Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
  • C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
  • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/24—Halogenated derivatives
  • C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
  • C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
  • C07C49/83—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups polycyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D207/333—Radicals substituted by oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/04—Indoles; Hydrogenated indoles
  • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
  • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/42—Singly bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/121—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
  • H10K59/1213—Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/122—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
  • 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
  • H10K59/131—Interconnections, e.g. wiring lines or terminals
• • 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
  • H10K59/17—Passive-matrix OLED displays
  • H10K59/173—Passive-matrix OLED displays comprising banks or shadow masks
• • 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
  • H10K59/17—Passive-matrix OLED displays
  • H10K59/179—Interconnections, e.g. wiring lines or terminals
• • 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
  • H10K59/30—Devices specially adapted for multicolour light emission
  • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/805—Electrodes
  • H10K59/8051—Anodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/805—Electrodes
  • H10K59/8052—Cathodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
  • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers

Definitions

• the invention relates to a photosensitive resin composition that can be suitably used for planarizing layers and insulating layers of display devices such as organic electroluminescence display devices, and to a phenol compound that can be contained in the photosensitive resin composition.
• organic EL display devices have a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes.
• photosensitive resin compositions that can form patterns by ultraviolet light irradiation are generally used as materials for the planarization layer and the insulating layer.
• photosensitive resin compositions using polyimide resins are preferably used because they have high heat resistance and generate little gas components from the cured product, allowing for the production of highly reliable organic EL display devices.
• TFTs thin film transistors
• it is required to reduce the transmittance of insulating layers and planarizing layers at wavelengths of around 450 nm in order to prevent malfunctions caused by the intrusion of light into TFTs.
• patterning a photosensitive resin composition it is required to have a high transmittance of ultraviolet light.
• the present invention aims to provide a photosensitive resin composition that can form a film that reduces the transmittance of light with a wavelength of around 450 nm after curing, even when the heating atmosphere during curing has a low oxygen concentration of less than 5%.
• the photosensitive resin composition of the present invention has the following composition.
• n is an integer from 2 to 4, and * represents a bond.
• n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ⁇ p+m ⁇ 4 is satisfied;
• X represents —NR 32 —, —O— or —S—;
• R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 34 and R 35 each independently represent —OR 36 , —SR 36 , —N(R 36 ) 2 , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R Each of 36 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atom
• a colorant (d-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm
• a colorant (d-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.
• the photosensitive resin composition according to any one of [1] to [8], wherein the component (a) includes one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof.
• An organic EL display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate,
• the planarization layer and/or the insulating layer comprises the cured product according to [10].
• An organic EL display device according to any one of [11] to [13], further comprising a color filter having a black matrix.
• a display device having at least metal wiring, the cured product described in [10], and multiple light-emitting elements, the light-emitting elements having a pair of electrode terminals on either side, the pair of electrode terminals being connected to multiple metal wirings extending through the cured product, and the multiple metal wirings being configured to maintain electrical insulation due to the cured product.
• n is an integer from 2 to 4, and * represents a bond.
• n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ⁇ p+m ⁇ 4 is satisfied;
• X represents —NR 32 —, —O— or —S—;
• R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 34 and R 35 each independently represent —OR 36 , —SR 36 , —N(R 36 ) 2 , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R Each of 36 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atom
• the photosensitive resin composition of the present invention can form a film with low transmittance at wavelengths around 450 nm after curing, even in a heating atmosphere with a low oxygen concentration of less than 5% during curing.
• FIG. 1 is a cross-sectional view of an example of an organic EL display device.
• FIG. 1 is a cross-sectional view of an example of a display device.
• 1 is a schematic diagram illustrating a procedure for producing an organic EL display device.
• the photosensitive resin composition of the present invention contains an alkali-soluble resin (a), a phenolic compound (b) having a structure represented by formula (1), and a photosensitive compound (c).
• n is an integer from 2 to 4, and * represents a bond.
• the photosensitive resin composition of the present invention contains an alkali-soluble resin (a) (hereinafter, may be referred to as component (a)).
• alkali-soluble means that the dissolution rate calculated from the reduction in film thickness when a solution of a resin dissolved in ⁇ -butyrolactone is applied onto a silicon wafer and prebaked at 120° C. for 4 minutes to form a prebaked film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m, the prebaked film is immersed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 23 ⁇ 1° C. for 1 minute, and then rinsed with pure water is 50 nm/min or more.
• Component (a) is alkali-soluble and therefore has hydroxyl groups and/or acidic groups in the structural units of the resin and/or at the ends of its main chain.
• acidic groups include carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups.
• Component (a) may contain known resins such as polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, polymer of radical polymerizable monomer having an acidic group such as acrylic resin or polyhydroxystyrene resin, siloxane resin, cardo resin, phenolic resin, etc., but is not limited to these.
• Component (a) may contain two or more of these alkali-soluble resins.
• the (a) component has high development adhesion, excellent heat resistance, and a small amount of outgassing at high temperatures, and therefore has high long-term reliability when used in an organic EL display device. Therefore, the (a) component preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, and more preferably contains polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers thereof. Furthermore, from the viewpoint of further improving sensitivity, the (a) component preferably contains a polyimide precursor or a polybenzoxazole precursor.
• the (a) component preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polyamide.
• the polyimide precursor refers to a resin that can be converted into a polyimide by heat treatment or chemical treatment, such as polyamic acid or polyamic acid ester.
• the polybenzoxazole precursor refers to a resin that can be converted into polybenzoxazole by heat treatment or chemical treatment, such as polyhydroxyamide.
• the above-mentioned polyimide precursor, polybenzoxazole precursor and polyamide have a structural unit represented by the following formula (3), and the polyimide has a structural unit represented by the following formula (4).
• the component (a) may contain two or more types of each of a resin having a structural unit represented by formula (3) and a resin having a structural unit represented by formula (4), or may contain a resin in which the structural unit represented by formula (3) and the structural unit represented by formula (4) are copolymerized.
• X represents a divalent to octavalent organic group having 4 to 40 carbon atoms
• Y represents a divalent to eleven organic group having 6 to 40 carbon atoms
• R 11 and R 13 each independently represent a hydroxyl group or a sulfonic acid group
• R 12 and R 14 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• t, u, and w each represent an integer of 0 to 3
• v each represent an integer of 0 to 6.
• the structural unit represented by formula (3) represents a structural unit of a polyimide precursor, u ⁇ 2, and when the structural unit represented by formula (3) represents a structural unit of a polybenzoxazole precursor, v ⁇ 2, and at least two of the multiple R 13s are hydroxyl groups, and u ⁇ 2 and v ⁇ 2, and at least two of the multiple R 13s are hydroxyl groups, are considered to be polyimide precursors.
• Those having a structural unit represented by formula (3) that does not fall under the above polyimide precursors or polybenzoxazole precursors are considered to be polyamides.
• E represents a tetravalent to decavalent organic group having 4 to 40 carbon atoms
• G represents a divalent to octavalent organic group having 6 to 40 carbon atoms
• R 15 and R 16 each independently represent a carboxy group, a sulfonic acid group, or a hydroxyl group.
• x and y each independently represent an integer of 0 to 6, provided that x+y>0.
• the polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof preferably has 5 to 100,000 structural units represented by formula (3) or formula (4).
• other structural units may be included.
• the structural units represented by formula (3) or formula (4) account for 50 mol % or more of 100 mol % of all structural units.
• X(R 11 ) t (COOR 12 ) u represents an acid residue.
• X is a divalent to octavalent organic group having 4 to 40 carbon atoms, and is preferably a divalent to octavalent organic group containing an aromatic ring or a cyclic aliphatic group.
• the acid residue examples include residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid, residues of tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid, residues of pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'
• tetracarboxylic acid residues examples include tetracarboxylic acid residues such as aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butane tetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentane tetracarboxylic acid.
• the component (a) may have two or more of these residues as X(R 11 ) t (COOR 12 ) u in formula (3).
• R20 represents an oxygen atom, C( CF3 ) 2 or C( CH3 ) 2 .
• R21 and R22 each independently represent a hydrogen atom or a hydroxyl group.
• one or two carboxy groups correspond to (COOR 12 ) in formula (3).
• E(R 15 ) x represents a residue of an acid dianhydride.
• E is a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and is preferably an organic group containing an aromatic ring or a cyclic aliphatic group.
• residue of the acid dianhydride examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)me
• dianhydride examples include aromatic tetracarboxylic dianhydrides such as ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis ⁇ 4-(3,4-dicarboxyphenoxy)phenyl ⁇ fluorene dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides having the structures shown below, aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride, and residues of alipha
• R20 represents an oxygen atom, C( CF3 ) 2 or C( CH3 ) 2 .
• R21 and R22 each independently represent a hydrogen atom or a hydroxyl group.
• Y(R 13 ) v (COOR 14 ) w in the above formula (3) and G(R 16 ) y in the above formula (4) represent a diamine residue.
• Y is a di- to eleven-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to eleven-valent organic group containing an aromatic ring or a cyclic aliphatic group.
• G is a di- to octavalent organic group having 6 to 40 carbon atoms, and is preferably a di- to octavalent organic group containing an aromatic ring or a cyclic aliphatic group.
• diamine residue examples include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis ⁇ 4-(4-aminophenoxy)phenyl ⁇ ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-die
• the aromatic diamine may contain residues of aromatic diamines such as phenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings are substituted with alkyl groups or halogen atoms; residues of aliphatic diamines containing cyclic aliphatic groups such as cyclohexyldiamine and methylenebis
• R 20 represents an oxygen atom, C(CF 3 ) 2 or C(CH 3 ) 2.
• R 21 to R 24 each independently represent a hydrogen atom or a hydroxyl group.
• the ends of these resins may be blocked with a known monoamine, acid anhydride, acid chloride, monocarboxylic acid, or active ester compound having an acidic group.
• Component (a) may be synthesized by a known method.
• polymers of radically polymerizable monomers having an acidic group include acrylic resins and polyhydroxystyrene resins.
• Known materials can be used as radically polymerizable monomers having an acidic group, but examples include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, as well as their alkyl and alkoxy substituted derivatives, methacrylic acid, and acrylic acid, as well as their ⁇ -position haloalkyl, alkoxy, halogen, nitro, and cyano substituted derivatives.
• Cardo resins include resins that have a cardo structure, i.e., a skeletal structure in which two ring structures are bonded to a quaternary carbon atom that constitutes a ring structure.
• a typical cardo structure is one in which a fluorene ring is bonded to a benzene ring.
• Phenol resins include well-known novolak phenolic resins and resol phenolic resins obtained by polycondensing various phenols alone or a mixture of multiple phenols with aldehydes such as formalin.
• siloxane resins examples include known siloxane resins obtained by hydrolyzing and dehydrating condensation of one or more organosilanes selected from tetrafunctional organosilanes, trifunctional organosilanes, bifunctional organosilanes, and monofunctional organosilanes.
• the photosensitive resin composition of the present invention contains a phenol compound (b) (hereinafter, sometimes referred to as component (b)) having a structure represented by formula (1).
• n is an integer from 2 to 4, and * represents a bond.
• the photosensitive resin composition of the present invention contains component (b), which allows the composition to develop color when heated even in a low oxygen concentration of less than 5% during curing, and reduces the transmittance at a wavelength of 450 nm after curing.
• component (b) takes on a quinone structure when heated, generating a color-developing substance with absorption at 300 nm to 500 nm.
• component (b) has three or more phenolic hydroxyl groups in the same aromatic ring and is electron-rich, so it is likely to become a quinone structure when heated even in a low oxygen concentration of less than 5%, and can reduce the transmittance at 450 nm after curing.
• component (b) does not have absorption at 300 nm to 500 nm, so before curing, it does not block the exposure wavelength range of 350 nm to 450 nm of mercury lamps, which are commonly used as exposure light sources, and patterns can be formed with high sensitivity.
• a colorant (d) described below a film with high visible light blocking properties after curing can be obtained.
• n represents an integer of 2 to 4, and from the viewpoint of availability of raw materials, n is preferably 2 to 3, and more preferably 2.
• component (b) may have multiple structures represented by formula (1) in one molecule, and from the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, component (b) preferably has two or more structures represented by formula (1) in one molecule. There is no particular upper limit to the number of structures represented by (1) contained in one molecule, but 10 or less is preferable, and 5 or less is even more preferable.
• the (b) component contains a phenolic compound that satisfies the condition (b1) that at least one substitution position of the phenolic hydroxyl group other than any of the phenolic hydroxyl groups in formula (1) is para-position.
• a phenolic compound hereinafter sometimes referred to as the (b1) component
• the (b1) component has a phenolic hydroxyl group that is in a para-position relationship in the positional relationship of the phenolic hydroxyl groups in formula (1), and thus can assume a paraquinone structure by heating, thereby further increasing the color development of the (b1) component.
• the (b1) component preferably contains a phenolic compound having the structure represented by the following formula, and particularly preferably contains a phenolic compound having a structure represented by formula (b1a).
• the substituent bonded to the benzyl position may be an amino group which may have a substituent, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, an alkenyl ether group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, or a heteroaryl group which may have a substituent.
• the substituent bonded to the benzyl position is preferably an amino group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and more preferably an amino group which may have a substituent and an aryl group which may have a substituent.
• the substituent include a phenolic hydroxyl group, a sulfo group, a carboxy group, an alkoxy group, and a hydrocarbon group having 1 to 10 carbon atoms, and it is preferable that the component (b) has a phenolic hydroxyl group.
• examples of the component (b) in which the substituent bonded to the benzyl position in the partial structure represented by formula (1) is an aryl group which may have a substituent are given, but are not limited to these.
• Each n independently represents an integer of 2 to 4, and each R3 independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• L represents a single bond, an oxygen atom, C( CF3 ) 2 , C( CH3 ) 2 , SO2 or CO.
• M represents a nitrogen atom, CH or CCH3 .
• the (b) component in which the substituent bonded to the benzyl position has an aryl group that may have a substituent, preferably satisfies condition (b1) from the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing.
• the (b) component contains at least one phenolic compound selected from the group consisting of the following phenolic compounds:
• the (b) component contains a phenol compound that satisfies the condition (b2) in which the substituent bonded to the benzyl position in formula (1) is an amino group that may have a substituent.
• the (b) component (hereinafter sometimes referred to as the (b2) component) that satisfies the condition (b2), it is preferable that the (b) component contains a phenol compound having a structure specifically represented by formula (b2).
• n is an integer from 2 to 4, and * represents a bond.
• the phenolic compound having the structure represented by formula (b2) satisfies the condition (b1) that at least one substitution position of the phenolic hydroxyl group other than any of the phenolic hydroxyl groups in formula (b2) is para-position.
• component (b) has a structure represented by formula (b2)
• the mechanism is unclear, but it is thought that this is because the substituent bonded to the benzyl position in formula (1) is an amino group which may have a substituent, and electrons are donated from the amino group to the quinone structure generated by heating component (b), shifting the absorption band of the quinone structure to longer wavelengths.
• the substituent adjacent to the nitrogen atom can be an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and examples of the phenol compounds having the structure shown below, but are not limited to these.
• Each n independently represents an integer of 2 to 4, and each of R1 and R2 independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• L represents a single bond, an oxygen atom, C( CF3 ) 2 , C( CH3 ) 2 , SO2 or CO.
• M represents a nitrogen atom, CH or CCH3 .
• the substituent adjacent to the nitrogen atom in formula (b2) is at least one of an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
• component (b) contains a phenol compound that satisfies condition (b1) and condition (b2).
• component (b) preferably contains one or more selected from the group consisting of phenol compounds having a structure represented by any of the following formulas (b12a) to (b12d), and it is particularly preferable that component (b) contains a phenol compound having a structure represented by formula (b12a).
• the (b) component contains one or more selected from the group consisting of a phenolic compound having a structure represented by formula (b3) (hereinafter, may be referred to as the (b3) component), a phenolic compound having a structure represented by formula (b4) (hereinafter, may be referred to as the (b4) component), and a phenolic compound having a structure represented by formula (b5) (hereinafter, may be referred to as the (b5) component).
• n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ⁇ p+m ⁇ 4 is satisfied;
• X represents —NR 32 —, —O— or —S—;
• R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 34 and R 35 each independently represent —OR 36 , —SR 36 , —N(R 36 ) 2 , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R Each of 36 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atom
• component (b) contains component (b3) and/or component (b4), and it is more preferable that component (b3) is contained.
• the component (b3) preferably contains a phenol compound in which X satisfies —NR 32 —, —O—, in formula (b3), and more preferably contains a phenol compound in which X satisfies —O—.
• one or more selected from the group consisting of the component (b3), the component (b4), and the component (b5) have two structures satisfying the condition (b1) in the same molecule.
• Specific examples of the above include components (b3) to (b5) that contain at least two structures represented by any of the above formulas (b1a) to (b1d) in the same molecule, and it is particularly preferable that the components (b3) to (b5) contain at least two structures represented by formula (b1a) in the same molecule.
• n is independently an integer from 2 to 4.
• Me represents a methyl group.
• the (b3) component preferably contains one or more selected from the group consisting of phenol compounds having a structure represented by any one of formulas (b3a) to (b3f), and more preferably contains a phenol compound having a structure represented by formula (b3a).
• the upper limit of the molecular weight of the (b), (b1), (b2), (b3), (b4), and (b5) components is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.
• the lower limit of the molecular weight of the (b) component is 126 or more.
• Component (b) can be synthesized by a known method.
• One known method is, for example, reacting a compound substituted with a methylol group or an alkoxymethyl group with a polyhydric phenol compound selected from trihydroxybenzene, tetrahydroxybenzene, and pentahydroxybenzene under acidic conditions.
• trihydroxybenzenes examples include phloroglucinol, pyrogallol, and 1,2,4-trihydroxybenzene
• tetrahydroxybenzenes examples include 1,2,3,4-tetrahydroxybenzene and 1,2,3,5-tetrahydroxybenzene
• Component (b) that satisfies condition (b1) can be obtained by using 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, or pentahydroxybenzene as the polyhydric phenol compound.
• component (b) that satisfies condition (b2)
• component (b) that satisfies condition (b2)
• any of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as the polyhydric phenol compound it is possible to obtain component (b) that satisfies conditions (b1) and (b2).
• Compounds in which a methylol group is substituted on the nitrogen atom can be obtained, for example, by reacting a primary amino group- or secondary amino group-containing compound with formaldehyde under basic conditions, and further, compounds in which an alkoxymethyl group is substituted on the nitrogen atom can be obtained by reacting the compound with an alcohol under acidic conditions.
• component (b3) can be obtained, and by using a compound in which methylol groups are substituted on the 1-, 4-, 1-, and 2-positions of the benzene skeleton, components (b4) and (b5) can be obtained, respectively.
• components (b3) to (b5) in which a structure represented by any of formulas (b1a) to (b1d) has been introduced can be obtained.
• the content of component (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (a).
• the content of component (b) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, per 100 parts by mass of component (a).
• the photosensitive resin composition of the present invention further contains a photosensitive compound (c) (hereinafter, may be referred to as component (c)).
• a photosensitive compound (c) hereinafter, may be referred to as component (c)
• the content of the component (c) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the component (a).
• the content of the component (c) is preferably 100% by mass of the component (a). It is preferably 100 parts by weight or less per part.
• the component (c) may contain a photoacid generator (c1) or a photopolymerization initiator (c2).
• the photoacid generator (c1) is a compound that generates an acid when irradiated with light
• the photopolymerization initiator (c2) is a compound that undergoes bond cleavage and/or reaction when exposed to light, generating radicals.
• a photoacid generator (c1) By including a photoacid generator (c1), an acid is generated in the light-irradiated area, increasing the solubility of the light-irradiated area in an alkaline aqueous solution, and a positive relief pattern in which the light-irradiated area dissolves can be obtained.
• a photoacid generator (c1) and an epoxy compound or a thermal crosslinking agent described later the acid generated in the light-irradiated area promotes the crosslinking reaction of the epoxy compound or the thermal crosslinking agent, and a negative relief pattern in which the light-irradiated area is insolubilized can be obtained.
• the (c) component includes a photoacid generator (c1) that can obtain a positive relief pattern.
• the photoacid generator (c1) may contain, for example, a quinone diazide compound.
• the photosensitive resin composition of the present invention preferably contains two or more types of photoacid generator (c1). When two or more types are contained, a photosensitive resin composition with higher sensitivity can be obtained.
• Quinone diazide compounds can include those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, those in which the sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, and those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy polyamino compound via an ester bond and/or a sulfonamide bond.
• quinone diazide structure either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used.
• a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.
• 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp, making them suitable for i-line exposure.
• 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending into the g-line region of a mercury lamp, making them suitable for g-line exposure.
• the above quinone diazide compounds can be synthesized by any esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. By using these quinone diazide compounds, the resolution, sensitivity, and film remaining rate are further improved.
• the content of the photoacid generator (c1) is preferably 0.1 parts by mass or more per 100 parts by mass of the component (a), more preferably 10 parts by mass or more, and even more preferably 25 parts by mass or more.
• the content of the photoacid generator (c1) is preferably 100 parts by mass or less per 100 parts by mass of the component (a).
• the photopolymerization initiator (c2) may contain, for example, a benzyl ketal-based photopolymerization initiator, an ⁇ -hydroxyketone-based photopolymerization initiator, an ⁇ -aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, a titanocene-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic ketoester-based photopolymerization initiator, a benzoic acid ester-based photopolymerization initiator, or the like.
• a benzyl ketal-based photopolymerization initiator an ⁇ -hydroxyketone-based photopolymerization initiator, an ⁇ -aminoke
• the photosensitive resin composition of the present invention may contain two or more types of photopolymerization initiator (c2). From the viewpoint of further improving the sensitivity, it is more preferable that the photopolymerization initiator (c2) contains an ⁇ -aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, or an oxime ester-based photopolymerization initiator.
• ⁇ -Aminoketone photopolymerization initiators may contain, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole, etc.
• Acylphosphine oxide photopolymerization initiators may contain, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, etc.
• oxime ester photopolymerization initiators include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9 -ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-di
• the content of photopolymerization initiator (c2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (a) and the radical polymerizable compound described below.
• the content of photopolymerization initiator (c2) is preferably 50 parts by mass or less, per 100 parts by mass of component (a) and the radical polymerizable compound described below.
• the photosensitive resin composition of the present invention preferably further contains a colorant (d) (hereinafter, may be referred to as component (d)).
• a colorant (d) hereinafter, may be referred to as component (d)
• component (d) a film having high visible light shielding properties after curing can be obtained.
• the component (d) preferably contains a dye (d1) and/or a pigment (d2).
• the component (d) preferably contains at least one type, and for example, it is preferable to contain one type of dye (d1) or pigment (d2), or two or more types of dyes (d1) or pigments (d2), or one or more types of dyes (d1) and one or more types of pigments (d2).
• the (d) component contains a dye (d1).
• the dye (d1) is an ionic dye that forms an ion pair between organic ions.
• the dye contains a pigment (d2).
• component (d) has a sulfonic acid group and/or a sulfonate group.
• the (d) component preferably contains a colorant (d-1) (hereinafter sometimes referred to as the (d-1) component) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and/or a colorant (d-2) (hereinafter sometimes referred to as the (d-2) component) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.
• d-1 colorant having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm
• d-2 hereinafter sometimes referred to as the (d-2) component
• the (d-1) component preferably contains a dye (d1-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and/or a pigment (d2-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm.
• a dye (d1-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm
• a pigment (d2-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm.
• the (d-2) component preferably contains a dye (d1-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm, and/or a pigment (d2-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.
• the photosensitive resin composition of the present invention contains the (d-1) component and the (d-2) component
• they may be simply referred to as the (d1-1) component, the (d2-1) component, the (d1-2) component, and the (d2-2) component, respectively.
• the dye (d1) preferably contains a dye that is soluble in a solvent that dissolves the (a) component and is compatible with the resin, and has high heat resistance and light resistance, from the viewpoints of storage stability and fading during curing and exposure to light.
• the (d1-1) component has a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and can contain, for example, a red dye or a purple dye.
• the (d1-2) component has a maximum absorption wavelength in the range of 580 nm or more and 800 nm in the range of 300 to 800 nm, and can contain, for example, a blue dye or a green dye.
• the photosensitive resin composition of the present invention contains the (d1-1) component and the (d1-2) component
• the (d1-1) component or the (d1-2) component has a xanthene structure from the viewpoint of improving heat resistance
• the skeletal structure of dye (d1) may include, but is not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, xanthene-based, etc.
• anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based are preferred.
• xanthene-based are even more preferred.
• each of these dyes may be used alone or as a metal-containing complex salt system.
• the dye (d1) preferably contains an ionic dye (d1a) (hereinafter, sometimes referred to as the (d1a) component) that forms an ion pair of an organic anion part and an organic cation part.
• the (d1a) component refers to a salt-forming compound consisting of an organic anion part and a non-dye organic cation part, a salt-forming compound consisting of an organic cation part of a basic dye and a non-dye organic anion part, or a salt-forming compound consisting of an organic anion part of an acid dye and an organic cation part of a basic dye.
• the ionic dye of the present invention preferably contains a salt-forming compound consisting of an organic anion part of an acid dye and an organic cation part of a basic dye. That is, it is preferable that the (d) component contains an ionic dye that forms an ion pair of an organic anion part and an organic cation part, and the organic anion part and the organic cation part are respectively composed of an organic anion part of an acid dye and an organic cation part of a basic dye.
• a salt-forming compound consisting of an organic anion part of an acid dye and an organic cation part of a non-dye can be produced by using an acid dye as a raw material and exchanging the counter cation with a non-dye organic cation by a known method.
• a salt-forming compound consisting of an organic cation part of a basic dye and an organic anion part of a non-dye can be produced by using a basic dye as a raw material and exchanging the counter anion with a non-dye organic anion by a known method.
• a salt-forming compound consisting of an organic anion part of an acid dye and an organic cation part of a basic dye can be produced by using an acid dye and a basic dye as raw materials and exchanging the respective counter ions by a known method.
• the acid dyes that are the raw material for component (d1a) are compounds that have acidic substituents such as sulfo groups or carboxy groups in the dye molecule, or are anionic water-soluble dyes that are salts of these compounds. Acid dyes include those that have acidic substituents such as sulfo groups or carboxy groups and are classified as direct dyes.
• Acid dyes include, for example, C.I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; C.I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C.I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; C.I. C.I. Acid Brown 2, 4, 13, 248; C.I. Acid Violet 11, 56, 58; C.I.
• Azo acid dyes such as Acid Blue 92, 102, 113, 117; C.I. Quinoline acid dyes such as Acid Yellow 2, 3, 5; C.I. Xanthene acid dyes such as Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289; C.I. Acid Red 82, 92; C.I. Acid Violet 41, 42, 43; C.I. Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127:1, 129, 145, 167, 230; C.I. Anthraquinone acid dyes such as Acid Green 25, 27; C.I. Examples of acid dyes include triarylmethane acid dyes such as C.I. Acid Violet 49, C.I.
• the acid dye preferably contains a xanthene acid dye in terms of high heat resistance.
• the xanthene acid dye more preferably contains a rhodamine acid dye such as C.I. Acid Red 50, 52, and 289.
• R in the ionic formula is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent and may have a heteroatom in the carbon chain.
• the molecular weight of the non-dye organic cation part is preferably 1000 or less, preferably 700 or less, and more preferably 400 or less.
• the lower limit of the molecular weight of the non-dye organic cation part is not particularly limited, but is preferably 1 or more, and more preferably 100 or more.
• the basic dye which is the raw material for component (d1a), is a compound that has a basic group such as an amino group or an imino group in the molecule, or a salt thereof, and is a dye that becomes a cation in an aqueous solution.
• Basic dyes include, for example, azo-based basic dyes such as C.I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46:1, 82; C.I. Basic Orange 2, 24, 25; C.I. Basic Violet 18; C.I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C.I. Basic Brown 1; C.I. Basic Blue 41, 54, 64, 66, 67, 129; C.I. Basic Red 1, 2; C.I. Basic Violet 10, 11; xanthene-based basic dyes; C.I. Basic Yellow 11, 13, 21, 23, 28; C.I. Basic Orange 21; C.I. Basic Red 13, 14; C.I. Methine basic dyes such as C.I.
• Basic Violet 16 and 39 anthraquinone basic dyes such as C.I. Basic Blue 22, 35, 45 and 47; triarylmethane basic dyes such as C.I. Basic Violet 1, 2, 3, 4, 13, 14 and 23; C.I. Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24 and 26; and C.I. Basic Green 1 and 4, as well as xanthene basic dyes having the structures shown below.
• R 25 to R 31 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent.
• the basic dye preferably contains a xanthene basic dye or a triarylmethane basic dye because it can increase the blackness of the cured product, and preferably contains a xanthene acidic dye because of its high heat resistance.
• non-dye organic anion portion that is the raw material of the component (d1a) include aliphatic or aromatic sulfonate ions, aliphatic or aromatic carboxylate ions, sulfonimide anion [(RSO 2 ) 2 N] ⁇ , borate anion (BR 4 ) ⁇ , etc.
• the non-dye organic anion portion is preferably an aliphatic or aromatic sulfonate ion, or an aliphatic or aromatic carboxylate ion.
• the non-dye organic anion portion is preferably an aliphatic or aromatic sulfonate ion.
• R in the ionic formula of the non-dye organic anion portion is a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent and may have a heteroatom in the carbon chain.
• the molecular weight of the non-dye organic anion portion is preferably 1000 or less, more preferably 700 or less, and more preferably 400 or less.
• the lower limit of the molecular weight of the non-dye anion portion is not particularly limited, but is preferably 1 or more, and more preferably 100 or more.
• the organic anion portion and/or the organic cation portion of the (d1a) component have a xanthene skeleton.
• organic anions having a xanthene skeleton include the above-mentioned xanthene acid dyes
• organic cations having a xanthene skeleton include the above-mentioned xanthene basic dyes.
• the (d1a) component preferably has an acidic group from the viewpoint of increasing the alkali solubility during development and improving sensitivity.
• the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, and a sulfonate group, with the sulfonic acid group and the sulfonate group being particularly preferred.
• Salt-forming compounds by ion exchange of acid dyes and basic dyes can be produced by known methods. For example, an aqueous solution of an acid dye and an aqueous solution of a basic dye are prepared and slowly mixed with stirring, resulting in the formation of a salt-forming compound consisting of the organic anion part of the acid dye and the organic cation part of the basic dye as a precipitate.
• the salt-forming compound can be obtained by recovering this by filtration.
• the obtained salt-forming compound is preferably dried at about 60 to 70°C.
• the photosensitive resin composition of the present invention may contain two or more kinds of (d1a) components, but when the photosensitive resin composition of the present invention contains n kinds of (d1a) components, it is preferable that the organic ions contained in the photosensitive resin composition are (n+1) kinds.
• n represents an integer of 2 to 10.
• the organic ions contained in the photosensitive resin composition here refer not only to the organic ions constituting the ionic dye, but also to all the organic ions contained in the photosensitive resin composition.
• the organic ions contained in the photosensitive resin composition are (n ⁇ 2) kinds.
• the presence of multiple kinds of organic anions and organic cations in the photosensitive resin composition increases the amount of foreign matter during frozen storage due to ion exchange between the ionic dyes, and a problem occurs in which the storage stability deteriorates.
• the (d1a) components are contained in n kinds and the organic ions contained in the photosensitive resin composition are (n+1), the storage stability during frozen storage is improved. This is presumably because the organic ion species for component (d1a) are limited, suppressing ion exchange between ionic dyes in the photosensitive resin composition.
• the organic anion moieties or organic cation moieties of the n types of (d1a) components are all the same.
• n 3
• the organic anion moieties and organic cation moieties of the n types of (d1a) components are two or more types each that are the same.
• n 3
• n 3
• n 3
• n 3
• the pigment (d2) is preferably a pigment with high heat resistance and light resistance from the viewpoint of fading during curing and exposure to light.
• the (d2-1) component has a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and can contain, for example, a red pigment or a purple pigment.
• the (d2-2) component has a maximum absorption wavelength in the range of 580 nm or more and 800 nm in the range of 300 to 800 nm, and can contain, for example, a blue pigment or a green pigment.
• organic pigments are expressed by Color Index (C.I.) numbers.
• Examples of (d2-1) components include red pigments such as Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254, and purple pigments such as Pigment Violet 19, 23, 29, 32, 33, 36, 37, and 38.
• Examples of (d2-2) components include blue pigments such as Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 22, 60, and 64, and green pigments such as Pigment Green 7, 10, 36, 47, and 58. Pigments other than these can also be included.
• the organic pigment used as the pigment (d2) may contain a pigment that has been subjected to a surface treatment such as rosin treatment, acidic group treatment, or basic group treatment, as necessary.
• a surface treatment such as rosin treatment, acidic group treatment, or basic group treatment
• it may contain a dispersant together with the pigment, if necessary.
• the dispersant may contain, for example, a cationic, anionic, nonionic, amphoteric, silicone, or fluorine-based surfactant.
• the content of component (d) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of component (a).
• the content of component (d) 0.1 parts by mass or more per 100 parts by mass of component (a)
• the content 300 parts by mass or less it is possible to absorb light of the corresponding wavelength while maintaining the adhesive strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.
• the photosensitive resin composition of the present invention may also contain a colorant other than component (d).
• a colorant other than component (d) By including other colorants in addition to component (d), it is possible to impart light-shielding properties that block light of wavelengths absorbed by other colorants from light that passes through the film of the photosensitive resin composition or light that is reflected from the film of the photosensitive resin composition.
• By imparting light-shielding properties it is possible to prevent deterioration, malfunction, leakage current, etc. due to light penetration into TFTs when the cured product of the present invention described below is used as a planarizing layer and/or insulating layer of an organic EL display device. Furthermore, it is possible to suppress reflection of external light from wiring and TFTs, and improve the contrast between light-emitting areas and non-light-emitting areas.
• the photosensitive resin composition of the present invention may contain a radical polymerizable compound.
• a radical polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bonds in the molecule.
• radical polymerization of the radical polymerizable compound proceeds due to the radicals generated from the photopolymerization initiator (c2), and the light-irradiated portion is insolubilized, thereby obtaining a negative pattern.
• the photocuring of the light-irradiated portion is promoted, and the sensitivity can be further improved.
• the crosslinking density after thermal curing is improved, so that the hardness of the cured product can be improved.
• the radical polymerizable compound a compound having a (meth)acrylic group, which is easy to undergo radical polymerization, is preferable. From the viewpoint of improving sensitivity during exposure and improving the hardness of the cured product, a compound having two or more (meth)acrylic groups in the molecule is more preferable. From the viewpoint of improving sensitivity during exposure and improving the hardness of the cured product, the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g/mol.
• the content of the radical polymerizable compound is preferably 15 parts by mass or more, and more preferably 30 parts by mass or more, per 100 parts by mass of the total of component (a) and the radical polymerizable compound.
• the content is preferably 65 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the total of component (a) and the radical polymerizable compound.
• the resin composition of the present invention may contain a thermal crosslinking agent.
• the thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as known alkoxymethyl groups, methylol groups, epoxy groups, and oxetanyl groups.
• crosslinking can be performed between the thermal crosslinking agent and the alkali-soluble resin (a) or between the thermal crosslinking agents themselves, thereby improving the heat resistance, chemical resistance, and bending resistance of the cured product after thermal curing.
• the thermal crosslinking agent a compound having low reactivity with phenolic hydroxyl groups is preferred as the thermal crosslinking agent, and an alkoxymethyl group is preferred. This is presumably because when the phenolic hydroxyl group of the (b) component reacts with the thermal crosslinking agent, the crosslinked product is less likely to have a quinone structure.
• a thermal crosslinking agent When a thermal crosslinking agent is included, its content is preferably 1% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of the resin composition excluding the solvent. If the content of the thermal crosslinking agent is 1% by mass or more, the chemical resistance and bending resistance of the cured product can be further improved. Furthermore, if the content of the thermal crosslinking agent is 30% by mass or less, the amount of outgassing from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the resin composition is also excellent.
• the photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, it can be made into a varnish state, and the coatability can be improved.
• Solvents include polar aprotic solvents such as ⁇ -butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and propylene 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, trip
• the amount of solvent is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. Furthermore, the proportion of solvents with a boiling point of 180°C or higher in the total amount of 100 parts by mass of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of solvents with a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.
• the photosensitive resin composition of the present invention may contain an adhesion improver.
• the adhesion improver may contain a known silane coupling agent, a titanium chelating agent, an aluminum chelating agent, a compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound, and the like. Two or more of these may be contained.
• a base substrate such as a silicon wafer, indium tin oxide (ITO), SiO 2 , or silicon nitride can be improved.
• ITO indium tin oxide
• SiO 2 silicon nitride
• the content of the adhesion improver is preferably 0.01 to 10 parts by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.
• the photosensitive resin composition of the present invention may contain a surfactant to improve wettability with a substrate.
• the surfactant may include known silicon-based surfactants, fluorine-based surfactants, acrylic and/or methacrylic surfactants, etc.
• a surfactant When a surfactant is included, its content is preferably 0.001 to 1 part by mass per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.
• the photosensitive resin composition of the present invention may contain inorganic particles.
• preferred inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc.
• the primary particle size of the inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less.
• the content of inorganic particles is preferably 5 to 90 parts by mass per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.
• the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is preferably 150 ppm by mass or less, more preferably 100 ppm by mass or less, relative to the total mass of solids excluding the solvent in the photosensitive resin composition, and further preferably less than 2 ppm by mass, which is the lower detection limit of combustion ion chromatography.
• the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition 150 mass ppm or less relative to the solid content of the photosensitive resin composition it is possible to suppress deterioration of the electrodes and light-emitting layers of an organic EL display device having a cured product obtained by curing the photosensitive resin composition, and to improve long-term reliability.
• the storage stability of the photosensitive resin composition of the present invention during freezing can be improved.
• the total mass of all chlorine atoms and all bromine atoms contained in a photosensitive resin composition can be measured, for example, by combustion ion chromatography using the photosensitive resin composition.
• the photosensitive resin composition of the present invention can be obtained by dissolving the components (a), (b) and (c), and, if necessary, the component (d), a radical polymerizable compound, a thermal crosslinking agent, a solvent, an adhesion improver, a surfactant, inorganic particles, etc.
• Methods for dissolving 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.
• There are no particular restrictions on the order in which the components are dissolved and an example is a method in which compounds with low solubility are dissolved in order.
• components that are prone to generating bubbles when dissolved by stirring such as surfactants and some adhesion improvers, they can be added last after the other components have been dissolved, thereby preventing poor dissolution of the other components due to the generation of bubbles.
• the obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles.
• filter pore sizes include, but are not limited to, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.07 ⁇ m, 0.05 ⁇ m, and 0.02 ⁇ m.
• Filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Of these, polyethylene and nylon are preferred.
• the method for producing a cured product of the present invention includes the steps of forming a resin film composed of the photosensitive resin composition of the present invention on a substrate, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film.
• the 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 the coating film.
• the substrate may be a known substrate such as a glass substrate.
• Methods for applying the photosensitive resin composition of the present invention include, for example, spin coating, slit coating, dip coating, spray coating, and printing.
• the slit coating method is preferred because it can be applied with a small amount of coating liquid and is advantageous in reducing costs.
• the amount of coating liquid required for the slit coating method is, for example, about 1/5 to 1/10 compared to the spin coating method.
• the slit nozzle used for application for example, those available from multiple manufacturers can be selected, such as the "Linear Coater" manufactured by Dainippon Screen Mfg.
• the application speed is generally in the range of 10 mm/s to 400 mm/s.
• the thickness of the coating film varies depending on the solids concentration and viscosity of the photosensitive resin composition, but it is usually applied so that the film thickness after drying is 0.1 to 10 ⁇ m, preferably 0.3 to 5 ⁇ m.
• the substrate to which the photosensitive resin composition is to be applied may be pretreated with the adhesion improver described above.
• Pretreatment methods include, for example, treating the substrate surface with a solution in which 0.5 to 20 mass % of the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate.
• Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.
• the reduced pressure drying speed depends on the vacuum chamber volume, the vacuum pump capacity, the diameter of the pipe between the chamber and the pump, etc., but it is preferable to set the condition such that, for example, the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate.
• a typical reduced pressure drying time is often about 30 to 100 seconds, and the ultimate pressure inside the vacuum chamber at the end of the reduced pressure drying is usually 100 Pa or less with a coated substrate present.
• the coating film After coating or drying under reduced pressure, the coating film is generally heated and dried. This process is also called pre-baking.
• a hot plate, oven, infrared rays, etc. are used for drying.
• the coating film When using a hot plate, the coating film is heated directly on the plate, or while held on a jig such as a proxy pin placed on the plate.
• the heating time is preferably from one minute to several hours.
• the heating temperature varies depending on the type and purpose of the coating film, but from the viewpoint of promoting solvent drying during pre-baking, 80°C or higher is preferable, and 90°C or higher is even more preferable. On the other hand, from the viewpoint of reducing the progress of curing during pre-baking, 150°C or lower is preferable, and 140°C or lower is even more preferable.
• the resin film of the present invention can be patterned.
• a desired pattern can be formed by exposing the resin film to actinic radiation through a photomask having a desired pattern, and then developing the resin film.
• the actinic rays used for exposure include ultraviolet light, visible light, electron beams, and X-rays.
• i-rays 365 nm
• h-rays 405 nm
• g-rays 436 nm
• the exposed portion is removed with a developer in the case of a positive type, and the unexposed portion is removed with a developer in the case of a negative type, to form a desired pattern.
• a developer an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine is preferable.
• an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine,
• polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, or dimethylacrylamide
• alcohols such as methanol, ethanol, or isopropanol
• esters such as ethyl lactate or propylene glycol monomethyl ether acetate
• ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone
• the developing method may be spray, paddle, immersion, ultrasonic, or the like.
• Alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may also be added to distilled water for rinsing.
• the heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgas generated from the cured product.
• the heat treatment time is preferably 30 minutes or more, from the viewpoint of further reducing the amount of outgas.
• the atmosphere during the heat treatment is preferably a low oxygen concentration of less than 5% in order to prevent the electrodes from being contaminated by outgassing components during heat curing, which deteriorates the current-voltage characteristics.
• the driving voltage of the organic EL display device can be further reduced, and the luminous efficiency and durability can be further improved.
• Specific examples of inert gases for making the oxygen concentration less than 5% include nitrogen and argon.
• the oxygen concentration in the inert gas atmosphere is preferably less than 5%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably less than 0.01%.
• the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.
• a heat treatment By subjecting the photosensitive resin composition of the present invention to a heat treatment, components with low heat resistance can be removed, so that the heat resistance and chemical resistance can be further improved.
• the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer thereof and a polyimide, an imide ring or an oxazole ring is formed by the heat treatment, so that the heat resistance and chemical resistance can be further improved.
• the photosensitive resin composition of the present invention contains component (b), which can reduce the ultraviolet light transmittance of the cured product. Furthermore, by using components (b) and (d) in combination in the present invention, the visible light transmittance of the cured product can be reduced, and a black cured product can be obtained.
• the heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgas generated from the cured product.
• it is preferably 500°C or lower, and more preferably 450°C or lower.
• the temperature may be raised stepwise or continuously.
• the heat treatment time is preferably 30 minutes or more, from the viewpoint of further reducing the amount of outgas. Also, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or less. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours can be mentioned.
• the photosensitive resin composition and cured product of the present invention are preferably used as a surface protection layer or interlayer insulating layer of a semiconductor element, an insulating layer of an organic electroluminescence (EL) element, a planarizing layer of a thin film transistor (TFT) substrate for driving a display device using an organic EL element, a wiring protection insulating layer of a circuit board, an on-chip microlens of a solid-state imaging element, and a planarizing layer for various displays and solid-state imaging elements.
• EL organic electroluminescence
• TFT thin film transistor
• insulating layer may also be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as an LCD, an ECD, an ELD, or a display device using an organic electroluminescent element (organic electroluminescent device).
• a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as an LCD, an ECD, an ELD, or a display device using an organic electroluminescent element (organic electroluminescent device).
• the organic EL display device of the present invention is an organic EL display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer and a second electrode on a substrate, and the planarizing layer and/or the insulating layer
• the layer comprises the cured product of the present invention.
• the planarization layer and/or insulating layer comprises the cured product of the present invention
• the transmittance at a wavelength of 450 nm is preferably less than 30%, more preferably less than 20%, and even more preferably less than 10%.
• the lower limit of the transmittance at a wavelength of 450 nm is not particularly limited, but is 0.01% or more.
• the OD value (optical density) in visible light per 1 ⁇ m of film thickness of the planarization layer and/or insulating layer is preferably 0.5 to 1.5.
• the cured product can improve the light blocking property, so that in a display device such as an organic EL display device or a liquid crystal display device, the reflection of external light can be further reduced and the contrast in image display can be improved.
• the OD value is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more.
• the OD value is 1.5 or less, the sensitivity during exposure can be improved when the photosensitive resin composition containing the photosensitive compound is used. From the viewpoint of high sensitivity, the OD value is 1.5 or less, more preferably 1.0 or less.
• the thickness of the insulating layer is preferably 1.0 to 5.0 ⁇ m, more preferably 1.5 ⁇ m or more, and even more preferably 2.0 ⁇ m or more.
• an active matrix display device it has TFTs and wiring located on the sides of the TFTs and connected to the TFTs on a substrate such as glass or various plastics, a planarization layer is formed on the planarization layer so as to cover the unevenness, and a display element is further provided on the planarization layer.
• the display element and wiring are connected via contact holes formed in the planarization layer.
• the substrate having the above-mentioned driving circuit is an organic EL display device containing a resin film.
• the cured product obtained by curing the photosensitive resin composition of the present invention is used as an insulating layer or planarization layer of such a flexible display device, it is particularly preferably used because it has excellent bending resistance.
• polyimide is particularly preferable as the resin film.
• the organic EL display device further includes a color filter having a black matrix.
• the black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a siloxane resin.
• the black matrix contains a colorant.
• the colorant may be, for example, a black organic pigment, a mixed-color organic pigment, or an inorganic pigment.
• the black organic pigment may be, for example, carbon black, perylene black, aniline black, or a benzofuranone-based pigment.
• the mixed-color organic pigment may be, for example, a mixture of two or more pigments, such as red, blue, green, purple, yellow, magenta, and/or cyan, to produce a pseudo-black color.
• the black inorganic pigment may be, for example, graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides.
• metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver
• metal oxides such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver
• metal oxides such as titanium composite oxides
• metal sulfides such as titanium nitrides
• metal oxynitrides such as silver
• the OD value of the black matrix is preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 4.5 or more.
• FIG. 1 shows a cross-sectional view of an example of an organic EL display device.
• Bottom-gate or top-gate TFTs (thin film transistors) 1 are arranged in a matrix on a substrate 6, and a TFT insulating layer 3 is formed to cover the TFTs 1.
• Wiring 2 connected to the TFTs 1 is also provided on the TFT insulating layer 3.
• a planarization layer 4 is further provided on the TFT insulating layer 3 in a state in which the wiring 2 is embedded.
• a contact hole 7 is provided in the planarization layer 4 to reach the wiring 2.
• An ITO (transparent electrode) 5 is formed on the planarization layer 4 in a state in which it is connected to the wiring 2 through the contact hole 7.
• the ITO 5 becomes an electrode of a display element (e.g., an organic EL element).
• An insulating layer 8 is formed to cover the periphery of the ITO 5.
• the organic EL element may be a top-emission type that emits emitted light from the side opposite the substrate 6, or a bottom-emission type that extracts light from the substrate 6 side. In this way, an active matrix organic EL display device is obtained in which a TFT 1 for driving each organic EL element is connected to the organic EL element.
• the TFT insulating layer 3, the planarizing layer 4 and/or the insulating layer 8 can be formed by the steps of forming a resin film made of the photosensitive resin composition of the present invention, exposing the resin film to light, developing the exposed resin film and heat treating the developed resin film, as described above.
• An organic EL display device can be obtained by a manufacturing method having these steps.
• a display device other than the organic EL display device of the present invention is a display device having at least metal wiring, the cured product of the present invention, and a plurality of light-emitting elements, wherein the light-emitting elements have a pair of electrode terminals on either one surface, the pair of electrode terminals are connected to a plurality of the metal wirings extending into the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.
• the display device 9 has a plurality of light-emitting elements 10 arranged on a counter substrate 15, and a cured product 11 arranged on the light-emitting elements 10.
• the term "on the light-emitting elements" may refer not only to the surface of the light-emitting elements, but also to the upper side of the support substrate or the light-emitting elements.
• a configuration in which a plurality of cured products 11 are further laminated on the cured product 11 arranged so as to contact at least a part of the light-emitting elements 10, totaling three layers, is illustrated, but the cured product 11 may be a single layer.
• the light-emitting element 10 has a pair of electrode terminals 14 on the surface opposite to the surface in contact with the counter substrate 13, and each electrode terminal 14 is connected to a metal wiring 12 extending in the cured product 11. Note that if the plurality of metal wirings 12 extending in the cured product 11 are covered by the cured product 11, the cured product 11 also functions as an insulating layer, so that the configuration maintains electrical insulation.
• the term "metal wiring maintains electrical insulation” means that the part of the metal wiring that requires electrical insulation is covered by a cured product obtained by curing a photosensitive resin composition containing an alkali-soluble resin (a).
• the insulating layer being electrically insulating means that the insulating layer has a volume resistivity of 10 12 ⁇ cm or more.
• the light emitting element 10 is electrically connected to a driving element 16 attached to a light emitting element driving substrate 15 provided at a position facing the counter substrate 13 through metal wiring 12 and 12c, so that the light emission of the light emitting element 10 can be controlled.
• the light emitting element driving substrate 15 is electrically connected to the metal wiring 12 through, for example, solder bumps 18.
• a barrier metal 17 may be provided to prevent diffusion of metal such as the metal wiring 12.
• the cured product 11 is preferably black and has an OD value of 0.5 to 1.5 in visible light per 1 ⁇ m of insulating layer thickness.
• the cured product can improve the light blocking properties, thereby making it possible to further reduce the visualization of electrode wiring and external light reflection in displays such as organic EL displays or liquid crystal displays, thereby improving the contrast in image display.
• the sensitivity during exposure can be improved when the photosensitive resin composition contains a photosensitive compound.
• the phenol compound of the present invention is a phenol compound having a structure represented by formula (b2).
• n is an integer from 2 to 4, and * represents a bond.
• the transmittance of a cured product of the photosensitive resin composition at wavelengths of 450 nm and 500 nm can be reduced. It is more preferable that the phenol compound having the structure represented by the formula (b2) satisfies the condition (b1) that the substitution position of at least one phenolic hydroxyl group other than any one of the phenolic hydroxyl groups in the formula (b2) is the para position.
• the upper limit of the molecular weight of the phenol compound having the structure represented by formula (b2) is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and more preferably 600 or less.
• the lower limit of the molecular weight of the phenol compound having the structure represented by formula (b2) is 126 or more.
• the phenolic compound of the present invention is a phenolic compound containing one or more selected from the group consisting of structures represented by the components (b3), (b4), and (b5).
• n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ⁇ p+m ⁇ 4 is satisfied;
• X represents —NR 32 —, —O— or —S—;
• R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R 34 and R 35 each independently represent —OR 36 , —SR 36 , —N(R 36 ) 2 , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
• R Each of 36 independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atom
• the transmittance of the photosensitive resin composition at a wavelength of 550 nm after curing can be further reduced.
• component (b3) and/or component (b4) are preferable to incorporate in the photosensitive resin composition, and it is more preferable to incorporate component (b3) in the photosensitive resin composition.
• the (b3), (b4) and (b5) components satisfy the condition (b1) that at least one substitution position of the phenolic hydroxyl group other than the phenolic hydroxyl group represented by formula (b3), formula (b4) or formula (b5) is para-position.
• the phenolic compound of the present invention is a phenolic compound having a structure represented by any of the following formulas:
• the transmittance of the cured product of the photosensitive resin composition at a wavelength of 450 nm can be further reduced.
• a film of the cured product (hereinafter, sometimes referred to as a cured film).
• the film thickness of the cured film was measured using a stylus profiler (P-15; manufactured by KLA Tencor Co., Ltd.).
• the transmission spectrum at wavelengths of 300 nm to 800 nm was measured using an ultraviolet-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at wavelengths of 450 nm (hereinafter referred to as T% 450 ) and 500 nm (hereinafter referred to as T% 500 ) in a film thickness of 2.0 ⁇ m after curing were determined.
• T% 450 and T% 500 at a film thickness of 2.0 ⁇ m after curing were less than 15%, the film was rated as "S”.
• T% 450 was less than 15% and T% 500 was 15% or more and less than 25%
• the film was rated as "A”.
• T% 450 was less than 15% and T% 500 was 25% or more and less than 35%, or when T% 450 was 15% or more and less than 20% and T% 500 was less than 35%, the film was rated as "B".
• T% 450 was 20% or more regardless of T% 500 , or when T% 500 was 35% or more regardless of T% 450 , the film was rated as "C”.
• T% 550 at a film thickness of 2.0 ⁇ m after curing was less than 5%, it was judged as “S”, when T% 550 was 5% or more and less than 20%, it was judged as “A”, when T% 550 was 20% or more and less than 35%, it was judged as "B”, and when T% 550 was 35% or more, it was judged as "C”.
• OD/ ⁇ m is 0.70 or more and T% 450 is less than 10%, it is rated as "S”; If OD/ ⁇ m is 0.70 or more and T% 450 is 10% or more but less than 20%, it is rated as "A”; If OD/ ⁇ m is 0.70 or more and T% 450 is 20% or more but less than 30%, it is rated as “B”; If OD/ ⁇ m is less than 0.70 and 0.50 or more and T% 450 is less than 10%, it is rated as "A”; If OD/ ⁇ m is less than 0.70 and 0.50 or more, and T% 450 is 10% or more and less than 20%, it is rated as "B”; If OD/ ⁇ m is less than 0.70 and 0.50 or more, and T% 450 is 20% or more and less than 30%, it is rated as "C”; When T% 450 was 30% or more regardless of OD/ ⁇ m, and when OD/ ⁇ m was less than 0.50 regardless of T% 450 , it was judged as
• FIG. 3 shows a schematic diagram of the procedure for producing an organic EL display device using the photosensitive resin composition obtained in each Example and Comparative Example.
• a 10 nm ITO transparent conductive film was formed on the entire surface of a 38 mm x 46 mm alkali-free glass substrate 19 by sputtering, and etched as a first electrode (transparent electrode) 20.
• an auxiliary electrode 21 for extracting a 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 composition obtained in each Example and Comparative Example was applied to the entire surface of the substrate by spin coating, and prebaked on a hot plate at 120 ° C. for 2 minutes.
• This film was exposed to light through a photomask with a high-pressure mercury lamp as a light source at the minimum exposure amount of each photosensitive resin composition, and then developed with a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution, unnecessary parts were dissolved, and rinsed with pure water.
• TMAH tetramethylammonium hydroxide
• an insulating layer 22 was formed in a limited area of the substrate, in which openings of 70 ⁇ m in width and 260 ⁇ m in length were arranged at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction, and each opening had a shape that exposed the first electrode.
• an insulating layer with an insulating layer aperture ratio of 25% was formed in the substrate effective area, which was a rectangle with one side of 16 mm.
• the thickness of the insulating layer was about 1.5 ⁇ m.
• an organic EL layer 23 including a light-emitting layer was formed by a vacuum deposition method.
• the degree of vacuum during deposition was 1 ⁇ 10 ⁇ 3 Pa or less, and the substrate was rotated relative to the deposition source during deposition.
• compound (HT-1) was deposited to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was deposited to a thickness of 50 nm as a hole transport layer.
• compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited to a thickness of 40 nm on the light-emitting layer 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 as electron transport materials.
• the structures of the compounds used in the organic EL layer are shown below.
• a compound (LiQ) was evaporated to a thickness of 2 nm, and then Mg and Ag were evaporated to a thickness of 10 nm in a volume ratio of 10:1 to form a second electrode (non-transparent electrode) 24.
• a cap-shaped glass plate was attached to the substrate in a low-humidity nitrogen atmosphere using an epoxy resin adhesive to seal the substrate, and four top-emission organic EL display devices were fabricated on one substrate, each of which was a rectangle with sides of 5 mm. Note that the film thickness referred to here is the value displayed on a quartz crystal oscillation film thickness monitor.
• the organic EL display device fabricated by the above method was driven with a direct current of 10 mA/ cm2 , and the driving voltage at that time was measured.
• the driving voltage of four organic EL display devices fabricated on one substrate was less than 4.0 V, it was judged as "A”, when it was 4.0 V or more and less than 4.2 V, it was judged as "B”, and when it was 4.2 V or more, 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 dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to ⁇ 15° C. A solution in which 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride was dissolved in 100 mL of acetone was added dropwise to the solution. After the dropwise addition, the mixture was reacted at ⁇ 15° C. for 4 hours, and then returned to room temperature. The precipitated white solid was filtered and dried in vacuum at 50° C.
• BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
• Synthesis Example 3 Synthesis of alkali-soluble resin (a-1) Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methylpyrrolidone (hereinafter referred to as NMP).
• ODPA 3,3',4,4'-diphenylethertetracarboxylic dianhydride
• NMP N-methylpyrrolidone
• Synthesis Example 4 Synthesis of Alkali-Soluble Resin (a-2) Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, and 2.18 g (0.02 mol) of MAP as a terminal blocking agent were dissolved in 150 g of NMP. 31.0 g (0.10 mol) of ODPA was added thereto together with 50 g of NMP, and the mixture was stirred at 60° C. for 1 hour, and then stirred at 180° C. for 5 hours. After the stirring was completed, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyimide (a-2), which is an alkali-soluble resin.
• Synthesis Example 5 Synthesis of Alkali-Soluble Resin (a-3) Under a dry nitrogen stream, 31.1 g (0.085 mol) of BAHF and 2.18 g (0.02 mol) of MAP were dissolved in 150 g of NMP and 52.8 g (0.6 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to -15°C. A solution in which 29.5 g (0.10 mol) of diphenyl ether dicarbonate dichloride (manufactured by Nippon Nohyaku Co., Ltd.) was dissolved in 50 g of NMP was added dropwise so that the internal temperature did not exceed 0°C.
• diphenyl ether dicarbonate dichloride manufactured by Nippon Nohyaku Co., Ltd.
• Synthesis Example 6 Synthesis of Alkali-Soluble Resin (a-4) Under a dry nitrogen stream, 8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 220 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). Next, 15 g of methacrylic acid, 25 g of glycidyl methacrylate, 10 g of p-isopropenylphenol, 25 g of methyl methacrylate, 5 g of lauryl methacrylate, and 20 g of N-(cyclohexyl)maleimide were added and stirred at 70 ° C. for 5 hours. After stirring, PGMEA was added to the resin solution until the solid content concentration became 30 mass%, and a 30 mass% solution of acrylic resin (a-4), which is an alkali-soluble resin, was obtained.
• PGMEA propylene glycol monomethyl ether acetate
• Synthesis Example 7 Synthesis of phenol compound (b1-1) Under a dry nitrogen stream, 1.68 g (0.01 mol) of 2,6-bis(hydroxymethyl)-p-cresol (hereinafter referred to as 26DPMC), 12.61 g (0.10 mol) of 1,2,4-trihydroxybenzene (hereinafter referred to as 124THB), and 0.29 g of p-toluenesulfonic acid monohydrate were dissolved in 40 g of water at room temperature and reacted for 4 hours at 65° C. Thereafter, the solid precipitated by cooling in an ice bath was collected by filtration, washed three times with water, and then dried for 24 hours in a vacuum dryer at 50° C. to obtain a phenol compound (b1-1) that satisfies the condition (b1).
• 26DPMC 2,6-bis(hydroxymethyl)-p-cresol
• 124THB 1,2,4-trihydroxybenzene
• p-toluenesulfonic acid monohydrate
• Synthesis Example 8 Synthesis of phenol compound (b1-2) A phenol compound (b1-2) satisfying the condition (b1) was obtained in the same manner as in Synthesis Example 7, except that 1.68 g (0.01 mol) of 26DPMC was replaced with 2.88 g (0.01 mol) of 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol).
• Synthesis Example 9 Synthesis of phenol compound (b12-1) Under a dry nitrogen stream, 16.72 g (0.10 mol) of carbazole and 12.99 g (0.16 mol) of a 37% aqueous formaldehyde solution were dissolved in 120 g of tetrahydrofuran at room temperature, 0.5 g of a 50% aqueous sodium hydroxide solution was added, and the mixture was allowed to react at room temperature for 8 hours. Thereafter, the solution was poured into 1 L of water to obtain a yellowish white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 40° C. for 24 hours to obtain an N-methylolated carbazole.
• a phenol compound (b12-1) satisfying conditions (b1) and (b2) was obtained in the same manner as in Synthesis Example 7, except that 1.68 g (0.01 mol) of 26DPMC was used to obtain 3.94 g (0.02 mol) of the N-methylol derivative of the obtained carbazole.
• Synthesis Example 10 Synthesis of phenol compound (b12-2) A phenol compound (b12-2) satisfying the conditions (b1) and (b2) was obtained in the same manner as in Synthesis Example 7, except that 4.56 g (0.01 mol) of a dimethylol derivative of bisindolefluorene synthesized with reference to JP-A-2004-145320 was used instead of 1.68 g (0.01 mol) of 26DPMC.
• Synthesis Example 11 Synthesis of phenol compound (b13-1) Under a dry nitrogen stream, 27.64 g (0.20 mol) of potassium carbonate was dissolved in 63 g of water, and nitrogen bubbling was performed for 30 minutes. Subsequently, 8.11 g (0.1 mol) of 1-methylpyrrole and 17.86 g (0.22 mol) of a 37% aqueous formaldehyde solution were added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 7 days. Thereafter, the solution was filtered, and the resulting solid was dissolved in acetone, and anhydrous sodium sulfate was added for dehydration, followed by concentration with a rotary evaporator and drying with a vacuum dryer at 50° C. for 24 hours to obtain a 2,5-dimethylol derivative of 1-methylpyrrole.
• Synthesis Example 12 Synthesis of phenol compound (b13-2) A phenol compound (b13-2) having a structure represented by formula (b3) was obtained in the same manner as in Synthesis Example 7, except that 1.68 g (0.01 mol) of 26DPMC was replaced with 1.28 g (0.01 mol) of 2,5-bis(hydroxymethyl)furan.
• Synthesis Example 13 Synthesis of phenol compound (b12-3) A tetramethylol derivative of 4,4'-diaminodiphenylsulfone was obtained in the same manner as in Synthesis Example 9, except that 16.72 g (0.10 mol) of carbazole was replaced with 24.83 g (0.10 mol) of 4,4'-diaminodiphenylsulfone and 38.97 g (0.48 mol) of a 37% aqueous formaldehyde solution.
• a phenolic compound (b12-3) that satisfies conditions (b1) and (b2) was obtained in the same manner as in Synthesis Example 7, except that 1.68 g (0.01 mol) of 26DPMC was used as 1.84 g (0.005 mol) of the tetramethylol derivative of the obtained 4,4'-diaminodiphenyl sulfone.
• Example 1 10.0 g of polyimide precursor (a-1), 2.0 g of phenolic compound (b1-1), and 2.0 g of photosensitive compound (c-1) were dissolved in a mixture of 10 g of GBL, 20 g of EL, and 70 g of PGME, and then filtered through a 0.2 ⁇ m polytetrafluoroethylene filter to obtain a positive-type photosensitive resin composition AA.
• the obtained varnish was used to evaluate the light shielding properties at 450 nm and 500 nm, chemical resistance, and current-voltage characteristics of an organic EL display device as described above. For each evaluation, a cured film cured under a nitrogen atmosphere with an oxygen concentration of about 1% was used.
• Example 2 to 16 Comparative Examples 1 to 5 and 7
• a varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 1, except that the components (a), (b), and (c), other components, and the solvent were changed as shown in Tables 1 to 3.
• the obtained varnish was used to evaluate the light shielding properties at 450 nm and 500 nm, the chemical resistance, and the current-voltage characteristics of an organic EL display device as described above. For each evaluation, a cured film cured in a nitrogen atmosphere with an oxygen concentration of about 1% was used.
• Comparative Example 6 The varnish obtained in Comparative Example 5 was used to evaluate the light shielding properties at 450 nm and 500 nm, the chemical resistance, and the current-voltage characteristics of an organic EL display device as described above. For each evaluation, a cured film cured in an air atmosphere was used.
• Examples 17 to 22 The light-shielding ability of 550 nm was evaluated as described above using the positive-type photosensitive resin compositions AD to AI obtained in Examples 4 to 9. For each evaluation, a cured film cured in a nitrogen atmosphere with an oxygen concentration of about 1% was used.
• Example 23 10.0 g of polyimide precursor (a-1), 4.0 g of phenol compound (b12-1), 2.0 g of photosensitive compound (c-1), 1.0 g of colorant (d1-1-1), 0.8 g of colorant (d1-2-1), and 2.0 g of crosslinking agent (e-1) were dissolved in a mixture of 10 g of GBL, 20 g of EL, and 70 g of PGME, and then filtered through a 0.2 ⁇ m polytetrafluoroethylene filter to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the visible light shielding property, chemical resistance, and current-voltage characteristics of an organic EL display device as described above. For each evaluation, a cured film cured under a nitrogen atmosphere with an oxygen concentration of about 1% was used.
• Example 24 to 27, Comparative Examples 8 and 9 A varnish of a positive photosensitive resin composition was obtained in the same manner as in Example 23, except that the components (a), (b), (c), (d), other components, and the solvent were changed as shown in Table 5. The varnish obtained was used to evaluate the visible light shielding property, chemical resistance, and current-voltage characteristics of an organic EL display device as described above. For each evaluation, a cured film cured in a nitrogen atmosphere with an oxygen concentration of about 1% was used.
• compositions and evaluation results for each example and comparative example are shown in Tables 1 to 5.
• TFT thin film transistor
• Wiring 3 TFT insulating layer 4: Planarizing layer 5: ITO (transparent electrode) 6: Substrate 7: Contact hole 8: Insulating layer 9: Display device 10: Light-emitting element 11: Cured product 12, 12c: Metal wiring 13: Counter substrate 14: Electrode terminal 15: Light-emitting element driving substrate 16: Driving element 17: Barrier metal 18: Solder bump 19: Non-alkali glass substrate 20: First electrode (transparent electrode) 21: auxiliary electrode 22: insulating layer 23: organic EL layer 24: second electrode (non-transparent electrode)

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