WO2015163174A1 - 発光素子 - Google Patents
発光素子 Download PDFInfo
- Publication number
- WO2015163174A1 WO2015163174A1 PCT/JP2015/061318 JP2015061318W WO2015163174A1 WO 2015163174 A1 WO2015163174 A1 WO 2015163174A1 JP 2015061318 W JP2015061318 W JP 2015061318W WO 2015163174 A1 WO2015163174 A1 WO 2015163174A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- atom
- ring
- formula
- substituent
- Prior art date
Links
- 0 Cc1c(*)c(*)c(C)nc1* Chemical compound Cc1c(*)c(*)c(C)nc1* 0.000 description 9
- DZBDKXPDKPFTRE-UHFFFAOYSA-N CCCCCCCCC(C(C=C)=C)(C(C=C)=C)c1cc(C(C)(C)C)ccc1 Chemical compound CCCCCCCCC(C(C=C)=C)(C(C=C)=C)c1cc(C(C)(C)C)ccc1 DZBDKXPDKPFTRE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
-
- 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
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- 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
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/135—Cross-linked structures
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/141—Side-chains having aliphatic units
- C08G2261/1412—Saturated aliphatic units
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
- C08G2261/3162—Arylamines
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
- C08G2261/374—Metal complexes of Os, Ir, Pt, Ru, Rh, Pd
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/52—Luminescence
- C08G2261/524—Luminescence phosphorescent
- C08G2261/5242—Luminescence phosphorescent electrophosphorescent
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/76—Post-treatment crosslinking
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
Definitions
- an object of the present invention is to provide a light emitting device having excellent external quantum efficiency.
- the polymer compound may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, or other embodiments.
- the terminal group of the polymer compound is preferably a stable group because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics or the luminance life may be lowered when the polymer compound is used for the production of a light emitting device. It is.
- the terminal group is preferably a group that is conjugated to the main chain, and examples thereof include a group that is bonded to an aryl group or a monovalent heterocyclic group via a carbon-carbon bond.
- the “alkyl group” may be either linear or branched.
- the number of carbon atoms of the linear alkyl group is usually 1 to 50, preferably 3 to 30, more preferably 4 to 20 or 4 to 10, excluding the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkyl group is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20, or 4 to 10, excluding the number of carbon atoms of the substituent.
- the alkyl group may have a substituent, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isoamyl group, 2-ethylbutyl group, Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3-propylheptyl group, decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-hexyl-decyl group, dodecyl group, and these And a group in which part or all of the hydrogen atoms in the group are substituted with a substituent.
- a substituent for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group,
- suitable substituents that the alkyl group may have include a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, and the like. It may have a substituent.
- alkyl group having a substituent include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a 3-phenylpropyl group, and 3- (4-methylphenyl). Examples thereof include a propyl group, 3- (3,5-di-hexylphenyl) propyl group, and 6-ethyloxyhexyl group.
- examples of a suitable substituent that the cycloalkyl group may have include an alkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, a fluorine atom, and the like. Furthermore, you may have a substituent. Examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.
- Aryl group means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
- the number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 18, 6 to 14, or 6 without including the number of carbon atoms of the substituent. ⁇ 10.
- the aryl group may have a substituent, such as a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, and groups in which part or all of the hydrogen atoms in these groups are substituted with substituents.
- a substituent such as a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2 -Pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group,
- the alkoxy group may have a substituent, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, Heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, and some or all of the hydrogen atoms in these groups are substituents
- the substituted group is mentioned, These groups may have a substituent further.
- alkoxy group may have include a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a fluorine atom.
- the number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 3 to 20, more preferably 4 to 10, not including the number of carbon atoms of the substituent.
- the cycloalkoxy group may have a substituent, for example, a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a part or all of the hydrogen atoms in these groups are substituted. And a group substituted with a group.
- the number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 6 to 48, more preferably 6 to 20, even more preferably 6 to 18, 6 to 14, excluding the number of carbon atoms of the substituent. Or 6-10.
- the aryloxy group may have a substituent, for example, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 1-anthracenyloxy group, 9-anthracenyloxy group, 1- Examples include a pyrenyloxy group and a group in which part or all of the hydrogen atoms in these groups are substituted with a substituent.
- examples of the preferable substituent that the aryloxy group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, and the like. Furthermore, you may have a substituent.
- heterocyclic group (p represents an integer of 1 or more) is p of hydrogen atoms directly bonded to a carbon atom or a hetero atom constituting a ring from a heterocyclic compound. This means the remaining atomic group excluding the hydrogen atom.
- Heterocyclic compound includes non-aromatic heterocyclic compounds such as oxirane, aziridine, azetidine, oxetane, thietane, pyrrolidine, tetrahydrofuran, dioxolane, imidazolidine, oxazolidine, piperidine, and aromatic heterocyclic compounds described later. Means.
- “Aromatic heterocyclic compounds” include azole, diazole, triazole, oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, diazabenzene (pyridazine, pyrimidine, pyrazine), triazine, azanaphthalene ( Quinoline, isoquinoline), diazanaphthalene (quinoxaline, quinazoline, etc.), carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, acridine and the like a compound in which the heterocyclic ring itself is aromatic, and phenoxazine, phenothiazine, dibenzoborol, Even if the heterocycle itself such as dibenzosilol and benzopyran does not show aromaticity, it means a compound in which an aromatic ring is condensed to the heterocycle.
- alkenyl group may be either linear or branched.
- the number of carbon atoms of the straight-chain alkenyl group is usually 2 to 30, preferably 2 to 20, more preferably 3 to 20, or 3 to 10, excluding the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkenyl group is usually 3 to 30, preferably 3 to 20, more preferably 4 to 20, or 4 to 10, excluding the number of carbon atoms of the substituent.
- the alkenyl group may have a substituent, for example, vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1 -Hexenyl group, 5-hexenyl group, 7-octenyl group, and groups in which some or all of the hydrogen atoms in these groups are substituted with substituents.
- substituent will be described later, examples of the preferable substituent that the alkenyl group may have include a halogen atom, an aryl group, and a monovalent heterocyclic group. These groups further have a substituent. You may do it.
- the number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 3 to 20, more preferably 4 to 20, or 4 to 10, excluding the number of carbon atoms of the substituent.
- the cycloalkenyl group may have a substituent, for example, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, and some or all of the hydrogen atoms in these groups are substituted. And a group substituted with a group.
- examples of the preferable substituent that the cycloalkenyl group may have include an alkyl group, a halogen atom, an aryl group, a monovalent heterocyclic group, and the like. It may have a substituent.
- alkynyl group may be either linear or branched.
- the number of carbon atoms of the alkynyl group is usually 2 to 20, preferably 3 to 20, and more preferably 3 to 10, excluding the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkynyl group is usually 4 to 30, preferably 4 to 20, and more preferably 4 to 10, excluding the number of carbon atoms of the substituent.
- the alkynyl group may have a substituent, for example, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, 1 -Hexynyl group, 5-hexynyl group, and groups in which some or all of the hydrogen atoms in these groups are substituted with substituents.
- substituent will be described later, examples of a suitable substituent that the alkynyl group may have include a halogen atom, an aryl group, and a monovalent heterocyclic group. These groups further have a substituent. You may do it.
- cycloalkynyl group may have include an alkyl group, a halogen atom, an aryl group, a monovalent heterocyclic group, and the like. It may have a substituent.
- “Arylene group” means an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon.
- the number of carbon atoms of the arylene group is usually 6 to 60, preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 18, 6 to 14, or 6 without including the number of carbon atoms of the substituent. ⁇ 10.
- the arylene group may have a substituent, for example, phenylene group, naphthalenediyl group, anthracenediyl group, phenanthrene diyl group, dihydrophenanthenediyl group, naphthacene diyl group, fluorenediyl group, pyrenediyl group, perylene diyl group, Examples include chrysenediyl groups and groups in which some or all of the hydrogen atoms in these groups have been substituted with substituents.
- examples of the preferable substituent that the arylene group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, and a monovalent heterocyclic group. These groups may further have a substituent.
- Preferable examples of the arylene group include groups represented by formulas (A-1) to (A-20). Groups in which at least two of these groups are directly bonded are also suitable as arylene groups.
- the “q-valent aromatic hydrocarbon group” (q represents an integer of 1 or more) is the rest of the aromatic hydrocarbon, excluding two hydrogen atoms directly bonded to the carbon atoms constituting the ring. It means atomic group.
- the monovalent aromatic hydrocarbon group and the divalent aromatic hydrocarbon group are also referred to as an aryl group and an arylene group, respectively, and details are as described above.
- the number of carbon atoms of the q-valent aromatic hydrocarbon group does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 30, more preferably 6 to 20, more preferably 6 to 18, 6 to 14, or 6 to 10.
- Dendrimer means a group having a regular dendritic branch structure (ie, a dendrimer structure) having an atom or ring as a branch point.
- dendrimer examples include, for example, International Publication No. 02/066733, Japanese Patent Application Laid-Open No. 2003-231692, International Publication No. 2003/079736, International Publication No. 2006/097717, etc. The structure described in the literature is mentioned.
- the dendron is preferably a group represented by the formula (DA) or the formula (DB).
- m DA1 , m DA2 and m DA3 each independently represent an integer of 0 or more.
- GDA represents a nitrogen atom, a trivalent aromatic hydrocarbon group, or a trivalent heterocyclic group, and these groups may have a substituent.
- Ar DA1 , Ar DA2 and Ar DA3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- T DA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
- the plurality of TDAs may be the same or different.
- m DA1 , m DA2 , m DA3 , m DA4 , m DA5 , m DA6 and m DA7 each independently represent an integer of 0 or more.
- GDA represents a nitrogen atom, a trivalent aromatic hydrocarbon group, or a trivalent heterocyclic group, and these groups may have a substituent.
- a plurality of GDA may be the same or different.
- Ar DA1 , Ar DA2 , Ar DA3 , Ar DA4 , Ar DA5 , Ar DA6 and Ar DA7 each independently represent an arylene group or a divalent heterocyclic group, and these groups may have a substituent. Good.
- T DA represents an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
- the plurality of TDAs may be the same or different.
- plurality of at least one of T DA is an aryl group with an alkyl group or 4 or more carbon atoms a cycloalkyl group having 4 or more carbon atoms as a substituent , or is preferably a monovalent heterocyclic group having as a substituent an alkyl group or 4 or more carbon atoms a cycloalkyl group having 4 or more carbon atoms, all of a plurality of T DA is 4 carbon atoms A monovalent having the above alkyl group or an aryl group having a cycloalkyl group having 4 or more carbon atoms as a substituent, or an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms as a substituent. It is more preferably a heterocyclic group.
- m DA1 , m DA2 , m DA3 , m DA4 , m DA5 , m DA6 and m DA7 are usually an integer of 10 or less, preferably an integer of 5 or less, more preferably 0 or 1.
- m DA1 , m DA2 , m DA3 , m DA4 , m DA5 , m DA6 and m DA7 are preferably the same integer.
- Trivalent aromatic hydrocarbon groups and the trivalent heterocyclic groups represented by G DA may have a substituent. But it is as previously described for the substituent group, the trivalent aromatic hydrocarbon groups and trivalent good suitable substituents be heterocyclic group optionally having represented by G DA, an alkyl group, a cycloalkyl Examples include an alkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a monovalent heterocyclic group, and the like, and these groups may further have a substituent.
- GDA is preferably a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups may have a substituent.
- G DA is more preferably a group represented by the formula (GDA-11) ⁇ formula (GDA-15).
- *** is, Ar DA3 in the formula (D-A), Ar DA3 in the formula (D-B), Ar DA5 in the formula (D-B), or, the bond between Ar DA7 in the formula (D-B) To express.
- R DA represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may further have a substituent. When a plurality of RDA are present, they may be the same or different. ]
- R DA is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups have a substituent. May be.
- Ar DA1 , Ar DA2 , Ar DA3 , Ar DA4 , Ar DA5 , Ar DA6 and Ar DA7 are preferably groups represented by the formulas (ArDA-1) to (ArDA-3).
- R DA represents the same meaning as described above.
- R DB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent. When two or more RDB exists, they may be the same or different. ]
- R DB is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group or a monovalent heterocyclic group, and still more preferably an aryl group.
- the group may have a substituent.
- T DA is preferably a group represented by formula (TDA-1) to formula (TDA-3).
- the group represented by the formula (DA) is preferably a group represented by the formula (D-A1) to the formula (D-A3).
- R p1 , R p2 and R p3 each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom, and these groups optionally have a substituent.
- R p1 and R p2 may be the same or different.
- np1 represents an integer of 0 to 5
- np2 represents an integer of 0 to 3
- np3 represents 0 or 1.
- a plurality of np1 may be the same or different.
- the group represented by the formula (DB) is preferably a group represented by the formula (D-B1) to the formula (D-B3).
- R p1 , R p2 and R p3 each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or a halogen atom, and these groups optionally have a substituent.
- R p1 and R p2 may be the same or different.
- np1 represents an integer of 0 to 5
- np2 represents an integer of 0 to 3
- np3 represents 0 or 1.
- np1 and np2 may be the same or different.
- Np1 is preferably 0 or 1, more preferably 1.
- np2 is preferably 0 or 1, more preferably 0.
- np3 is preferably 0.
- R p1 , R p2 and R p3 are preferably an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.
- At least one of a plurality of R p1 is an alkyl group having 4 or more carbon atoms or a carbon atom It is preferably a cycloalkyl group having a number of 4 or more, and all of a plurality of R p1 are preferably an alkyl group having 4 or more carbon atoms or a cycloalkyl group having 4 or more carbon atoms.
- the r-membered aromatic carbocycle (r is 5 or 6) means an aromatic carbocycle containing an r-membered ring in its structure.
- a 6-membered aromatic carbocyclic ring is a monocyclic aromatic carbocyclic ring (benzene ring) as long as it contains a 6-membered ring, and a polycyclic aromatic carbocyclic ring (naphthalene ring, anthracene). Ring, phenanthrene ring, fluorene ring, etc.). The same applies to the “r-membered aromatic heterocycle”.
- the light emitting device of the present invention is The anode, A cathode, A first light emitting layer provided between the anode and the cathode; A second light emitting layer provided between the anode and the cathode,
- the first light-emitting layer is a layer obtained using a polymer compound containing a structural unit having a crosslinking group and a phosphorescent structural unit
- the second light-emitting layer is a layer obtained by using a composition containing a non-phosphorescent low-molecular compound having a heterocyclic structure and at least two phosphorescent compounds.
- the structural unit having a crosslinking group is preferably a structural unit having at least one crosslinking group selected from the crosslinking group A group.
- Crosslinking group A group [Wherein R XL represents a methylene group, an oxygen atom or a sulfur atom, and n XL represents an integer of 0 to 5. When a plurality of R XL are present, they may be the same or different, and when a plurality of n XL are present, they may be the same or different. * Represents a bonding position. These crosslinking groups may have a substituent. ]
- the structural unit having a crosslinking group is preferably at least one structural unit selected from the group consisting of a structural unit represented by formula (11) and a structural unit represented by formula (12), It may be a structural unit represented by the following formula.
- the structural unit represented by the following formula may have a substituent.
- the structural unit having a crosslinking group is preferably at least one structural unit selected from the group consisting of a structural unit represented by formula (11) and a structural unit represented by formula (12). Especially, since the high molecular compound which is excellent in crosslinkability is obtained, it is preferable that the structural unit which has a crosslinking group is at least 1 type of structural unit chosen from the structural unit represented by Formula (11).
- nA represents an integer of 0 to 5, and n represents 1 or 2.
- Ar 3 represents an (n + 2) -valent aromatic hydrocarbon group or a (n + 2) -valent heterocyclic group, and these groups may have a substituent.
- L A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good.
- R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent.
- X represents a crosslinking group selected from the crosslinking group A group. When two or more X exists, they may be the same or different.
- NA is preferably an integer of 1 to 5, more preferably 1 or 2, since a light emitting device having a better luminance life can be obtained.
- N is preferably 2, since a light-emitting element having a better luminance life can be obtained.
- Ar 3 is preferably an (n + 2) -valent aromatic hydrocarbon group which may have a substituent since a light-emitting element that is superior in luminance lifetime can be obtained.
- the (n + 2) -valent aromatic hydrocarbon group and the (n + 2) -valent heterocyclic group represented by Ar 3 may have a substituent, and suitable substituents include an alkyl group, a cycloalkyl group, Examples include an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group, and a cyano group, and these groups may further have a substituent.
- the (n + 2) -valent aromatic hydrocarbon group represented by Ar 3 is preferably a group represented by the formula (A-1) to the formula (A-20) (provided that n of R and R a are n More preferably formula (A-1), formula (A-2), formula (A-6) to formula (A-10), formula (A-19) or formula (A -20) (wherein n of R and R a are a bond), more preferably the formula (A-1), the formula (A-2), the formula (A- 7), a group represented by formula (A-9) or formula (A-19) (wherein n of R and R a are a bond).
- the (n + 2) -valent heterocyclic group represented by Ar 3 is preferably a group represented by the formula (AA-1) to (AA-34) (provided that n of R and R a are a bond). Is.)
- L A number of carbon atoms of the alkylene group represented by the not including the carbon atom number of substituent is usually 1 to 10, preferably 1 to 5, more preferably 1-3.
- L A number of carbon atoms of the cycloalkylene group represented by, not including the carbon atom number of substituent is usually 3 to 10.
- the alkylene group and cycloalkylene group may have a substituent, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, an octylene group, and a hydrogen atom in these groups A group in which a part or all of is substituted with a substituent.
- alkylene group and optionally suitable substituents be cycloalkylene group have represented by L A, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group A halogen atom and a cyano group, and these groups may further have a substituent.
- arylene group represented by L A Preferable examples of the arylene group represented by L A, o-phenylene, m- phenylene, p- phenylene, and, include groups partially or entirely substituted with a substituent of the hydrogen atoms in these groups It is done.
- suitable substituents which may be possessed by the arylene group represented by L A, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, an aryl group, an aryl Examples include an oxy group, a monovalent heterocyclic group, a halogen atom, a cyano group, and a bridging group selected from the bridging group A. These groups may further have a substituent.
- L A is preferably an alkylene group or an arylene group, more preferably an alkylene group or a phenylene group, since these facilitate the production of the polymer compound, and these groups may have a substituent.
- the crosslinking group represented by X is preferably a formula (XL-1), formula (XL-3), formula (XL-5), or formula (XL-7) because a polymer compound having excellent crosslinking properties can be obtained.
- Examples of the structural unit represented by the formula (11) include structural units represented by the formula (11-1) to the formula (11-30).
- the content of the structural unit represented by the formula (11) in the polymer compound is such that a polymer compound having excellent stability and crosslinkability is obtained, so the total amount of the structural units contained in the polymer compound is 100 mol%. When used, it is preferably 0.5 to 40 mol%, more preferably 5 to 40 mol%, still more preferably 10 to 40 mol%.
- the structural unit represented by the formula (11) may be included in the polymer compound alone or in combination of two or more.
- Ar 5 is a (m + 2) -valent aromatic hydrocarbon group, a (m + 2) -valent heterocyclic group, or a (m + 2) -valent group in which at least one aromatic carbocyclic ring and at least one heterocyclic ring are directly bonded. These groups may have a substituent.
- Ar 4 and Ar 6 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- Ar 4 , Ar 5 and Ar 6 are each bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded, directly or via an oxygen atom or a sulfur atom to form a ring.
- K A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good.
- R ′ represents the same meaning as described above. When a plurality of K A are present, they may be the same or different.
- X ′ represents a bridging group selected from the bridging group A group, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent. When a plurality of X ′ are present, they may be the same or different. However, at least one X ′ is a crosslinking group selected from the crosslinking group A group. ]
- MA is preferably 0 or 1, more preferably 0, because a light-emitting element that is superior in luminance life can be obtained.
- M is preferably 2, since a light-emitting element having a better luminance life can be obtained.
- C is preferably 0 because it facilitates the production of the polymer compound and provides a light-emitting device that is superior in luminance life.
- Ar 5 is preferably a (m + 2) -valent aromatic hydrocarbon group that may have a substituent since a light-emitting element that is superior in luminance lifetime can be obtained.
- the group represented by Ar 5 may have a substituent, and suitable substituents include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, 1 Examples thereof include a valent heterocyclic group and a cyano group, and these groups may further have a substituent.
- the (m + 2) -valent aromatic hydrocarbon group represented by Ar 5 is preferably represented by formula (A-1), formula (A-6), formula (A-7), formula (A-9) to formula (A-9) A-11) or a group represented by the formula (A-19) (provided that m of R and R a are a bond).
- Ar 4 and Ar 6 are preferably an arylene group which may have a substituent since a light-emitting element having better luminance life can be obtained.
- the structural unit represented by the formula (1G) is a terminal structural unit.
- n 2 is 0 or 1, and more preferably 0.
- R G29 to R G32 , R G34 , R G35 and R G38 are each preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group or a cycloalkoxy group, and a hydrogen atom More preferably, it is an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom, and these groups optionally have a substituent.
- the definition of the ring portion excluding the bond of the ring R 2G1 is the same as the definition of the ring R 2G described above.
- R G1 to R G8 represents a bond
- R G2 , R G3 , R G6 or R G7 is preferably a bond
- R G2 , R G6 or R G7 is more preferably a bond
- R G2 or R G6 is more preferably a bond
- R G6 is a bond. It is particularly preferred.
- Examples of the anionic bidentate ligand represented by A 1 -G 1 -A 2 include a ligand represented by the following formula.
- L 2 and L 3 each independently represent an oxygen atom, a sulfur atom, a group represented by —N (R A ) —, a group represented by —C (R B ) 2 —, or —C (R B ) Represents a group represented by ⁇ C (R B ) —, a group represented by —C ⁇ C—, an arylene group or a divalent heterocyclic group, and these groups each optionally have a substituent.
- R A and R B represent the same meaning as described above.
- n b1 and n c1 each independently represent an integer of 0 or more.
- a plurality of n b1 may be the same or different.
- Ar 1M represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and these groups may have a substituent.
- the group is preferably a group in which three hydrogen atoms directly bonded are removed, and three hydrogen atoms directly bonded to carbon atoms constituting the ring are excluded from a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring or dihydrophenanthrene ring. More preferably a group obtained by removing three hydrogen atoms directly bonded to the carbon atoms constituting the ring from the benzene ring or fluorene ring, and the carbon constituting the ring from the benzene ring. Particularly a group excluding three hydrogen atoms directly bonded to the atom Preferably, these groups may have a substituent.
- the definition of the ring portion excluding the bond of the ring R 1G2 is the same as the definition of the ring R 1G described above.
- ring R 2G2 When ring R 2G2 does not have a bond, the definition of ring R 2G2 is the same as the definition of ring R 2G described above.
- the substituent that the ring R 1G2 and the ring R 2G2 may have is the same as the substituent that the ring R 1G and the ring R 2G may have.
- Each of the ring R 1G2 and the ring R 2G2 preferably has one bond.
- the ligand represented by ring R 1G2 -ring R 2G2 is preferably a ligand represented by formula (GM-L1) to formula (GM-L4), and is represented by formula (GM-L1) or formula A ligand represented by (GM-L2) is more preferable.
- R G1 to R G8 represent a bond
- R G2 , R G3 , R G6 and R Of G7 two are preferably bonds
- R G2 and R G6 , R G2 and R G7 , R G3 and R G6 , or R G3 and R G7 are more preferably bonds.
- R G9 to R G18 represent a bond
- R G10 , R G16 and R G17 Two are preferably bonds
- R G10 and R G16 , or R G10 and R G17 are more preferably bonds.
- R G29 to R G38 represent a bond
- R G36 , R G37 and R G33 Two are preferably bonds
- R G36 and R G33 , or R G37 and R G33 are more preferably bonds.
- M 3G is preferably a group represented by the formula (GM-4).
- n 5 represents 0 or 1.
- n 6 represents 1 or 3.
- M is a ruthenium atom, a rhodium atom, or an iridium atom
- n 5 is 0 and n 6 is 3.
- M is a palladium atom or a platinum atom
- n 5 is 1 and n 6 is 1.
- Examples of the structural unit represented by the formula (1G) include structural units represented by the formula (1G-1) to the formula (1G-12).
- Examples of the structural unit represented by the formula (3G) include structural units represented by the formulas (3G-1) to (3G-20).
- Examples of the structural unit represented by the formula (4G) include structural units represented by the formula (4G-1) to the formula (4G-7).
- the content of the phosphorescent constituent unit in the polymer compound is such that a light emitting device having excellent external quantum efficiency can be obtained. Therefore, when the total amount of the constituent units contained in the polymer compound is 100 mol%, preferably 0.01 It is -30 mol%, more preferably 0.05-20 mol%, still more preferably 0.1-10 mol%.
- Only one type of phosphorescent structural unit may be contained in the polymer compound, or two or more types may be contained.
- the polymer compound containing a structural unit having a crosslinking group and a phosphorescent structural unit is further selected from the group consisting of a structural unit represented by formula (X) and a structural unit represented by formula (Y). It preferably contains one type of structural unit.
- a X1 and a X2 each independently represent an integer of 0 or more.
- Ar X1 and Ar X3 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- Ar X2 and Ar X4 each independently represent an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded to each other. And these groups may have a substituent.
- Ar X2 and Ar X4 When a plurality of Ar X2 and Ar X4 are present, they may be the same or different.
- R X1 , R X2 and R X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
- R X2 and R X3 may be the same or different.
- a X1 is preferably 2 or less, more preferably 1 because a light emitting device having a better luminance life can be obtained.
- a X2 is preferably 2 or less, and more preferably 0, because a light-emitting element that is superior in luminance life can be obtained.
- R X1 , R X2 and R X3 are preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. Also good.
- the arylene group represented by Ar X1 and Ar X3 is preferably a group represented by the formula (A-1) or the formula (A-9), more preferably a group represented by the formula (A-1). It is.
- the divalent heterocyclic group represented by Ar X1 and Ar X3 is preferably the formula (AA-1), formula (AA-2), formula (AA-4), formula (AA-7) to formula (AA) -26).
- Ar X1 and Ar X3 are preferably an arylene group which may have a substituent.
- the arylene group represented by Ar X2 and Ar X4 is preferably represented by formula (A-1), formula (A-6), formula (A-7), formula (A-9) to formula (A-11) or A group represented by formula (A-19);
- Suitable examples of the divalent heterocyclic group represented by Ar X2 and Ar X4 are preferably the formula (AA-1), the formula (AA-2), the formula (AA-4), and the formula (AA-7). Is a group represented by formula (AA-26).
- the number of carbon atoms of the divalent group in which at least one arylene group represented by Ar X2 and Ar X4 and at least one divalent heterocyclic group are directly bonded does not include the number of carbon atoms of the substituent. And usually 10 to 80, preferably 10 to 60, and more preferably 12 to 28. Preferred examples of the arylene group and the divalent heterocyclic group in such a divalent group are the same as the preferred examples of the arylene group and the divalent heterocyclic group represented by Ar X1 and Ar X3 , respectively. is there.
- Examples of the divalent group in which at least one arylene group represented by Ar X2 and Ar X4 and at least one divalent heterocyclic group are directly bonded include groups represented by the following formulae: These may have a substituent.
- R XX represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent.
- R XX is preferably an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.
- Ar X2 and Ar X4 are preferably an arylene group which may have a substituent.
- Suitable substituents that the groups represented by Ar X1 to Ar X4 and R X1 to R X3 may have are an alkyl group, a cycloalkyl group, and an aryl group, and these groups further have a substituent. It may be.
- the structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1) to the formula (X-7), more preferably the formula (X-3) to the formula (X— 7), more preferably structural units represented by formulas (X-3) to (X-6).
- R X4 and R X5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, a monovalent heterocyclic group or cyano. Represents a group, and these groups may have a substituent.
- a plurality of R X4 may be the same or different.
- a plurality of R X5 may be the same or different, and adjacent R X5 may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
- the content of the structural unit represented by the formula (X) in the polymer compound is excellent in hole transportability. Therefore, when the total amount of the structural units contained in the polymer compound is 100 mol%, the content is preferably 0.8. It is 1 to 65 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 50 mol%.
- Examples of the structural unit represented by the formula (X) include structural units represented by the formula (X1-1) to the formula (X1-19), preferably the formula (X1-6) to the formula (X1 -14).
- the structural unit represented by the formula (X) may be included alone or in combination of two or more.
- Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded, and these This group may have a substituent.
- the arylene group represented by Ar Y1 is preferably formula (A-1), formula (A-6), formula (A-7), formula (A-9) to formula (A-11), formula (A-11), -13) or a group represented by formula (A-19), more preferably a group represented by formula (A-1), formula (A-7), formula (A-9) or formula (A-19).
- the divalent heterocyclic group represented by Ar Y1 is preferably the formula (AA-4), formula (AA-10), formula (AA-13), formula (AA-15), formula (AA-18) Or a group represented by formula (AA-20), more preferably a group represented by formula (AA-4), formula (AA-10), formula (AA-18) or formula (AA-20) It is.
- Preferred examples of the arylene group and the divalent heterocyclic group in the divalent group in which at least one arylene group represented by Ar Y1 and at least one divalent heterocyclic group are directly bonded are as follows: These are the same as the preferred examples of the arylene group and divalent heterocyclic group represented by Ar Y1 described above.
- the number of carbon atoms and preferred examples of a divalent group in which at least one arylene group represented by Ar Y1 and at least one divalent heterocyclic group are directly bonded to each other are represented by Ar in formula (X), respectively. This is the same as the divalent group in which at least one arylene group represented by X2 and Ar X4 and at least one divalent heterocyclic group are directly bonded.
- the substituent which the group represented by Ar Y1 may have is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group.
- a cycloalkyl group or an aryl group, and these groups may further have a substituent.
- Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-1) to (Y-7), and the luminance lifetime of the light-emitting element using the polymer compound. From the viewpoint, it is preferably a structural unit represented by the formula (Y-1) or the formula (Y-2), and from the viewpoint of electron transport properties, the formula (Y-3) or the formula (Y-4) is preferable. From the viewpoint of hole transportability, it is preferably a structural unit represented by formula (Y-5) to formula (Y-7).
- R Y11 is preferably an alkyl group, a cycloalkyl group, or an aryl group, more preferably an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.
- the combination of two R Y2 in the group represented by —C (R Y2 ) ⁇ C (R Y2 ) — is preferably both an alkyl group or a cycloalkyl group, or one of which is an alkyl group Alternatively, a cycloalkyl group and the other is an aryl group, and these groups optionally have a substituent.
- R Y2 in the group represented by —C (R Y2 ) 2 —C (R Y2 ) 2 — are preferably an alkyl group or a cycloalkyl group, and these groups are substituent groups. You may have.
- a plurality of R Y2 may be bonded to each other to form a ring together with the atoms to which each is bonded.
- R Y2 forms a ring —C (R Y2 ) 2 —C (R Y2 ) 2 —
- the group represented is preferably a group represented by the formula (Y-B1) to the formula (Y-B5), more preferably a group represented by the formula (Y-B3). It may have a substituent.
- R Y2 represents the same meaning as described above.
- the structural unit represented by the formula (Y-2) is preferably a structural unit represented by the formula (Y-2 ′).
- R Y1 represents the same meaning as described above.
- R Y3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
- R Y3 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.
- R Y1 represents the same meaning as described above.
- R Y4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent.
- R Y4 is preferably an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups have a substituent. May be.
- Examples of the structural unit represented by the formula (Y) include structural units represented by the formulas (Y-11) to (Y-55).
- the content of the structural unit represented by the formula (Y) in the polymer compound provides a light-emitting device that is superior in luminance life, so that the composition contained in the polymer compound
- the total amount of units is 100 mol%, it is preferably 0.5 to 70 mol%, more preferably 5 to 60 mol%.
- the structural unit represented by the formula (Y) in the polymer compound (wherein Ar Y1 is a divalent heterocyclic group, or at least one arylene group and at least one divalent heterocyclic group).
- the content of the directly bonded divalent group is such that a light-emitting element having excellent charge transportability can be obtained. Therefore, when the total amount of structural units contained in the polymer compound is 100 mol%, the content is preferably 0.8. It is 5 to 30 mol%, more preferably 3 to 40 mol%.
- the structural unit represented by the formula (Y) may be included in the polymer compound alone or in combination of two or more.
- a light-emitting element having excellent light emission efficiency can be produced. Therefore, a structural unit having a group represented by the formula (13) A polymer compound containing a phosphorescent structural unit is preferred.
- L B is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, the group represented by -NR'-, an oxygen atom or a sulfur atom, these groups have a substituent Also good.
- R ′ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent.
- LB When a plurality of LB are present, they may be the same or different.
- the benzocyclobutene ring may have a substituent. When a plurality of the substituents are present, they may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
- L B is preferably an alkylene group or an arylene group.
- the phosphorescent structural unit is as described above.
- the polymer compound containing a structural unit having a group represented by the formula (13) and a phosphorescent structural unit is further composed of a structural unit represented by the formula (X) and a structure represented by the formula (Y). It may contain at least one structural unit selected from the group consisting of units.
- the structural units represented by the formula (X) and the formula (Y) are as described above.
- the content of the structural unit having the group represented by the formula (13) in the polymer compound containing the structural unit having the group represented by the formula (13) and the phosphorescent structural unit is excellent in crosslinkability. Since a polymer compound is obtained, when the total amount of structural units contained in the polymer compound is 100 mol%, it is preferably 0.5 to 40 mol%, more preferably 5 to 40 mol%. More preferably, it is 10 to 40 mol%.
- any polymer compound that emits phosphorescence in the visible region (400 nm to 700 nm) may be used.
- the polymer compound has an emission peak wavelength of preferably 490 nm to 700 nm, more preferably 550 nm to 700 nm, and further preferably 570 nm to 700 nm.
- the polymer compound containing a structural unit having a crosslinking group and a phosphorescent structural unit may contain one phosphorescent structural unit or two or more phosphorescent structural units. Since it is excellent, it is preferable to contain it individually by 1 type. That is, it is preferable that the polymer compound containing the structural unit having a group represented by the formula (13) and the phosphorescent constituent unit contains one phosphorescent constituent unit alone.
- Examples of the polymer compound containing a structural unit having a crosslinking group and a phosphorescent structural unit include polymer compounds P-1 to P-8 shown in Table 1.
- the polymer compound containing a structural unit having a crosslinking group and a phosphorescent structural unit preferably exhibits a desired luminescent color in the light-emitting element.
- the light emission peak wavelength of the polymer compound containing the structural unit having a crosslinking group and the phosphorescent structural unit is, for example, in the evaluation light-emitting element in which the polymer compound is formed between the cathode and the anode, when a voltage is applied. This can be confirmed by measuring the emission peak wavelength.
- the materials of the cathode and anode used for the evaluation element, the film thickness of the polymer compound, and the voltage to be applied may be appropriately determined according to the light-emitting element intended as a product.
- the polymer compound may be cross-linked or non-cross-linked, but must be cross-linked under the cross-linking reaction conditions applied when manufacturing a light-emitting element intended as a product. Is preferred.
- At least one compound selected from the group consisting of compounds represented by formulas (M-1) and (M-2), and formulas (M-3) to (M-6) Condensation polymerization of at least one compound selected from the group consisting of compounds and, if necessary, at least one compound selected from the group consisting of compounds represented by formula (M-7) and formula (M-8) Can be manufactured.
- the compounds used for the production of the polymer compound are sometimes collectively referred to as “raw material monomers”.
- the compounds represented by formula (M-1) and formula (M-2) are structural units having a crosslinking group, more specifically, structural units represented by formula (11) and formula (12), respectively.
- the content of the at least two phosphorescent compounds in the second light emitting layer is usually 0.05 to 80 parts by weight when the total of the materials contained in the second light emitting layer is 100 parts by weight,
- the amount is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight.
- the lowest excited triplet state (T 1 ) possessed by the non-phosphorescent low molecular weight compound having a heterocyclic structure can provide a light emitting device having excellent external quantum efficiency, and therefore, among the at least two types of phosphorescent compounds. It is preferable that the energy level is equal to or higher than that of a phosphorescent compound having a high T 1 energy.
- the non-phosphorescent low molecular weight compound having a heterocyclic structure can be produced in a solvent capable of dissolving the at least two phosphorescent compounds because the light emitting device of the present invention can be produced by a solution coating process. It is preferable to do.
- the non-phosphorescent low molecular weight compound having a heterocyclic structure is at least one selected from the group consisting of a carbazole ring, a phenanthroline ring, a triazine ring, an azole ring, a thiophene ring, a furan ring, a pyridine ring and a diazabenzene ring.
- a compound having a heterocyclic structure is preferred.
- the non-phosphorescent low molecular weight compound having a heterocyclic structure is preferably a compound represented by the formula (H-1).
- Ar H1 and Ar H2 represent an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.
- n H1 and n H2 each independently represent 0 or 1. When a plurality of n H1 are present, they may be the same or different. A plurality of n H2 may be the same or different.
- n H3 represents an integer of 1 or more.
- L H1 represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent. When a plurality of L H1 are present, they may be the same or different.
- L H2 represents a group represented by —N (—L H3 —R HA ) — or a group represented by — [C (R HB ) 2 ] n H4 —.
- R HA represents an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups optionally have a substituent.
- L H3 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups may have a substituent.
- R HB represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
- a plurality of R HBs may be the same or different, and may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
- n H4 represents an integer of 1 to 10.
- Ar H1 , Ar H2 , L H1 and L H2 is a monovalent or divalent heterocyclic group, or a group containing a monovalent or divalent heterocyclic group.
- L H1 may have, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, or a monovalent heterocyclic group is preferable, and an alkyl group, an alkoxy group, an aryl group is preferable.
- a group or a monovalent heterocyclic group is more preferable, an alkyl group, an aryl group or a monovalent heterocyclic group is more preferable, and these groups may further have a substituent.
- Examples of the aryl group and monovalent heterocyclic group in the substituent that L H1 may have are the same as the examples of the aryl group and monovalent heterocyclic group represented by Ar H1 and Ar H2 .
- R HA is preferably an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
- Examples of the arylene group and divalent heterocyclic group represented by L H3 are the same as the examples of the arylene group and divalent heterocyclic group represented by L H1 .
- n H2 is preferably 0.
- n H3 is usually 1 or more and 10 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and particularly preferably 1.
- the compound represented by the formula (H-1) is preferably a compound represented by the formula (H-2).
- the at least two phosphorescent compounds can be suitably used as long as they have a high emission quantum yield at room temperature.
- the at least two phosphorescent compounds have at least one phosphorescent compound (B) having an emission spectrum having a maximum peak wavelength of 400 nm or more and less than 480 nm, and an emission spectrum having a maximum peak wavelength of 480 nm. It is preferable to contain at least one phosphorescent compound (G) having a wavelength of 680 nm or less.
- the maximum peak wavelength of the emission spectrum of the phosphorescent compound is obtained by dissolving the phosphorescent compound in an organic solvent such as toluene, xylene, chloroform, tetrahydrofuran, and preparing a dilute solution (1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 3 about wt%), it can be evaluated by measuring at room temperature the PL spectra of rare-thin solution.
- Xylene is preferred as the organic solvent for dissolving the phosphorescent compound.
- the content of the phosphorescent compound (B) in the second light emitting layer is usually 75 when the total of the phosphorescent compound (B) and the phosphorescent compound (G) is 100 parts by weight. It is 0.0 to 99.9 parts by weight, preferably 90.0 to 99.9 parts by weight, and more preferably 98 to 99.5 parts by weight.
- the second light emitting layer of the present invention may contain three or more phosphorescent compounds.
- M represents a ruthenium atom, a rhodium atom, a palladium atom, an iridium atom or a platinum atom.
- n 1 represents an integer of 1 or more
- n 2 represents an integer of 0 or more
- n 1 + n 2 is 2 or 3.
- M is a ruthenium atom, rhodium atom or iridium atom
- n 1 + n 2 is 3
- M is a palladium atom or platinum atom
- n 1 + n 2 is 2.
- E 1 and E 2 each independently represent a carbon atom or a nitrogen atom. However, at least one of E 1 and E 2 is a carbon atom.
- Ring R 1 represents a 5-membered or 6-membered aromatic heterocyclic ring, and these rings may have a substituent. When a plurality of the substituents are present, they may be the same or different, and may be bonded to each other to form a ring together with the atoms to which each is bonded. When a plurality of rings R 1 are present, they may be the same or different. However, if the ring R 1 is a 6-membered heteroaromatic ring, E 1 is a carbon atom.
- Ring R 2 represents a 5-membered or 6-membered aromatic carbocyclic ring, or a 5-membered or 6-membered aromatic heterocyclic ring, and these rings may have a substituent.
- a 1 and A 2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring.
- G 1 represents a single bond or an atomic group constituting a bidentate ligand together with A 1 and A 2 .
- a 1 -G 1 -A 2 When a plurality of A 1 -G 1 -A 2 are present, they may be the same or different.
- n 1 is preferably 2 or 3, and more preferably 3.
- n 1 is preferably 1 or 2, and more preferably 2.
- Ring R 1 is a 5-membered aromatic heterocycle having 1 to 3 nitrogen atoms as constituent atoms, or a 6-membered aromatic heterocycle having 1 to 4 nitrogen atoms as constituent atoms It is preferably a 5-membered aromatic heterocycle having 1 to 3 nitrogen atoms as constituent atoms, more preferably an imidazole ring or a triazole ring.
- Ring R 2 is preferably a 6-membered aromatic carbocycle, or a 5-membered or 6-membered aromatic heterocycle, and is a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, pyridine ring, diazabenzene. It is more preferably a ring, pyrrole ring, furan ring or thiophene ring, more preferably a benzene ring, naphthalene ring, fluorene ring, pyridine ring or diazabenzene ring, and a benzene ring, pyridine ring or pyrimidine ring. Particularly preferred, these rings may have a substituent.
- Examples of the substituent that the ring R 1 and the ring R 2 may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a halogen atom,
- a dendron is preferable, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, a halogen atom or a dendron is more preferable, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom or a dendron is further preferable, and these groups May further have a substituent.
- the electron withdrawing group that ring R 2 has is a halogen atom, an alkyl group having a halogen atom as a substituent, a cycloalkyl group, or a halogen atom.
- Aryl having a substituent is preferable, and a fluorine atom, an alkyl group or cycloalkyl group having a fluorine atom as a substituent, or an aryl group having a fluorine atom as a substituent is more preferable, and a fluorine atom, a trifluoromethyl group or pentafluoro is preferable. More preferred is a phenyl group.
- the anionic bidentate ligand represented by A 1 -G 1 -A 2 is as described above.
- Examples of the phosphorescent compound represented by the formula (1) include a phosphorescent compound represented by the formula (1-A).
- n 1 , n 2 and A 1 -G 1 -A 2 represent the same meaning as described above.
- M 1 represents an iridium atom or a platinum atom.
- E 1A , E 2A , E 3A , E 4A , E 2B , E 3B , E 4B and E 5B each independently represent a nitrogen atom or a carbon atom.
- E 1A , E 2A , E 3A , E 4A , E 2B , E 3B , E 4B and E 5B may be the same or different.
- E 2A , E 3A and E 4A are nitrogen atoms
- R 2A , R 3A and R 4A may or may not be present.
- R 2A , R 3A , R 4A , R 2B , R 3B , R 4B and R 5B are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, It represents a monovalent heterocyclic group, a halogen atom or a dendron, and these groups optionally have a substituent.
- R 2A , R 3A , R 4A , R 2B , R 3B , R 4B and R 5B they may be the same or different.
- R 2A and R 3A , R 3A and R 4A , R 2A and R 2B , R 2B and R 3B , R 3B and R 4B , and R 4B and R 5B are bonded to each other together with the atoms to which they are bonded.
- a ring may be formed.
- Ring R 1A represents a triazole ring or an imidazole ring constituted by a nitrogen atom, E 1A , E 2A , E 3A and E 4A .
- Ring R 1B represents a benzene ring, a pyridine ring or a pyrimidine ring composed of two carbon atoms, E 2B , E 3B , E 4B and E 5B .
- the bond between the atoms constituting the ring R 1A is not necessarily a single bond, and may be a double bond. Moreover, the bond between each atom which comprises ring R1B does not need to be a single bond, and may be a double bond. “When E 2A , E 3A and E 4A are nitrogen atoms, R 2A , R 3A and R 4A may or may not be present.” Means “when E 2A is a nitrogen atom, R 2A 2A may or may not be present. When E 3A is a nitrogen atom, R 3A may or may not be present. When E 4A is a nitrogen atom, R 4A may be present or absent. It does not have to exist. ”
- n 1A represents an integer of 2 or 3.
- M 1 is iridium
- n 1A is 3
- M 1 is platinum
- n 1A is 2.
- Examples of the phosphorescent compound (G) include a phosphorescent compound represented by the formula (2).
- Ring R 4 represents a 5-membered or 6-membered aromatic carbocyclic ring, or a 5-membered or 6-membered aromatic heterocyclic ring, and these rings optionally have a substituent.
- a plurality of the substituents may be the same or different, and may be bonded to each other to form a ring together with the atoms to which each is bonded.
- a plurality of rings R 4 are present, they may be the same or different.
- the anionic bidentate ligand represented by A 1 -G 1 -A 2 is as described above.
- At least one of the substituents is preferably a dendron, and is a group represented by the formula (DA) or the formula (DB). More preferably, it is more preferably a group represented by the formula (DA).
- Examples of the phosphorescent compound (G) include the metal complexes shown below.
- the light-emitting element of the present invention includes an anode, a cathode, and first and second light-emitting layers provided between the anode and the cathode.
- the light emitting device of the present invention preferably further has one or more layers selected from a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer.
- the light emitting element may have the following layer structure, for example.
- the symbol “/” indicates that the layers described with the symbol in between are adjacently stacked.
- D1 Anode / first light emitting layer / second light emitting layer / cathode
- D2 anode / first light emitting layer / second light emitting layer / electron transport layer / cathode
- D3 anode / first light emitting layer / Second light emitting layer / electron injection layer / cathode
- D4 anode / first light emitting layer / second light emitting layer / electron transport layer / electron injection layer / cathode
- D5 anode / hole injection layer / first Light emitting layer / second light emitting layer / cathode
- D6 anode / hole injection layer / first light emitting layer / second light emitting layer / electron transport layer / cathode
- D7 anode / hole injection layer / first Light emitting layer
- the first light emitting layer is preferably provided between the anode and the second light emitting layer.
- the light-emitting element of the present invention further includes a functional layer having a function of emitting light, a function of suppressing carrier movement, or a function of suppressing diffusion of excitons between the first light-emitting layer and the second light-emitting layer.
- a functional layer having a function of emitting light, a function of suppressing carrier movement, or a function of suppressing diffusion of excitons between the first light-emitting layer and the second light-emitting layer.
- the first light emitting layer and the second light emitting layer are adjacent to each other.
- the light emitting device of the present invention preferably further has at least one layer selected from the group consisting of a hole transport layer and a hole injection layer between the first light emitting layer and the anode.
- the light emitting device of the present invention preferably further comprises at least one layer selected from the group consisting of an electron transport layer and an electron injection layer between the second light emitting layer and the cathode.
- the thickness of these layers is usually 1 nm to 10 ⁇ m.
- each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be provided in two or more layers as necessary.
- Examples of the electron transport material used for the electron transport layer include compounds containing a structural unit represented by the formula (ET-1) or the formula (ET-2).
- An electron transport material may be used individually by 1 type, or may use 2 or more types together.
- nE1 represents an integer of 1 or more.
- Ar E1 represents a (nE1 + 2) -valent aromatic hydrocarbon group or a (nE1 + 2) -valent heterocyclic group, and these groups optionally have a substituent other than R E1 .
- R E1 represents a group represented by the following formula (ES-1). When a plurality of R E1 are present, they may be the same or different. ]
- Y E1 represents —CO 2 ⁇ , —SO 3 ⁇ , —SO 2 — or PO 3 2 ⁇ .
- M E2 represents a metal cation or an ammonium cation, and this ammonium cation may have a substituent. When a plurality of M E2 are present, they may be the same or different.
- Z E1 represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R E4 SO 3 ⁇ , R E4 COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ .
- R E4 represents an alkyl group, a cycloalkyl group or an aryl group, and these groups optionally have a substituent.
- Z E1 When a plurality of Z E1 are present, they may be the same or different.
- aE1 and bE1 are selected so that the charge of the group represented by the formula (ES-1) is zero. ]
- Examples of the (nE1 + 2) -valent group represented by Ar E1 include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 2,6-naphthalenediyl group, and 1,4-naphthalenediyl group.
- a divalent aromatic hydrocarbon group selected from the group consisting of a group, 2,7-fluorenediyl group, 3,6-fluorenediyl group, 2,7-phenanthrenediyl group, and 2,7-carbazolediyl group
- the remaining atomic group remove
- Examples of the substituent other than R E1 that Ar E1 may have include a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group, a cycloalkoxy group, and an aryloxy group.
- n ′ and m ′ are integers of 1 or more, nx is an integer of 1 or more that represents the number of repeating alkylene oxide moieties.
- nE1 is preferably an integer of 1 to 4, more preferably 1 or 2.
- Q E1 is preferably an alkylene group, an arylene group, or an oxygen atom.
- Y E1 is preferably —CO 2 — or —SO 3 — .
- M E2 Li + , Na + , K + , Cs + , N (CH 3 ) 4 + , NH (CH 3 ) 3 + , NH 2 (CH 3 ) 2 + , or N (C 2 H 5 ) 4 + is preferred.
- Z E1 is preferably F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R E4 SO 3 ⁇ , or R E4 COO ⁇ .
- R E3 may have include an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, and a group represented by the formula (ES-3).
- R E3 preferably has a group represented by the formula (ES-3) as a substituent since the external quantum efficiency of the light-emitting element of the present invention is excellent.
- Examples of the group represented by the formula (ES-1) include a group represented by the following formula.
- M + represents Li + , Na + , K + , Cs + , N (CH 3 ) 4 + , NH (CH 3 ) 3 + , NH 2 (CH 3 ) 2 + , and N (C 2 H 5 ) 4 + . ]
- nE2 represents an integer of 1 or more.
- Ar E2 represents a (nE2 + 2) -valent aromatic hydrocarbon group or a (nE2 + 2) -valent heterocyclic group, and these groups optionally have a substituent other than R E2 .
- R E2 represents a group represented by the following formula (ES-2). When a plurality of R E2 are present, they may be the same or different. ]
- nE6 represents an integer of 0 or more
- bE2 represents an integer of 1 or more
- aE2 represents an integer of 0 or more
- R E6 represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- Q E2 represents an alkylene group, an arylene group, an oxygen atom, or a sulfur atom, and these groups may have a substituent. When a plurality of Q E2 are present, they may be the same or different.
- Y E2 represents a carbocation, an ammonium cation, a phosphonyl cation or a sulfonyl cation.
- M E3 represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , R E7 SO 3 ⁇ , R E7 COO ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , SCN ⁇ , CN ⁇ .
- R E7 represents an alkyl group, a perfluoroalkyl group, or an aryl group, and these groups optionally have a substituent.
- M E3 represents an alkyl group, a perfluoroalkyl group, or an aryl group, and these groups optionally have a substituent.
- Z E2 represents a metal ion or an ammonium ion, and this ammonium ion may have a substituent. When a plurality of Z E2 are present, they may be the same or different.
- aE2 and bE2 are selected so that the charge of the group represented by the formula (ES-2) becomes zero. ]
- Examples of the (nE2 + 2) -valent group represented by Ar E2 include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 2,6-naphthalenediyl group, and 1,4-naphthalenediyl group.
- a divalent aromatic hydrocarbon group selected from the group consisting of a group, 2,7-fluorenediyl group, 3,6-fluorenediyl group, 2,7-phenanthrenediyl group, and 2,7-carbazolediyl group
- the remaining atomic group remove
- nE2 is preferably an integer of 1 to 4, more preferably 1 or 2.
- Q E2 is preferably an alkylene group, an arylene group, or an oxygen atom.
- Y E2 is preferably a carbocation or an ammonium cation.
- M E3 F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , tetraphenylborate, CF 3 SO 3 ⁇ , or CH 3 COO ⁇ is preferable.
- Examples of the structural units represented by the formula (ET-1) and the formula (ET-2) include structural units represented by the following formulas (ET-31) to (ET-34).
- polymer compound examples include polyvinyl carbazole and derivatives thereof; polyarylene having an aromatic amine structure in the side chain or main chain and derivatives thereof.
- the polymer compound may be a compound to which an electron accepting site is bonded. Examples of the electron accepting site include fullerene, tetrafluorotetracyanoquinodimethane, tetracyanoethylene, trinitrofluorenone, and fullerene is preferable.
- each layer such as the first light emitting layer, the second light emitting layer, the hole transporting layer, the electron transporting layer, the hole injecting layer, and the electron injecting layer is the material used. It may be determined appropriately according to In the case of using a low molecular compound, for example, a vacuum deposition method from a powder, a method by film formation from a solution or a molten state is exemplified, and in a case of using a polymer compound, for example, a method by film formation from a solution or a molten state is used. Can be mentioned.
- the order, number, and thickness of the layers to be stacked may be adjusted in consideration of external quantum efficiency and device lifetime.
- the polymer compound containing a structural unit having a crosslinking group and a phosphorescent structural unit used in the first light-emitting layer has a crosslinking group
- the polymer compound is crosslinked by an external stimulus such as heating or light irradiation, A first light emitting layer can be obtained.
- the crosslinked first light emitting layer is substantially insoluble in a solvent, the first light emitting layer is suitable for manufacturing a light emitting element by a method of film formation from a solution (also referred to as “solution coating method”).
- the light used for light irradiation for crosslinking the first light emitting layer is, for example, ultraviolet light, near ultraviolet light, or visible light.
- the first light-emitting layer is formed using a solution (also referred to as “ink”) containing a polymer compound including a structural unit having a crosslinking group and a phosphorescent structural unit, for example, spin coating, casting, micro Gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, capillary coating method, nozzle It can be produced by a coating method.
- a solution also referred to as “ink”
- the thickness of the first light emitting layer is usually 1 nm to 10 ⁇ m.
- the second light-emitting layer is obtained using a composition containing a non-phosphorescent low-molecular compound having a heterocyclic structure and at least two phosphorescent compounds.
- a composition containing a non-phosphorescent low-molecular compound having a heterocyclic structure and at least two phosphorescent compounds When forming from a solution or a molten state, it can form into a film using the method similar to a 1st light emitting layer.
- the thickness of the second light emitting layer is usually 1 nm to 10 ⁇ m.
- an electron transport layer or an electron injection layer is further laminated on the second light emitting layer by utilizing the difference in solubility
- a solution having a low solubility with respect to the second light emitting layer is used.
- a transport layer or an electron injection layer can be laminated.
- Solvents used in such solutions include water, alcohols, ethers, esters, nitrile compounds, nitro compounds, fluorinated alcohols, thiols, sulfides, sulfoxides, thioketones, amides, carboxylic acids, etc. Is preferred.
- the solvent include methanol, ethanol, 2-propanol, 1-butanol, tert-butyl alcohol, acetonitrile, 1,2-ethanediol, N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, nitromethane, propylene carbonate, Examples thereof include pyridine, carbon disulfide, and a mixed solvent of these solvents.
- a mixed solvent When using a mixed solvent, it is selected from water, alcohols, ethers, esters, nitrile compounds, nitro compounds, fluorinated alcohols, thiols, sulfides, sulfoxides, thioketones, amides, carboxylic acids, etc. It may be a mixed solvent of one or more types of solvents and one or more types of solvents selected from chlorine-based solvents, aromatic hydrocarbon-based solvents, aliphatic hydrocarbon-based and ketone-based solvents.
- planar anode and the cathode may be arranged so as to overlap each other.
- pattern-like light emission a method in which a mask having a pattern-like window is provided on the surface of a planar light-emitting element, a layer that is desired to be a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There is a method, a method of forming an anode or a cathode, or both electrodes in a pattern.
- a segment type display device capable of displaying numbers, characters, and the like can be obtained.
- both the anode and the cathode may be formed in stripes and arranged orthogonally. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors, or a method using a color filter or a fluorescence conversion filter.
- the dot matrix display device can be driven passively or can be driven actively in combination with TFTs. These display devices can be used for displays of computers, televisions, portable terminals and the like.
- the planar light emitting element can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source and display device.
- LC-MS Liquid chromatography mass spectrometry
- Kaseisorb LC ODS 2000 manufactured by Tokyo Chemical Industry
- ODS column As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry) or an ODS column having equivalent performance was used.
- the detector a photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used.
- Compounds 11a and 11b were synthesized according to the method described in JP2012-33845A.
- Compound 12 was synthesized according to the method described in International Publication No. 2013/201188.
- Compound 13 was synthesized according to the method described in JP 2010-215886 A.
- Compound 14 was synthesized according to the method described in International Publication No. 2013/021180.
- Compound (H-21) was prepared by Luminescence Technology Corp. The one purchased from the company was used.
- Compound (1-A3-6) was synthesized according to the method described in International Publication No. 2008/090795.
- Compound (1-A1-12) was synthesized according to the method described in JP2013-147551A.
- the resulting reaction mixture was filtered to collect the filtrate, and the filtrate was further washed with 1,4-dioxane (2.5 L), and the obtained filtrate and washing were concentrated.
- the obtained residue was dissolved in a mixed solvent of hexane / dichloromethane (1/1 (volume basis)), filtered using 770 g of silica gel, and further mixed with hexane / dichloromethane (1/1 (volume basis)).
- the silica gel was washed with a solvent (2.5 L).
- the obtained filtrate and washing solution were concentrated, methanol (1500 mL) was added to the obtained residue, and ultrasonic washing was performed for 30 minutes.
- the obtained suspension was filtered through 440 g of silica gel, the silica gel was further washed with dichloromethane (2 L), and the solution was concentrated. Methanol (1100 mL) and dichloromethane (110 mL) were added to the obtained residue, and the mixture was refluxed for 1 hour. After cooling to room temperature, it was filtered. The obtained filtrate was washed with methanol (500 mL), and the obtained solid was dried to obtain compound S1 (220.85 g, 0.380 mol).
- 5-Bromo-2-phenylpyridine was synthesized according to the method described in JP-A-2008-179617. After the inside of the reaction vessel was placed in an argon gas atmosphere, 5-bromo-2-phenylpyridine (36.17 g, 155 mmol), compound S1 (94.20 g, 162 mmol), toluene (1545 mL), 20 wt% tetraethylammonium hydroxide An aqueous solution (341.28 g, 463.5 mmol) and tetrakis (triphenylphosphine) palladium (0) (8.927 g, 7.725 mmol) were added, and the mixture was stirred at 80 ° C.
- the obtained residue (8.05 g) was dissolved in dichloromethane (80 mL), and methanol (80 mL) was added to this solution.
- the resulting precipitate was collected by filtration and dried under reduced pressure to obtain compound COM-9 (6.25 g, 3.1 mmol) as a metal complex.
- Step 1 Synthesis of polymer compound 1 (Step 1) After making the inside of the reaction vessel an inert gas atmosphere, Compound 1 (0.673 g), Compound 2 (0.304 g), Compound 3 (0.222 g) , Compound 4 (1.95 g), Compound 5 (0.238 g), Compound 6 (0.0953 g), dichlorobis (tris-o-methoxyphenylphosphine) palladium (2.0 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 mL) and toluene (50 mL) were added, and the mixture was stirred under reflux for 4 hours.
- Step 1 After making the inside of the reaction vessel an inert gas atmosphere, Compound 1 (0.673 g), Compound 2 (0.304 g), Compound 3 (0.222 g) , Compound 4 (1.95 g), Compound 5 (0.238 g), Compound 6 (0.0953 g), dichlorobis (tris-
- Step 2 After the reaction, phenylboronic acid (27 mg), dichlorobis (tris-o-methoxyphenylphosphine) palladium (2.0 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 mL) were added thereto, Further, the mixture was stirred for 17 hours under reflux. (Step 3) Thereafter, an aqueous solution in which sodium N, N-diethyldithiocarbamate (1.25 g) was dissolved in ion-exchanged water (25 ml) was added thereto, followed by stirring at 85 ° C. for 2 hours.
- Step 2 A 20 wt% tetraethylammonium hydroxide aqueous solution (8.5 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 9.5 hours.
- Step 3 After the reaction, phenylboronic acid (61 mg) and dichlorobis (tris-o-methoxyphenylphosphine) palladium (2.2 mg) were added thereto and refluxed for 19 hours.
- Step 4 Thereafter, an aqueous sodium diethyldithiocarbamate solution (10 mL, concentration: 0.05 g / mL) was added thereto, and the mixture was stirred at 85 ° C. for 2 hours.
- the Mn of the polymer compound 3 was 8.0 ⁇ 10 4 and the Mw was 2.6 ⁇ 10 5 .
- Step 1 Synthesis of polymer compound 4
- compound 11a (0.55 g)
- compound 11b (0.61 g)
- triphenylphosphine palladium (0. 01 g)
- methyl trioctyl ammonium chloride manufactured by Aldrich, trade name Aliquat 336 (registered trademark)
- toluene (10 mL)
- Step 2 A 2M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction solution and refluxed for 8 hours.
- the polymer compound 6 is derived from the structural unit derived from the compound 1, the structural unit derived from the compound 12, the structural unit derived from the compound 5, and the compound 13. It is a copolymer containing a derived structural unit and a structural unit derived from the compound 14 in a molar ratio of 50: 30: 5: 5: 10.
- the light emitting layer On the light emitting layer, about 7 nm of sodium fluoride and then about 120 nm of aluminum were vapor-deposited as a cathode, and the light emitting element E1 was produced. Note that metal deposition was started after the degree of vacuum reached 1 ⁇ 10 ⁇ 4 Pa or less.
- Example 2 Production and Evaluation of Light-Emitting Element D1 An anode was formed by attaching an ITO film with a thickness of 45 nm to a glass substrate by a sputtering method.
- AQ-1200 manufactured by Spectronics Co., Ltd.
- a polythiophene / sulfonic acid-based hole injecting agent was formed on the anode in a thickness of 35 nm by a spin coating method, and was 170 ° C. on a hot plate in an air atmosphere.
- the hole injection layer was formed by heating for 15 minutes.
- Examples 4 and 5 and Comparative Example 2 Production and Evaluation of Light-Emitting Elements D3 and D4 and Light-Emitting Element CD2 1) Using the polymer compound shown in Table 4, the first light-emitting layer (in Comparative Example 2) 2) The second light emitting layer (the light emitting layer in Comparative Example 2) is formed using the inks changed to the constituent materials and constituent ratios shown in Table 4 instead of the ink D1. Except for the points described above, light-emitting elements D3 and D4 and light-emitting element CD2 were fabricated in the same manner as in Example 2. Table 4 also shows the evaluation results of the light emitting elements D3 and D4 and the light emitting element CD2 at an emission luminance of 1000 cd / m 2 .
- Polymer compound 3 was dissolved in xylene at a concentration of 0.6% by weight. Using the obtained xylene solution, a film having a thickness of 20 nm was formed on the hole injection layer by spin coating, and heated in a nitrogen gas atmosphere on a hot plate at 180 ° C. for 60 minutes. A transport layer was formed.
- Ink P1 was prepared by dissolving polymer compound 5 at a concentration of 0.25 wt% in 2,2,3,3,4,4,5,5-octafluoro-1-pentanol.
- the ink P1 was formed to a thickness of 10 nm on the second light emitting layer by spin coating, and an electron transport layer was formed by heating at 130 ° C. for 10 minutes on a hot plate in a nitrogen gas atmosphere. .
- On the electron transport layer about 7 nm of sodium fluoride and then about 120 nm of aluminum were vapor-deposited as a cathode, and a light emitting device D10 was produced. Note that metal deposition was started after the degree of vacuum reached 1 ⁇ 10 ⁇ 4 Pa or less.
- the external quantum efficiency of the light emitting element D10 is superior to the external quantum efficiency of the light emitting element CD4.
Abstract
Description
陽極と、
陰極と、
陽極及び陰極の間に設けられた第1の発光層と、
陽極及び陰極の間に設けられた第2の発光層とを有し、
第1の発光層が、架橋基を有する構成単位と燐光発光性構成単位とを含む高分子化合物を用いて得られる層であり、
第2の発光層が、複素環構造を有する非燐光発光性の低分子化合物と、少なくとも2種の燐光発光性化合物とを含有する組成物を用いて得られる層である、発光素子を提供する。
式(13)で表される基を有する構成単位と燐光発光性構成単位とを含む高分子化合物を提供する。
nBは1~5の整数を表す。
LBは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LBが複数存在する場合、それらは同一でも異なっていてもよい。
ベンゾシクロブテン環は、置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成してもよい。]
本明細書で共通して用いられる用語は、特記しない限り、以下の意味である。
mDA1、mDA2及びmDA3は、それぞれ独立に、0以上の整数を表す。
GDAは、窒素原子、3価の芳香族炭化水素基又は3価の複素環基を表し、これらの基は置換基を有していてもよい。
ArDA1、ArDA2及びArDA3は、それぞれ独立に、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。ArDA1、ArDA2及びArDA3が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
TDAは、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるTDAは、同一でも異なっていてもよい。]
mDA1、mDA2、mDA3、mDA4、mDA5、mDA6及びmDA7は、それぞれ独立に、0以上の整数を表す。
GDAは、窒素原子、3価の芳香族炭化水素基又は3価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるGDAは、同一でも異なっていてもよい。
ArDA1、ArDA2、ArDA3、ArDA4、ArDA5、ArDA6及びArDA7は、それぞれ独立に、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。ArDA1、ArDA2、ArDA3、ArDA4、ArDA5、ArDA6及びArDA7が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
TDAは、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。複数あるTDAは、同一でも異なっていてもよい。]
*は、式(D-A)におけるArDA1、式(D-B)におけるArDA1、式(D-B)におけるArDA2、又は、式(D-B)におけるArDA3との結合を表す。
**は、式(D-A)におけるArDA2、式(D-B)におけるArDA2、式(D-B)におけるArDA4、又は、式(D-B)におけるArDA6との結合を表す。
***は、式(D-A)におけるArDA3、式(D-B)におけるArDA3、式(D-B)におけるArDA5、又は、式(D-B)におけるArDA7との結合を表す。
RDAは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は1価の複素環基を表し、これらの基はさらに置換基を有していてもよい。RDAが複数存在する場合、それらは同一でも異なっていてもよい。]
RDAは前記と同じ意味を表す。
RDBは、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。RDBが複数存在する場合、それらは同一でも異なっていてもよい。]
Rp1、Rp2及びRp3は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Rp1及びRp2が複数存在する場合、それらはそれぞれ同一であっても異なっていてもよい。
np1は、0~5の整数を表し、np2は0~3の整数を表し、np3は0又は1を表す。複数あるnp1は、同一でも異なっていてもよい。]
Rp1、Rp2及びRp3は、それぞれ独立に、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基又はハロゲン原子を表し、これらの基は置換基を有していてもよい。Rp1及びRp2が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
np1は0~5の整数を表し、np2は0~3の整数を表し、np3は0又は1を表す。np1及びnp2が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。]
本発明の発光素子は、
陽極と、
陰極と、
陽極及び陰極の間に設けられた第1の発光層と、
陽極及び陰極の間に設けられた第2の発光層とを有し、
第1の発光層が、架橋基を有する構成単位と燐光発光性構成単位とを含む高分子化合物を用いて得られる層であり、
第2の発光層が、複素環構造を有する非燐光発光性の低分子化合物と、少なくとも2種の燐光発光性化合物とを含有する組成物を用いて得られる層であることを特徴とする。
第1の発光層は、架橋基を有する構成単位と燐光発光性構成単位とを含む高分子化合物を用いて得られる層である。
(架橋基A群)
nAは0~5の整数を表し、nは1又は2を表す。nAが複数存在する場合、それらは同一でも異なっていてもよい。
Ar3は、(n+2)価の芳香族炭化水素基又は(n+2)価の複素環基を表し、これらの基は置換基を有していてもよい。
LAは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LAが複数存在する場合、それらは同一でも異なっていてもよい。
Xは、架橋基A群から選ばれる架橋基を表す。Xが複数存在する場合、それらは同一でも異なっていてもよい。]
mAは0~5の整数を表し、mは1~4の整数を表し、cは0又は1の整数を表す。mAが複数存在する場合、それらは同一でも異なっていてもよい。
Ar5は、(m+2)価の芳香族炭化水素基、(m+2)価の複素環基、又は、少なくとも1種の芳香族炭素環と少なくとも1種の複素環とが直接結合した(m+2)価の基を表し、これらの基は置換基を有していてもよい。
Ar4及びAr6は、それぞれ独立に、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。
Ar4、Ar5及びAr6はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接又は酸素原子若しくは硫黄原子を介して結合して、環を形成していてもよい。
KAは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、前記と同じ意味を表す。KAが複数存在する場合、それらは同一でも異なっていてもよい。
X’は、架橋基A群から選ばれる架橋基、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。X’が複数存在する場合、それらは同一でも異なっていてもよい。但し、少なくとも1つのX’は、架橋基A群から選ばれる架橋基である。]
M1Gは、燐光発光性化合物から、該化合物を構成する炭素原子又はヘテロ原子に直接結合する1個の水素原子を取り除いてなる基を表す。
L1は、酸素原子、硫黄原子、-N(RA)-で表される基、-C(RB)2-で表される基、-C(RB)=C(RB)-で表される基、-C≡C-で表される基、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。RAは、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。RBは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するRBは、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。L1が複数存在する場合、それらは同一でも異なっていてもよい。
na1は0以上の整数を表す。]
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子又は白金原子を表す。
n1は1以上の整数を表す。n2は0以上の整数を表す。但し、n1+n2は1又は2である。Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n1+n2は2であり、Mがパラジウム原子又は白金原子の場合、n1+n2は1である。
E4は、炭素原子又は窒素原子を表す。複数存在するE4は同一でも異なっていてもよい。
環R1G及び環R1G1は、6員環の芳香族複素環を表し、該環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R1Gが複数存在する場合、それらは同一でも異なっていてもよい。
環R2G及び環R2G1は、5員環若しくは6員環の芳香族炭素環、又は、5員環若しくは6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R2Gが複数存在する場合、それらは同一でも異なっていてもよい。但し、環R2Gが6員環の芳香族複素環である場合、E4は炭素原子である。
但し、環R1G1及び環R2G1の一方は、1つの結合手を有する。
A1-G1-A2は、アニオン性の2座配位子を表す。A1及びA2は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。G1は、単結合、又は、A1及びA2と共に2座配位子を構成する原子団を表す。A1-G1-A2が複数存在する場合、それらは同一でも異なっていてもよい。]
RG1~RG8は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、1価の複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基又はデンドロンを表し、これらの基は置換基を有していてもよい。RG1とRG2、RG2とRG3、RG3とRG4、RG4とRG5、RG5とRG6、RG6とRG7、及び、RG7とRG8は、それぞれ結合して、それぞれが結合する原子と共に環を形成していてもよい。]
RG9~RG18は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、1価の複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基又はデンドロンを表し、これらの基は置換基を有していてもよい。RG9とRG10、RG10とRG11、RG11とRG12、RG12とRG13、RG13とRG14、RG14とRG15、RG15とRG16、RG16とRG17、及び、RG17とRG18は、それぞれ結合して、それぞれが結合する原子と共に環を形成していてもよい。]
RG19~RG28は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、1価の複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基又はデンドロンを表し、これらの基は置換基を有していてもよい。RG19とRG20、RG20とRG21、RG21とRG22、RG22とRG23、RG23とRG24、RG24とRG25、RG25とRG26、RG26とRG27、及び、RG27とRG28は、それぞれ結合して、それぞれが結合する原子と共に環を形成していてもよい。]
RG29~RG38は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、1価の複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基又はデンドロンを表し、これらの基は置換基を有していてもよい。RG29とRG30、RG30とRG31、RG31とRG32、RG32とRG33、RG33とRG34、RG34とRG35、RG35とRG36、RG36とRG37、及び、RG37とRG38は、それぞれ結合して、それぞれが結合する原子と共に環を形成していてもよい。]
M1Gは前記と同じ意味を表す。
L2及びL3は、それぞれ独立に、酸素原子、硫黄原子、-N(RA)-で表される基、-C(RB)2-で表される基、-C(RB)=C(RB)-で表される基、-C≡C-で表される基、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。RA及びRBは、前記と同じ意味を表す。L2及びL3が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
nb1及びnc1は、それぞれ独立に、0以上の整数を表す。複数存在するnb1は、同一でも異なっていてもよい。
Ar1Mは、3価の芳香族炭化水素基又は3価の複素環基を表し、これらの基は置換基を有していてもよい。]
M、E4、環R1G、環R2G、A1-G1-A2、環R1G1、環R2G1、n1、及びn2は前記と同じ意味を表す。
n3及びn4は、それぞれ独立に、0以上の整数を表す。但し、n3+n4は0又は1である。Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n3+n4は1であり、Mがパラジウム原子又は白金原子の場合、n3+n4は0である。
環R1G2は、6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。
環R2G2は、5員環若しくは6員環の芳香族炭素環、又は、5員環若しくは6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。
但し、環R1G2及び環R2G2の一方は2つの結合手を有するか、又は、環R1G2及び環R2G2は、それぞれ、結合手を1つずつ有する。]
M、E4、環R1G1、環R2G1、環R1G2、及び環R2G2は前記と同じ意味を表す。
n5は0又は1を表す。n6は1又は3を表す。但し、Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n5は0であり、且つ、n6は3である。Mがパラジウム原子又は白金原子の場合、n5は1であり、且つ、n6は1である。]
aX1及びaX2は、それぞれ独立に、0以上の整数を表す。
ArX1及びArX3は、それぞれ独立に、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。
ArX2及びArX4は、それぞれ独立に、アリーレン基、2価の複素環基、又は、少なくとも1種のアリーレン基と少なくとも1種の2価の複素環基とが直接結合した2価の基を表し、これらの基は置換基を有していてもよい。ArX2及びArX4が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
RX1、RX2及びRX3は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。RX2及びRX3が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。]
nBは1~5の整数を表す。
LBは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LBが複数存在する場合、それらは同一でも異なっていてもよい。
ベンゾシクロブテン環は、置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成してもよい。]
nA、n、Ar3、LA、X、mA、m、c、Ar4~Ar6、KA、X’、L1、L2、L3、na1、nb1、nc1、M1G、M2G、M3G、ArY1、a1、a2、ArX1~ArX4、RX1~RX3は、前記と同じ意味を表す。
ZC1~ZC16は、それぞれ独立に、置換基A群及び置換基B群からなる群から選ばれる基を表す。]
塩素原子、臭素原子、ヨウ素原子、-O-S(=O)2RC1(式中、RC1は、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。)で表される基。
-B(ORC2)2(式中、RC2は、水素原子、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。複数存在するRC2は同一でも異なっていてもよく、互いに結合して、それぞれが結合する酸素原子と共に環構造を形成していてもよい。)で表される基;
-BF3Q’(式中、Q’は、Li、Na、K、Rb又はCsを表す。)で表される基;
-MgY’(式中、Y’は、塩素原子、臭素原子又はヨウ素原子を表す。)で表される基;
-ZnY’’(式中、Y’’は、塩素原子、臭素原子又はヨウ素原子を表す。)で表される基;及び、
-Sn(RC3)3(式中、RC3は、水素原子、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。複数存在するRC3は同一でも異なっていてもよく、互いに結合して、それぞれが結合するスズ原子と共に環構造を形成していてもよい。)で表される基。
第2の発光層は、複素環構造を有する非燐光発光性の低分子化合物と、少なくとも2種の燐光発光性化合物とを含有する組成物を用いて得られる層である。
ArH1及びArH2は、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。
nH1及びnH2は、それぞれ独立に、0又は1を表す。nH1が複数存在する場合、それらは同一でも異なっていてもよい。複数存在するnH2は、同一でも異なっていてもよい。
nH3は1以上の整数を表す。
LH1は、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。LH1が複数存在する場合、それらは同一でも異なっていてもよい。
LH2は、-N(-LH3-RHA)-で表される基又は-[C(RHB)2]nH4-で表される基を表す。RHAは、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LH3は、単結合、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。RHBは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するRHBは、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。nH4は1以上10以下の整数を表す。LH2が複数存在する場合、それらは同一でも異なっていてもよい。
但し、ArH1、ArH2、LH1、LH2の少なくとも一つは1価若しくは2価の複素環基であるか、又は1価若しくは2価の複素環基を含む基である。]
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子又は白金原子を表す。
n1は1以上の整数を表し、n2は0以上の整数を表し、n1+n2は2又は3である。Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n1+n2は3であり、Mがパラジウム原子又は白金原子の場合、n1+n2は2である。
E1及びE2は、それぞれ独立に、炭素原子又は窒素原子を表す。但し、E1及びE2の少なくとも一方は炭素原子である。
環R1は、5員環又は6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R1が複数存在する場合、それらは同一でも異なっていてもよい。但し、環R1が6員環の芳香族複素環である場合、E1は炭素原子である。
環R2は、5員環若しくは6員環の芳香族炭素環、又は、5員環若しくは6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R2が複数存在する場合、それらは同一でも異なっていてもよい。但し、環R2が6員環の芳香族複素環である場合、E2は炭素原子である。
但し、環R1が6員環の芳香族複素環である場合、環R2は電子求引基を有する。
A1-G1-A2は、アニオン性の2座配位子を表す。A1及びA2は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。G1は、単結合、又は、A1及びA2と共に2座配位子を構成する原子団を表す。A1-G1-A2が複数存在する場合、それらは同一でも異なっていてもよい。]
n1、n2及びA1-G1-A2は、前記と同じ意味を表す。
M1は、イリジウム原子又は白金原子を表す。
E1A、E2A、E3A、E4A、E2B、E3B、E4B及びE5Bは、それぞれ独立に、窒素原子又は炭素原子を表す。E1A、E2A、E3A、E4A、E2B、E3B、E4B及びE5Bが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。E2A、E3A及びE4Aが窒素原子の場合、R2A、R3A及びR4Aは、存在しても存在しなくてもよい。E2B、E3B、E4B及びE5Bが窒素原子の場合、R2B、R3B、R4B及びR5Bは、存在しない。
R2A、R3A、R4A、R2B、R3B、R4B及びR5Bは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、1価の複素環基、ハロゲン原子又はデンドロンを表し、これらの基は置換基を有していてもよい。R2A、R3A、R4A、R2B、R3B、R4B及びR5Bが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。R2AとR3A、R3AとR4A、R2AとR2B、R2BとR3B、R3BとR4B、及び、R4BとR5Bは、それぞれ結合して、それぞれが結合する原子と共に環を形成していてもよい。
環R1Aは、窒素原子、E1A、E2A、E3A及びE4Aにより構成されるトリアゾール環又はイミゾール環を表す。
環R1Bは、2つの炭素原子、E2B、E3B、E4B及びE5Bにより構成されるベンゼン環、ピリジン環又はピリミジン環を表す。]
M1、R2A、R3A、R4A、R2B、R3B、R4B及びR5Bは、前記と同じ意味を表す。
n1Aは2又は3の整数を表し、M1がイリジウムの場合、n1Aは3であり、M1が白金の場合、n1Aは2である。]
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子又は白金原子を表す。
n3は1以上の整数を表し、n4は0以上の整数を表し、n3+n4は2又は3である。Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n3+n4は3であり、Mがパラジウム原子又は白金原子の場合、n3+n4は2である。
E4は、炭素原子又は窒素原子を表す。
環R3は、6員環の芳香族複素環を表し、この環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R3が複数存在する場合、それらは同一でも異なっていてもよい。
環R4は、5員環若しくは6員環の芳香族炭素環、又は、5員環若しくは6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R4が複数存在する場合、それらは同一でも異なっていてもよい。但し、環R4が6員環の芳香族複素環である場合、E4は炭素原子である。
A1-G1-A2は、アニオン性の2座配位子を表す。A1及びA2は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。G1は、単結合、又は、A1及びA2と共に2座配位子を構成する原子団を表す。A1-G1-A2が複数存在する場合、それらは同一でも異なっていてもよい。]
RD1~RD8及びRD11~RD20は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、1価の複素環基、ハロゲン原子又はデンドロンを表し、これらの基は置換基を有していてもよい。RD1~RD8及びRD11~RD20が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
A1-G1-A2は、前記と同じ意味を表す。
nD1は、1、2又は3を表し、nD2は、1又は2を表す。]
本発明の発光素子は、陽極と、陰極と、陽極及び陰極の間に設けられた第1及び第2の発光層とを有する。本発明の発光素子は、更に、正孔輸送層、正孔注入層、電子輸送層、及び電子注入層から選ばれる1種以上の層を有することが好ましい。
(D1)陽極/第1の発光層/第2の発光層/陰極
(D2)陽極/第1の発光層/第2の発光層/電子輸送層/陰極
(D3)陽極/第1の発光層/第2の発光層/電子注入層/陰極
(D4)陽極/第1の発光層/第2の発光層/電子輸送層/電子注入層/陰極
(D5)陽極/正孔注入層/第1の発光層/第2の発光層/陰極
(D6)陽極/正孔注入層/第1の発光層/第2の発光層/電子輸送層/陰極
(D7)陽極/正孔注入層/第1の発光層/第2の発光層/電子注入層/陰極
(D8)陽極/正孔注入層/第1の発光層/第2の発光層/電子輸送層/電子注入層/陰極
(D9)陽極/正孔輸送層/第1の発光層/第2の発光層/陰極
(D10)陽極/正孔輸送層/第1の発光層/第2の発光層/電子輸送層/陰極
(D11)陽極/正孔輸送層/第1の発光層/第2の発光層/電子注入層/陰極
(D12)陽極/正孔輸送層/第1の発光層/第2の発光層/電子輸送層/電子注入層/陰極
(D13)陽極/正孔注入層/正孔輸送層/第1の発光層/第2の発光層/陰極
(D14)陽極/正孔注入層/正孔輸送層/第1の発光層/第2の発光層/電子輸送層/陰極
(D15)陽極/正孔注入層/正孔輸送層/第1の発光層/第2の発光層/電子注入層/陰極
(D16)陽極/正孔注入層/正孔輸送層/第1の発光層/第2の発光層/電子輸送層/電子注入層/陰極
(D17)陽極/第2の発光層/第1の発光層/陰極
(D18)陽極/第2の発光層/第1の発光層/電子輸送層/陰極
(D19)陽極/第2の発光層/第1の発光層/電子注入層/陰極
(D20)陽極/第2の発光層/第1の発光層/電子輸送層/電子注入層/陰極
(D21)陽極/正孔注入層/第2の発光層/第1の発光層/陰極
(D22)陽極/正孔注入層/第2の発光層/第1の発光層/電子輸送層/陰極
(D23)陽極/正孔注入層/第2の発光層/第1の発光層/電子注入層/陰極
(D24)陽極/正孔注入層/第2の発光層/第1の発光層/電子輸送層/電子注入層/陰極
(D25)陽極/正孔輸送層/第2の発光層/第1の発光層/陰極
(D26)陽極/正孔輸送層/第2の発光層/第1の発光層/電子輸送層/陰極
(D27)陽極/正孔輸送層/第2の発光層/第1の発光層/電子注入層/陰極
(D28)陽極/正孔輸送層/第2の発光層/第1の発光層/電子輸送層/電子注入層/陰極
(D29)陽極/正孔注入層/正孔輸送層/第2の発光層/第1の発光層/陰極
(D30)陽極/正孔注入層/正孔輸送層/第2の発光層/第1の発光層/電子輸送層/陰極
(D31)陽極/正孔注入層/正孔輸送層/第2の発光層/第1の発光層/電子注入層/陰極
(D32)陽極/正孔注入層/正孔輸送層/第2の発光層/第1の発光層/電子輸送層/電子注入層/陰極
電子輸送層に用いられる電子輸送材料としては、例えば、式(ET-1)又は式(ET-2)で表される構造単位を含む化合物が挙げられる。電子輸送材料は、一種単独で用いても二種以上を併用してもよい。
nE1は、1以上の整数を表す。
ArE1は、(nE1+2)価の芳香族炭化水素基又は(nE1+2)価の複素環基を表し、これらの基はRE1以外の置換基を有していてもよい。
RE1は、下記式(ES-1)で表される基を表す。RE1が複数存在する場合、それらは同一でも異なっていてもよい。]
[式中、
cE1は0又は1を表し、nE4は0以上の整数を表し、aE1は1以上の整数を表し、bE1は0以上の整数を表す。
RE3は、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。
QE1は、アルキレン基、アリーレン基、酸素原子、又は硫黄原子を表し、これらの基は置換基を有していてもよい。QE1が複数存在する場合、それらは同一でも異なっていてもよい。
YE1は、-CO2 -、-SO3 -、-SO2 -又はPO3 2-を表す。
ME2は、金属カチオン又はアンモニウムカチオンを表し、このアンモニウムカチオンは置換基を有していてもよい。ME2が複数存在する場合、それらは同一でも異なっていてもよい。
ZE1は、F-、Cl-、Br-、I-、OH-、RE4SO3 -、RE4COO-、ClO-、ClO2 -、ClO3 -、ClO4 -、SCN-、CN-、NO3 -、SO4 2-、HSO4 -、PO4 3-、HPO4 2-、H2PO4 -、BF4 -又はPF6 -を表す。RE4は、アルキル基、シクロアルキル基又はアリール基を表し、これらの基は置換基を有していてもよい。ZE1が複数存在する場合、それらは同一でも異なっていてもよい。
aE1及びbE1は、式(ES-1)で表される基の電荷が0となるように選択される。]
[式中、
n’及びm’は、1以上の整数であり、
nxは、アルキレンオキシド部の繰り返し数を表す1以上の整数である。]
nE2は1以上の整数を表す。
ArE2は、(nE2+2)価の芳香族炭化水素基又は(nE2+2)価の複素環基を表し、これらの基はRE2以外の置換基を有していてもよい。
RE2は、下記式(ES-2)で表される基を表す。RE2が複数存在する場合、それらは同一でも異なっていてもよい。]
[式中、
cE2は0又は1を表し、nE6は0以上の整数を表し、bE2は1以上の整数を表し、aE2は0以上の整数を表す。
RE6は、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。
QE2は、アルキレン基、アリーレン基、酸素原子、又は硫黄原子を表し、これらの基は置換基を有していてもよい。QE2が複数存在する場合、それらは同一でも異なっていてもよい。
YE2は、カルボカチオン、アンモニウムカチオン、ホスホニルカチオン又はスルホニルカチオンを表す。
ME3は、F-、Cl-、Br-、I-、OH-、RE7SO3 -、RE7COO-、ClO-、ClO2 -、ClO3 -、ClO4 -、SCN-、CN-、NO3 -、SO4 2-、HSO4 -、PO4 3-、HPO4 2-、H2PO4 -、テトラフェニルボレート、BF4 -又はPF6 -を表す。RE7は、アルキル基、パーフルオロアルキル基、又はアリール基を表し、これらの基は置換基を有していてもよい。ME3が複数存在する場合、それらは同一でも異なっていてもよい。
ZE2は、金属イオン又はアンモニウムイオンを表し、このアンモニウムイオンは置換基を有していてもよい。ZE2が複数存在する場合、それらは同一でも異なっていてもよい。
aE2及びbE2は、式(ES-2)で表される基の電荷が0となるように選択される。]
正孔輸送層に用いられる正孔輸送材料は、低分子化合物と高分子化合物とに分類され、高分子化合物が好ましい。正孔輸送材料は、架橋基を有していてもよい。
電子注入層及び正孔注入層に用いられる電子注入材料及び正孔注入材料は、各々、低分子化合物と高分子化合物とに分類される。電子注入材料及び正孔注入材料は、架橋基を有していてもよい。
本発明の発光素子を製造するにあたって、第1の発光層、第2の発光層、正孔輸送層、電子輸送層、正孔注入層、電子注入層等の各層の形成方法は、使用する材料に応じて適宜決定してよい。低分子化合物を用いる場合、例えば、粉末からの真空蒸着法、溶液又は溶融状態からの成膜による方法が挙げられ、高分子化合物を用いる場合、例えば、溶液又は溶融状態からの成膜による方法が挙げられる。
発光素子における基板は、電極を形成することができ、かつ、機能層を形成する際に化学的に変化しない基板であればよく、例えば、ガラス、プラスチック、シリコン等の材料からなる基板である。不透明な基板を使用する場合には、基板から最も遠くにある電極が透明又は半透明であることが好ましい。
発光素子を用いて面状の発光を得るためには、面状の陽極と陰極が重なり合うように配置すればよい。パターン状の発光を得るためには、面状の発光素子の表面にパターン状の窓を設けたマスクを設置する方法、非発光部にしたい層を極端に厚く形成し実質的に非発光とする方法、陽極若しくは陰極、又は両方の電極をパターン状に形成する方法がある。これらのいずれかの方法でパターンを形成し、いくつかの電極を独立にON/OFFできるように配置することにより、数字、文字等を表示できるセグメントタイプの表示装置が得られる。ドットマトリックス表示装置とするためには、陽極と陰極を共にストライプ状に形成して直交するように配置すればよい。複数の種類の発光色の異なる高分子化合物を塗り分ける方法、カラーフィルター又は蛍光変換フィルターを用いる方法により、部分カラー表示、マルチカラー表示が可能となる。ドットマトリックス表示装置は、パッシブ駆動も可能であるし、TFT等と組み合わせてアクティブ駆動も可能である。これらの表示装置は、コンピュータ、テレビ、携帯端末等のディスプレイに用いることができる。面状の発光素子は、液晶表示装置のバックライト用の面状光源、又は、面状の照明用光源として好適に用いることができる。フレキシブルな基板を用いれば、曲面状の光源及び表示装置としても使用できる。
測定する高分子化合物を約0.05重量%の濃度でTHFに溶解させ、SECに10μL注入した。SECの移動相としてTHFを用い、2.0mL/分の流量で流した。カラムとして、PLgel MIXED-B(ポリマーラボラトリーズ製)を用いた。検出器にはUV-VIS検出器(島津製作所製、商品名:SPD-10Avp)を用いた。
測定試料を約2mg/mLの濃度になるようにクロロホルム又はTHFに溶解させ、LC-MS(アジレントテクノロジー製、商品名:1100LCMSD)に約1μL注入した。LC-MSの移動相には、アセトニトリル及びTHFの比率を変化させながら用い、0.2mL/分の流量で流した。カラムは、L-column 2 ODS(3μm)(化学物質評価研究機構製、内径:2.1mm、長さ:100mm、粒径3μm)を用いた。
5~10mgの測定試料を約0.5mLの重クロロホルム(CDCl3)、重テトラヒドロフラン(THF-d8)又は重塩化メチレン(CD2Cl2)に溶解させ、NMR装置(バリアン(Varian, Inc.)製、商品名:MERCURY 300)を用いて測定した。
化合物1は、特開2010-189630号公報に記載の方法に従って合成した。
化合物2、3及び4は、国際公開第2013/146806号に記載の方法に従って合成した。
化合物5は、特開2008-106241号公報に記載の方法に従って合成した。
化合物6は、国際公開第2009/157424号に記載の方法に従って合成した。
化合物7は、特開2011-174062号公報に記載の方法に従って合成した。
化合物8は、国際公開第2005/049546号に記載の方法に従って合成した。
化合物9は、市販の化合物を用いた。
化合物10は、特開2011-105701号公報に記載の方法に従って合成した。
化合物11a及び11bは、特開2012-33845号公報に記載の方法に従って合成した。
化合物12は、国際公開第2013/191088号に記載の方法に従って合成した。
化合物13は、特開2010-215886号公報に記載の方法に従って合成した。
化合物14は、国際公開第2013/021180号に記載の方法に従って合成した。
化合物(H-21)は、Luminescence Technology Corp.社から購入したものを用いた。
化合物(1-A3-6)は、国際公開第2008/090795号に記載の方法に準じて合成した。
化合物(1-A1-12)は、特開2013-147551号公報に記載の方法に従って合成した。
化合物COM-1は、特開2013-237789号公報に記載の方法に準じて合成した。
化合物COM-2は、国際公開第2002/44189号に記載の方法に準じて合成した。
化合物COM-4は、国際公開第2009/131255号に記載の方法に従って合成した。
化合物COM-8は、特開2011-105701号公報に記載の方法に従って合成した。
化合物COM-9は、下記調製例1に従って調製した。
[化合物S1]
反応容器内を窒素ガス気流下とした後、4-tert-オクチルフェノール(250.00g、1.21mol、Aldrich製品)、N,N-ジメチル-4-アミノピリジン(177.64g、1.45mol)およびジクロロメタン(3100mL)を加え、これを5℃に氷冷した。その後、これに、トリフルオロメタンスルホン酸無水物(376.06g、1.33mol)を45分かけて滴下した。滴下終了後、氷冷下で30分間攪拌し、次いで、室温に戻して更に1.5時間攪拌した。得られた反応混合物にヘキサン(3100mL)を加え、この反応混合物を、410gのシリカゲルを用いてろ過し、更に、ヘキサン/ジクロロメタン(1/1(体積基準))の混合溶媒(2.5L)でシリカゲルを洗浄した。得られたろ液と洗浄液を濃縮し、無色オイルの化合物S1-a(410.94g、1.21mol、LC純度99.7%)を得た。
反応容器内を窒素ガス気流下とした後、化合物S1-a(410.94g、1.21mol)、ビス(ピナコレート)ジボロン(338.47g、1.33mol)、酢酸カリウム(237.83g、2.42mol)、1,4-ジオキサン(2600mL)、酢酸パラジウム(4.08g、0.018mol)およびトリシクロヘキシルホスフィン(10.19g、0.036mol)を加え、2時間還流した。室温に冷却後、得られた反応混合物をろ過してろ液を集め、さらにろ過物を1,4-ジオキサン(2.5L)で洗浄し、得られたろ液と洗浄液を濃縮した。得られた残渣を、ヘキサン/ジクロロメタン(1/1(体積基準))の混合溶媒に溶解させ、770gのシリカゲルを用いてろ過し、更に、ヘキサン/ジクロロメタン(1/1(体積基準))の混合溶媒(2.5L)でシリカゲルを洗浄した。得られたろ液と洗浄液を濃縮し、得られた残渣にメタノール(1500mL)を加えて30分間超音波洗浄を行った。その後、これをろ過することにより、化合物S1-b(274.27g)を得た。ろ液と洗浄液を濃縮し、メタノールを加え、超音波洗浄を行い、ろ過するという操作を繰り返すことにより、化合物S1-b(14.29g)を得た。得られた化合物S1-bの合計の収量は288.56gであった。
反応容器内を窒素ガス気流下とした後、1,3-ジブロモベンゼン(102.48g、0.434mol)、化合物S1-b(288.56g、0.912mol)、トルエン(2100mL)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(962.38g、1.31mol)およびビス(トリフェニルホスフィン)パラジウム(II)ジクロリド(3.04g、0.004mol)を加え、7時間還流した。室温に冷却後、水層と有機層を分離し、有機層を集めた。この水層にトルエン(1L)を加えて、有機層をさらに抽出した。得られた有機層を合わせて、これを蒸留水/飽和食塩水(1.5L/1.5L)の混合水溶液で洗浄した。得られた有機層を400gのシリカゲルでろ過し、更にトルエン(2L)でシリカゲルを洗浄した。得られた溶液を濃縮し、得られた残渣をヘキサンに溶解させた。これをシリカゲルカラムクロマトグラフィーで精製した。展開溶媒であるヘキサンで不純物を溶出させた後に、ヘキサン/ジクロロメタン(10/1(体積基準))の混合溶媒で展開した。得られた各フラクションを減圧濃縮により溶媒を除去し、無色結晶の化合物S1-c(154.08g、LC純度99.1%)、および、粗製の化合物S1-c(38.64g、LC純度83%)を得た。この粗製の化合物S1-cを再び同様の展開条件にてカラム精製し、溶媒を減圧留去し、化合物S1-c(28.4g、LC純度99.6%)を得た。得られた化合物S1-cの合計の収量は182.48g(0.40mol)であった。
反応容器内を窒素ガス気流下とした後、化合物S1-c(182.48g、0.401mol)、ビス(ピナコラート)ジボロン(112.09g、0.441mol)、4,4’-ジ-tert-ブチル-2,2’-ジピリジル(3.23g、0.012mol)、シクロヘキサン(2000mL)およびビス(1,5-シクロオクタジエン)ジ-μ-メトキシジイリジウム(I)(3.99g、0.006mol)を加え、2時間還流した。室温に空冷後、得られた反応混合物を攪拌しながらシリカゲル(220g)を20分かけて加えた。得られた懸濁液を440gのシリカゲルでろ過し、さらにジクロロメタン(2L)でシリカゲルを洗浄し、溶液を濃縮した。得られた残渣に、メタノール(1100mL)およびジクロロメタン(110mL)を加え、1時間還流した。室温に冷却後、これをろ過した。得られたろ過物をメタノール(500mL)で洗浄し、得られた固体を乾燥させて、化合物S1(220.85g、0.380mol)を得た。
5-ブロモ-2-フェニルピリジンは、特開2008-179617号公報に記載の方法に従って合成した。
反応容器内をアルゴンガス雰囲気下とした後、5-ブロモ-2-フェニルピリジン(36.17g、155mmol)、化合物S1(94.20g、162mmol)、トルエン(1545mL)、20重量%テトラエチルアンモニウムヒドロキシド水溶液(341.28g、463.5mmol)およびテトラキス(トリフェニルホスフィン)パラジウム(0)(8.927g、7.725mmol)を加え、80℃で4時間攪拌した。室温に冷却後、得られた反応溶液に水(1545mL)を加え、有機層を抽出した。得られた有機層を、水(1545mL)で2回、食塩水(1545mL)で1回洗浄した。得られた有機層を、188gのシリカゲルを用いてろ過し、得られたろ液を減圧下で濃縮した。得られた残渣に、トルエン(235g)およびメタノール(1174g)を加え、60℃で30分間加熱した。その後、これを氷浴で5℃に冷却し、固体を析出させた。得られた固体をろ過し、冷メタノールで洗浄した。得られた固体を減圧乾燥させることにより、上記式で表される化合物L4(82.0g、135mmol)を得た。
反応容器内を窒素ガス雰囲気下とした後、塩化イリジウム三水和物(11.51g、32.3mmol)およびイオン交換水(114mL)を加え、50℃に加温して溶解させた。別の窒素ガス雰囲気下とした反応容器に、化合物L4(43.80g、72.1mmol)、2-エトキシエタノール(792mL)およびイオン交換水(57mL)を加え、100℃で1時間加熱攪拌した。その後、この溶液に、先に準備した塩化イリジウム水溶液(全量)をゆっくりと滴下した。滴下終了後、120℃で15時間攪拌した。室温に冷却後、得られた反応混合物にメタノール(207g)を加え、ろ過した。得られた固体を、メタノール(207g)で4回、ヘキサン(115g)で1回洗浄した。得られた固体を減圧乾燥させることにより、金属錯体M4-a(42.88g)を得た。
反応容器内を窒素ガス雰囲気下とした後、金属錯体M4-a(7.61g、2.64mmol)、化合物L4(16.05g、26.40mmol)、トリフルオロメタンスルホン酸銀(1.63g、6.34mmol)およびジエチレングリコールジメチルエーテル(79mL)を加え、160℃で16時間撹拌した。室温に冷却後、得られた反応混合物にメタノール(304mL)を加え、生じた沈澱をろ過した。得られた沈澱を、シリカゲルカラムクロマトグラフィー(ヘキサン/トルエン=4/6.5(体積基準)の混合溶媒)で精製し、減圧下で溶媒を除去した。得られた残渣(8.05g)をジクロロメタン(80mL)に溶解させ、この溶液にメタノール(80mL)を加えた。生じた沈澱をろ別して集め、これを減圧乾燥させることにより、金属錯体である化合物COM-9(6.25g、3.1mmol)を得た。
(工程1)反応容器内を不活性ガス雰囲気とした後、化合物1(0.673g)、化合物2(0.304g)、化合物3(0.222g)、化合物4(1.95g)、化合物5(0.238g)、化合物6(0.0953g)、ジクロロビス(トリス-o-メトキシフェニルホスフィン)パラジウム(2.0mg)、20重量%水酸化テトラエチルアンモニウム水溶液(7.5mL)およびトルエン(50mL)を加え、還流下で4時間撹拌した。
(工程2)反応後、そこに、フェニルボロン酸(27mg)、ジクロロビス(トリス-o-メトキシフェニルホスフィン)パラジウム(2.0mg)および20重量%水酸化テトラエチルアンモニウム水溶液(7.5mL)を加え、更に、還流下で17時間撹拌した。
(工程3)その後、そこに、N,N-ジエチルジチオカルバミド酸ナトリウム(1.25g)をイオン交換水(25ml)に溶解させた水溶液を加え、85℃で2時間撹拌した。反応液を室温まで冷却し、水層を除去した後、得られた有機層をイオン交換水で洗浄した、得られた有機層をメタノールに滴下したところ、沈澱が生じたので、沈殿物をろ取し、乾燥させることにより、固体を得た。この固体をトルエンに溶解させ、セライトカラムに通すことにより精製した。得られた溶液をメタノールに滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物1(2.3g)を得た。高分子化合物1のMnは4.0×104であり、Mwは2.0×105であった。
(工程1)反応容器内を不活性ガス雰囲気とした後、化合物7(2.5625mmol)、化合物8(1.5000mmol)、化合物9(0.4750mmol)、化合物5(0.3750mmol)、化合物10(0.1500mmol)、ジクロロビス(トリス-o-メトキシフェニルホスフィン)パラジウム(4.5mg)及びトルエン(83mL)を加え、100℃に加熱した。
(工程2)反応液に、20重量%水酸化テトラエチルアンモニウム水溶液(8.5mL)を滴下し、9.5時間還流させた。
(工程3)反応後、そこに、フェニルボロン酸(61mg)及びジクロロビス(トリス-o-メトキシフェニルホスフィン)パラジウム(2.2mg)を加え、19時間還流させた。
(工程4)その後、そこに、ジエチルジチオカルバミン酸ナトリウム水溶液(10mL、濃度:0.05g/mL)を加え、85℃で2時間撹拌した。冷却後、反応液を、3.6重量%塩酸、2.5重量%アンモニア水、水で洗浄し、得られた溶液をメタノールに滴下したところ、沈澱が生じた。沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムに順に通すことにより精製した。得られた溶液をメタノールに滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物2を3.152g得た。高分子化合物2のMnは4.4×104であり、Mwは1.5×105であった。
高分子化合物3は、化合物7、化合物8、化合物9及び化合物5を用いて、特開2012-144722号公報に記載の方法に従って合成した。
(工程1)反応容器内を不活性ガス雰囲気とした後、化合物11a(0.55g)、化合物11b(0.61g)、トリフェニルホスフィンパラジウム(0.01g)、メチルトリオクチルアンモニウムクロライド(アルドリッチ製、商品名Aliquat336(登録商標))(0.20g)、及びトルエン(10mL)を混合し、105℃に加熱した。
(工程2)反応液に、2M炭酸ナトリウム水溶液(6mL)を滴下し、8時間還流させた。
(工程3)反応液に、4-tert-ブチルフェニルボロン酸(0.01g)を加え、6時間還流させた。
(工程4)次いで、ジエチルジチオカルバミン酸ナトリウム水溶液(10mL、濃度:0.05g/mL)を加え、2時間撹拌した。混合溶液をメタノール300mL中に滴下して1時間攪拌した後、析出した沈殿をろ過して2時間減圧乾燥させ、テトラヒドロフラン20mlに溶解させた。得られた溶液をメタノール120ml、3重量%酢酸水溶液50mLの混合溶媒中に滴下して1時間攪拌した後、析出した沈殿をろ過し、テトラヒドロフラン20mlに溶解させた。
(工程5)こうして得られた溶液をメタノール200mlに滴下して30分攪拌した後、析出した沈殿をろ過して固体を得た。得られた固体をテトラヒドロフランに溶解させ、アルミナカラム、シリカゲルカラムに順に通すことにより精製した。得られた溶液をメタノールに滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物4を520mg得た。高分子化合物4のMnは5.2×104であった。
高分子化合物4(200mg)を100mLフラスコに入れ、該フラスコの雰囲気を窒素ガスで置換した。該フラスコに、テトラヒドロフラン(20mL)、及びエタノール(20mL)を添加し、混合物を55℃に昇温した。そこに、水酸化セシウム(200mg)を水(2mL)に溶解させた水溶液を添加し、55℃で6時間撹拌した。混合物を室温まで冷却した後、反応溶媒を減圧留去した。生じた固体を水で洗浄し、減圧乾燥させることで薄黄色の固体として高分子化合物5(150mg)を得た。NMRスペクトルにより、高分子化合物4内のエチルエステル部位のエチル基由来のシグナルが完全に消失していることを確認した。
(工程1)反応容器内を不活性ガス雰囲気とした後、化合物1(0.85675g)、化合物12(0.86638g)、化合物5(0.09367g)、化合物13(0.08090g)、化合物14(0.56072g)、ジクロロビス(トリス-o‐メトキシフェニルホスフィン)パラジウム(1.54mg)およびトルエン(36mL)を加え、105℃に加熱した。
(工程2)反応液に、20重量%水酸化テトラエチルアンモニウム水溶液(5.9mL)を滴下し、6時間還流させた。
(工程3)反応後、そこに、フェニルボロン酸(85.4mg)およびジクロロビス(トリス-o‐メトキシフェニルホスフィン)パラジウム(1.54mg)を加え、14.5間還流させた。
(工程4)その後、そこに、ジエチルジチオカルバミン酸ナトリウム水溶液(10mL、濃度:0.05g/mL)を加え、80℃で2時間撹拌した。冷却後、得られた反応液を、水で2回、3重量%酢酸水溶液で2回、水で2回洗浄し、得られた溶液をメタノールに滴下したところ、沈澱が生じた。得られた沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムに順に通すことにより精製した。得られた溶液をメタノールに滴下し、撹拌した後、得られた沈殿物をろ取し、乾燥させることにより、高分子化合物6を1.33g得た。高分子化合物6のポリスチレン換算の数平均分子量は7.0×104であり、ポリスチレン換算の重量平均分子量は1.8×105であった。
<評価例E1> 発光素子E1の作製と評価
ガラス基板にスパッタ法により45nmの厚みでITO膜を付けることにより陽極を形成した。該陽極上に、ポリチオフェン・スルホン酸系の正孔注入剤であるAQ-1200(Plectronics社製)をスピンコート法により35nmの厚さで成膜し、大気雰囲気中において、ホットプレート上で170℃、15分間加熱することにより正孔注入層を形成した。
高分子化合物1に代えて高分子化合物2を用いた以外は評価例E1と同様にして、発光素子E2を作製した。
ガラス基板にスパッタ法により45nmの厚みでITO膜を付けることにより陽極を形成した。該陽極上に、ポリチオフェン・スルホン酸系の正孔注入剤であるAQ-1200(Plectronics社製)をスピンコート法により35nmの厚さで成膜し、大気雰囲気中において、ホットプレート上で170℃、15分間加熱することにより正孔注入層を形成した。
燐光発光性化合物である化合物(1-A3-6)、化合物(1-A1-12)、化合物COM-1、化合物COM-4、化合物COM-9、化合物COM-2及び化合物COM-8の発光スペクトルの最大ピーク波長は、分光光度計(日本分光株式会社製、FP6500)により室温にて測定した。燐光発光性化合物をキシレンに、約0.8×10-4重量%の濃度で溶解させたキシレン溶液を試料として用いた。励起光としては、波長325nmのUV光を用いた。評価結果を表2に示す。
ガラス基板にスパッタ法により45nmの厚みでITO膜を付けることにより陽極を形成した。該陽極上に、ポリチオフェン・スルホン酸系の正孔注入剤であるAQ-1200(Plectronics社製)をスピンコート法により35nmの厚さで成膜し、大気雰囲気中において、ホットプレート上で170℃、15分間加熱することにより正孔注入層を形成した。
1)高分子化合物1に代えて、表3に示す高分子化合物を用いて第1の発光層(比較例1では正孔輸送層)を形成した点、2)インクD1に代えて、表3に示す構成材料と構成比率に変更したインクを使用して第2の発光層(比較例1では発光層)を形成した点以外は実施例2と同様にして、発光素子D2および発光素子CD1を作製した。発光素子D2および発光素子CD1の発光輝度1000cd/m2における評価結果についても表3に示す。
1)表4に示す高分子化合物を用いて第1の発光層(比較例2では正孔輸送層)を形成した点、2)インクD1に代えて、表4に示す構成材料と構成比率に変更したインクを使用して第2の発光層(比較例2では発光層)を形成した点以外は実施例2と同様にして、発光素子D3およびD4、並びに、発光素子CD2を作製した。発光素子D3およびD4、並びに、発光素子CD2の発光輝度1000cd/m2における評価結果についても表4に示す。
インクD1に代えて、表5に示す構成材料と構成比率に変更したインクを使用して第2の発光層を形成した以外は実施例2と同様にして、発光素子D5を作製した。発光素子D5の発光輝度1000cd/m2における評価結果についても表5に示す。
1)表6に示す高分子化合物を用いて第1の発光層(比較例3では正孔輸送層)を形成した点、2)インクD1に代えて、表6に示す構成材料と構成比率に変更したインクを使用して第2の発光層(比較例3では発光層)を形成した点以外は実施例2と同様にして、発光素子D6およびD7、並びに、発光素子CD3を作製した。発光素子D6およびD7、並びに、発光素子CD3の発光輝度1000cd/m2における評価結果についても表6に示す。
1)表7に示す高分子化合物を用いて第1の発光層(比較例4では正孔輸送層)を形成した点、2)インクD1に代えて、表7に示す構成材料と構成比率に変更したインクを使用して第2の発光層(比較例4では発光層)を形成した点以外は実施例2と同様にして、発光素子D8およびD9、並びに、発光素子CD4を作製した。発光素子D8およびD9、並びに、発光素子CD4の発光輝度1000cd/m2における評価結果についても表7に示す。
ガラス基板にスパッタ法により45nmの厚みでITO膜を付けることにより陽極を形成した。該陽極上に、ポリチオフェン・スルホン酸系の正孔注入剤であるAQ-1200(Plectronics社製)をスピンコート法により35nmの厚さで成膜し、大気雰囲気中において、ホットプレート上で170℃、15分間加熱することにより正孔注入層を形成した。
Claims (13)
- 陽極と、
陰極と、
陽極及び陰極の間に設けられた第1の発光層と、
陽極及び陰極の間に設けられた第2の発光層とを有し、
第1の発光層が、架橋基を有する構成単位と燐光発光性構成単位とを含む高分子化合物を用いて得られる層であり、
第2の発光層が、複素環構造を有する非燐光発光性の低分子化合物と、少なくとも2種の燐光発光性化合物とを含有する組成物を用いて得られる層である、発光素子。 - 前記第1の発光層が、前記陽極と前記第2の発光層との間に設けられている、請求項1に記載の発光素子。
- 前記複素環構造を有する非燐光発光性の低分子化合物が、式(H-1)で表される化合物である、請求項1又は2に記載の発光素子。
ArH1及びArH2は、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。
nH1及びnH2は、それぞれ独立に、0又は1を表す。nH1が複数存在する場合、それらは同一でも異なっていてもよい。複数存在するnH2は、同一でも異なっていてもよい。
nH3は、1以上の整数を表す。
LH1は、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。LH1が複数存在する場合、それらは同一でも異なっていてもよい。
LH2は、-N(-LH3-RHA)-で表される基又は-[C(RHB)2]nH4-で表される基を表す。RHAは、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LH3は、単結合、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。RHBは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するRHBは、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。nH4は1以上10以下の整数を表す。LH2が複数存在する場合、それらは同一でも異なっていてもよい。
但し、ArH1、ArH2、LH1及びLH2の少なくとも一つは、1価若しくは2価の複素環基であるか、又は1価若しくは2価の複素環基を含む基である。] - 前記少なくとも2種の燐光発光性化合物が、
発光スペクトルの最大ピーク波長が400nm以上480nm未満である少なくとも1種の燐光発光性化合物(B)及び発光スペクトルの最大ピーク波長が480nm以上680nm未満である少なくとも1種の燐光発光性化合物(G)を含む、請求項1~3のいずれか一項に記載の発光素子。 - 前記燐光発光性化合物(B)が、式(1)で表される燐光発光性化合物である、請求項4に記載の発光素子。
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子又は白金原子を表す。
n1は1以上の整数を表し、n2は0以上の整数を表し、n1+n2は2又は3である。Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n1+n2は3であり、Mがパラジウム原子又は白金原子の場合、n1+n2は2である。
E1及びE2は、それぞれ独立に、炭素原子又は窒素原子を表す。但し、E1及びE2の少なくとも一方は炭素原子である。
環R1は、5員環又は6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R1が複数存在する場合、それらは同一でも異なっていてもよい。但し、環R1が6員環の芳香族複素環である場合、E1は炭素原子である。
環R2は、5員環若しくは6員環の芳香族炭素環、又は、5員環若しくは6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R2が複数存在する場合、それらは同一でも異なっていてもよい。但し、環R2が6員環の芳香族複素環である場合、E2は炭素原子である。
但し、環R1が6員環の芳香族複素環である場合、環R2は電子求引基を有する。
A1-G1-A2は、アニオン性の2座配位子を表す。A1及びA2は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。G1は、単結合、又は、A1及びA2と共に2座配位子を構成する原子団を表す。A1-G1-A2が複数存在する場合、それらは同一でも異なっていてもよい。] - 前記式(1)で表される燐光発光性化合物が、式(1-A)で表される燐光発光性化合物である、請求項5に記載の発光素子。
n1、n2及びA1-G1-A2は、前記と同じ意味を表す。
M1は、イリジウム原子又は白金原子を表す。
E1A、E2A、E3A、E4A、E2B、E3B、E4B及びE5Bは、それぞれ独立に、窒素原子又は炭素原子を表す。E1A、E2A、E3A、E4A、E2B、E3B、E4B及びE5Bが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。E2A、E3A及びE4Aが窒素原子の場合、R2A、R3A及びR4Aは、存在しても存在しなくてもよい。E2B、E3B、E4B及びE5Bが窒素原子の場合、R2B、R3B、R4B及びR5Bは、存在しない。
R2A、R3A、R4A、R2B、R3B、R4B及びR5Bは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基、アリールオキシ基、1価の複素環基、ハロゲン原子又はデンドロンを表し、これらの基は置換基を有していてもよい。R2A、R3A、R4A、R2B、R3B、R4B及びR5Bが複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。R2AとR3A、R3AとR4A、R2AとR2B、R2BとR3B、R3BとR4B、及び、R4BとR5Bは、それぞれ結合して、それぞれが結合する原子と共に環を形成していてもよい。
環R1Aは、窒素原子、E1A、E2A、E3A及びE4Aにより構成されるトリアゾール環又はイミダゾール環を表す。
環R1Bは、2つの炭素原子、E2B、E3B、E4B及びE5Bにより構成されるベンゼン環、ピリジン環又はピリミジン環を表す。] - 燐光発光性化合物(G)が、式(2)で表される燐光発光性化合物である、請求項4~6のいずれか一項に記載の発光素子。
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子又は白金原子を表す。
n3は1以上の整数を表し、n4は0以上の整数を表し、n3+n4は2又は3である。Mがルテニウム原子、ロジウム原子又はイリジウム原子の場合、n3+n4は3であり、Mがパラジウム原子又は白金原子の場合、n3+n4は2である。
E4は、炭素原子又は窒素原子を表す。
環R3は、6員環の芳香族複素環を表し、この環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R3が複数存在する場合、それらは同一でも異なっていてもよい。
環R4は、5員環若しくは6員環の芳香族炭素環、又は、5員環若しくは6員環の芳香族複素環を表し、これらの環は置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する原子と共に環を形成していてもよい。環R4が複数存在する場合、それらは同一でも異なっていてもよい。但し、環R4が6員環の芳香族複素環である場合、E4は炭素原子である。
A1-G1-A2は、アニオン性の2座配位子を表す。A1及びA2は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。G1は、単結合、又は、A1及びA2と共に2座配位子を構成する原子団を表す。A1-G1-A2が複数存在する場合、それらは同一でも異なっていてもよい。] - 前記架橋基を有する構成単位が、式(11)で表される構成単位及び式(12)で表される構成単位からなる群から選ばれる少なくとも1種の構成単位である、請求項8に記載の発光素子。
nAは0~5の整数を表し、nは1又は2を表す。nAが複数存在する場合、それらは同一でも異なっていてもよい。
Ar3は、(n+2)価の芳香族炭化水素基又は(n+2)価の複素環基を表し、これらの基は置換基を有していてもよい。
LAは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LAが複数存在する場合、それらは同一でも異なっていてもよい。
Xは、架橋基A群から選ばれる架橋基を表す。Xが複数存在する場合、それらは同一でも異なっていてもよい。]
mAは0~5の整数を表し、mは1~4の整数を表し、cは0又は1の整数を表す。mAが複数存在する場合、それらは同一でも異なっていてもよい。
Ar5は、(m+2)価の芳香族炭化水素基、(m+2)価の複素環基、又は、少なくとも1種の芳香族炭素環と少なくとも1種の複素環とが直接結合した(m+2)価の基を表し、これらの基は置換基を有していてもよい。
Ar4及びAr6は、それぞれ独立に、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。
Ar4、Ar5及びAr6はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接又は酸素原子若しくは硫黄原子を介して結合して、環を形成していてもよい。
KAは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、前記と同じ意味を表す。KAが複数存在する場合、それらは同一でも異なっていてもよい。
X’は、架橋基A群から選ばれる架橋基、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。X’が複数存在する場合、それらは同一でも異なっていてもよい。但し、少なくとも1つのX’は、架橋基A群から選ばれる架橋基である。] - 前記燐光発光性構成単位が、式(1G)、式(2G)、式(3G)及び式(4G)で表される構成単位群から選ばれる少なくとも1種の構成単位である、請求項1~9のいずれか一項に記載の発光素子。
M1Gは、燐光発光性化合物から、該化合物を構成する炭素原子又はヘテロ原子に直接結合する1個の水素原子を取り除いてなる基を表す。
L1は、酸素原子、硫黄原子、-N(RA)-で表される基、-C(RB)2-で表される基、-C(RB)=C(RB)-で表される基、-C≡C-で表される基、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。RAは、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。RBは、水素原子、アルキル基、シクロアルキル基、アルコキシ基、シクロアルコキシ基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。複数存在するRBは、同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成していてもよい。L1が複数存在する場合、それらは同一でも異なっていてもよい。
na1は0以上の整数を表す。]
M1Gは前記と同じ意味を表す。
L2及びL3は、それぞれ独立に、酸素原子、硫黄原子、-N(RA)-で表される基、-C(RB)2-で表される基、-C(RB)=C(RB)-で表される基、-C≡C-で表される基、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。RA及びRBは、前記と同じ意味を表す。L2及びL3が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
nb1及びnc1は、それぞれ独立に、0以上の整数を表す。複数存在するnb1は、同一でも異なっていてもよい。
Ar1Mは、3価の芳香族炭化水素基又は3価の複素環基を表し、これらの基は置換基を有していてもよい。]
L2及びnb1は、前記と同じ意味を表す。
M2Gは、燐光発光性化合物から、該化合物を構成する炭素原子又はヘテロ原子に直接結合する2個の水素原子を取り除いてなる基を表す。]
L2及びnb1は、前記と同じ意味を表す。
M3Gは、燐光発光性化合物から、該化合物を構成する炭素原子又はヘテロ原子に直接結合する3個の水素原子を取り除いてなる基を表す。] - 前記架橋基を有する構成単位と燐光発光性構成単位とを含む高分子化合物が、更に、式(X)で表される構成単位及び式(Y)で表される構成単位からなる群から選ばれる少なくとも1種の構成単位を含む、請求項1~10のいずれか一項に記載の発光素子。
a1及びa2は、それぞれ独立に、0以上の整数を表す。
ArX1及びArX3は、それぞれ独立に、アリーレン基又は2価の複素環基を表し、これらの基は置換基を有していてもよい。
ArX2及びArX4は、それぞれ独立に、アリーレン基、2価の複素環基、又は、少なくとも1種のアリーレン基と少なくとも1種の2価の複素環基とが直接結合した2価の基を表し、これらの基は置換基を有していてもよい。ArX2及びArX4が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。
RX1、RX2及びRX3は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。RX2及びRX3が複数存在する場合、それらはそれぞれ同一でも異なっていてもよい。]
- 前記第2の発光層と前記陰極との間に、電子輸送層及び電子注入層からなる群から選ばれる少なくとも1層を更に有する、請求項1~11のいずれか一項に記載の発光素子。
- 式(13)で表される基を有する構成単位と燐光発光性構成単位とを含む高分子化合物。
nBは1~5の整数を表す。
LBは、アルキレン基、シクロアルキレン基、アリーレン基、2価の複素環基、-NR’-で表される基、酸素原子又は硫黄原子を表し、これらの基は置換基を有していてもよい。R’は、水素原子、アルキル基、シクロアルキル基、アリール基又は1価の複素環基を表し、これらの基は置換基を有していてもよい。LBが複数存在する場合、それらは同一でも異なっていてもよい。
ベンゾシクロブテン環は、置換基を有していてもよい。該置換基が複数存在する場合、それらは同一でも異なっていてもよく、互いに結合して、それぞれが結合する炭素原子と共に環を形成してもよい。]
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167028210A KR20160148528A (ko) | 2014-04-25 | 2015-04-13 | 발광 소자 |
JP2016514866A JP6675304B2 (ja) | 2014-04-25 | 2015-04-13 | 発光素子 |
EP15782884.9A EP3136462A4 (en) | 2014-04-25 | 2015-04-13 | Light-emitting element |
CN201580020764.XA CN106415872B (zh) | 2014-04-25 | 2015-04-13 | 发光元件 |
US15/305,611 US20170040538A1 (en) | 2014-04-25 | 2015-04-13 | Light-emitting device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014091611 | 2014-04-25 | ||
JP2014-091611 | 2014-04-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015163174A1 true WO2015163174A1 (ja) | 2015-10-29 |
Family
ID=54332341
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/061318 WO2015163174A1 (ja) | 2014-04-25 | 2015-04-13 | 発光素子 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20170040538A1 (ja) |
EP (1) | EP3136462A4 (ja) |
JP (1) | JP6675304B2 (ja) |
KR (1) | KR20160148528A (ja) |
CN (1) | CN106415872B (ja) |
WO (1) | WO2015163174A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017099013A1 (ja) * | 2015-12-07 | 2017-06-15 | 住友化学株式会社 | 組成物及びそれを用いた発光素子 |
WO2017146083A1 (ja) * | 2016-02-25 | 2017-08-31 | 住友化学株式会社 | 発光素子及び該発光素子に用いる高分子化合物 |
EP3235891A4 (en) * | 2015-02-03 | 2017-12-27 | Sumitomo Chemical Company, Ltd. | Composition and light-emitting element using same |
JP2018085505A (ja) * | 2016-11-14 | 2018-05-31 | 住友化学株式会社 | 発光素子 |
WO2018131320A1 (ja) | 2017-01-10 | 2018-07-19 | 住友化学株式会社 | 有機デバイスの製造方法 |
JPWO2017130828A1 (ja) * | 2016-01-28 | 2018-08-02 | 住友化学株式会社 | 膜の製造方法 |
JPWO2017099012A1 (ja) * | 2015-12-07 | 2018-09-20 | 住友化学株式会社 | 発光素子 |
WO2018198974A1 (ja) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | 発光素子 |
US11225602B2 (en) | 2016-06-24 | 2022-01-18 | Sumitomo Chemical Company, Limited | Light emitting device |
US11588119B2 (en) | 2017-04-27 | 2023-02-21 | Sumitomo Chemical Company, Limited | Light emitting device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10008679B2 (en) | 2014-04-14 | 2018-06-26 | Universal Display Corporation | Organic electroluminescent materials and devices |
US9847498B2 (en) | 2014-04-14 | 2017-12-19 | Universal Display Corporation | Organic electroluminescent materials and devices |
KR20170066442A (ko) * | 2014-09-30 | 2017-06-14 | 스미또모 가가꾸 가부시키가이샤 | 발광 소자 |
CN110547049A (zh) * | 2017-04-27 | 2019-12-06 | 住友化学株式会社 | 组合物和使用了该组合物的发光元件 |
WO2019208648A1 (ja) * | 2018-04-26 | 2019-10-31 | 住友化学株式会社 | 発光素子 |
JP6934967B2 (ja) * | 2019-03-29 | 2021-09-15 | 住友化学株式会社 | 発光素子及び発光素子用組成物 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008106241A (ja) * | 2006-09-25 | 2008-05-08 | Sumitomo Chemical Co Ltd | 高分子化合物及びそれを用いた高分子発光素子 |
WO2011078387A1 (ja) * | 2009-12-25 | 2011-06-30 | 住友化学株式会社 | 組成物及び該組成物を用いてなる発光素子 |
JP2012502485A (ja) * | 2008-09-04 | 2012-01-26 | ユニバーサル ディスプレイ コーポレイション | 白色燐光有機発光装置 |
WO2013005031A1 (en) * | 2011-07-04 | 2013-01-10 | Cambridge Display Technology Limited | Organic light emitting device and method |
WO2013021180A1 (en) * | 2011-08-05 | 2013-02-14 | Cambridge Display Technology Limited | Light emitting polymers and devices |
WO2013108037A1 (en) * | 2012-01-18 | 2013-07-25 | Cambridge Display Technology Limited | Electroluminescence from a plurality of electroluminescent zones in a laterally separated arrangement |
WO2013164647A2 (en) * | 2012-05-04 | 2013-11-07 | Cambridge Display Technology Limited | Organic light emitting device and method |
JP2013256655A (ja) * | 2012-05-16 | 2013-12-26 | Sumitomo Chemical Co Ltd | 高分子化合物およびそれを用いた発光素子 |
JP2014148663A (ja) * | 2012-12-21 | 2014-08-21 | Cambridge Display Technology Ltd | ポリマーおよび有機発光デバイス |
JP2014239219A (ja) * | 2013-06-05 | 2014-12-18 | ケンブリッジ ディスプレイ テクノロジー リミテッド | 有機発光素子 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001185357A (ja) | 1999-12-27 | 2001-07-06 | Nichia Chem Ind Ltd | 有機電界発光素子 |
EP3093898B1 (en) | 2006-03-30 | 2017-12-13 | Konica Minolta Holdings, Inc. | Organic electroluminescence device and lighting device |
US8288187B2 (en) * | 2010-01-20 | 2012-10-16 | Universal Display Corporation | Electroluminescent devices for lighting applications |
KR101911971B1 (ko) * | 2011-01-31 | 2018-10-25 | 캠브리지 디스플레이 테크놀로지 리미티드 | 중합체 |
-
2015
- 2015-04-13 US US15/305,611 patent/US20170040538A1/en not_active Abandoned
- 2015-04-13 JP JP2016514866A patent/JP6675304B2/ja active Active
- 2015-04-13 WO PCT/JP2015/061318 patent/WO2015163174A1/ja active Application Filing
- 2015-04-13 CN CN201580020764.XA patent/CN106415872B/zh active Active
- 2015-04-13 EP EP15782884.9A patent/EP3136462A4/en not_active Withdrawn
- 2015-04-13 KR KR1020167028210A patent/KR20160148528A/ko not_active Application Discontinuation
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008106241A (ja) * | 2006-09-25 | 2008-05-08 | Sumitomo Chemical Co Ltd | 高分子化合物及びそれを用いた高分子発光素子 |
JP2012502485A (ja) * | 2008-09-04 | 2012-01-26 | ユニバーサル ディスプレイ コーポレイション | 白色燐光有機発光装置 |
WO2011078387A1 (ja) * | 2009-12-25 | 2011-06-30 | 住友化学株式会社 | 組成物及び該組成物を用いてなる発光素子 |
WO2013005031A1 (en) * | 2011-07-04 | 2013-01-10 | Cambridge Display Technology Limited | Organic light emitting device and method |
WO2013021180A1 (en) * | 2011-08-05 | 2013-02-14 | Cambridge Display Technology Limited | Light emitting polymers and devices |
WO2013108037A1 (en) * | 2012-01-18 | 2013-07-25 | Cambridge Display Technology Limited | Electroluminescence from a plurality of electroluminescent zones in a laterally separated arrangement |
WO2013164647A2 (en) * | 2012-05-04 | 2013-11-07 | Cambridge Display Technology Limited | Organic light emitting device and method |
JP2013256655A (ja) * | 2012-05-16 | 2013-12-26 | Sumitomo Chemical Co Ltd | 高分子化合物およびそれを用いた発光素子 |
JP2014148663A (ja) * | 2012-12-21 | 2014-08-21 | Cambridge Display Technology Ltd | ポリマーおよび有機発光デバイス |
JP2014239219A (ja) * | 2013-06-05 | 2014-12-18 | ケンブリッジ ディスプレイ テクノロジー リミテッド | 有機発光素子 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3136462A4 * |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3235891A4 (en) * | 2015-02-03 | 2017-12-27 | Sumitomo Chemical Company, Ltd. | Composition and light-emitting element using same |
CN108369993A (zh) * | 2015-12-07 | 2018-08-03 | 住友化学株式会社 | 组合物及使用了其的发光元件 |
WO2017099013A1 (ja) * | 2015-12-07 | 2017-06-15 | 住友化学株式会社 | 組成物及びそれを用いた発光素子 |
CN108369993B (zh) * | 2015-12-07 | 2020-03-27 | 住友化学株式会社 | 组合物及使用了其的发光元件 |
JPWO2017099013A1 (ja) * | 2015-12-07 | 2018-11-01 | 住友化学株式会社 | 組成物及びそれを用いた発光素子 |
JPWO2017099012A1 (ja) * | 2015-12-07 | 2018-09-20 | 住友化学株式会社 | 発光素子 |
US10964902B2 (en) | 2016-01-28 | 2021-03-30 | Sumitomo Chemical Company, Limited | Film production method |
EP3410828A4 (en) * | 2016-01-28 | 2019-07-31 | Sumitomo Chemical Company Limited | METHOD FOR MANUFACTURING FILM |
US11770941B2 (en) | 2016-01-28 | 2023-09-26 | Sumitomo Chemical Company, Limited | Film production method |
EP3883345A1 (en) * | 2016-01-28 | 2021-09-22 | Sumitomo Chemical Company Limited | Film production method |
JPWO2017130828A1 (ja) * | 2016-01-28 | 2018-08-02 | 住友化学株式会社 | 膜の製造方法 |
TWI714712B (zh) * | 2016-01-28 | 2021-01-01 | 日商住友化學股份有限公司 | 膜的製造方法 |
JPWO2017146083A1 (ja) * | 2016-02-25 | 2018-12-20 | 住友化学株式会社 | 発光素子及び該発光素子に用いる高分子化合物 |
WO2017146083A1 (ja) * | 2016-02-25 | 2017-08-31 | 住友化学株式会社 | 発光素子及び該発光素子に用いる高分子化合物 |
US11225602B2 (en) | 2016-06-24 | 2022-01-18 | Sumitomo Chemical Company, Limited | Light emitting device |
JP2018085505A (ja) * | 2016-11-14 | 2018-05-31 | 住友化学株式会社 | 発光素子 |
JP7017907B2 (ja) | 2016-11-14 | 2022-02-09 | 住友化学株式会社 | 発光素子 |
WO2018131320A1 (ja) | 2017-01-10 | 2018-07-19 | 住友化学株式会社 | 有機デバイスの製造方法 |
JPWO2018198974A1 (ja) * | 2017-04-27 | 2019-06-27 | 住友化学株式会社 | 発光素子 |
US11588119B2 (en) | 2017-04-27 | 2023-02-21 | Sumitomo Chemical Company, Limited | Light emitting device |
WO2018198974A1 (ja) | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | 発光素子 |
Also Published As
Publication number | Publication date |
---|---|
CN106415872A (zh) | 2017-02-15 |
KR20160148528A (ko) | 2016-12-26 |
EP3136462A1 (en) | 2017-03-01 |
EP3136462A4 (en) | 2017-12-20 |
JPWO2015163174A1 (ja) | 2017-04-13 |
US20170040538A1 (en) | 2017-02-09 |
CN106415872B (zh) | 2019-05-28 |
JP6675304B2 (ja) | 2020-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6675304B2 (ja) | 発光素子 | |
KR102345329B1 (ko) | 조성물, 인광 발광성 화합물 및 발광 소자 | |
JP5867580B2 (ja) | 発光素子 | |
JP5842989B2 (ja) | 組成物およびそれを用いた発光素子 | |
JP6108056B2 (ja) | 組成物およびそれを用いた発光素子 | |
JP6468289B2 (ja) | 発光素子 | |
JP6323093B2 (ja) | 高分子化合物およびそれを用いた発光素子 | |
JP2015110751A (ja) | 組成物およびそれを用いた発光素子 | |
WO2016043097A1 (ja) | 金属錯体およびそれを用いた発光素子 | |
JP6303658B2 (ja) | 高分子化合物およびそれを用いた発光素子 | |
JP5880679B2 (ja) | 発光素子の製造方法 | |
WO2017077904A1 (ja) | 発光素子の駆動方法および発光装置 | |
JP2015174824A (ja) | 金属錯体およびそれを用いた発光素子 | |
WO2015141603A1 (ja) | 金属錯体およびそれを用いた発光素子 | |
JP6543902B2 (ja) | 金属錯体およびそれを用いた発光素子 | |
JP7215957B2 (ja) | ブロック共重合体及び組成物、並びにそれらを用いた発光素子 | |
JP7282078B2 (ja) | ブロック共重合体及びそれを用いた発光素子 | |
WO2017099012A1 (ja) | 発光素子 | |
WO2017099013A1 (ja) | 組成物及びそれを用いた発光素子 | |
JP6907739B2 (ja) | 組成物及びそれを用いた発光素子 | |
JP6825494B2 (ja) | 組成物、高分子化合物及びそれらを用いた発光素子 | |
JP2017155180A (ja) | 高分子化合物及びそれを用いた発光素子 | |
JP6491420B2 (ja) | 金属錯体及び該金属錯体を用いた発光素子 | |
JP2016129140A (ja) | 発光素子の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15782884 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016514866 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20167028210 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15305611 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015782884 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015782884 Country of ref document: EP |