imidization rate of 100%, the absorption intensity of 1371 cm -1 derived from the polyimide CNC of each sample (A (1371 cm -1).
  • X (%) represents the imidization rate. If the imidization rate of the cured film at 200 ° C. is 90% or more, it is judged as "A”, if it is less than 90% and 75% or more, it is judged as "B", and if it is less than 75%, it is judged as "C”. did. Even if the imidization rate of the cured film at 200 ° C. was 75% or more, if the imidization rate of the prebaked film was 30% or more, it was judged as “C”.
  • TMAH 2.38 mass% tetramethylammonium aqueous solution
  • the obtained pattern was observed with an FDP microscope MX61 (manufactured by Olympus Corporation) at a magnification of 20 times, and the opening diameter of the contact hole was measured. The minimum exposure amount at which the opening diameter of the contact hole reached 10 ⁇ m was determined, and this was used as the sensitivity. If the sensitivity is less than 150 mJ / cm 2 "S", the case was 150 mJ / cm 2 or more 200 mJ / cm less than 2 "A”, 200 mJ / cm 2 or more 250 mJ / cm if it was less than 2 When it was "B” and 250 mJ / m 2 or more, it was judged as "C".
  • FIG. 5 shows a schematic diagram of a manufacturing procedure of the organic EL display device.
  • an ITO transparent conductive film of 10 nm was formed on the entire surface of a 38 mm ⁇ 46 mm non-alkali glass substrate 19 by a sputtering method, and etched as a first electrode (transparent electrode) 20.
  • an auxiliary electrode 21 for taking out the second electrode was also formed.
  • the obtained substrate was ultrasonically cleaned with Semicoclean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then washed with ultrapure water.
  • Semicoclean 56 trade name, manufactured by Furuuchi Chemical Co., Ltd.
  • the photosensitive resin compositions shown in Tables 2 and 3 were applied to the entire surface of the substrate by a spin coating method, and prebaked on a hot plate at 120 ° C. for 2 minutes. After UV exposure to this film via a photomask, the film was developed with a 2.38 mass% TMAH aqueous solution, unnecessary portions were dissolved, and the film was rinsed with pure water. The obtained resin pattern was heat-treated for 1 hour at 200 ° C. in a nitrogen atmosphere having an oxygen concentration of 0.01% using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.).
  • openings having a width of 70 ⁇ 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 the insulating layer 22 having a shape in which each opening exposes the first electrode is provided on the substrate. It was formed only in the effective area. In this way, an insulating layer having an insulating layer opening ratio of 25% was formed in a substrate effective area having a square shape with a side of 16 mm. The thickness of the insulating layer was about 1.0 ⁇ m.
  • an organic EL layer 23 including a light emitting layer was formed by a vacuum vapor deposition method.
  • the degree of vacuum during vapor deposition was 1 ⁇ 10 -3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition.
  • the compound (HT-1) was deposited at 10 nm as the hole injection layer, and the compound (HT-2) was deposited at 50 nm as the hole transport layer.
  • a compound as a host material (GH-1) and a compound as a dopant material (GD-1) were deposited on the light emitting layer to a thickness of 40 nm so that the doping concentration was 10%.
  • compound (ET-1) and compound (LiQ) were laminated to a thickness of 40 nm at a volume ratio of 1: 1.
  • the structure of the compound used in the organic EL layer is shown below.
  • a second electrode non-transparent electrode 24.
  • the cap-shaped glass plate is sealed by adhering it with an epoxy resin adhesive in a low-humidity nitrogen atmosphere, and a top-emission organic EL having a square shape with a side of 5 mm on one substrate is used.
  • the film thickness referred to here is a display value on the 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 .
  • UV light having a wavelength of 365 nm and an illuminance of 0.6 mW / cm 2 .
  • light is emitted by direct current drive of the organic EL display device 0.625 mA, and the area ratio of the light emitting portion to the area of the light emitting pixel (pixel light emitting area ratio) is measured. did.
  • the pixel emission area ratio after 1000 hours by this evaluation method is "S" when it is 80% or more, “A” when it is less than 80% and 70% or more, and less than 70% and 60% or more. If it was, it was judged as “B”, and if it was less than 60%, it was judged as "C”.
  • 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. It was dissolved in 17.4 g (0.3 mol) of propylene 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 dropping, the reaction was carried out at ⁇ 15 ° C. for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.
  • BAHF 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
  • Synthesis Example 2 Synthesis of quinonediazide compound (c-1) 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 36 of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) under a dry nitrogen air flow. .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 temperature inside the system did not exceed 35 ° C. After the dropping, the mixture was stirred at 30 ° C. for 2 hours.
  • TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
  • Synthesis Examples 4 to 15, Comparative Synthesis Examples 1 to 3 Polyimide precursors (a-2) to (a-13), (a'-1) to (a'-3) in the same manner as in Synthesis Example 3 except that the amine component and the acid component were changed as shown in Table 1. ) was obtained.
  • o-tolidine o-tolidine (Ip6.58eV, literature value)
  • DAE 4,4'-diaminodiphenyl ether (Ip6.78eV, literature value) (diamine having an ether bond)
  • MDA 4,4'-diaminodiphenylmethane (Ip6.94eV, literature value)
  • TDE-R 1,3-bis (4-aminophenoxy) benzene (Ip7.08eV, calculated value) (diamine with ether bond)
  • BAHF 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Ip7.88eV, calculated value)
  • SiDA 1,3-bis (3-aminopropyl) tetramethyldisiloxane (Ip8.03
  • Example 1 10.0 g of the polyimide precursor (a-1), 2.0 g of the phenol compound (b-1), and 2.0 g of the quinonediazide compound (c-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. .. Using the obtained varnish, the imidization rate, sensitivity, residual film rate, and long-term reliability of the organic EL display device were evaluated as described above.
  • Examples 2 to 23, Comparative Examples 1 to 7, Comparative Examples 10 to 15 Varnish of positive photosensitive resin composition in the same manner as in Example 1 except that the polyimide precursor (a), the phenol compound (b), the photosensitive compound (c), and other additives were changed as shown in Table 2.
  • the imidization rate, sensitivity, residual film rate, and long-term reliability of the organic EL display device were evaluated as described above.
  • Example 24 The long-term reliability of the organic EL display device was evaluated in the same manner as in Example 2 except that the heat treatment temperature of the resin pattern was changed from 200 ° C. to 250 ° C. using the varnish obtained in Example 2. ..
  • Example 25 Using the varnish obtained in Example 2, the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 1%, in the same manner as in Example 2. The long-term reliability of the organic EL display device was evaluated.
  • Example 26 Using the varnish obtained in Example 2, the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 5%, in the same manner as in Example 2. The long-term reliability of the organic EL display device was evaluated.
  • Example 27 Using the varnish obtained in Example 2, the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to an air atmosphere having an oxygen concentration of 21%, in the same manner as in Example 2. The long-term reliability of the organic EL display device was evaluated.
  • Example 28 Polyimide precursor (a-2) 10.0 g, phenol compound (b-1) 2.0 g, quinonediazide compound (c-1) 2.0 g, 4,4', 4 ′′ -methyridentrisphenol (e-) 1) 2.5 g, 1.5 g of Varifast Red 1308 (d1-2-1), and 2.5 g of Oil Blue 613 (d1-3-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. .. Using the obtained varnish, the imidization rate, sensitivity, residual film rate, and long-term reliability of the organic EL display device were evaluated as described above.
  • the heat treatment atmosphere of the resin pattern was an air atmosphere having an oxygen concentration of 21%, and the heat treatment temperature was 200 ° C.
  • a cured film having a film thickness of 1.0 ⁇ m and heat-treated at 200 ° C. was prepared on a non-alkali glass substrate by the same method as (1) imidization rate.
  • the incident light intensity (I0) and the transmitted light intensity (I) of the produced cured film were measured using a transmission densitometer (X-Rite 361T (V); manufactured by X-Rite), respectively.
  • X-Rite 361T (V); manufactured by X-Rite a transmission densitometer
  • the OD value was calculated by the following formula as an index of light-shielding property, the OD value was 0.6.
  • OD value log 10 (I0 / I).
  • Example 29 Using the varnish obtained in Example 28, the long-term reliability of the organic EL display device was evaluated in the same manner as in Example 28, except that the heat treatment temperature of the resin pattern was changed from 200 ° C. to 250 ° C. ..
  • Comparative Example 8 10.0 g of the polyimide precursor (a'-1) and 2.0 g of the quinonediazide compound (c-1) were added to 30 g of GBL. 1.0 g of TsOH was added thereto to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, the imidization rate, sensitivity, residual film rate, and long-term reliability of the organic EL display device were evaluated as described above.
  • Comparative Example 9 10.0 g of the polyimide precursor (a'-1) and 2.0 g of the quinonediazide compound (c-1) were added to 30 g of GBL. When 1.0 g of DBU was added thereto, the varnish turned black and a decomposition product of the quinonediazide compound was precipitated, so the evaluation was stopped.
  • Comparative Example 16 Using the varnish obtained in Comparative Example 1, the long-term reliability of the organic EL display device was evaluated in the same manner as in Comparative Example 1 except that the heat treatment temperature of the resin pattern was changed from 200 ° C. to 250 ° C. ..
  • Comparative Example 17 Using the varnish obtained in Comparative Example 1, the organic EL display was performed in the same manner as in Comparative Example 1 except that the heat treatment atmosphere of the resin pattern was changed from an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 1%. The long-term reliability of the device was evaluated.
  • Comparative Example 18 Using the varnish obtained in Comparative Example 1, the organic EL display was performed in the same manner as in Comparative Example 1 except that the heat treatment atmosphere of the resin pattern was changed from an oxygen concentration of 0.01% to a nitrogen atmosphere having an oxygen concentration of 5%. The long-term reliability of the device was evaluated.
  • Comparative Example 19 Using the varnish obtained in Comparative Example 1, the heat treatment atmosphere of the resin pattern was changed from a nitrogen atmosphere having an oxygen concentration of 0.01% to an air atmosphere having an oxygen concentration of 21%, in the same manner as in Comparative Example 1. The long-term reliability of the organic EL display device was evaluated.
  • Tables 2 to 5 show the compositions and evaluation results of each Example and Comparative Example.
  • TFT thin film transistor
  • Wiring 3 TFT insulation layer 4: Flattening layer 5: ITO (transparent electrode) 6: Substrate 7: Contact hole 8: Insulation layer 9: Silicon wafer 10: Al pad 11: Passivation layer 12: Insulation layer 13: Metal (Cr, Ti, etc.) Layer 14: Metal wiring (Al, Cu, etc.) 15: Insulation layer 16: Barrier metal 17: Scrivener line 18: Solder bump 19: Non-alkali glass substrate 20: First electrode (transparent electrode) 21: Auxiliary electrode 22: Insulation layer 23: Organic EL layer 24: Second electrode (non-transparent electrode)

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  • Physics & Mathematics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Theoretical Computer Science (AREA)
  • Electroluminescent Light Sources (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
PCT/JP2020/009104 2019-03-14 2020-03-04 感光性樹脂組成物、感光性樹脂シート、硬化膜、硬化膜の製造方法、有機ｅｌ表示装置、および電子部品 Ceased WO2020184326A1 (ja)

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CN114890873B (zh) * 2022-03-18 2024-03-19 上海邃铸科技有限公司 一种组合物以及提高酰亚胺化率的方法

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