WO2015186539A1 - 発光素子 - Google Patents
発光素子 Download PDFInfo
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- WO2015186539A1 WO2015186539A1 PCT/JP2015/064766 JP2015064766W WO2015186539A1 WO 2015186539 A1 WO2015186539 A1 WO 2015186539A1 JP 2015064766 W JP2015064766 W JP 2015064766W WO 2015186539 A1 WO2015186539 A1 WO 2015186539A1
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- 0 Cc1c(*)c(*)c(C)c(*)c1* Chemical compound Cc1c(*)c(*)c(C)c(*)c1* 0.000 description 10
- RUOJEQXQCGXQBF-UHFFFAOYSA-O CC(C)(C)c(cc1)ccc1C(OC(c1cc(C(OC(c2ccc(C(C)(C)C)cc2)=[NH2+])=N)ccc1)=N)=N Chemical compound CC(C)(C)c(cc1)ccc1C(OC(c1cc(C(OC(c2ccc(C(C)(C)C)cc2)=[NH2+])=N)ccc1)=N)=N RUOJEQXQCGXQBF-UHFFFAOYSA-O 0.000 description 1
- ZYDUIXGYVYNUTH-UHFFFAOYSA-N CC(CCOC)CCOCC1COCC1 Chemical compound CC(CCOC)CCOCC1COCC1 ZYDUIXGYVYNUTH-UHFFFAOYSA-N 0.000 description 1
- PXEOGWNOWAUDEI-UHFFFAOYSA-N Cc(cc1)cc(c2c3cccc2)c1[n]3-c(cc1)ccc1-[n]1c(ccc(C)c2)c2c2ccccc12 Chemical compound Cc(cc1)cc(c2c3cccc2)c1[n]3-c(cc1)ccc1-[n]1c(ccc(C)c2)c2c2ccccc12 PXEOGWNOWAUDEI-UHFFFAOYSA-N 0.000 description 1
- MJSSEZYEKFDHGF-UHFFFAOYSA-N Cc(cc1)ccc1-c1ncc(C)c2ccccc12 Chemical compound Cc(cc1)ccc1-c1ncc(C)c2ccccc12 MJSSEZYEKFDHGF-UHFFFAOYSA-N 0.000 description 1
- PTBRNAVGPWOGSE-UHFFFAOYSA-N Cc(cc1)ccc1-c1ncc(C)cc1 Chemical compound Cc(cc1)ccc1-c1ncc(C)cc1 PTBRNAVGPWOGSE-UHFFFAOYSA-N 0.000 description 1
- SDHNJSIZTIODFW-UHFFFAOYSA-N c(cc1)cc(c2c3cccc2)c1[n]3-c1ccc2[s]c(ccc(-[n]3c4ccccc4c4c3cccc4)c3)c3c2c1 Chemical compound c(cc1)cc(c2c3cccc2)c1[n]3-c1ccc2[s]c(ccc(-[n]3c4ccccc4c4c3cccc4)c3)c3c2c1 SDHNJSIZTIODFW-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N c(cc1)ccc1-[n]1c(-c2cc(-c3nc(cccc4)c4[n]3-c3ccccc3)cc(-c3nc4ccccc4[n]3-c3ccccc3)c2)nc2c1cccc2 Chemical compound c(cc1)ccc1-[n]1c(-c2cc(-c3nc(cccc4)c4[n]3-c3ccccc3)cc(-c3nc4ccccc4[n]3-c3ccccc3)c2)nc2c1cccc2 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- HBQUOLGAXBYZGR-UHFFFAOYSA-N c(cc1)ccc1-c1nc(-c2ccccc2)nc(-c2ccccc2)n1 Chemical compound c(cc1)ccc1-c1nc(-c2ccccc2)nc(-c2ccccc2)n1 HBQUOLGAXBYZGR-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
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- 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 Table
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- 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- 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
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- C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
- C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- 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
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- 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
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- 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
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- 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
- H10K85/151—Copolymers
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- 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
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- 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
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- 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
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- 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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
Definitions
- the present invention relates to a light emitting element.
- Light emitting elements such as organic electroluminescence elements (organic EL elements) can be suitably used for display and lighting applications because of their characteristics such as high luminous efficiency and low voltage drive, and have recently been attracting attention.
- This light-emitting element includes organic layers such as a light-emitting layer and a charge transport layer.
- Patent Document 1 discloses a light emitting layer formed using a phosphorescent compound, a hole transport layer formed using a polymer compound containing a fluorene structural unit, an aromatic amine structural unit and a crosslinkable structural unit. A light emitting device having the following is described. In addition, only the high molecular compound containing a fluorene structural unit, an aromatic amine structural unit, and a crosslinkable structural unit is used for formation of a positive hole transport layer.
- an object of the present invention is to provide a light-emitting element with excellent luminance life.
- the present invention provides the following [1] to [10].
- a light emitting device having an anode, a cathode, a first organic layer provided between the anode and the cathode, and a second organic layer provided between the anode and the first organic layer.
- the first organic layer is a layer containing one or more phosphorescent compounds;
- the second organic layer is a layer containing one or more phosphorescent compounds and a crosslinked material of a crosslinking material;
- 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 represents a carbon atom or a nitrogen atom. However, at least one of E 1 and E 2 is a carbon atom.
- Ring L 1 represents a 5-membered or 6-membered aromatic heterocyclic ring, and these rings may have a substituent. When a plurality of such 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 L 1 are present, they may be the same or different. However, when the ring L 1 is a 6-membered aromatic heterocyclic ring, E 1 is a carbon atom.
- Ring L 2 represents a 5-membered or 6-membered aromatic hydrocarbon ring, or a 5-membered or 6-membered aromatic heterocycle, and these rings may have a substituent.
- substituents When a plurality of such 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.
- rings L 2 When a plurality of rings L 2 are present, they may be the same or different.
- E 2 is a carbon atom.
- at least one ring selected from the group consisting of ring L 1 and ring L 2 has a group represented by formula (2).
- a 1 -G 1 -A 2 represents an anionic bidentate ligand.
- 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.
- -R 2 (2) [Wherein R 2 represents an aryl group, a monovalent heterocyclic group or a substituted amino group, and these groups optionally have a substituent. ]
- [2] The light emitting device according to [1], wherein the group represented by the formula (2) is a group represented by the formula (DA) or a group represented by the formula (DB).
- m DA1 , m DA2 and m DA3 each independently represent an integer of 0 or more.
- GDA represents a nitrogen atom, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally 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.
- TDA 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, an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent.
- a plurality of GDAs 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.
- TDA 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.
- Ar 1 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally 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 may have a substituent. When a plurality of LA are present, they may be the same or different.
- X represents a crosslinking group selected from the crosslinking group A group.
- X When two or more X exists, they may be the same or different.
- mA represents an integer of 0 to 5
- m represents an integer of 1 to 4
- c represents 0 or 1.
- Ar 3 represents an aromatic hydrocarbon group, a heterocyclic group, or a group in which at least one aromatic hydrocarbon ring and at least one heterocyclic ring are directly bonded, and these groups have a substituent. It may be.
- Ar 2 and Ar 4 each independently represent an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- Ar 2 , Ar 3, and Ar 4 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 sulfur atom, to form a ring. It may be.
- K A is an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic group, -NR '' -, a group represented by an oxygen atom or a sulfur atom, these groups have a substituent May be.
- 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 bridging group selected from the bridging group A, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent. However, at least one X ′ is a crosslinking group selected from the crosslinking group A group.
- [5] The light emitting device according to any one of [1] to [4], wherein the phosphorescent compound represented by the formula (1) is a phosphorescent compound represented by the formula (1-A) .
- E11A , E12A , E13A , E21A , E22A , E23A and E24A each independently represent a nitrogen atom or a carbon atom.
- E 11A , E 12A , E 13A , E 21A , E 22A , E 23A and E 24A they may be the same or different.
- E 11A , E 12A and E 13A are nitrogen atoms, R 11A , R 12A and R 13A may or may not be present.
- R 21A , E 22A , E 23A and E 24A are nitrogen atoms, R 21A , R 22A , R 23A and R 24A are not present.
- R 11A , R 12A , R 13A , R 21A , R 22A , R 23A and R 24A 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 substituted amino group, or a halogen atom, and these groups may have a substituent.
- R 11A , R 12A , R 13A , R 21A , R 22A , R 23A and R 24A are present, they may be the same or different.
- R 11A and R 12A , R 12A and R 13A , R 11A and R 21A , R 21A and R 22A , R 22A and R 23A , and R 23A and R 24A are bonded to each other, together with the atoms to which they are bonded A ring may be formed.
- at least one selected from the group consisting of R 11A , R 12A , R 13A , R 21A , R 22A , R 23A and R 24A is a group represented by the formula (2).
- Ring L 1A represents a triazole ring or an imidazole ring composed of a nitrogen atom, E 1 , E 11A , E 12A and E 13A .
- Ring L 2A represents a benzene ring, a pyridine ring or a pyrimidine ring composed of two carbon atoms, E 21A , E 22A , E 23A and E 24A .
- the phosphorescent compound represented by the formula (1-A) is a phosphorescent compound represented by the formula (1-A1), (1-A2), (1-A3) or (1-A4).
- E 11B , E 12B , E 13B , E 14B , E 21B , E 22B , E 23B and E 24B each independently represent a nitrogen atom or a carbon atom.
- E 11B , E 12B , E 13B , E 14B , E 21B , E 22B , E 23B and E 24B may be the same or different.
- E 11B , E 12B , E 13B , E 14B , E 21B , E 22B , E 23B and E 24B are nitrogen atoms, R 11B , R 12B , R 13B , R 14B , R 21B , R 22B , R 23B and R 24B is not present.
- R 11B , R 12B , R 13B , R 14B , R 21B , R 22B , R 23B and R 24B are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryl It represents an oxy group, a monovalent heterocyclic group or a halogen atom, and these groups optionally have a substituent.
- R 11B , R 12B , R 13B , R 14B , R 21B , R 22B , R 23B and R 24B may be the same or different.
- R 11B and R 12B , R 12B and R 13B , R 13B and R 14B , R 11B and R 21B , R 21B and R 22B , R 22B and R 23B , and R 23B and R 24B are combined, You may form the ring with the atom to which each couple
- Ring L 1B represents a pyridine ring or a pyrimidine ring composed of a nitrogen atom, a carbon atom, E 11B , E 12B , E 13B and E 14B .
- Ring L 2B represents a benzene ring, a pyridine ring or a pyrimidine ring composed of two carbon atoms, E 21B , E 22B , E 23B and E 24B .
- the phosphorescent compound represented by the formula (1-B) is a phosphorescent compound represented by the formula (1-B1), (1-B2), or (1-B3). 7].
- n 11 and n 12 each independently represents an integer of 1 or more, and n 11 + n 12 is 2 or 3.
- M is a ruthenium atom, rhodium atom or iridium atom, n 11 + n 12 is 3, and when M is a palladium atom or platinum atom, n 11 + n 12 is 2.
- R 15B , R 16B , R 17B and R 18B are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryl group, aryloxy group, monovalent heterocyclic group, substituted amino group Represents a group or a halogen atom, and these groups optionally have a substituent.
- R 15B , R 16B , R 17B and R 18B may be the same or different.
- R 13B and R 15B , R 15B and R 16B , R 16B and R 17B , R 17B and R 18B , and R 18B and R 21B are bonded to each other to form a ring together with the atoms to which they are bonded. Also good. However, at least one selected from the group consisting of R 11B , R 12B , R 13B , R 14B , R 21B , R 22B , R 23B and R 24B is a group represented by the formula (2).
- the first organic layer is a layer containing one or more phosphorescent compounds and a polymer compound containing a structural unit represented by the formula (Y). ]
- the light emitting element in any one of.
- 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 first organic layer is a layer containing one or more phosphorescent compounds and a compound represented by the formula (H-1).
- the light emitting element as described in. [Where: Ar H1 and Ar H2 each independently represent an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
- n H1 and n H2 each independently represent 0 or 1.
- n H1 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 0 or more. L H1 represents an arylene group, a divalent heterocyclic group, or a group represented by — [C (R H11 ) 2 ] n H11 —, and these groups optionally have a substituent. When a plurality of L H1 are present, they may be the same or different. n H11 represents an integer of 1 or more and 10 or less.
- R H11 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.
- a plurality of R H11 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 H2 represents a group represented by —N (—L H21 —R H21 ) —. When a plurality of L H2 are present, they may be the same or different.
- L H21 represents a single bond, an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- R H21 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.
- Me represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- i-Pr represents an isopropyl group
- t-Bu represents a tert-butyl group.
- the hydrogen atom may be a deuterium atom or a light hydrogen atom.
- the solid line representing the bond with the central metal means a covalent bond or a coordinate bond.
- the “polymer compound” means a polymer having a molecular weight distribution and having a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 8 .
- 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.
- Low molecular weight compound means a compound having no molecular weight distribution and a molecular weight of 1 ⁇ 10 4 or less.
- “Structural unit” means one or more units present in a polymer compound.
- the “alkyl group” may be linear or branched.
- the number of carbon atoms of the straight chain alkyl group is usually 1 to 50, preferably 3 to 30, and more preferably 4 to 20, 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, 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-hexyldecyl group, dodecyl group, and these Examples include groups in which the hydrogen atom in the group is substituted with a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, a fluorine atom, etc., for example, a trifluoromethyl group, a pentafluoroeth
- the number of carbon atoms of the “cycloalkyl group” is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20, excluding the number of carbon atoms of the substituent.
- the cycloalkyl group may have a substituent, and examples thereof include a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylethyl 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 20, more preferably 6 to 10, not including the number of carbon atoms of the substituent.
- the “alkoxy group” may be linear or branched.
- the number of carbon atoms of the straight-chain alkoxy group is usually 1 to 40, preferably 4 to 10, excluding the number of carbon atoms of the substituent.
- the number of carbon atoms of the branched alkoxy group is usually 3 to 40, preferably 4 to 10, excluding the number of carbon atoms of the substituent.
- 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 the hydrogen atom in these groups is a cycloalkyl group, an alkoxy group, And a group substituted with a cycloalkoxy group, an aryl group, a fluorine atom, or the like.
- a substituent for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, tert-buty
- the number of carbon atoms of the “cycloalkoxy group” is usually 3 to 40, preferably 4 to 10, not including the number of carbon atoms of the substituent.
- the cycloalkoxy group may have a substituent, and examples thereof include a cyclohexyloxy group.
- the number of carbon atoms of the “aryloxy group” is usually 6 to 60, preferably 7 to 48, not including the number of carbon atoms of the substituent.
- the aryloxy group may have a substituent, for example, a 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 a hydrogen atom in these groups is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom, or the like.
- P-valent heterocyclic group (p represents an integer of 1 or more) is a p-group 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.
- this is an atomic group obtained by removing p hydrogen atoms from an aromatic heterocyclic compound directly bonded to carbon atoms or heteroatoms constituting the ring.
- a “p-valent aromatic heterocyclic group” is preferable.
- Aromatic heterocyclic compounds '' are oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc.
- a compound in which the ring itself exhibits aromaticity and a heterocyclic ring such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran itself does not exhibit aromaticity, but the aromatic ring is condensed to the heterocyclic ring.
- the number of carbon atoms of the monovalent heterocyclic group is usually 2 to 60, preferably 4 to 20, excluding the number of carbon atoms of the substituent.
- the monovalent heterocyclic group may have a substituent, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidinyl group, quinolinyl group, isoquinolinyl group, pyrimidinyl group, triazinyl group, and these And a group in which the hydrogen atom in the group is substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or the like.
- Halogen atom means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- the “amino group” may have a substituent, and a substituted amino group is preferable.
- a substituent which an amino group has an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group is preferable.
- the substituted amino group include a dialkylamino group, a dicycloalkylamino group, and a diarylamino group.
- the amino group include dimethylamino group, diethylamino group, diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, bis (3,5-di-tert- Butylphenyl) amino group.
- the “alkenyl group” may be linear or branched.
- the number of carbon atoms of the straight-chain alkenyl group is usually 2-30, preferably 3-20, 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 4 to 20, not including the number of carbon atoms of the substituent.
- the number of carbon atoms of the “cycloalkenyl group” is usually 3 to 30, preferably 4 to 20, not including the number of carbon atoms of the substituent.
- the alkenyl group and the cycloalkenyl group may have a substituent, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 3-butenyl group, a 3-pentenyl group, a 4-pentenyl group, Examples include a pentenyl group, a 1-hexenyl group, a 5-hexenyl group, a 7-octenyl group, and a group in which these groups have a substituent.
- the “alkynyl group” may be linear or branched.
- the number of carbon atoms of the alkynyl group is usually 2 to 20, preferably 3 to 20, not including the carbon atom of the substituent.
- the number of carbon atoms of the branched alkynyl group is usually from 4 to 30, and preferably from 4 to 20, not including the carbon atom of the substituent.
- the number of carbon atoms of the “cycloalkynyl group” is usually 4 to 30, preferably 4 to 20, not including the carbon atom of the substituent.
- the alkynyl group and cycloalkynyl group may have a substituent, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4- Examples include a pentynyl group, 1-hexynyl group, 5-hexynyl group, and groups in which these groups have a substituent.
- the “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, and more preferably 6 to 18, excluding the number of carbon atoms of the substituent.
- the arylene group may have a substituent. Examples include chrysenediyl groups and groups in which these groups have substituents, and groups represented by formulas (A-1) to (A-20) are preferable.
- the arylene group includes a group in which a plurality of these groups are bonded.
- R and R a each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group.
- a plurality of R and R a may be the same or different, and R a may be bonded to each other to form a ring together with the atoms to which each is bonded.
- the number of carbon atoms of the divalent heterocyclic group is usually 2 to 60, preferably 3 to 20, and more preferably 4 to 15 excluding the number of carbon atoms of the substituent.
- the divalent heterocyclic group may have a substituent, for example, pyridine, diazabenzene, triazine, azanaphthalene, diazanaphthalene, carbazole, dibenzofuran, dibenzothiophene, dibenzosilol, phenoxazine, phenothiazine, acridine, Divalent acridine, furan, thiophene, azole, diazole, and triazole include divalent groups obtained by removing two hydrogen atoms from hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring, and preferably Is a group represented by formula (AA-1) to formula (AA-34).
- the divalent heterocyclic group includes a group in which a plurality of these groups
- crosslinking group is a group capable of generating a new bond by being subjected to a heat treatment, an ultraviolet irradiation treatment, a radical reaction, or the like.
- a heat treatment an ultraviolet irradiation treatment, a radical reaction, or the like.
- XL-1 the above-mentioned formula (XL-1 ) To (XL-17).
- “Substituent” means a halogen atom, cyano group, alkyl group, cycloalkyl group, aryl group, monovalent heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group, amino group, substituted amino group, alkenyl group. Represents a cycloalkenyl group, an alkynyl group or a cycloalkynyl group.
- the substituent may be a crosslinking group.
- the light emitting device of the present invention has an anode, a cathode, a first organic layer provided between the anode and the cathode, and a second organic layer provided between the anode and the first organic layer.
- the first organic layer is a layer formed using one or more phosphorescent compounds
- the second organic layer contains one or more phosphorescent compounds and a crosslinking material.
- At least one phosphorescent compound used for forming the first organic layer and at least one phosphorescent compound used for forming the second organic layer, which are layers formed using the composition Are light-emitting elements that are the same phosphorescent compound represented by the formula (1).
- “To be formed using” in relation to the relationship between the first organic layer and the phosphorescent compound means that the first organic layer is formed using the phosphorescent compound.
- the phosphorescent compound may be contained as it is in the first organic layer, or the phosphorescent compound is crosslinked in the molecule, between the molecules, or both (crosslinked product of the phosphorescent compound). It may be contained in the first organic layer.
- “To be formed using” in relation to the relationship between the second organic layer and the composition means that the second organic layer is formed using the composition.
- the phosphorescent compound and the crosslinking material contained in the composition may be included in the second organic layer as they are, or the phosphorescent compound or the crosslinking material contained in the composition is intramolecular, intermolecular, or In addition, they may be contained in the second organic layer in a state in which they are both crosslinked (crosslinked body of phosphorescent compound or crosslinked material).
- Examples of the method for forming the first organic layer and the second organic layer include a vacuum deposition method and a coating method typified by a spin coating method and an ink jet printing method.
- the phosphorescent compound can be crosslinked by heating or light irradiation.
- the first organic layer is substantially insolubilized in the solvent. Therefore, the first organic layer can be suitably used for stacking light emitting elements.
- the second organic layer is formed by a coating method, it is preferable to use an ink of a second organic layer described later.
- the phosphorescent compound or the crosslinking material contained in the composition can be crosslinked by heating or light irradiation.
- the phosphorescent compound or the crosslinking material is contained in the second organic layer in a state in which the phosphorescent compound or the crosslinking material is crosslinked (crosslinked body of the phosphorescent compound or the crosslinked material)
- the second organic layer is against the solvent. It is substantially insolubilized. Therefore, the second organic layer can be suitably used for stacking light emitting elements.
- the light-emitting element of the present invention is preferably contained in the second organic layer in a state where the crosslinking material contained in the composition is crosslinked (crosslinked product of the crosslinking material).
- the light-emitting element of the present invention includes an anode, a cathode, a first organic layer provided between the anode and the cathode, and a second organic layer provided between the anode and the first organic layer.
- the first organic layer is a layer containing one or more phosphorescent compounds
- the second organic layer is composed of one or more phosphorescent compounds and a crosslinking material.
- a layer containing a crosslinked product, and at least one phosphorescent compound contained in the first organic layer and at least one phosphorescent compound contained in the second organic layer have the formula It is preferable that it is a light emitting element which is the same phosphorescent compound represented by (1).
- the heating temperature for crosslinking is usually 25 to 300 ° C, preferably 50 to 250 ° C, more preferably 150 to 200 ° C.
- the type of light used for light irradiation for crosslinking is, for example, ultraviolet light, near ultraviolet light, or visible light.
- the form of the first organic layer (whether the phosphorescent compound is contained as it is or a crosslinked product of the phosphorescent compound is contained) and the form of the second organic layer (the phosphorescent compound and the crosslinking material are used as they are)
- chemical separation analysis methods such as extraction, infrared spectroscopy (IR) (IR) (IR cross-linked product or cross-linked product of phosphorescent compound) ), Nuclear magnetic resonance spectroscopy (NMR), instrumental analysis methods represented by mass spectrometry (MS), and the like, and analysis methods combining chemical separation analysis methods and instrumental analysis methods.
- the organic solvent typified by toluene, xylene, chloroform, tetrahydrofuran or the like
- it is substantially insoluble in the organic solvent. It is possible to separate into a component (insoluble component) and a component that dissolves in an organic solvent (dissolved component).
- the obtained insoluble component can be analyzed by infrared spectroscopy (IR) or nuclear magnetic resonance spectroscopy (NMR), and the obtained dissolved component can be analyzed by nuclear magnetic resonance spectroscopy (NMR) or mass spectrometry. It is possible to analyze by the method (MS).
- the first organic layer is a layer formed using one or more phosphorescent compounds. As described above, the first organic layer is preferably a layer containing one or more phosphorescent compounds.
- the phosphorescent compound used for forming the first organic layer is preferably a phosphorescent compound represented by the formula (1).
- the phosphorescent compound used for forming the second organic layer described later is also preferably a phosphorescent compound represented by the formula (1).
- at least one phosphorescent compound used for forming the first organic layer and at least one phosphorescent compound used for forming the second organic layer are represented by the formula (1). And the same phosphorescent compound.
- the phosphorescent compound represented by the formula (1) has M as a central metal, a ligand whose number is defined by the subscript n 1 , and its number is defined by the subscript n 2 . It consists of a ligand.
- M is preferably an iridium atom or a platinum atom, and more preferably an iridium atom, because the light emitting efficiency of the light emitting device of the present invention is excellent.
- n 1 is preferably 2 or 3, and more preferably 3.
- n 1 is preferably 2.
- E 1 and E 2 are preferably carbon atoms.
- Ring L 1 is preferably a pyridine ring, a pyrimidine ring, an imidazole ring or a triazole ring, and these rings may have a substituent.
- Ring L 2 is preferably a benzene ring, naphthalene ring, fluorene ring, phenanthrene ring, pyridine ring, diazabenzene ring or triazine ring, more preferably a benzene ring, a pyridine ring or a pyrimidine ring, and these rings are It may have a substituent.
- At least one ring selected from the group consisting of ring L 1 and ring L 2 has a group represented by formula (2).
- Ring L 2 preferably has a group represented by formula (2).
- At least one of the rings may have a group represented by the formula (2).
- all of the plurality of rings L 1 are present in plural.
- all ring L 2, or all of the rings L 1 and the ring L 2 there are a plurality of preferably has a group represented by the formula (2), all ring L 2 there are a plurality of the formula (2 It is more preferable to have a group represented by:
- R 2 is preferably an aryl group or a monovalent heterocyclic group, more preferably an aryl group, and these groups may have a substituent.
- Examples of the substituent that the aryl group, monovalent heterocyclic group and substituted amino group represented by R 2 may have include an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, and an alkoxy group.
- a cycloalkoxy group, an aryloxy group or a substituted amino group is preferred, an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, an alkoxy group or a cycloalkoxy group is more preferred, and an alkyl group, a cycloalkyl group or an aryl group A group is further preferred, an alkyl group is particularly preferred, and these groups may further have a substituent.
- the aryl group, monovalent heterocyclic group or substituted amino group represented by R 2 is preferably a dendron because the luminance lifetime of the light emitting device of the present invention is more excellent.
- Dendrimer means a group having a regular dendritic branched structure (ie, a dendrimer structure) having an atom or a ring as a branching point.
- dendrimer examples include, for example, International Publication No. 02/067343, Japanese Patent Application Laid-Open No. 2003-231692, International Publication No. 2003/079736, International Publication No. 2006/097717. And the structure described in the literature.
- the dendron is preferably a group represented by the formula (D-A) or (D-B).
- 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.
- G DA is preferably a group represented by the formula (GDA-11) ⁇ (GDA -15), these groups may have a substituent.
- 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 there are a plurality of RDA , 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 may have a substituent. When there are a plurality of RDBs , 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, still more preferably an aryl group, The group may have a substituent.
- T DA is preferably a group represented by the formula (TDA-1) ⁇ (TDA -3).
- R DA and R DB represent the same meaning as described above.
- the group represented by the formula (D-A) is preferably a group represented by the formulas (D-A1) to (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.
- 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 (D-B) is preferably a group represented by the formulas (D-B1) to (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.
- R p1 and R p2 they 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.
- Examples of the anionic bidentate ligand represented by A 1 -G 1 -A 2 include the ligands represented by the following.
- the anionic bidentate ligand represented by A 1 -G 1 -A 2 may be a ligand represented by the following. However, the anionic bidentate ligand represented by A 1 -G 1 -A 2 is different from the ligand whose number is defined by the subscript n 1 .
- R L1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a halogen atom, and these groups optionally have a substituent.
- a plurality of R L1 may be the same or different.
- R L2 represents an alkyl group, a cycloalkyl group or a halogen atom, and these groups optionally have a substituent.
- the phosphorescent compound represented by the formula (1) is excellent in the luminous efficiency of the light emitting device of the present invention, and therefore is represented by the phosphorescent compound represented by the formula (1-A) or the formula (1-B).
- a phosphorescent compound is preferable.
- ring L 1A is an imidazole ring
- E 11A is a nitrogen atom or an imidazole ring in which E 12A is a nitrogen atom is preferable
- an imidazole ring in which E 11A is a nitrogen atom is more preferable.
- ring L 1A is a triazole ring
- a triazole ring in which E 11A and E 12A are nitrogen atoms or a triazole ring in which E 11A and E 13A are nitrogen atoms is preferable, and E 11A and E 12A are nitrogen atoms
- a triazole ring is more preferred.
- R 11A is preferably an alkyl group, a cycloalkyl group, or a group represented by Formula (2), and these groups have a substituent. You may do it.
- R 11A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. More preferably, it is more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.
- R 12A is preferably an alkyl group, a cycloalkyl group or a group represented by formula (2), and these groups have a substituent. You may do it.
- R 12A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. More preferably, it is more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.
- R 13A is preferably an alkyl group, a cycloalkyl group or a group represented by the formula (2), and these groups have a substituent. You may do it.
- R 13A is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. More preferably, it is more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and these groups optionally have a substituent.
- R 11A or R 12A is preferably a group represented by the formula (2)
- R 11A is a group represented by the formula (2). It is more preferable that The group represented by the formula (2) is preferably a dendron.
- ring L 2A is a pyridine ring
- a pyridine ring in which E 21A is a nitrogen atom a pyridine ring in which E 22A is a nitrogen atom, or a pyridine ring in which E 23A is a nitrogen atom is preferable, and E 22A is a nitrogen atom.
- a certain pyridine ring is more preferable.
- ring L 2A is a pyrimidine ring
- a pyrimidine ring in which E 21A and E 23A are nitrogen atoms, or a pyrimidine ring in which E 22A and E 24A are nitrogen atoms is preferable, and E 22A and E 24A are nitrogen atoms
- a pyrimidine ring is more preferred.
- Ring L 2A is preferably a benzene ring.
- R 21A , R 22A , R 23A and R 24A are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or a group represented by the formula (2), preferably a hydrogen atom or a group represented by the formula (2) It is more preferable that these groups may have a substituent.
- R 22A or R 23A is preferably a group represented by the formula (2)
- R 22A is a group represented by the formula (2). It is more preferable that The group represented by the formula (2) is preferably a dendron.
- ring L 1B is a pyrimidine ring
- a pyrimidine ring in which E 11B is a nitrogen atom or a pyrimidine ring in which E 13B is a nitrogen atom is preferable
- a pyrimidine ring in which E 11B is a nitrogen atom is more preferable.
- R 11B , R 12B , R 13B and R 14B are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or a group represented by the formula (2), and preferably a hydrogen atom or a group represented by the formula (2) It is more preferable that these groups may have a substituent.
- R 11B , R 12B or R 13B is preferably a group represented by formula (2), and R 11B or R 13B is represented by formula (2). It is more preferable that R 11B is a group represented by the formula (2).
- the group represented by the formula (2) is preferably a dendron.
- ring L 2B is a pyridine ring
- a pyridine ring in which E 21B is a nitrogen atom a pyridine ring in which E 22B is a nitrogen atom, or a pyridine ring in which E 23B is a nitrogen atom is preferable, and E 22B is a nitrogen atom.
- a certain pyridine ring is more preferable.
- ring L 2B is a pyrimidine ring
- a pyrimidine ring in which E 21B and E 23B are nitrogen atoms or a pyrimidine ring in which E 22B and E 24B are nitrogen atoms is preferable, and E 22B and E 24B are nitrogen atoms
- a pyrimidine ring is more preferred.
- Ring L 2B is preferably a benzene ring.
- R 21B , R 22B , R 23B and R 24B are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or a group represented by the formula (2), preferably a hydrogen atom or a group represented by the formula (2). It is more preferable that these groups may have a substituent.
- R 22B or R 23B is preferably a group represented by the formula (2)
- R 22B is a group represented by the formula (2). It is more preferable that The group represented by the formula (2) is preferably a dendron.
- the phosphorescent compound represented by the formula (1-A) includes the phosphorescent compound represented by the formula (1-A1), the phosphorescent compound represented by the formula (1-A2), the formula (1- A phosphorescent compound represented by A3) or a phosphorescent compound represented by formula (1-A4) is preferred, and a phosphorescent compound represented by formula (1-A1) or formula (1- A phosphorescent compound represented by A3) is more preferred, and a phosphorescent compound represented by formula (1-A3) is more preferred.
- the phosphorescent compound represented by the formula (1-B) is a phosphorescent compound represented by the formula (1-B1), a phosphorescent compound represented by the formula (1-B2), or the formula (1-
- the phosphorescent compound represented by B3) is preferable, and the phosphorescent compound represented by the formula (1-B1) or the phosphorescent compound represented by the formula (1-B2) is more preferable. preferable.
- Examples of the phosphorescent compound represented by the formula (1) include phosphorescent compounds represented by the following.
- At least one phosphorescent compound used for forming the first organic layer is at least one phosphorescent compound represented by formula (1) (at least one kind used for forming the second organic layer).
- the first organic layer is formed by using the phosphorescent compound represented by the formula (1) and another phosphorescent compound in combination. It may be a layer that contains the phosphorescent compound represented by the formula (1) and another phosphorescent compound. Examples of other phosphorescent compounds include phosphorescent compounds represented by the following formula.
- Examples of the phosphorescent compound used for forming the first organic layer include, for example, JP-T-2004-530254, JP-A-2008-179617, JP-A-2011-105701, JP-T-2007-504272, They can be synthesized according to the methods described in JP2013-147449A and JP2013-147450A.
- the first organic layer is composed of one or more phosphorescent compounds and a group consisting of a hole injecting property, a hole transporting property, an electron injecting property, and an electron transporting property. It is preferably a layer formed using a composition containing a host material having at least one selected function, and one or more phosphorescent compounds, a hole injection property, a hole transport property, an electron More preferably, it is a layer containing a host material having at least one function selected from the group consisting of injecting properties and electron transporting properties. In the composition, the host material may be contained singly or in combination of two or more.
- the content of the phosphorescent compound is usually 0.1 to 50 parts by weight when the total of the phosphorescent compound and the host material is 100 parts by weight. Yes, preferably 1 to 45 parts by weight, more preferably 5 to 40 parts by weight.
- the energy level equivalent to that of T 1 of the phosphorescent compound used for forming the first organic layer is used. It is preferable that the energy level is higher.
- the host material since the light-emitting element of the present invention can be manufactured by a solution coating process, the host material is soluble in a solvent capable of dissolving the phosphorescent compound used for forming the first organic layer. Preferably there is.
- Host materials are classified into low molecular compounds and high molecular compounds.
- Low molecular host The low molecular weight compound (hereinafter referred to as “low molecular weight host”) preferable as the host material will be described.
- the low molecular host is preferably a compound represented by the formula (H-1).
- Ar H1 and Ar H2 are phenyl group, fluorenyl group, spirobifluorenyl group, pyridyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, thienyl group, benzothienyl group, dibenzothienyl group, furyl group, benzofuryl Group, dibenzofuryl group, pyrrolyl group, indolyl group, azaindolyl group, carbazolyl group, azacarbazolyl group, diazacarbazolyl group, phenoxazinyl group or phenothiazinyl group, phenyl group, spirobifluorenyl group, A pyridyl group, pyrimidinyl group, triazinyl group, dibenzothienyl group, dibenzofuryl group, carbazolyl group or azacarbazolyl group is more prefer
- Ar H1 and Ar H2 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, a cyclo An alkoxy group, an alkoxy group or a cycloalkoxy group is more preferable, an alkyl group or a cycloalkoxy group is more preferable, and these groups may further have a substituent.
- n H1 is preferably 1.
- n H2 is preferably 0.
- n H3 is generally an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1.
- n H11 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and even more preferably 1.
- R H11 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and a hydrogen atom or an alkyl group. It is more preferable that these groups may have a substituent.
- L H1 is preferably an arylene group or a divalent heterocyclic group.
- L H1 represents formulas (A-1) to (A-3), formulas (A-8) to (A-10), formulas (AA-1) to (AA-6), formulas (AA-10) to A group represented by formula (AA-21) or formulas (AA-24) to (AA-34) is preferred.
- Formula (AA-4), Formula (AA-10), Formula (AA-12) or Formula A group represented by (AA-14) is particularly preferred, and is represented by formula (A-1), formula (A-2), formula (AA-2), formula (AA-4) or formula (AA-14). It is especially preferable that it is group represented by.
- 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 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.
- L H21 is preferably a single bond or an arylene group, more preferably a single bond, and this arylene group may have a substituent.
- the definition and examples of the arylene group or divalent heterocyclic group represented by L H21 are the same as the definitions and examples of the arylene group or divalent heterocyclic group represented by L H1 .
- R H21 is preferably an aryl group or a monovalent heterocyclic group, and these groups optionally have a substituent.
- aryl group and monovalent heterocyclic group represented by R H21 are the same as those of the aryl group and monovalent heterocyclic group represented by Ar H1 and Ar H2 .
- the compound represented by the formula (H-1) is preferably a compound represented by the formula (H-2).
- Examples of the compound represented by the formula (H-1) include compounds represented by the following formulas (H-101) to (H-118).
- Examples of the polymer compound used for the host material include a polymer compound that is a hole transport material described later and a polymer compound that is an electron transport material described later.
- Polymer host A polymer compound preferable as the host compound (hereinafter referred to as “polymer host”) will be described.
- the polymer host is preferably a polymer compound containing a structural unit represented by the formula (Y).
- the arylene group represented by Ar Y1 is more preferably the formula (A-1), the formula (A-2), the formula (A-6)-(A-10), the formula (A-19) or the formula (A A-20), more preferably a group represented by formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19) These groups may have a substituent.
- the divalent heterocyclic group represented by Ar Y1 is more preferably a formula (AA-1)-(AA-4), a formula (AA-10)-(AA-15), a formula (AA-18) -(AA-21), a group represented by formula (AA-33) or formula (AA-34), and more preferably a group represented by formula (AA-4), formula (AA-10), formula (AA- 12) a group represented by formula (AA-14) or formula (AA-33), and these groups may have a substituent.
- the ranges are the same as the more preferable ranges and further preferable ranges of the above-mentioned arylene group and divalent heterocyclic group represented by Ar Y1 .
- divalent group in which at least one arylene group and at least one divalent heterocyclic group are directly bonded examples include groups represented by the following formulas, which have a substituent. You may do it.
- 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.
- the substituent that the group represented by Ar Y1 may have is 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)-(Y-10). From the viewpoint of the luminance life of the light emitting device of the present invention, Preferably, it is a structural unit represented by the formula (Y-1)-(Y-3), and from the viewpoint of electron transport properties of the light emitting device of the present invention, preferably the formula (Y-4)-(Y-7 From the viewpoint of the hole transport property of the light emitting device of the present invention, it is preferably a structural unit represented by the formula (Y-8)-(Y-10).
- R Y1 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.
- a plurality of R Y1 may be the same or different, and adjacent R Y1 may be bonded to each other to form a ring together with the carbon atom to which each is bonded.
- R Y1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and these groups optionally have a substituent.
- the structural unit represented by the formula (Y-1) is preferably a structural unit represented by the formula (Y-1 ′).
- R Y11 represents 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.
- a plurality of R Y11 may be the same or different.
- 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.
- R Y1 represents the same meaning as described above.
- X Y1 is, -C (R Y2) 2 -
- R Y2 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 Y2 may be the same or different, and R Y2 may be bonded to each other to form a ring together with the carbon atom to which each is bonded. ]
- R Y2 is preferably an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, more preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups have a substituent. You may do it.
- the combination of two R Y2 in the group represented by —C (R Y2 ) 2 — is preferably an alkyl group or a cycloalkyl group, both are aryl groups, and both are monovalent complex A cyclic group, or one is an alkyl group or a cycloalkyl group and the other is an aryl group or a monovalent heterocyclic group, more preferably one is an alkyl group or a cycloalkyl group and the other is an aryl group. May have a substituent.
- Two R Y2 s may be bonded to each other to form a ring together with the atoms to which they are bonded.
- R Y2 forms a ring
- the group represented by —C (R Y2 ) 2 — Is preferably a group represented by the formula (Y-A1)-(Y-A5), more preferably a group represented by the formula (Y-A4), and these groups have a substituent. It may be.
- the combination of two R Y2 in the group represented by —C (R Y2 ) ⁇ C (R Y2 ) — is preferably such that both are alkyl groups or cycloalkyl groups, or one is an alkyl group Alternatively, a cycloalkyl group and the other is an aryl group, and these groups may 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 which may have a substituent. It is. A plurality of R Y2 may be bonded to each other to form a ring together with the atoms to which each is bonded. When 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)-(Y-B5), more preferably a group represented by the formula (Y-B3), and these groups are substituted. It may have a group.
- 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 ′).
- the structural unit represented by the formula (Y-3) is preferably a structural unit represented by the formula (Y-3 ′).
- 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.
- the structural unit represented by the formula (Y-4) is preferably a structural unit represented by the formula (Y-4 ′), and the structural unit represented by the formula (Y-6) is represented by the formula (Y -6 ′) is preferred.
- 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.
- a structural unit represented by the formula (Y) for example, a structural unit comprising an arylene group represented by the formula (Y-101)-(Y-121), a formula (Y-201)-(Y-206)
- the structural unit represented by the formula (Y), in which Ar Y1 is an arylene group, has a higher luminance life of the light-emitting element of the present invention, so that the total amount of the structural units contained in the polymer compound is On the other hand, it is preferably 0.5 to 80 mol%, more preferably 30 to 60 mol%.
- the structural unit that is a group is preferably 0.5 to 30 mol%, more preferably 3%, based on the total amount of the structural units contained in the polymer compound, because the charge transport property of the light emitting device of the present invention is excellent. ⁇ 20 mol%.
- the polymer host is excellent in hole transport properties, it is preferable that the polymer host further contains a structural unit represented by the following formula (X).
- 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.
- 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 optionally have a substituent.
- a X1 is preferably 2 or less, more preferably 1 because the luminance life of the light emitting device of the present invention is more excellent.
- a X2 is preferably 2 or less, more preferably 0, because the luminance lifetime of the light emitting device of the present invention is more excellent.
- 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 more preferably a group represented by the formula (A-1) or the formula (A-9), more preferably a formula (A-1). These groups may have a substituent.
- the divalent heterocyclic group represented by Ar X1 and Ar X3 is more preferably represented by the formula (AA-1), the formula (AA-2) or the formula (AA-7)-(AA-26). These groups may have a substituent.
- Ar X1 and Ar X3 are preferably an arylene group which may have a substituent.
- the more preferable range of the divalent heterocyclic group represented by Ar X2 and Ar X4 is the same as the more preferable range of the divalent heterocyclic group represented by Ar X1 and Ar X3 .
- Further preferred ranges are the same as the more preferred ranges and further preferred ranges of the arylene group and divalent heterocyclic group represented by Ar X1 and Ar X3 , respectively.
- 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 to each other is at least represented by Ar Y1 in the formula (Y) Examples thereof include the same divalent groups in which one kind of arylene group and at least one kind of divalent heterocyclic group are directly bonded.
- Ar X2 and Ar X4 are preferably an arylene group which may have a substituent.
- the substituent that the groups represented by Ar X1 to Ar X4 and R X1 to R X3 may have is preferably an alkyl group, a cycloalkyl group or an aryl group, and these groups further have a substituent. You may do it.
- the structural unit represented by the formula (X) is preferably a structural unit represented by the formula (X-1)-(X-7), more preferably the formula (X-1)-(X-6) And more preferably a structural unit represented by the formula (X-3)-(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 structural unit represented by the formula (X) has excellent hole transportability, it is preferably 0.1 to 50 mol%, more preferably 1 to 5 mol% with respect to the total amount of the structural units contained in the polymer host. It is 40 mol%, more preferably 5 to 30 mol%.
- Examples of the structural unit represented by the formula (X) include structural units represented by the formula (X1-1)-(X1-11), preferably the formula (X1-3)-(X1-10). ).
- Examples of the polymer host include polymer compounds (P-1) to (P-6) shown in Table 1.
- p, q, r, s and t represent the molar ratio of each constituent unit.
- p + q + r + s + t 100 and 100 ⁇ p + q + r + s ⁇ 70.
- the other structural unit means a structural unit other than the structural unit represented by the formula (Y) and the structural unit represented by the formula (X). ]
- the polymer host may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may be in other modes.
- a copolymer obtained by polymerization is preferred.
- the polymer host can be produced by using a known polymerization method described in Chemical Review (Chem. Rev.), Vol. 109, pp. 897-1091 (2009), etc., and Suzuki reaction, Yamamoto reaction, Buchwald Examples of the polymerization method include a coupling reaction using a transition metal catalyst such as a reaction, Stille reaction, Negishi reaction, and Kumada reaction.
- a method of charging the monomer a method of charging the entire amount of the monomer into the reaction system at once, a part of the monomer is charged and reacted, and then the remaining monomer is batched, Examples thereof include a method of charging continuously or divided, a method of charging monomer continuously or divided, and the like.
- transition metal catalysts examples include palladium catalysts and nickel catalysts.
- Post-treatment of the polymerization reaction is a known method, for example, a method of removing water-soluble impurities by liquid separation, adding the reaction solution after polymerization reaction to a lower alcohol such as methanol, filtering the deposited precipitate, and then drying. These methods are performed alone or in combination.
- a lower alcohol such as methanol
- filtering the deposited precipitate and then drying.
- These methods are performed alone or in combination.
- the purity of the polymer host is low, it can be purified by a usual method such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, or the like.
- the first organic layer is different from at least one phosphorescent compound and the above-described host material, hole transport material, hole injection material, electron transport material, electron injection material, and light emitting material (phosphorescent compound). .), A layer formed using a composition containing at least one material selected from the group consisting of an antioxidant and a solvent (hereinafter also referred to as “composition of the first organic layer”). There may be. That is, the first organic layer includes at least one phosphorescent compound and the above-described host material, hole transport material, hole injection material, electron transport material, electron injection material, light emitting material (phosphorescent compound and And a layer containing at least one material selected from the group consisting of antioxidants.
- the hole transport material is classified into a low molecular compound and a high molecular compound, and is preferably a high molecular compound.
- the hole transport material may have a crosslinking group.
- 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.
- the compounding amount of the hole transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight when the phosphorescent compound is 100 parts by weight. .
- the hole transport material may be used alone or in combination of two or more.
- Electron transport materials are classified into low molecular compounds and high molecular compounds.
- the electron transport material may have a crosslinking group.
- Low molecular weight compounds include, for example, metal complexes having 8-hydroxyquinoline as a ligand, oxadiazole, anthraquinodimethane, benzoquinone, naphthoquinone, anthraquinone, tetracyanoanthraquinodimethane, fluorenone, diphenyldicyanoethylene and diphenoquinone. As well as these derivatives.
- polymer compound examples include polyphenylene, polyfluorene, and derivatives thereof.
- the polymer compound may be doped with a metal.
- the compounding amount of the electron transport material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight when the phosphorescent compound is 100 parts by weight.
- the electron transport material may be used alone or in combination of two or more.
- the hole injection material and the electron injection material are each classified into a low molecular compound and a high molecular compound.
- the hole injection material and the electron injection material may have a crosslinking group.
- low molecular weight compounds include metal phthalocyanines such as copper phthalocyanine; carbon; metal oxides such as molybdenum and tungsten; and metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.
- metal phthalocyanines such as copper phthalocyanine
- carbon such as carbon
- metal oxides such as molybdenum and tungsten
- metal fluorides such as lithium fluoride, sodium fluoride, cesium fluoride, and potassium fluoride.
- polymer compound examples include polyaniline, polythiophene, polypyrrole, polyphenylene vinylene, polythienylene vinylene, polyquinoline and polyquinoxaline, and derivatives thereof; conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain. A functional polymer.
- the compounding amounts of the hole injecting material and the electron injecting material are each usually 1 to 400 parts by weight, preferably 5 parts when the phosphorescent compound is 100 parts by weight. ⁇ 150 parts by weight.
- Each of the electron injection material and the hole injection material may be used alone or in combination of two or more.
- the electrical conductivity of the conductive polymer is preferably 1 ⁇ 10 ⁇ 5 S / cm to 1 ⁇ 10 3 S / cm.
- the conductive polymer can be doped with an appropriate amount of ions.
- the kind of ions to be doped is an anion for a hole injection material and a cation for an electron injection material.
- the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, and camphor sulfonate ion.
- the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.
- the ions to be doped may be used alone or in combination of two or more.
- Luminescent materials are classified into low molecular compounds and high molecular compounds.
- the light emitting material may have a crosslinking group.
- Examples of the low molecular weight compound include naphthalene and its derivatives, anthracene and its derivatives, and perylene and its derivatives.
- Examples of the polymer compound include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a fluorenediyl group, a phenanthrene diyl group, a dihydrophenanthenediyl group, a group represented by the formula (X), a carbazole diyl group, and a phenoxazine diyl. And a polymer compound containing a group, a phenothiazinediyl group, a pyrenediyl group, and the like.
- the amount of the light emitting material is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight, when the phosphorescent compound is 100 parts by weight.
- Fluorescent materials may be used alone or in combination of two or more.
- the antioxidant may be any compound that is soluble in the same solvent as the phosphorescent compound and does not inhibit light emission and charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.
- the blending amount of the antioxidant is usually 0.001 to 10 parts by weight when the phosphorescent compound is 100 parts by weight.
- Antioxidants may be used alone or in combination of two or more.
- the composition of the first organic layer containing a solvent (hereinafter also referred to as “the ink of the first organic layer”) is a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, Suitable for coating methods such as roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, inkjet printing, capillary coating, nozzle coating, etc. be able to.
- the viscosity of the ink of the first organic layer may be adjusted according to the type of coating method. However, when a solution such as an ink jet printing method is applied to a printing method that passes through a discharge device, clogging and flight at the time of discharge are performed. Since bending is difficult to occur, the pressure is preferably 1 to 20 mPa ⁇ s at 25 ° C.
- the solvent contained in the ink of the first organic layer is preferably a solvent that can dissolve or uniformly disperse the solid content in the ink.
- the solvent include chlorine solvents such as 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene; ether solvents such as THF, dioxane, anisole and 4-methylanisole; Aromatic hydrocarbon solvents such as xylene, mesitylene, ethylbenzene, n-hexylbenzene, cyclohexylbenzene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n- Aliphatic hydrocarbon solvents such as decane, n-dodecane, and bicyclohexyl; ketone solvents such as
- the amount of the solvent is usually 1000 to 100,000 parts by weight, preferably 2000 to 20000 parts by weight when the phosphorescent compound is 100 parts by weight.
- the second organic layer is a layer formed using a composition containing one or more phosphorescent compounds and a crosslinking material. As described above, the second organic layer is preferably a layer containing one or more phosphorescent compounds and a crosslinked material of a crosslinking material.
- the phosphorescent compound used for forming the second organic layer is preferably a phosphorescent compound represented by the formula (1).
- the phosphorescent compound used for forming the first organic layer described above is also preferably a phosphorescent compound represented by the formula (1).
- at least one phosphorescent compound used for forming the second organic layer and at least one phosphorescent compound used for forming the first organic layer are represented by the formula (1). And the same phosphorescent compound.
- Definition and examples of the phosphorescent compound represented by the formula (1) used for forming the second organic layer are the phosphorescent compound represented by the formula (1) used for forming the first organic layer. Definitions and examples are the same.
- the at least one phosphorescent compound used for forming the second organic layer is a phosphorescent compound represented by the formula (1) (at least one phosphorescent compound used for forming the first organic layer).
- the second organic layer is formed by using the phosphorescent compound represented by the formula (1) and another phosphorescent compound in combination. It may be a layer, and may be a layer containing the phosphorescent compound represented by the formula (1) and another phosphorescent compound. Examples of other phosphorescent compounds used for forming the second organic layer are the same as examples of other phosphorescent compounds used for forming the first organic layer.
- the cross-linking material may be a low-molecular compound or a high-molecular compound.
- the cross-linking material is a material having at least one cross-linking group selected from the cross-linking group A group.
- it is a polymer compound containing a crosslinked structural unit having at least one kind of crosslinking group selected from the crosslinking group A group (hereinafter also referred to as “polymer compound of the second organic layer”).
- polymer compound of the second organic layer a polymer compound containing a crosslinked structural unit having at least one kind of crosslinking group selected from the crosslinking group A group
- the formulas (XL-1), (XL-3), (XL-9), (XL-) are preferable. 16) or a crosslinkable group represented by (XL-17), more preferably a crosslinkable group represented by the formula (XL-1), (XL-16) or (XL-17), still more preferred. Is a bridging group represented by the formula (XL-1) or (XL-17).
- Examples of the low molecular weight compound having at least one type of crosslinking group selected from the crosslinkable group A group include the low molecular weight compounds represented by the following.
- the cross-linking structural unit having at least one cross-linking group selected from the cross-linking group A group contained in the polymer compound of the second organic layer is a structural unit represented by the formula (3) described later and the formula (4). Is preferably a structural unit represented by the following formula.
- the cross-linking structural unit having at least one cross-linking group selected from the cross-linking group A group contained in the polymer compound of the second organic layer is represented by the structural unit represented by the formula (3) or the formula (4). It is preferable that it is a structural unit.
- NA is preferably 0 or 1, more preferably 0, because the light-emitting efficiency of the light-emitting device of the present invention is excellent.
- N is preferably 2 because the light emitting efficiency of the light emitting device of the present invention is excellent.
- Ar 1 is preferably an aromatic hydrocarbon group which may have a substituent since the light-emitting efficiency of the light-emitting device of the present invention is excellent.
- the number of carbon atoms of the aromatic hydrocarbon group represented by Ar 1 is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 18, excluding the number of carbon atoms of the substituent. is there.
- the arylene group portion excluding n substituents of the aromatic hydrocarbon group represented by Ar 1 is preferably a group represented by the formula (A-1) to the formula (A-20), More preferably, groups represented by formula (A-1), formula (A-2), formula (A-6) to formula (A-10), formula (A-19) or formula (A-20) And more preferably a group represented by formula (A-1), formula (A-2), formula (A-7), formula (A-9) or formula (A-19), This group may have a substituent.
- the number of carbon atoms of the heterocyclic group represented by Ar 1 is usually 6 to 60, preferably 6 to 30, more preferably 6 to 18, excluding the number of carbon atoms of the substituent.
- the divalent heterocyclic group moiety excluding n substituents of the heterocyclic group represented by Ar 1 is preferably a group represented by the formulas (AA-1) to (AA-34). .
- the aromatic hydrocarbon group and heterocyclic group represented by Ar 1 may have a substituent.
- substituents that the aromatic hydrocarbon group and the heterocyclic group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, a halogen atom, and a monovalent Examples include a heterocyclic group and a cyano group.
- Alkylene group represented by L A is not including the carbon atom number of substituent is usually 1 to 10, preferably 1 to 5, more preferably 1 to 3. Cycloalkylene group represented by L A is not including the carbon atom number of substituent is usually 3 to 10.
- the alkylene group and the cycloalkylene group may have a substituent, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, and an octylene group.
- Alkylene group and cycloalkylene group represented by L A may have a substituent.
- substituents that the alkylene group and the cycloalkylene group may have include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, a halogen atom, and a cyano group.
- the aryl group represented by L A may have a substituent.
- the aryl group include o-phenylene, m-phenylene, and p-phenylene.
- substituent that the aryl group may have include, for example, 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 cyano group, and a bridge. Examples thereof include a crosslinking group selected from the group A.
- L A is preferably a phenylene group or a methylene group because synthesis of the polymer compound of the second organic layer is facilitated, and these groups may have a substituent.
- the preferred range, more preferred range and further preferred range of the crosslinking group represented by X are the same as the preferred range, more preferred range and further preferred range of the crosslinking group selected from the aforementioned crosslinking group A group.
- the structural unit represented by the formula (3) is preferable with respect to the total amount of the structural units contained in the polymer compound of the second organic layer since the crosslinkability of the polymer compound of the second organic layer is excellent. Is from 0.5 to 25 mol%, more preferably from 3 to 25 mol%, still more preferably from 3 to 20 mol%.
- the structural unit represented by the formula (3) may be included in the high molecular compound of the second organic layer, or may be included in two or more types.
- MA is preferably 0 or 1, more preferably 0, because the light-emitting efficiency of the light-emitting device of the present invention is excellent.
- M is preferably 2 because the light emission efficiency of the light emitting device of the present invention is excellent.
- C is preferably 0 because it facilitates the synthesis of the polymer compound of the second organic layer and the light emitting efficiency of the light emitting device of the present invention is excellent.
- Ar 3 is preferably an aromatic hydrocarbon group which may have a substituent since the light emitting efficiency of the light emitting device of the present invention is excellent.
- the definition and example of the arylene group part excluding m substituents of the aromatic hydrocarbon group represented by Ar 3 are the same as the definition and example of the arylene group represented by Ar X2 in the above formula (X). It is.
- the definition and example of the divalent heterocyclic group part excluding m substituents of the heterocyclic group represented by Ar 3 are the divalent heterocyclic group represented by Ar X2 in the above formula (X). Same as definition and example of part.
- the definition and examples of the divalent group excluding m substituents of the group in which at least one aromatic hydrocarbon ring represented by Ar 3 and at least one heterocycle are directly bonded are defined by the above formula (
- the definition and examples of the divalent group in which at least one arylene group represented by Ar X2 in X) and at least one divalent heterocyclic group are directly bonded are the same.
- Ar 2 and Ar 4 are preferably an arylene group which may have a substituent since the luminance lifetime of the light emitting device of the present invention is more excellent.
- the definitions and examples of the arylene group represented by Ar 2 and Ar 4 are the same as the definitions and examples of the arylene group represented by Ar X1 and Ar X3 in the above formula (X).
- the definitions and examples of the divalent heterocyclic group represented by Ar 2 and Ar 4 are the same as the definitions and examples of the divalent heterocyclic group represented by Ar X1 and Ar X3 in the above formula (X). is there.
- the groups represented by Ar 2 , Ar 3 and Ar 4 may have a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, Examples thereof include a halogen atom, a monovalent heterocyclic group, and a cyano group.
- L A the alkylene group represented by L A
- a cycloalkylene group an arylene group
- a divalent heterocyclic The definition and examples of the ring group are the same.
- the preferred range, more preferred range, and further preferred range of the crosslinking group represented by X ′ are the same as the preferred range, more preferred range, and further preferred range of the crosslinking group selected from the aforementioned crosslinking group A group.
- the structural unit represented by the formula (4) has excellent crosslinkability of the second organic layer, it is preferably 0.5% with respect to the total amount of the structural units contained in the polymer compound of the second organic layer. -25 mol%, more preferably 3-25 mol%, still more preferably 3-20 mol%.
- the structural unit represented by the formula (4) may be included in the high molecular compound of the second organic layer, or may be included in two or more types.
- Examples of the structural unit represented by formula (3) include structural units represented by formula (3-1) to formula (3-30).
- Examples of the structural unit represented by formula (4) include: Examples thereof include structural units represented by the formulas (4-1) to (4-13).
- it is preferably a structural unit represented by the formula (3-1) to the formula (3-30), more preferably the formula (3-1) to (3-15), (3-19), (3-20), (3-23), (3-25) or (3-30) More preferred are structural units represented by formulas (3-1) to (3-13) or (3-30), and particularly preferred are formulas (3-1) to (3-1).
- the polymer compound of the second organic layer is excellent in hole transportability, it is preferable that the polymer compound further contains a structural unit represented by the formula (X).
- the structural unit represented by the formula (X) may be included in the high molecular compound of the second organic layer, or may be included in two or more types.
- the polymer compound of the second organic layer preferably further contains a structural unit represented by the formula (Y) because the light emitting efficiency of the light emitting device of the present invention is excellent.
- the definition and example of the structural unit represented by the formula (Y) that the polymer compound of the second organic layer may contain are represented by the formula (Y) that the polymer host may contain. This is the same as the definition and example of the structural unit.
- the structural unit represented by the formula (Y) may be included in the high molecular compound of the second organic layer, or may be included in two or more types.
- the polymer compound of the second organic layer includes both the structural unit represented by the formula (X) and the structural unit represented by the formula (Y) because the light emitting element of the present invention has excellent luminous efficiency. It is preferable.
- Examples of the polymer compound in the second organic layer include polymer compounds (P-11) to (P-25) shown in Table 2.
- p ′, q ′, r ′, s ′, u ′ and v ′ represent the molar ratio of each constituent unit.
- p ′ + q ′ + r ′ + s ′ + u ′ + v ′ 100 and 70 ⁇ p ′ + q ′ + r ′ + s ′ + u ′ ⁇ 100.
- the other structural unit is a structural unit represented by formula (3), a structural unit represented by formula (4), a structural unit represented by formula (X), or a structural unit represented by formula (Y). This means a structural unit other than.
- the polymer compound of the second organic layer may be any of a block copolymer, a random copolymer, an alternating copolymer, and a graft copolymer, and may be in other modes.
- a copolymer obtained by copolymerizing seed raw material monomers is preferable.
- the polymer compound of the second organic layer can be produced by the same method as the polymer host production method described above.
- the content of the phosphorescent compound is usually 0.1 to 50 when the total of the phosphorescent compound and the crosslinking material is 100 parts by weight. , Preferably 0.2 to 45, more preferably 0.3 to 40.
- the second organic layer is different from one or more phosphorescent compounds, a crosslinking material, a hole transport material, a hole injection material, an electron transport material, an electron injection material, and a light emitting material (a phosphorescent compound). ), At least one material selected from the group consisting of an antioxidant and a solvent (hereinafter also referred to as “composition of the second organic layer”). May be. That is, the second organic layer includes one or more phosphorescent compounds, a crosslinking material, a hole transport material, a hole injection material, an electron transport material, an electron injection material, and a light emitting material (what is a phosphorescent compound?
- a layer containing at least one material selected from the group consisting of antioxidants, one or more phosphorescent compounds, a crosslinked material of a crosslinking material, and a hole transport material A layer containing at least one material selected from the group consisting of a hole injection material, an electron transport material, an electron injection material, a light emitting material (different from a phosphorescent compound) and an antioxidant. preferable.
- Examples and preferred ranges of the hole transport material, electron transport material, hole injection material, electron injection material and light-emitting material contained in the composition of the second organic layer are contained in the composition of the first organic layer.
- Examples of the hole transporting material, electron transporting material, hole injecting material, electron injecting material, and light emitting material are the same as the examples and preferred ranges.
- the amount of the hole transport material, the electron transport material, the hole injection material, the electron injection material, and the light emitting material is 100 wt. The amount is usually 1 to 400 parts by weight, preferably 5 to 150 parts by weight.
- the blending amount of the antioxidant is usually 0.001 to 10 parts by weight when the total of the phosphorescent compound and the crosslinking material is 100 parts by weight.
- composition of the second organic layer containing a solvent (hereinafter also referred to as “ink of the second organic layer”) is the same as the ink of the first organic layer, such as spin coating and ink jet printing. It can be suitably used for the coating method.
- the preferable range of the viscosity of the ink of the second organic layer is the same as the preferable range of the viscosity of the ink of the first organic layer.
- Examples and preferred ranges of the solvent contained in the ink of the second organic layer are the same as examples and preferred ranges of the solvent contained in the ink of the first organic layer.
- the blending amount of the solvent is usually 1000 to 100,000 parts by weight, preferably 2000 to 20000 parts by weight when the total of the phosphorescent compound and the crosslinking material is 100 parts by weight. It is.
- the light-emitting element of the present invention includes an anode, a cathode, a first organic layer provided between the anode and the cathode, and a second organic layer provided between the anode and the first organic layer.
- the light emitting device of the present invention may have layers other than the anode, the cathode, the first organic layer, and the second organic layer.
- the first organic layer is usually a light emitting layer.
- the first organic layer and the second organic layer are preferably adjacent to each other because the luminance life of the light emitting device of the present invention is more excellent.
- the light emitting device of the present invention has at least one selected from the group consisting of a hole transport layer and a hole injection layer between the anode and the second organic layer. It is preferable to further have a layer.
- at least one layer selected from the group consisting of an electron transport layer and an electron injection layer is provided between the cathode and the first organic layer. It is preferable to further have.
- the layer structure of the light emitting device of the present invention include layer structures represented by the following (D1) to (D19).
- the light-emitting element of the present invention usually has a substrate, but may be laminated from the anode on the substrate, or may be laminated from the cathode on the substrate.
- “/” means that the layers before and after are adjacently stacked.
- “second organic layer / first organic layer” means that the second organic layer and the first organic layer are stacked adjacent to each other.
- two or more hole injection layers, hole transport layers, electron transport layers, and electron injection layers may be provided as necessary.
- the thickness of the anode, cathode, first organic layer, second organic layer, hole injection layer, hole transport layer, electron injection layer and electron transport layer is usually 1 nm to 1 ⁇ m, preferably 2 nm to It is 500 nm, more preferably 5 nm to 150 nm.
- the order, the number, and the thickness of the layers to be stacked may be adjusted in consideration of the light-emitting efficiency and the element life of the light-emitting element.
- the hole transport layer is usually a layer formed using a hole transport material, and is a layer containing a hole transport material.
- a hole transport material used for formation of a hole transport layer the hole transport material which the composition of the above-mentioned 1st organic layer may contain is mentioned, for example.
- a hole transport material may be used individually by 1 type, or may use 2 or more types together.
- the electron transport layer is usually a layer formed using an electron transport material, and is a layer containing an electron transport material.
- the electron transport material used for forming the electron transport layer include an electron transport material that may be contained in the composition of the first organic layer described above, a structural unit represented by the formula (ET-1), and a formula A polymer compound containing at least one structural unit selected from the group consisting of structural units represented by (ET-2), and includes a structural unit represented by the formula (ET-1) and a formula (ET-2
- the polymer compound containing at least one structural unit selected from the group consisting of structural units represented by 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 an aromatic hydrocarbon group or a heterocyclic group, and these groups optionally have a substituent other than R E1 .
- R E1 represents a group represented by the formula (ES-1). When a plurality of R E1 are present, they may be the same or different. ]
- nE4 represents an integer of 0 or more
- aE1 represents an integer of 1 or more
- bE1 represents an integer of 0 or more
- R E3 represents an arylene group or a divalent heterocyclic group, and these groups optionally have a substituent.
- Q E1 represents an alkylene group, an arylene group, an oxygen atom or a sulfur atom, and these groups optionally have a substituent. When a plurality of Q 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. ]
- NE1 is preferably an integer of 1 to 4, more preferably 1 or 2.
- Examples of the aromatic hydrocarbon group or heterocyclic group represented by Ar E1 include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 2,6-naphthalenediyl group, 1,4 Hydrogen bonded directly to the atoms constituting the ring from a naphthalenediyl group, a 2,7-fluorenediyl group, a 3,6-fluorenediyl group, a 2,7-phenanthenediyl group or a 2,7-carbazolediyl group
- the remaining atomic group excluding one atom nE1 is preferable, and may have a substituent other than R E1 .
- 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.
- CE1 is preferably 0 or 1
- nE4 is preferably an integer of 0 to 6.
- R E3 is preferably an arylene group.
- Q E1 is preferably an alkylene group, an arylene group or an oxygen atom.
- Y E1 is preferably —CO 2 — or —SO 3 — .
- 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 because the light-emitting element of the present invention is excellent in luminous efficiency.
- 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 + or N (C 2 H 5 ) Represents 4 + .
- nE2 represents an integer of 1 or more.
- Ar E2 represents an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a substituent other than R E2 .
- R E2 represents a group represented by the 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 optionally have a substituent.
- 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. ]
- NE2 is preferably an integer of 1 to 4, more preferably 1 or 2.
- Examples of the aromatic hydrocarbon group or heterocyclic group represented by Ar E2 include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 2,6-naphthalenediyl group, 1,4 Hydrogen bonded directly to the atoms constituting the ring from a naphthalenediyl group, a 2,7-fluorenediyl group, a 3,6-fluorenediyl group, a 2,7-phenanthenediyl group or a 2,7-carbazolediyl group
- the remaining atomic group excluding 2 atoms nE is preferable, and may have a substituent other than R E2 .
- the substituent group other than Ar E2 is may have R E2, is the same as the substituent other than optionally Ar E1 is have R E1.
- CE2 is preferably 0 or 1
- nE6 is preferably an integer of 0 to 6.
- R E6 is preferably an arylene group which may have a substituent.
- Q E2 is preferably an alkylene group, an arylene group or an oxygen atom, and these groups optionally have a substituent.
- Y E2 is preferably a carbocation or an ammonium cation.
- R E6 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 E6 preferably has a group represented by the formula (ES-3) as a substituent because the light-emitting efficiency of the light-emitting element of the present invention is excellent.
- Examples of the group represented by the formula (ES-2) include a group represented by the following formula.
- X ⁇ represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , tetraphenyl borate, CF 3 SO 3 ⁇ , or CH 3 COO ⁇ .
- Examples of the structural units represented by formula (ET-1) and formula (ET-2) include structural units represented by the following formula (ET-31) to formula (ET-34).
- a material used for forming a hole injection layer a material used for forming a hole transport layer, a material used for forming a second organic layer, a material used for forming a first organic layer, and a material for forming an electron transport layer.
- the materials used and the materials used to form the electron injection layer are a hole injection layer, a hole transport layer, a second organic layer, a first organic layer, an electron transport layer, and an electron in the manufacture of the light-emitting element, respectively.
- a method for avoiding dissolution of the material i) a method using a material having a crosslinking group, or ii) a method of providing a difference in solubility between adjacent layers is preferable.
- the layer after forming a layer using a material having a crosslinking group, the layer can be insolubilized by crosslinking the crosslinking group.
- the electron transport layer When the electron transport layer is stacked on the first organic layer using a difference in solubility, the electron transport layer may be stacked by using a solution having low solubility with respect to the first organic layer. it can.
- Solvents used for laminating the electron transport layer on the first organic layer using the difference in solubility include water, alcohols, ethers, esters, nitrile compounds, nitro compounds, fluorine Preferred are fluorinated alcohols, thiols, sulfides, sulfoxides, thioketones, amides, carboxylic acids and the like.
- 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 , Pyridine, carbon disulfide, and a mixed solvent of these solvents.
- 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.
- a mixed solvent of one or more kinds of solvents and one or more kinds of solvents selected from chlorine-based solvents, aromatic hydrocarbon-based solvents, aliphatic hydrocarbon-based solvents, and ketone-based solvents may be used.
- the hole injection layer is usually a layer formed using a hole injection material, and is a layer containing a hole injection material.
- a hole injection material used for formation of a hole injection layer the hole injection material which the composition of the above-mentioned 1st organic layer may contain is mentioned, for example.
- a hole injection material may be used individually by 1 type, or may use 2 or more types together.
- the electron injection layer is usually a layer formed using an electron injection material, and is a layer containing an electron injection material.
- an electron injection material used for formation of an electron injection layer the electron injection material which the composition of the above-mentioned 1st organic layer may contain is mentioned, for example.
- An electron injection material may be used individually by 1 type, or may use 2 or more types together.
- the substrate in the light-emitting element may be any substrate that can form electrodes and does not change chemically when the organic layer is formed.
- the substrate is made of a material such as glass, plastic, or silicon.
- the electrode farthest from the substrate is transparent or translucent.
- Examples of the material for the anode include conductive metal oxides and translucent metals, preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium zinc oxide, etc.
- conductive metal oxides and translucent metals preferably indium oxide, zinc oxide, tin oxide; indium tin oxide (ITO), indium zinc oxide, etc.
- ITO indium tin oxide
- Examples of the material of the cathode include metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, zinc, indium; two or more kinds of alloys thereof; Alloys of one or more species with one or more of silver, copper, manganese, titanium, cobalt, nickel, tungsten, tin; and graphite and graphite intercalation compounds.
- the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, and a calcium-aluminum alloy.
- the anode and the cathode may each have a laminated structure of two or more layers.
- At least one of the anode and the cathode is usually transparent or translucent, but the anode is preferably transparent or translucent.
- Examples of the method for forming the anode and the cathode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and a laminating method.
- a low molecular compound is used as a method for forming each of the first organic layer, the second organic layer, the hole transport layer, the electron transport layer, the hole injection layer, the electron injection layer, and the like.
- a vacuum deposition method from a powder a method by film formation from a solution or a molten state can be mentioned, and when a polymer compound is used, for example, a method by film formation from a solution or a molten state can be mentioned.
- the first organic layer uses the ink of the first organic layer
- the second organic layer uses the ink of the second organic layer
- the layer can be formed by a coating method typified by a spin coating method and an ink jet printing method, using inks each containing the above-described hole transport material, electron transport material, hole injection material, and electron injection material. .
- 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 also be used as a curved light source and display device.
- the polystyrene-equivalent number average molecular weight (Mn) and polystyrene-equivalent weight average molecular weight (Mw) of the polymer compound are size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Determined by The SEC measurement conditions are as follows.
- the polymer compound to be measured was dissolved in THF at a concentration of about 0.05% by weight, and 10 ⁇ L was injected into SEC. THF was used as the mobile phase of SEC and flowed at a flow rate of 2.0 mL / min.
- PLgel MIXED-B manufactured by Polymer Laboratories
- a UV-VIS detector manufactured by Shimadzu Corporation, trade name: SPD-10Avp was used as the detector.
- NMR measurement was performed by the following method. 5 to 10 mg of a measurement sample is dissolved in about 0.5 mL of deuterated chloroform (CDCl 3 ), deuterated tetrahydrofuran (THF-d 8 ) or methylene dichloride (CD 2 Cl 2 ), and an NMR apparatus (Agilent, trade name: INOVA300). Alternatively, measurement was performed using MERCURY 400VX).
- Step 1 After making the inside of the reaction vessel an inert gas atmosphere, monomer CM1 (0.9950 g) synthesized according to the method described in JP 2010-189630 A, described in JP 2008-106241 A Monomer CM2 (0.1064 g) synthesized according to the method, monomer CM3 (0.0924 g) synthesized according to the method described in JP 2010-215886 A, according to the method described in JP 2002-539292 A The synthesized monomer CM4 (0.7364 g), dichlorobis [tris (2-methoxyphenyl) phosphine] palladium (1.8 mg) and toluene (47 ml) were added and heated to 105 ° C.
- Step 2 A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 ml) was added dropwise to the reaction solution, and the mixture was refluxed for 5.5 hours.
- Step 3 Thereafter, phenylboronic acid (24.4 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 ml) and dichlorobis [tris (2-methoxyphenyl) phosphine] palladium (1.8 mg) were added thereto. The mixture was refluxed for 14 hours.
- Step 4 Thereafter, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the reaction solution was washed twice with water, twice with a 3% by weight aqueous acetic acid solution and twice with water, and the resulting solution was added dropwise to methanol, resulting in precipitation. The precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 0.91 g of a polymer compound P1. The Mn of the polymer compound P1 was 5.2 ⁇ 10 4 and the Mw was 2.5 ⁇ 10 5 .
- the polymer compound P1 has a constitutional unit derived from the monomer CM1, a constitutional unit derived from the monomer CM2, and a constitution derived from the monomer CM3 in terms of theoretical values obtained from the amounts of raw materials charged. It is a copolymer in which the unit and the structural unit derived from the monomer CM4 are configured in a molar ratio of 50: 5: 5: 40.
- the polymer compound P2 includes monomer CM1, monomer CM5 synthesized according to the method described in International Publication No. 2012/86671, and monomer CM6 synthesized according to the method described in JP 2010-189630 A. Was synthesized according to the method described in JP2012-036388.
- the Mn of the polymer compound P2 was 9.1 ⁇ 10 4 and the Mw was 2.3 ⁇ 10 5 .
- the polymer compound P2 has a constitutional unit derived from the monomer CM1, a constitutional unit derived from the monomer CM5, and a constitution derived from the monomer CM6 according to theoretical values obtained from the amounts of the raw materials charged.
- a unit is a copolymer composed of a molar ratio of 50:40:10.
- Step 1 After making the inside of the reaction vessel an inert gas atmosphere, monomer CM7 (0.55 g) synthesized according to the method described in JP 2012-33845 A, described in JP 2012-33845 A Monomer CM8 (0.61 g) synthesized according to the method, triphenylphosphine palladium (0.01 g), methyltrioctyl ammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (0.20 g) and toluene (10 mL) ) And heated to 105 ° C.
- Step 2 A 2M aqueous sodium carbonate solution (6 mL) was added dropwise to the reaction solution and refluxed for 8 hours.
- Step 3 Thereafter, 4-tert-butylphenylboronic acid (0.01 g) was added thereto and refluxed for 6 hours.
- Step 4 Thereafter, an aqueous sodium diethyldithiocarbamate solution (10 mL, concentration: 0.05 g / mL) was added thereto and stirred for 2 hours.
- the resulting reaction solution was added dropwise to methanol (300 mL) and stirred for 1 hour. Thereafter, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in tetrahydrofuran (20 mL).
- the obtained solution was added dropwise to a mixed solvent of methanol (120 mL) and 3% by weight acetic acid aqueous solution (50 mL), and stirred for 1 hour. Thereafter, the deposited precipitate was filtered and dissolved in tetrahydrofuran (20 mL). (Step 5)
- the obtained solution was added dropwise to methanol (200 mL) and stirred for 30 minutes. Thereafter, the deposited precipitate was filtered.
- the obtained solid was dissolved in tetrahydrofuran and then purified by passing through an alumina column and a silica gel column in this order.
- the obtained solution was added dropwise to methanol and stirred, and then the deposited precipitate was filtered.
- the obtained solid was dried to obtain 520 mg of a polymer compound P3.
- the Mn of the polymer compound P3 was 5.2 ⁇ 10 4 and the Mw was 1.5 ⁇ 10 5 .
- the polymer compound P3 has a theoretical value calculated from the amount of the raw material charged, and the structural unit derived from the monomer CM7 and the structural unit derived from the monomer CM8 are configured in a molar ratio of 50:50. It is a copolymer obtained.
- the polymer compound P4 is a copolymer composed of structural units represented by the following in terms of theoretical values determined from the amount of raw materials charged for the polymer compound P3.
- Example 1 Production and evaluation of light-emitting element 1 (formation of anode and hole injection layer) An anode was formed by attaching an ITO film with a thickness of 45 nm to the glass substrate by sputtering.
- AQ-1200 manufactured by Plextronics
- AQ-1200 which is 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.
- the substrate on which the light emitting layer is formed is depressurized to 1.0 ⁇ 10 ⁇ 4 Pa or less in a vapor deposition machine, and then, as a cathode, sodium fluoride is about 4 nm on the light emitting layer, and then on the sodium fluoride layer.
- Aluminum was deposited at about 80 nm. After vapor deposition, the light emitting element 1 was produced by sealing using a glass substrate.
- EL light emission was observed by applying a voltage to the light emitting element 1.
- the driving voltage at 1000 cd / m 2 was 6.1 [V]
- the luminous efficiency was 76.5 [cd / A]
- the chromaticity coordinates (x, y) were (0.30, 0.64).
- the current value was set so that the initial luminance would be 28000 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured to be 7.3 hours.
- Example 2 Production and Evaluation of Light-Emitting Element 2
- polymer compound P1 / compound G1 70% by weight / 30% by weight
- EL light emission was observed by applying a voltage to the light emitting element 2.
- the driving voltage at 1000 cd / m 2 was 5.7 [V]
- the luminous efficiency was 74.0 [cd / A]
- the chromaticity coordinates (x, y) were (0.30, 0.64).
- the current value was set so that the initial luminance was 28000 cd / m 2 , the device was then driven at a constant current, and the luminance half-life was measured to be 8.5 hours.
- Example 3 Production and Evaluation of Light-Emitting Element 3
- polymer compound P1 / compound G1 60% by weight / 40% by weight
- polymer compound P1 and compound G1 dissolved in Example 1
- a light-emitting element 3 was produced.
- EL light emission was observed by applying a voltage to the light emitting element C1.
- the driving voltage at 1000 cd / m 2 was 6.1 [V]
- the luminous efficiency was 82.7 [cd / A]
- the chromaticity coordinates (x, y) were (0.30, 0.64).
- the current value was set so that the initial luminance was 28000 cd / m 2 , the device was then driven at a constant current, and the luminance half-life was measured to be 5.2 hours.
- Example 4 Production and evaluation of light-emitting element 4 (formation of anode and hole injection layer)
- An anode was formed by attaching an ITO film with a thickness of 45 nm to the glass substrate by sputtering.
- AQ-1200 manufactured by Plextronics
- AQ-1200 which is 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.
- Formation of cathode After depressurizing the substrate on which the electron transport layer is formed to 1.0 ⁇ 10 ⁇ 4 Pa or less in a vapor deposition machine, about 4 nm of sodium fluoride is formed on the light emitting layer as a cathode, and then on the sodium fluoride layer. Aluminum was evaporated to about 80 nm.
- the light emitting element 4 was produced by sealing using a glass substrate after vapor deposition.
- EL light emission was observed by applying a voltage to the light emitting element 4.
- the driving voltage at 1000 cd / m 2 was 6.1 [V]
- the luminous efficiency was 3.5 [cd / A]
- the chromaticity coordinates (x, y) were (0.19, 0.40).
- the current value was set so that the initial luminance was 400 cd / m 2 , the device was then driven at a constant current, and the luminance half-life was measured to be 94.1 hours.
- EL light emission was observed by applying a voltage to the light emitting element 5.
- the driving voltage at 1000 cd / m 2 was 5.9 [V]
- the luminous efficiency was 3.5 [cd / A]
- the chromaticity coordinates (x, y) were (0.19, 0.39).
- the current value was set so that the initial luminance was 400 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured. As a result, it was 45.4 hours.
- EL light emission was observed by applying a voltage to the light emitting element C2.
- the driving voltage at 1000 cd / m 2 was 7.6 [V]
- the luminous efficiency was 1.4 [cd / A]
- the chromaticity coordinates (x, y) were (0.19, 0.40).
- the current value was set so that the initial luminance was 400 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured to be 2.7 hours.
- Example 6 Production and Evaluation of Light-Emitting Element 6
- EL light emission was observed by applying a voltage to the light emitting element 6.
- the driving voltage at 1000 cd / m 2 was 8.5 [V]
- the luminous efficiency was 4.5 [cd / A]
- the chromaticity coordinates (x, y) were (0.26, 0.41).
- the current value was set so that the initial luminance was 1000 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured to be 21.8 hours.
- Example 7 Production and Evaluation of Light-Emitting Element 7
- DCzDBT / compound G2 70 wt% / 30 wt%) in which DCzDBT and compound G2 are dissolved
- EL light emission was observed by applying a voltage to the light emitting element 7.
- the driving voltage at 1000 cd / m 2 was 9.3 [V]
- the luminous efficiency was 6.2 [cd / A]
- the chromaticity coordinates (x, y) were (0.23, 0.40).
- the current value was set so that the initial luminance was 1000 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured to be 11.2 hours.
- EL light emission was observed by applying a voltage to the light emitting element 8.
- the driving voltage at 1000 cd / m 2 was 8.7 [V]
- the luminous efficiency was 7.1 [cd / A]
- the chromaticity coordinates (x, y) were (0.24, 0.40).
- the current value was set so that the initial luminance was 1000 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured. As a result, it was 14.0 hours.
- EL light emission was observed by applying a voltage to the light emitting element C3.
- the driving voltage at 1000 cd / m 2 was 10.4 [V]
- the luminous efficiency was 3.8 [cd / A]
- the chromaticity coordinates (x, y) were (0.23, 0.40).
- the current value was set so that the initial luminance was 1000 cd / m 2 , the device was then driven at a constant current, and the luminance half life was measured to be 2.6 hours.
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Abstract
Description
第1の有機層が、1種以上の燐光発光性化合物を含有する層であり、
第2の有機層が、1種以上の燐光発光性化合物と、架橋材料の架橋体とを含有する層であり、
第1の有機層に含有される少なくとも1種の燐光発光性化合物と、第2の有機層に含有される少なくとも1種の燐光発光性化合物とが、式(1)で表される同一の燐光発光性化合物である発光素子。
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子または白金原子を表す。
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または3である。Mがルテニウム原子、ロジウム原子またはイリジウム原子の場合、n1+n2は3であり、Mがパラジウム原子または白金原子の場合、n1+n2は2である。
E1およびE2は、それぞれ独立に、炭素原子または窒素原子を表す。但し、E1およびE2の少なくとも一方は炭素原子である。
環L1は、5員環または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ともに環を形成していてもよい。環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。但し、環L1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L2は、5員環もしくは6員環の芳香族炭化水素環、または、5員環もしくは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ともに環を形成していてもよい。環L2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L2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。
また、環L1および環L2からなる群から選ばれる少なくとも1つの環は、式(2)で表される基を有する。
A1-G1-A2は、アニオン性の2座配位子を表す。A1およびA2は、それぞれ独立に、炭素原子、酸素原子または窒素原子を表し、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、または、A1およびA2とともに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。]
-R2 (2)
[式中、R2は、アリール基、1価の複素環基または置換アミノ基を表し、これらの基は置換基を有していてもよい。]
[2]前記式(2)で表される基が、式(D-A)で表される基または式(D-B)で表される基である、[1]に記載の発光素子。
mDA1、mDA2およびmDA3は、それぞれ独立に、0以上の整数を表す。
GDAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
ArDA1、ArDA2およびArDA3は、それぞれ独立に、アリーレン基または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およびArDA3が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
TDAは、アリール基または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およびmDA7は、それぞれ独立に、0以上の整数を表す。
GDAは、窒素原子、芳香族炭化水素基または複素環基を表し、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およびArDA7は、それぞれ独立に、アリーレン基または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およびArDA7が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
TDAは、アリール基または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。]
[3]前記架橋材料が、架橋基A群から選ばれる少なくとも1種の架橋基を有する架橋構成単位を含む高分子化合物である、[1]または[2]に記載の発光素子。
(架橋基A群)
[4]前記架橋構成単位が、式(3)で表される構成単位または式(4)で表される構成単位である、[3]に記載の発光素子。
nAは0~5の整数を表し、nは1または2を表す。
Ar1は、芳香族炭化水素基または複素環基を表し、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、酸素原子または硫黄原子を表し、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、アリール基または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または1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。
Ar3は、芳香族炭化水素基、複素環基、または、少なくとも1種の芳香族炭化水素環と少なくとも1種の複素環とが直接結合した基を表し、これらの基は置換基を有していてもよい。
Ar2およびAr4は、それぞれ独立に、アリーレン基または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。
Ar2、Ar3およびAr4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、直接または酸素原子も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、酸素原子または硫黄原子を表し、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、アリール基または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。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、アリール基または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。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。]
[5]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、[1]~[4]のいずれかに記載の発光素子。
M、n1、n2、E1およびA1-G1-A2は、前記と同じ意味を表す。
E11A、E12A、E13A、E21A、E22A、E23AおよびE24Aは、それぞれ独立に、窒素原子または炭素原子を表す。E11A、E12A、E13A、E21A、E22A、E23AおよびE24A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。E11A、E12AおよびE13Aが窒素原子の場合、R11A、R12AおよびR13Aは、存在しても存在しなくてもよい。E21A、E22A、E23AおよびE24Aが窒素原子の場合、R21A、R22A、R23AおよびR24Aは、存在しない。
R11A、R12A、R13A、R21A、R22A、R23AおよびR24A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、置換アミノ基また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。R11A、R12A、R13A、R21A、R22A、R23AおよびR24A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。R11AとR12A、R12AとR13A、R11AとR21A、R21AとR22A、R22AとR23A、および、R23AとR24Aは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。但し、R11A、R12A、R13A、R21A、R22A、R23AおよびR24Aからなる群から選ばれる少なくとも1つは、式(2)で表される基である。
環L1Aは、窒素原子、E1、E11A、E12AおよびE13Aとで構成されるトリアゾール環またはイミダゾール環を表す。
環L2Aは、2つの炭素原子、E21A、E22A、E23AおよびE24Aとで構成されるベンゼン環、ピリジン環またはピリミジン環を表す。]
[6]前記式(1-A)で表される燐光発光性化合物が、式(1-A1)、(1-A2)、(1-A3)または(1-A4)で表される燐光発光性化合物である、[5]に記載の発光素子。
M、n1、n2、R11A、R12A、R13A、R21A、R22A、R23A、R24AおよびA1-G1-A2は、前記と同じ意味を表す。]
[7]前記式(1)で表される燐光発光性化合物が、式(1-B)で表される燐光発光性化合物である、[1]~[4]のいずれかに記載の発光素子。
M、n1、n2およびA1-G1-A2は、前記と同じ意味を表す。
E11B、E12B、E13B、E14B、E21B、E22B、E23BおよびE24Bは、それぞれ独立に、窒素原子または炭素原子を表す。E11B、E12B、E13B、E14B、E21B、E22B、E23BおよびE24B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。E11B、E12B、E13B、E14B、E21B、E22B、E23BおよびE24Bが窒素原子の場合、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bは、存在しない。
R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24B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価の複素環基また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。R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24B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。R11BとR12B、R12BとR13B、R13BとR14B、R11BとR21B、R21BとR22B、R22BとR23B、および、R23BとR24Bは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。但し、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bからなる群から選ばれる少なくとも1つは、式(2)で表される基である。
環L1Bは、窒素原子、炭素原子、E11B、E12B、E13BおよびE14Bとで構成されるピリジン環またはピリミジン環を表す。
環L2Bは、2つの炭素原子、E21B、E22B、E23BおよびE24Bとで構成されるベンゼン環、ピリジン環またはピリミジン環を表す。]
[8]前記式(1-B)で表される燐光発光性化合物が、式(1-B1)、(1-B2)または(1-B3)で表される燐光発光性化合物である、[7]に記載の発光素子。
M、n1、n2、A1-G1-A2、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bは、前記と同じ意味を表す。
n11およびn12は、それぞれ独立に、1以上の整数を表し、n11+n12は2または3である。Mがルテニウム原子、ロジウム原子またはイリジウム原子の場合、n11+n12は3であり、Mがパラジウム原子または白金原子の場合、n11+n12は2である。
R15B、R16B、R17BおよびR18B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、置換アミノ基また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。R15B、R16B、R17BおよびR18B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。R13BとR15B、R15BとR16B、R16BとR17B、R17BとR18B、および、R18BとR21Bは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。
但し、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bからなる群から選ばれる少なくとも1つは、式(2)で表される基である。]
[9]前記第1の有機層が、1種以上の燐光発光性化合物と、式(Y)で表される構成単位を含む高分子化合物とを含有する層である、[1]~[8]のいずれかに記載の発光素子。
[10]前記第1の有機層が、1種以上の燐光発光性化合物と、式(H-1)で表される化合物とを含有する層である、[1]~[8]のいずれかに記載の発光素子。
ArH1およびArH2は、それぞれ独立に、アリール基または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およびnH2は、それぞれ独立に、0または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、0以上の整数を表す。
LH1は、アリーレン基、2価の複素環基、または、-[C(RH11)2]nH11-で表される基を表し、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。nH11は、1以上10以下の整数を表す。RH11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、アリール基または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RH11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ともに環を形成していてもよい。
LH2は、-N(-LH21-RH21)-で表される基を表す。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。LH21は、単結合、アリーレン基または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。RH21は、水素原子、アルキル基、シクロアルキル基、アリール基または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。]
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。
アルキル基は、置換基を有していてもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソアミル基、2-エチルブチル基、ヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基、3-プロピルヘプチル基、デシル基、3,7-ジメチルオクチル基、2-エチルオクチル基、2-ヘキシルデシル基、ドデシル基、および、これらの基における水素原子が、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、フッ素原子等で置換された基が挙げられ、例えば、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基、3-フェニルプロピル基、3-(4-メチルフェニル)プロピル基、3-(3,5-ジ-ヘキシルフェニル)プロピル基、6-エチルオキシヘキシル基が挙げられる。
「シクロアルキル基」の炭素原子数は、置換基の炭素原子数を含めないで、通常3~50であり、好ましくは3~30であり、より好ましくは4~20である。
シクロアルキル基は、置換基を有していてもよく、例えば、シクロヘキシル基、シクロヘキシルメチル基、シクロヘキシルエチル基が挙げられる。
アリール基は、置換基を有していてもよく、例えば、フェニル基、1-ナフチル基、2-ナフチル基、1-アントラセニル基、2-アントラセニル基、9-アントラセニル基、1-ピレニル基、2-ピレニル基、4-ピレニル基、2-フルオレニル基、3-フルオレニル基、4-フルオレニル基、2-フェニルフェニル基、3-フェニルフェニル基、4-フェニルフェニル基、および、これらの基における水素原子が、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、フッ素原子等で置換された基が挙げられる。
アルコキシ基は、置換基を有していてもよく、例えば、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブチルオキシ基、イソブチルオキシ基、tert-ブチルオキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、2-エチルヘキシルオキシ基、ノニルオキシ基、デシルオキシ基、3,7-ジメチルオクチルオキシ基、ラウリルオキシ基、および、これらの基における水素原子が、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、フッ素原子等で置換された基が挙げられる。
「シクロアルコキシ基」の炭素原子数は、置換基の炭素原子数を含めないで、通常3~40であり、好ましくは4~10である。
シクロアルコキシ基は、置換基を有していてもよく、例えば、シクロヘキシルオキシ基が挙げられる。
アリールオキシ基は、置換基を有していてもよく、例えば、フェノキシ基、1-ナフチルオキシ基、2-ナフチルオキシ基、1-アントラセニルオキシ基、9-アントラセニルオキシ基、1-ピレニルオキシ基、および、これらの基における水素原子が、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、フッ素原子等で置換された基が挙げられる。
「芳香族複素環式化合物」は、オキサジアゾール、チアジアゾール、チアゾール、オキサゾール、チオフェン、ピロール、ホスホール、フラン、ピリジン、ピラジン、ピリミジン、トリアジン、ピリダジン、キノリン、イソキノリン、カルバゾール、ジベンゾホスホール等の複素環自体が芳香族性を示す化合物、および、フェノキサジン、フェノチアジン、ジベンゾボロール、ジベンゾシロール、ベンゾピラン等の複素環自体は芳香族性を示さなくとも、複素環に芳香環が縮環されている化合物を意味する。
1価の複素環基は、置換基を有していてもよく、例えば、チエニル基、ピロリル基、フリル基、ピリジル基、ピペリジニル基、キノリニル基、イソキノリニル基、ピリミジニル基、トリアジニル基、および、これらの基における水素原子が、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等で置換された基が挙げられる。
置換アミノ基としては、例えば、ジアルキルアミノ基、ジシクロアルキルアミノ基およびジアリールアミノ基が挙げられる。
アミノ基としては、例えば、ジメチルアミノ基、ジエチルアミノ基、ジフェニルアミノ基、ビス(4-メチルフェニル)アミノ基、ビス(4-tert-ブチルフェニル)アミノ基、ビス(3,5-ジ-tert-ブチルフェニル)アミノ基が挙げられる。
「シクロアルケニル基」の炭素原子数は、置換基の炭素原子数を含めないで、通常3~30であり、好ましくは4~20である。
アルケニル基およびシクロアルケニル基は、置換基を有していてもよく、例えば、ビニル基、1-プロペニル基、2-プロペニル基、2-ブテニル基、3-ブテニル基、3-ペンテニル基、4-ペンテニル基、1-ヘキセニル基、5-ヘキセニル基、7-オクテニル基、および、これらの基が置換基を有する基が挙げられる。
「シクロアルキニル基」の炭素原子数は、置換基の炭素原子を含めないで、通常4~30であり、好ましくは4~20である。
アルキニル基およびシクロアルキニル基は、置換基を有していてもよく、例えば、エチニル基、1-プロピニル基、2-プロピニル基、2-ブチニル基、3-ブチニル基、3-ペンチニル基、4-ペンチニル基、1-ヘキシニル基、5-ヘキシニル基、および、これらの基が置換基を有する基が挙げられる。
アリーレン基は、置換基を有していてもよく、例えば、フェニレン基、ナフタレンジイル基、アントラセンジイル基、フェナントレンジイル基、ジヒドロフェナントレンジイル基、ナフタセンジイル基、フルオレンジイル基、ピレンジイル基、ペリレンジイル基、クリセンジイル基、および、これらの基が置換基を有する基が挙げられ、好ましくは、式(A-1)~式(A-20)で表される基である。アリーレン基は、これらの基が複数結合した基を含む。
2価の複素環基は、置換基を有していてもよく、例えば、ピリジン、ジアザベンゼン、トリアジン、アザナフタレン、ジアザナフタレン、カルバゾール、ジベンゾフラン、ジベンゾチオフェン、ジベンゾシロール、フェノキサジン、フェノチアジン、アクリジン、ジヒドロアクリジン、フラン、チオフェン、アゾール、ジアゾール、トリアゾールから、環を構成する炭素原子またはヘテロ原子に直接結合している水素原子のうち2個の水素原子を除いた2価の基が挙げられ、好ましくは、式(AA-1)~式(AA-34)で表される基である。2価の複素環基は、これらの基が複数結合した基を含む。
次に、本発明の発光素子について説明する。
本発明の発光素子は、組成物に含有される架橋材料が架橋された状態(架橋材料の架橋体)で、第2の有機層に含有されていることが好ましい。
第1の有機層は、1種以上の燐光発光性化合物を用いて形成される層である。前述のとおり、第1の有機層は、1種以上の燐光発光性化合物を含有する層であることが好ましい。
第1の有機層の形成に用いられる燐光発光性化合物は、式(1)で表される燐光発光性化合物であることが好ましい。後述する第2の有機層の形成に用いられる燐光発光性化合物も、式(1)で表される燐光発光性化合物であることが好ましい。但し、第1の有機層の形成に用いられる少なくとも1種の燐光発光性化合物と、第2の有機層の形成に用いられる少なくとも1種の燐光発光性化合物とは、式(1)で表される同一の燐光発光性化合物である。
*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、または、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、または、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、または、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、アリール基または1価の複素環基を表し、これらの基は更に置換基を有していてもよい。RDAが複数ある場合、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、アリール基または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が複数ある場合、それらは同一でも異なっていてもよい。]
Rp1、Rp2および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またはハロゲン原子を表す。Rp1およびRp2が複数ある場合、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または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および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またはハロゲン原子を表す。Rp1およびRp2が複数ある場合、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または1を表す。np1およびnp2が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。]
*は、Mと結合する部位を表す。
RL1は、水素原子、アルキル基、シクロアルキル基また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。複数存在するRL1は、同一でも異なっていてもよい。
RL2は、アルキル基、シクロアルキル基また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。]
本発明の発光素子の発光効率が優れるため、第1の有機層は、1種以上の燐光発光性化合物と、正孔注入性、正孔輸送性、電子注入性および電子輸送性からなる群から選ばれる少なくとも1つの機能を有するホスト材料とを含有する組成物を用いて形成される層であることが好ましく、1種以上の燐光発光性化合物と、正孔注入性、正孔輸送性、電子注入性および電子輸送性からなる群から選ばれる少なくとも1つの機能を有するホスト材料とを含有する層であることがより好ましい。該組成物において、ホスト材料は、1種単独で含有されていても、2種以上含有されていてもよい。
ホスト材料として好ましい低分子化合物(以下、「低分子ホスト」と言う。)に関して説明する。
ホスト化合物として好ましい高分子化合物(以下、「高分子ホスト」と言う。)に関して説明する。
aX1およびaX2は、それぞれ独立に、0以上の整数を表す。
ArX1およびArX3は、それぞれ独立に、アリーレン基または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およびArX4は、それぞれ独立に、アリーレン基、2価の複素環基、または、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。
RX1、RX2および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、アリール基または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。]
[表中、p、q、r、sおよびtは、各構成単位のモル比率を示す。p+q+r+s+t=100であり、かつ、100≧p+q+r+s≧70である。その他の構成単位とは、式(Y)で表される構成単位、式(X)で表される構成単位以外の構成単位を意味する。]
高分子ホストは、ケミカルレビュー(Chem. Rev.),第109巻,897-1091頁(2009年)等に記載の公知の重合方法を用いて製造することができ、Suzuki反応、Yamamoto反応、Buchwald反応、Stille反応、Negishi反応およびKumada反応等の遷移金属触媒を用いるカップリング反応により重合させる方法が例示される。
第1の有機層は、1種以上の燐光発光性化合物と、前述のホスト材料、正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料(燐光発光性化合物とは異なる。)、酸化防止剤および溶媒からなる群から選ばれる少なくとも1種の材料とを含有する組成物(以下、「第1の有機層の組成物」ともいう。)を用いて形成される層であってもよい。すなわち、第1の有機層は、1種以上の燐光発光性化合物と、前述のホスト材料、正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料(燐光発光性化合物とは異なる。)および酸化防止剤からなる群から選ばれる少なくとも1種の材料とを含有する層であってもよい。
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、好ましくは高分子化合物である。正孔輸送材料は、架橋基を有していてもよい。
電子輸送材料は、低分子化合物と高分子化合物とに分類される。電子輸送材料は、架橋基を有していてもよい。
正孔注入材料および電子注入材料は、各々、低分子化合物と高分子化合物とに分類される。正孔注入材料および電子注入材料は、架橋基を有していてもよい。
正孔注入材料または電子注入材料が導電性高分子を含む場合、導電性高分子の電気伝導度は、好ましくは、1×10-5S/cm~1×103S/cmである。導電性高分子の電気伝導度をかかる範囲とするために、導電性高分子に適量のイオンをドープすることができる。
発光材料(燐光発光性化合物とは異なる。)は、低分子化合物と高分子化合物とに分類される。発光材料は、架橋基を有していてもよい。
酸化防止剤は、燐光発光性化合物と同じ溶媒に可溶であり、発光および電荷輸送を阻害しない化合物であればよく、例えば、フェノール系酸化防止剤、リン系酸化防止剤が挙げられる。
溶媒を含有する第1の有機層の組成物(以下、「第1の有機層のインク」ともいう。)は、スピンコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイヤーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、フレキソ印刷法、オフセット印刷法、インクジェット印刷法、キャピラリ-コート法、ノズルコート法等の塗布法に好適に使用することができる。
第2の有機層は、1種以上の燐光発光性化合物と、架橋材料とを含有する組成物を用いて形成される層である。前述のとおり、第2の有機層は、1種以上の燐光発光性化合物と、架橋材料の架橋体とを含有する層であることが好ましい。
第2の有機層の形成に用いられる燐光発光性化合物は、式(1)で表される燐光発光性化合物であることが好ましい。前述した第1の有機層の形成に用いられる燐光発光性化合物も、式(1)で表される燐光発光性化合物であることが好ましい。但し、第2の有機層の形成に用いられる少なくとも1種の燐光発光性化合物と、第1の有機層の形成に用いられる少なくとも1種の燐光発光性化合物とは、式(1)で表される同一の燐光発光性化合物である。
架橋材料は、低分子化合物であっても高分子化合物であってもよいが、本発明の発光素子の発光効率が優れるので、架橋基A群から選ばれる少なくとも1種の架橋基を有する材料であることが好ましく、架橋基A群から選ばれる少なくとも1種の架橋基を有する架橋構成単位を含む高分子化合物(以下、「第2の有機層の高分子化合物」ともいう。)であることが好ましい。
Ar1で表される芳香族炭化水素基のn個の置換基を除いたアリーレン基部分としては、好ましくは、式(A-1)~式(A-20)で表される基であり、より好ましくは、式(A-1)、式(A-2)、式(A-6)~式(A-10)、式(A-19)または式(A-20)で表される基であり、さらに好ましくは、式(A-1)、式(A-2)、式(A-7)、式(A-9)または式(A-19)で表される基であり、これらの基は置換基を有していてもよい。
Ar1で表される複素環基のn個の置換基を除いた2価の複素環基部分としては、好ましくは、式(AA-1)~(AA-34)で表される基である。
アルキレン基およびシクロアルキレン基は、置換基を有していてもよく、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、シクロヘキシレン基、オクチレン基が挙げられる。
[表中、p’、q’、r’、s’、u’およびv’は、各構成単位のモル比率を表す。p’+q’+r’+s’+u’+v’=100であり、かつ、70≦p’+q’+r’+s’+u’≦100である。その他の構成単位とは、式(3)で表される構成単位、式(4)で表される構成単位、式(X)で表される構成単位、式(Y)で表される構成単位以外の構成単位を意味する。]
第2の有機層の高分子化合物は、前述の高分子ホストの製造方法と同様の方法で製造することができる。
第2の有機層の形成に用いられる組成物において、燐光発光性化合物の含有量は、燐光発光性化合物と架橋材料との合計を100重量部とした場合、通常、0.1~50であり、好ましくは0.2~45であり、より好ましくは0.3~40である。
第2の有機層は、1種以上の燐光発光性化合物と、架橋材料と、正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料(燐光発光性化合物とは異なる。)、酸化防止剤および溶媒からなる群から選ばれる少なくとも1種の材料とを含有する組成物(以下、「第2の有機層の組成物」ともいう。)を用いて形成される層であってもよい。すなわち、第2の有機層は、1種以上の燐光発光性化合物と、架橋材料と、正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料(燐光発光性化合物とは異なる。)および酸化防止剤からなる群から選ばれる少なくとも1種の材料とを含有する層であってもよく、1種以上の燐光発光性化合物と、架橋材料の架橋体と、正孔輸送材料、正孔注入材料、電子輸送材料、電子注入材料、発光材料(燐光発光性化合物とは異なる。)および酸化防止剤からなる群から選ばれる少なくとも1種の材料とを含有する層であることが好ましい。
溶媒を含有する第2の有機層の組成物(以下、「第2の有機層のインク」ともいう。)は、第1の有機層のインクと同様に、スピンコート法、インクジェット印刷法等の塗布法に好適に使用することができる。
本発明の発光素子は、陽極と、陰極と、陽極および陰極の間に設けられた第1の有機層と、陽極および第1の有機層の間に設けられた第2の有機層とを有する。本発明の発光素子は、陽極、陰極、第1の有機層および第2の有機層以外の層を有していてもよい。
(D2)陽極/第2の有機層/第1の有機層/電子輸送層/陰極
(D3)陽極/第2の有機層/第1の有機層/電子注入層/陰極
(D4)陽極/第2の有機層/第1の有機層/電子輸送層/電子注入層/陰極
(D5)陽極/正孔注入層/第2の有機層/第1の有機層/陰極
(D6)陽極/正孔注入層/第2の有機層/第1の有機層/電子輸送層/陰極
(D7)陽極/正孔注入層/第2の有機層/第1の有機層/電子注入層/陰極
(D8)陽極/正孔注入層/第2の有機層/第1の有機層/電子輸送層/電子注入層/陰極
(D9)陽極/正孔輸送層/第2の有機層/第1の有機層/陰極
(D10)陽極/正孔輸送層/第2の有機層/第1の有機層/電子輸送層/陰極
(D11)陽極/正孔輸送層/第2の有機層/第1の有機層/電子注入層/陰極
(D12)陽極/正孔輸送層/第2の有機層/第1の有機層/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2の有機層/第1の有機層/陰極
(D14)陽極/正孔注入層/正孔輸送層/第2の有機層/第1の有機層/電子輸送層/陰極
(D15)陽極/正孔注入層/正孔輸送層/第2の有機層/第1の有機層/電子注入層/陰極
(D16)陽極/正孔注入層/正孔輸送層/第2の有機層/第1の有機層/電子輸送層/電子注入層/陰極
正孔輸送層は、通常、正孔輸送材料を用いて形成される層であり、正孔輸送材料を含有する層である。正孔輸送層の形成に用いる正孔輸送材料としては、例えば、前述の第1の有機層の組成物が含有していてもよい正孔輸送材料が挙げられる。正孔輸送材料は、1種単独で用いても、2種以上を併用してもよい。
電子輸送層は、通常、電子輸送材料を用いて形成される層であり、電子輸送材料を含有する層である。電子輸送層の形成に用いる電子輸送材料としては、例えば、前述の第1の有機層の組成物が含有していてもよい電子輸送材料、式(ET-1)で表される構成単位および式(ET-2)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高分子化合物が挙げられ、式(ET-1)で表される構成単位および式(ET-2)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高分子化合物が好ましい。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、芳香族炭化水素基または複素環基を表し、これらの基はRE1以外の置換基を有していてもよい。
RE1は、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または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、アリーレン基または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、酸素原子または硫黄原子を表し、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 -またはPO3 2-を表す。
ME2は、金属カチオンまた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 -またはPF6 -を表す。RE4は、アルキル基、シクロアルキル基また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および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’、m’およびnxは、1以上の整数を表す。]
nE2は1以上の整数を表す。
ArE2は、芳香族炭化水素基または複素環基を表し、これらの基はRE2以外の置換基を有していてもよい。
RE2は、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または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、アリーレン基または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、酸素原子または硫黄原子を表し、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また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 -またはPF6 -を表す。RE7は、アルキル基、パーフルオロアルキル基、また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、金属イオンまた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および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。]
正孔注入層は、通常、正孔注入材料を用いて形成される層であり、正孔注入材料を含有する層である。正孔注入層の形成に用いる正孔注入材料としては、例えば、前述の第1の有機層の組成物が含有していてもよい正孔注入材料が挙げられる。正孔注入材料は、1種単独で用いても、2種以上を併用してもよい。
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、有機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または半透明であることが好ましい。
本発明の発光素子において、第1の有機層、第2の有機層、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としては、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、溶液また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、溶液また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、また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、カラーフィルターまた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、または、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、曲面状の光源およ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。
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)または重塩化メチレン(CD2Cl2)に溶解させ、NMR装置(Agilent製、商品名:INOVA300またはMERCURY 400VX)を用いて測定した。
化合物G1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G2は、国際公開第2008/090795号に記載の方法に従って合成した。
化合物G3は、特開2006-188673号公報に記載の方法に従って合成した。
(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(6.6ml)を滴下し、5.5時間還流させた。
(工程3)その後、そこに、フェニルボロン酸(24.4mg)、20重量%水酸化テトラエチルアンモニウム水溶液(6.6ml)およびジクロロビス〔トリス(2-メトキシフェニル)ホスフィン〕パラジウム(1.8mg)を加え、14時間還流させた。
(工程4)その後、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、80℃で2時間撹拌した。冷却後、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、沈殿が生じた。沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムの順番で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P1を0.91g得た。高分子化合物P1のMnは5.2×104であり、Mwは2.5×105であった。
(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)その後、そこに、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)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、2時間撹拌した。得られた反応溶液をメタノール(300mL)に滴下し、1時間攪拌した。その後、析出した沈殿をろ過し、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)および3重量%酢酸水溶液(50mL)の混合溶媒に滴下し、1時間攪拌した。その後、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)得られた溶液を、メタノール(200mL)に滴下し、30分攪拌した。その後、析出した沈殿をろ過した。得られた固体をテトラヒドロフランに溶解させた後、アルミナカラム、シリカゲルカラムに順に通液する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、析出した沈殿をろ過した。得られた固体を乾燥させることにより、高分子化合物P3を520mg得た。高分子化合物P3のMnは5.2×104であり、Mwは1.5×105であった。
高分子化合物P3(200mg)を反応容器に加えた後、反応容器内を窒素ガス雰囲気とした。その後、そこへ、テトラヒドロフラン(20mL)およびエタノール(20mL)を加え、55℃に昇温した。その後、そこに、水酸化セシウム(200mg)を水(2mL)に溶解させた水酸化セシウム水溶液を加え、55℃で6時間撹拌した。得られた反応混合物を室温まで冷却した後、溶媒を減圧留去した。得られた固体を水で洗浄した後、減圧乾燥させることにより、高分子化合物P4(150mg)を得た。高分子化合物P4の1H-NMR解析により、高分子化合物P4中のエチルエステル部位のシグナルが消失し、反応が完了したことを確認した。
(陽極および正孔注入層の形成)
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(Plextronics社製)をスピンコート法により35nmの厚さで成膜し、大気雰囲気下において、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。
キシレンに、高分子化合物P1および化合物G1(高分子化合物P1/化合物G1=80重量%/20重量%)を0.6重量%の濃度で溶解させた。得られたキシレン溶液を用いて、正孔注入層の上にスピンコート法により20nmの厚さで成膜し、窒素ガス雰囲気下において、ホットプレート上で180℃、60分間加熱させることにより正孔輸送層を形成した。ホットプレート上で180℃、60分間加熱させることにより、高分子化合物P1は、高分子化合物P1の架橋体となる。
キシレンに、高分子化合物P2および化合物G1(高分子化合物P2/化合物G1=70重量%/30重量%)を2.5重量%の濃度で溶解させた。得られたキシレン溶液を用いて、正孔輸送層の上にスピンコート法により80nmの厚さで成膜し、窒素ガス雰囲気下において、130℃、10分間加熱させることにより発光層を形成した。
発光層の形成した基板を蒸着機内において、1.0×10-4Pa以下にまで減圧した後、陰極として、発光層の上にフッ化ナトリウムを約4nm、次いで、フッ化ナトリウム層の上にアルミニウムを約80nm蒸着した。蒸着後、ガラス基板を用いて封止することにより、発光素子1を作製した。
発光素子1に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は6.1[V]、発光効率は76.5[cd/A]、色度座標(x,y)は(0.30,0.64)であった。初期輝度が28000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、7.3時間であった。
実施例1における、高分子化合物P1および化合物G1を溶解させたキシレン溶液(0.6重量%、高分子化合物P1/化合物G1=80重量%/20重量%)に代えて、高分子化合物P1および化合物G1を溶解させたキシレン溶液(0.6重量%、高分子化合物P1/化合物G1=70重量%/30重量%)を用いた以外は、実施例1と同様にして、発光素子2を作製した。
発光素子2に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は5.7[V]、発光効率は74.0[cd/A]、色度座標(x,y)は(0.30,0.64)であった。初期輝度が28000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、8.5時間であった。
実施例1における、高分子化合物P1および化合物G1を溶解させたキシレン溶液(0.6重量%、高分子化合物P1/化合物G1=80重量%/20重量%)に代えて、高分子化合物P1および化合物G1を溶解させたキシレン溶液(0.6重量%、高分子化合物P1/化合物G1=60重量%/40重量%)を用いた以外は、実施例1と同様にして、発光素子3を作製した。
発光素子3に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は5.7[V]、発光効率は70.2[cd/A]、色度座標(x,y)は(0.30,0.64)であった。初期輝度が28000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、9.6時間であった。
実施例1における、高分子化合物P1および化合物G1を溶解させたキシレン溶液(0.6重量%、高分子化合物P1/化合物G1=80重量%/20重量%)に代えて、高分子化合物P1のみを溶解させたキシレン溶液(0.6重量%)用いた以外は、実施例1と同様にして、発光素子C1を作製した。
発光素子C1に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は6.1[V]、発光効率は82.7[cd/A]、色度座標(x,y)は(0.30,0.64)であった。初期輝度が28000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、5.2時間であった。
(陽極および正孔注入層の形成)
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(Plextronics社製)をスピンコート法により35nmの厚さで成膜し、大気雰囲気下において、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。
クロロベンゼンに、高分子化合物P1および化合物G2(高分子化合物P1/化合物G2=85重量%/15重量%)を0.5重量%の濃度で溶解させた。得られたクロロベンゼン溶液を用いて、正孔注入層の上にスピンコート法により20nmの厚さで成膜し、窒素ガス雰囲気下において、ホットプレート上で180℃、60分間加熱させることにより正孔輸送層を形成した。ホットプレート上で180℃、60分間加熱させることにより、高分子化合物P1は、高分子化合物P1の架橋体となる。
クロロベンゼンに、2,8-di(9H-carbazol-9-yl)dibenzo[b,d]thiophene(DCzDBT)(Luminescence Technology Corp社製)および化合物G2(DCzDBT/化合物G2=70重量%/30重量%)を2.0重量%の濃度で溶解させた。得られたクロロベンゼン溶液を用いて、正孔輸送層の上にスピンコート法により60nmの厚さで成膜し、窒素ガス雰囲気下において、130℃、10分間加熱させることにより発光層を形成した。
2,2,3,3,4,4,5,5-オクタフルオロ‐1-ペンタノールに、高分子化合物P4を0.25重量%の濃度で溶解させた。得られた2,2,3,3,4,4,5,5-オクタフルオロ‐1-ペンタノール溶液を用いて、発光層の上にスピンコート法により10nmの厚さで成膜し、窒素ガス雰囲気下において、130℃、10分加熱させることにより電子輸送層を形成した。
電子輸送層の形成した基板を蒸着機内において、1.0×10-4Pa以下にまで減圧した後、陰極として、発光層の上にフッ化ナトリウムを約4nm、次いで、フッ化ナトリウム層の上にアルミニウムを約80nm蒸着した。蒸着後、ガラス基板を用いて封止することにより、発光素子4を作製した。
発光素子4に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は6.1[V]、発光効率は3.5[cd/A]、色度座標(x,y)は(0.19,0.40)であった。初期輝度が400cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、94.1時間であった。
実施例4における、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=85重量%/15重量%)に代えて、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=70重量%/30重量%)を用いた以外は、実施例4と同様にして、発光素子5を作製した。
発光素子5に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は5.9[V]、発光効率は3.5[cd/A]、色度座標(x,y)は(0.19,0.39)であった。初期輝度が400cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、45.4時間であった。
実施例4における、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=85重量%/15重量%)に代えて、高分子化合物P1のみを溶解させたクロロベンゼン溶液(0.5重量%)用いた以外は、実施例4と同様にして、発光素子C2を作製した。
発光素子C2に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は7.6[V]、発光効率は1.4[cd/A]、色度座標(x,y)は(0.19,0.40)であった。初期輝度が400cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、2.7時間であった。
実施例4における、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=85重量%/15重量%)に代えて、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=70重量%/30重量%)を用い、さらに、DCzDBTおよび化合物G2を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2=70重量%/30重量%)に代えて、DCzDBT、化合物G2、化合物G1および化合物G3を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2/化合物G1/化合物G3=69重量%/30重量%/0.6重量%/0.4重量%)を用いた以外は、実施例4と同様にして、発光素子6を作製した。
発光素子6に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は8.5[V]、発光効率は4.5[cd/A]、色度座標(x,y)は(0.26,0.41)であった。初期輝度が1000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、21.8時間であった。
実施例4における、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=85重量%/15重量%)に代えて、高分子化合物P1、化合物G1および化合物G3を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G1/化合物G3=95重量%/3重量%/2重量%)を用い、さらに、DCzDBTおよび化合物G2を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2=70重量%/30重量%)に代えて、DCzDBT、化合物G2、化合物G1および化合物G3を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2/化合物G1/化合物G3=69重量%/30重量%/0.6重量%/0.4重量%)を用いた以外は、実施例4と同様にして、発光素子7を作製した。
発光素子7に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は9.3[V]、発光効率は6.2[cd/A]、色度座標(x,y)は(0.23,0.40)であった。初期輝度が1000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、11.2時間であった。
実施例4における、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=85重量%/15重量%)に代えて、高分子化合物P1、化合物G1および化合物G3を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G1/化合物G3=90重量%/6重量%/4重量%)を用い、さらに、DCzDBTおよび化合物G2を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2=70重量%/30重量%)に代えて、DCzDBT、化合物G2、化合物G1および化合物G3を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2/化合物G1/化合物G3=69重量%/30重量%/0.6重量%/0.4重量%)を用いた以外は、実施例4と同様にして、発光素子8を作製した。
発光素子8に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は8.7[V]、発光効率は7.1[cd/A]、色度座標(x,y)は(0.24,0.40)であった。初期輝度が1000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、14.0時間であった。
実施例4における、高分子化合物P1および化合物G2を溶解させたクロロベンゼン溶液(0.5重量%、高分子化合物P1/化合物G2=85重量%/15重量%)に代えて、高分子化合物P1のみを溶解させたクロロベンゼン溶液(0.5重量%)を用い、さらに、DCzDBTおよび化合物G2を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2=70重量%/30重量%)に代えて、DCzDBT、化合物G2、化合物G1および化合物G3を溶解させたクロロベンゼン溶液(2.0重量%、DCzDBT/化合物G2/化合物G1/化合物G3=69重量%/30重量%/0.6重量%/0.4重量%)を用いた以外は、実施例4と同様にして、発光素子C3を作製した。
発光素子C3に電圧を印加することによりEL発光が観測された。1000cd/m2における駆動電圧は10.4[V]、発光効率は3.8[cd/A]、色度座標(x,y)は(0.23,0.40)であった。初期輝度が1000cd/m2となるように電流値を設定後、定電流で駆動させ、輝度半減寿命を測定したところ、2.6時間であった。
Claims (10)
- 陽極と、
陰極と、
陽極および陰極の間に設けられた第1の有機層と、
陽極および第1の有機層の間に設けられた第2の有機層とを有する発光素子であって、
第1の有機層が、1種以上の燐光発光性化合物を含有する層であり、
第2の有機層が、1種以上の燐光発光性化合物と、架橋材料の架橋体とを含有する層であり、
第1の有機層に含有される少なくとも1種の燐光発光性化合物と、第2の有機層に含有される少なくとも1種の燐光発光性化合物とが、式(1)で表される同一の燐光発光性化合物である発光素子。
[式中、
Mは、ルテニウム原子、ロジウム原子、パラジウム原子、イリジウム原子または白金原子を表す。
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または3である。Mがルテニウム原子、ロジウム原子またはイリジウム原子の場合、n1+n2は3であり、Mがパラジウム原子または白金原子の場合、n1+n2は2である。
E1およびE2は、それぞれ独立に、炭素原子または窒素原子を表す。但し、E1およびE2の少なくとも一方は炭素原子である。
環L1は、5員環または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ともに環を形成していてもよい。環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。但し、環L1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L2は、5員環もしくは6員環の芳香族炭化水素環、または、5員環もしくは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ともに環を形成していてもよい。環L2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L2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。
また、環L1および環L2からなる群から選ばれる少なくとも1つの環は、式(2)で表される基を有する。
A1-G1-A2は、アニオン性の2座配位子を表す。A1およびA2は、それぞれ独立に、炭素原子、酸素原子または窒素原子を表し、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、または、A1およびA2とともに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。]
-R2 (2)
[式中、R2は、アリール基、1価の複素環基または置換アミノ基を表し、これらの基は置換基を有していてもよい。] - 前記式(2)で表される基が、式(D-A)で表される基または式(D-B)で表される基である、請求項1に記載の発光素子。
[式中、
mDA1、mDA2およびmDA3は、それぞれ独立に、0以上の整数を表す。
GDAは、窒素原子、芳香族炭化水素基または複素環基を表し、これらの基は置換基を有していてもよい。
ArDA1、ArDA2およびArDA3は、それぞれ独立に、アリーレン基または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およびArDA3が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
TDAは、アリール基または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。]
[式中、
mDA1、mDA2、mDA3、mDA4、mDA5、mDA6およびmDA7は、それぞれ独立に、0以上の整数を表す。
GDAは、窒素原子、芳香族炭化水素基または複素環基を表し、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およびArDA7は、それぞれ独立に、アリーレン基または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およびArDA7が複数ある場合、それらはそれぞれ同一でも異なっていてもよい。
TDAは、アリール基または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。] - 前記架橋構成単位が、式(3)で表される構成単位または式(4)で表される構成単位である、請求項3に記載の発光素子。
[式中、
nAは0~5の整数を表し、nは1または2を表す。
Ar1は、芳香族炭化水素基または複素環基を表し、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、酸素原子または硫黄原子を表し、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、アリール基または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。]
[式中、
mAは0~5の整数を表し、mは1~4の整数を表し、cは0または1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。
Ar3は、芳香族炭化水素基、複素環基、または、少なくとも1種の芳香族炭化水素環と少なくとも1種の複素環とが直接結合した基を表し、これらの基は置換基を有していてもよい。
Ar2およびAr4は、それぞれ独立に、アリーレン基または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。
Ar2、Ar3およびAr4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、直接または酸素原子も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、酸素原子または硫黄原子を表し、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、アリール基または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。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、アリール基または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。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1~4のいずれか一項に記載の発光素子。
[式中、
M、n1、n2、E1およびA1-G1-A2は、前記と同じ意味を表す。
E11A、E12A、E13A、E21A、E22A、E23AおよびE24Aは、それぞれ独立に、窒素原子または炭素原子を表す。E11A、E12A、E13A、E21A、E22A、E23AおよびE24A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。E11A、E12AおよびE13Aが窒素原子の場合、R11A、R12AおよびR13Aは、存在しても存在しなくてもよい。E21A、E22A、E23AおよびE24Aが窒素原子の場合、R21A、R22A、R23AおよびR24Aは、存在しない。
R11A、R12A、R13A、R21A、R22A、R23AおよびR24A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、置換アミノ基また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。R11A、R12A、R13A、R21A、R22A、R23AおよびR24A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。R11AとR12A、R12AとR13A、R11AとR21A、R21AとR22A、R22AとR23A、および、R23AとR24Aは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。但し、R11A、R12A、R13A、R21A、R22A、R23AおよびR24Aからなる群から選ばれる少なくとも1つは、式(2)で表される基である。
環L1Aは、窒素原子、E1、E11A、E12AおよびE13Aとで構成されるトリアゾール環またはイミダゾール環を表す。
環L2Aは、2つの炭素原子、E21A、E22A、E23AおよびE24Aとで構成されるベンゼン環、ピリジン環またはピリミジン環を表す。] - 前記式(1)で表される燐光発光性化合物が、式(1-B)で表される燐光発光性化合物である、請求項1~4のいずれか一項に記載の発光素子。
[式中、
M、n1、n2およびA1-G1-A2は、前記と同じ意味を表す。
E11B、E12B、E13B、E14B、E21B、E22B、E23BおよびE24Bは、それぞれ独立に、窒素原子または炭素原子を表す。E11B、E12B、E13B、E14B、E21B、E22B、E23BおよびE24B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。E11B、E12B、E13B、E14B、E21B、E22B、E23BおよびE24Bが窒素原子の場合、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bは、存在しない。
R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24B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価の複素環基また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。R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24B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。R11BとR12B、R12BとR13B、R13BとR14B、R11BとR21B、R21BとR22B、R22BとR23B、および、R23BとR24Bは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。但し、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bからなる群から選ばれる少なくとも1つは、式(2)で表される基である。
環L1Bは、窒素原子、炭素原子、E11B、E12B、E13BおよびE14Bとで構成されるピリジン環またはピリミジン環を表す。
環L2Bは、2つの炭素原子、E21B、E22B、E23BおよびE24Bとで構成されるベンゼン環、ピリジン環またはピリミジン環を表す。] - 前記式(1-B)で表される燐光発光性化合物が、式(1-B1)、(1-B2)または(1-B3)で表される燐光発光性化合物である、請求項7に記載の発光素子。
[式中、
M、n1、n2、A1-G1-A2、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bは、前記と同じ意味を表す。
n11およびn12は、それぞれ独立に、1以上の整数を表し、n11+n12は2または3である。Mがルテニウム原子、ロジウム原子またはイリジウム原子の場合、n11+n12は3であり、Mがパラジウム原子または白金原子の場合、n11+n12は2である。
R15B、R16B、R17BおよびR18B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、置換アミノ基また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。R15B、R16B、R17BおよびR18B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。R13BとR15B、R15BとR16B、R16BとR17B、R17BとR18B、および、R18BとR21Bは、それぞれ結合して、それぞれが結合する原子とともに環を形成していてもよい。
但し、R11B、R12B、R13B、R14B、R21B、R22B、R23BおよびR24Bからなる群から選ばれる少なくとも1つは、式(2)で表される基である。] - 前記第1の有機層が、1種以上の燐光発光性化合物と、式(H-1)で表される化合物とを含有する層である、請求項1~8のいずれか一項に記載の発光素子。
[式中、
ArH1およびArH2は、それぞれ独立に、アリール基または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およびnH2は、それぞれ独立に、0または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、0以上の整数を表す。
LH1は、アリーレン基、2価の複素環基、または、-[C(RH11)2]nH11-で表される基を表し、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。nH11は、1以上10以下の整数を表す。RH11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、アリール基または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RH11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ともに環を形成していてもよい。
LH2は、-N(-LH21-RH21)-で表される基を表す。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。LH21は、単結合、アリーレン基または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。RH21は、水素原子、アルキル基、シクロアルキル基、アリール基または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。]
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| KR1020167036661A KR102376847B1 (ko) | 2014-06-04 | 2015-05-22 | 발광 소자 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017061332A1 (ja) * | 2015-10-06 | 2017-04-13 | 住友化学株式会社 | 発光素子 |
| WO2019049225A1 (ja) * | 2017-09-06 | 2019-03-14 | 住友化学株式会社 | 発光素子 |
| EP3478030A4 (en) * | 2016-06-24 | 2020-01-22 | Sumitomo Chemical Company, Limited | LIGHT-EMITTING ELEMENT |
| EP3428989B1 (en) * | 2016-03-10 | 2021-04-21 | Sumitomo Chemical Company Limited | Light-emitting element |
| JP7015406B1 (ja) | 2020-09-24 | 2022-02-02 | 住友化学株式会社 | 発光素子及び組成物 |
| WO2022065102A1 (ja) | 2020-09-24 | 2022-03-31 | 住友化学株式会社 | 発光素子及び組成物 |
| JP2022094314A (ja) * | 2020-12-14 | 2022-06-24 | 住友化学株式会社 | 高分子化合物の製造方法 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016052337A1 (ja) * | 2014-09-30 | 2016-04-07 | 住友化学株式会社 | 発光素子 |
| JP2017155125A (ja) * | 2016-03-01 | 2017-09-07 | Jxtgエネルギー株式会社 | 発光組成物、発光電気化学素子、及び発光装置 |
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| JP6519718B2 (ja) * | 2017-04-27 | 2019-05-29 | 住友化学株式会社 | 組成物及びそれを用いた発光素子 |
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| WO2018198975A1 (ja) * | 2017-04-27 | 2018-11-01 | 住友化学株式会社 | 発光素子 |
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| JP7194072B2 (ja) * | 2018-04-26 | 2022-12-21 | 住友化学株式会社 | 発光素子 |
| JP6600110B1 (ja) * | 2019-02-26 | 2019-10-30 | 住友化学株式会社 | 発光素子 |
| JP6941711B2 (ja) * | 2019-07-26 | 2021-09-29 | 住友化学株式会社 | 金属錯体及びそれを含有する発光素子 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002071813A1 (en) | 2001-03-02 | 2002-09-12 | The Trustees Of Princeton University | Double doped-layer, phosphorescent organic light emitting devices |
| JP2008098619A (ja) * | 2006-09-14 | 2008-04-24 | Sumitomo Chemical Co Ltd | 有機エレクトロルミネッセンス素子 |
| US8927115B2 (en) | 2006-09-14 | 2015-01-06 | Sumitomo Chemical Company, Limited | Organic electroluminescent device |
| JP2008147425A (ja) * | 2006-12-11 | 2008-06-26 | Idemitsu Kosan Co Ltd | 有機エレクトロルミネッセンス素子 |
| JP2008174499A (ja) * | 2007-01-19 | 2008-07-31 | Sumitomo Chemical Co Ltd | デンドリマー錯体化合物およびそれを利用する別のデンドリマー錯体化合物の製造方法 |
| JP2008218987A (ja) * | 2007-02-06 | 2008-09-18 | Sumitomo Chemical Co Ltd | 組成物及び該組成物を用いてなる発光素子 |
| WO2008101842A1 (en) * | 2007-02-23 | 2008-08-28 | Basf Se | Electroluminescent metal complexes with benzotriazoles |
| JP5484690B2 (ja) | 2007-05-18 | 2014-05-07 | ユー・ディー・シー アイルランド リミテッド | 有機電界発光素子 |
| US8242488B2 (en) | 2007-05-30 | 2012-08-14 | Konica Minolta Holdings, Inc. | Organic electroluminescent element, display device, and illuminating device |
| JP2009152435A (ja) | 2007-12-21 | 2009-07-09 | Konica Minolta Holdings Inc | 白色有機エレクトロルミネッセンス素子、白色有機エレクトロルミネッセンス素子の製造方法、表示装置及び照明装置 |
| KR101708064B1 (ko) * | 2008-08-13 | 2017-02-17 | 미쓰비시 가가꾸 가부시키가이샤 | 유기 전계 발광 소자, 유기 el 표시 장치 및 유기 el 조명 |
| JP5516317B2 (ja) * | 2009-10-22 | 2014-06-11 | 住友化学株式会社 | 有機エレクトロルミネッセンス素子 |
| EP2492988B1 (en) | 2009-10-22 | 2018-12-26 | Sumitomo Chemical Company, Limited | Organic electroluminescent element |
| WO2011132550A1 (ja) | 2010-04-20 | 2011-10-27 | コニカミノルタホールディングス株式会社 | 有機エレクトロルミネッセンス素子、表示装置及び照明装置 |
| WO2012008550A1 (ja) | 2010-07-16 | 2012-01-19 | 住友化学株式会社 | 高分子化合物、該高分子化合物を含有する組成物、液状組成物、薄膜及び素子、並びに該素子を備える面状光源及び表示装置 |
| WO2012137640A1 (ja) * | 2011-04-07 | 2012-10-11 | コニカミノルタホールディングス株式会社 | 有機エレクトロルミネッセンス素子及び照明装置 |
| WO2013027711A1 (ja) * | 2011-08-23 | 2013-02-28 | コニカミノルタホールディングス株式会社 | 有機エレクトロルミネッセンス素子、照明装置及び表示装置 |
| JP5905270B2 (ja) | 2012-01-18 | 2016-04-20 | 住友化学株式会社 | 金属錯体及び該金属錯体を含む発光素子 |
| JP5905271B2 (ja) * | 2012-01-18 | 2016-04-20 | 住友化学株式会社 | 金属錯体及び該金属錯体を含む発光素子 |
| KR101667799B1 (ko) * | 2012-09-07 | 2016-10-20 | 삼성디스플레이 주식회사 | 유기금속 화합물 및 이를 포함한 유기 발광 소자 |
-
2014
- 2014-12-25 JP JP2014262000A patent/JP5867580B2/ja active Active
-
2015
- 2015-05-22 EP EP15803761.4A patent/EP3154101B1/en active Active
- 2015-05-22 CN CN201580029549.6A patent/CN106463635B/zh active Active
- 2015-05-22 WO PCT/JP2015/064766 patent/WO2015186539A1/ja not_active Ceased
- 2015-05-22 US US15/315,110 patent/US10431760B2/en active Active
- 2015-05-22 KR KR1020167036661A patent/KR102376847B1/ko active Active
- 2015-06-02 TW TW104117748A patent/TWI664760B/zh not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 EP3154101A4 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2017061332A1 (ja) * | 2015-10-06 | 2017-10-05 | 住友化学株式会社 | 発光素子 |
| JP2018117127A (ja) * | 2015-10-06 | 2018-07-26 | 住友化学株式会社 | 発光素子 |
| US11005044B2 (en) | 2015-10-06 | 2021-05-11 | Sumitomo Chemical Company, Limited | Light emitting device |
| WO2017061332A1 (ja) * | 2015-10-06 | 2017-04-13 | 住友化学株式会社 | 発光素子 |
| EP3428989B1 (en) * | 2016-03-10 | 2021-04-21 | Sumitomo Chemical Company Limited | Light-emitting element |
| EP3478030A4 (en) * | 2016-06-24 | 2020-01-22 | Sumitomo Chemical Company, Limited | LIGHT-EMITTING ELEMENT |
| US11515477B2 (en) | 2017-09-06 | 2022-11-29 | Sumitomo Chemical Company, Limited | Light emitting device having thermally activated delayed fluorescent (TADF) compound |
| WO2019049225A1 (ja) * | 2017-09-06 | 2019-03-14 | 住友化学株式会社 | 発光素子 |
| JPWO2019049225A1 (ja) * | 2017-09-06 | 2019-11-07 | 住友化学株式会社 | 発光素子 |
| JP7015406B1 (ja) | 2020-09-24 | 2022-02-02 | 住友化学株式会社 | 発光素子及び組成物 |
| WO2022065102A1 (ja) | 2020-09-24 | 2022-03-31 | 住友化学株式会社 | 発光素子及び組成物 |
| JP2022053497A (ja) * | 2020-09-24 | 2022-04-05 | 住友化学株式会社 | 発光素子及び組成物 |
| JP2022053496A (ja) * | 2020-09-24 | 2022-04-05 | 住友化学株式会社 | 発光素子及び組成物 |
| JP7058792B2 (ja) | 2020-09-24 | 2022-04-22 | 住友化学株式会社 | 発光素子及び組成物 |
| WO2022065101A1 (ja) * | 2020-09-24 | 2022-03-31 | 住友化学株式会社 | 発光素子及び組成物 |
| KR20230074204A (ko) | 2020-09-24 | 2023-05-26 | 스미또모 가가꾸 가부시키가이샤 | 발광 소자 및 조성물 |
| CN116194447A (zh) * | 2020-09-24 | 2023-05-30 | 住友化学株式会社 | 发光元件及组合物 |
| JP2022094314A (ja) * | 2020-12-14 | 2022-06-24 | 住友化学株式会社 | 高分子化合物の製造方法 |
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| EP3154101A4 (en) | 2017-12-06 |
| TW201614887A (en) | 2016-04-16 |
| EP3154101A1 (en) | 2017-04-12 |
| KR20170013928A (ko) | 2017-02-07 |
| US10431760B2 (en) | 2019-10-01 |
| JP2016012551A (ja) | 2016-01-21 |
| JP5867580B2 (ja) | 2016-02-24 |
| EP3154101B1 (en) | 2019-10-16 |
| KR102376847B1 (ko) | 2022-03-21 |
| CN106463635B (zh) | 2019-05-14 |
| CN106463635A (zh) | 2017-02-22 |
| US20170194584A1 (en) | 2017-07-06 |
| TWI664760B (zh) | 2019-07-01 |
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