WO2019131079A1 - ホウ素をスピロ原子とした化合物およびその高分子化合物 - Google Patents

ホウ素をスピロ原子とした化合物およびその高分子化合物 Download PDF

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WO2019131079A1
WO2019131079A1 PCT/JP2018/045231 JP2018045231W WO2019131079A1 WO 2019131079 A1 WO2019131079 A1 WO 2019131079A1 JP 2018045231 W JP2018045231 W JP 2018045231W WO 2019131079 A1 WO2019131079 A1 WO 2019131079A1
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ring
aryl
hydrogen
heteroaryl
formula
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PCT/JP2018/045231
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French (fr)
Japanese (ja)
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琢次 畠山
麻由 亀田
靖宏 近藤
笹田　康幸
梁井　元樹
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学校法人関西学院
Jnc株式会社
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Priority to CN201880083233.9A priority Critical patent/CN111527094B/zh
Priority to KR1020207021715A priority patent/KR102674465B1/ko
Priority to JP2019562931A priority patent/JP7341412B2/ja
Publication of WO2019131079A1 publication Critical patent/WO2019131079A1/ja

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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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/95—Use in organic luminescent diodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a compound having a spiro atom of boron and a polymer compound having the same as a repeating unit, an organic electroluminescent device using these compounds, an organic field effect transistor and an organic thin film solar cell, and a display device and a lighting device About.
  • a display device using a light emitting element that emits electric field can be variously studied because power saving and thinning can be achieved, and furthermore, an organic electroluminescent element made of an organic material can be easily reduced in weight and size. It has been actively considered from that.
  • organic materials having emission characteristics such as blue, which is one of the three primary colors of light and organic materials provided with charge transport ability (having the possibility of becoming a semiconductor or a superconductor) such as holes and electrons
  • charge transport ability having the possibility of becoming a semiconductor or a superconductor
  • the organic EL element has a structure comprising a pair of electrodes comprising an anode and a cathode, and one or more layers disposed between the pair of electrodes and containing an organic compound.
  • Layers containing an organic compound include a light emitting layer, and a charge transport / injection layer that transports or injects a charge such as a hole or an electron, and various organic materials suitable for these layers have been developed.
  • benzofluorene compounds and the like As materials for light emitting layers, for example, benzofluorene compounds and the like have been developed (WO 2004/061047).
  • a hole transport material for example, triphenylamine compounds and the like have been developed (Japanese Patent Laid-Open No. 2001-172232).
  • an electron transport material for example, an anthracene compound and the like have been developed (Japanese Patent Laid-Open No. 2005-170911).
  • the present inventors found a novel compound having boron as a spiro atom, and succeeded in producing it. Moreover, it discovered that the outstanding organic EL element was obtained by arrange
  • Item 1 The compound represented by following General formula (1), or the high molecular compound which makes the structure represented by General formula (1) a repeating unit.
  • Ring A, ring C and ring D are each independently an aryl ring or heteroaryl ring
  • ring B is a heteroaryl ring
  • ring A and ring B and / or ring C and ring D combine
  • the ring structure may be formed, and at least one hydrogen in these rings may be substituted, provided that the acridine-based substituent is removed as a substituent to ring A alone and ring D alone
  • X 1 to X 4 are each independently C or N
  • Ring A, ring C and ring D are each independently an aryl ring having 6 to 30 carbon atoms or a heteroaryl ring having 2 to 30 carbon atoms
  • ring B is a heteroaryl ring having 2 to 30 carbon atoms
  • a ring and B ring and / or C ring and D ring may form a ring structure, and at least one hydrogen in these rings may be substituted, provided that A ring alone and D ring Acridine based substituents are excluded as substituents to the ring alone
  • X 1 to X 4 are each independently C or N
  • Ring A, ring C and ring D are each independently a benzene ring, naphthalene ring, indane ring, indene ring, indene ring, furan ring, thiophene ring, benzofuran ring or benzothiophene ring
  • ring B is a pyrrole ring, pyridine A ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring or isoquinoline ring, wherein A ring and B ring and / or C ring and D ring may combine to form a ring structure, and at least at these rings
  • One hydrogen may be substituted, provided that the acridine-based substituent is removed as a substituent to ring A alone and ring D alone,
  • X 1 to X 4 are C
  • Z 1 and Z 2 are each independently a single bond
  • -CR 2- , -CR CR-, -
  • Item 4 The compound according to any one of Items 1 to 3, which is represented by the following General Formula (2).
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se-, -NR- or 1,2-phenylene, wherein R is hydrogen, aryl , Heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R is aryl, heteroaryl, alkyl or cycloalkyl
  • Z 1 and Z 2 can not simultaneously be a single bond
  • R 1 to R 16 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or ary
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 30 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in these being aryl , Heteroaryl, alkyl or cycloalkyl, provided that they contain a ring or d ring Acridine system substituents excluded as substituents to, At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen or deuterium.
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se-, -NR- or 1,2-phenylene, wherein R is hydrogen, aryl , Heteroaryl, alkyl or cycloalkyl, provided that Z 1 and Z 2 are not simultaneously a single bond, R 1 to R 16 are each independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these is aryl, heteroaryl, alkyl or cyclo Optionally substituted with alkyl, with the exception of acridine based substituents as R 1 -R 4 and R 13 -R 16 , Further, adjacent groups among R 1 to R 4 and R 9 to R 16 are combined to form an aryl ring having 9 to 16 carbon atoms or a heteroaryl having 6 to 15 carbon atoms together with the a ring, c
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 15 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen may be substituted by aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted by aryl, heteroaryl, alkyl or cycloalkyl
  • the acridine-based substituent is removed as a substituent to the ring formed to include the a ring or the d ring
  • At least one hydrogen in the compound represented by the formula (2) may be substituted with cyano, halogen or deuterium. 5.
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se-, -NR- or 1,2-phenylene, wherein R is hydrogen, carbon number 6-16 aryl, C2-C15 heteroaryl, C1-C6 alkyl or C3-C12 cycloalkyl, provided that Z 1 and Z 2 are not simultaneously a single bond, R 1 to R 16 each independently represent hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), or 1 to 6 carbon atoms 6 alkyl, cycloalkyl having 3 to 12 carbons, alkoxy having 1 to 6 carbons or aryloxy having 6 to 16 carbons, and at least one hydrogen in these is aryl having 6 to 16 carbons, having carbons It may be substituted with 2 to 15 heteroaryl, alkyl having 1 to 6 carbons or
  • R 1 to R 4 and R 9 to R 16 are combined to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl having 6 to 10 carbon atoms together with a ring, c ring or d ring.
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 10 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen is aryl having 6 to 16 carbons, heteroaryl having 2 to 15 carbons, diarylamino (wherein aryl is aryl having 6 to 12 carbons), alkyl having 1 to 6 carbons, 3 to 6 carbons 12 cycloalkyl, alkoxy having 1 to 6 carbons or aryloxy having 6 to 16 carbons, and at least one hydrogen in these may be aryl having 6 to 16 carbons, 2 carbons 15 heteroaryl, alkyl substituted with 1 to 6 carbons or cycloalkyl substituted with 3 to 12 carbons, with acridine substitution as a substituent to the ring formed including the a ring or the d ring Groups are removed, At least one hydrogen in the compound represented by the formula (2) may be substituted with cyano, halogen or
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se-, -NR- or 1,2-phenylene, wherein R is hydrogen, carbon Aryl of 6 to 16, aryl of 2 to 15 carbons, alkyl of 1 to 6 carbons or cycloalkyl of 3 to 12 carbons, provided that Z 1 and Z 2 are not simultaneously a single bond , R 1 to R 4 and R 9 to R 16 are hydrogen, R 5 to R 8 each independently represent hydrogen, aryl having 6 to 16 carbon atoms, heteroaryl having 2 to 15 carbon atoms, diarylamino (wherein aryl is aryl having 6 to 12 carbon atoms), or 1 to 6 carbon atoms 6 alkyl, cycloalkyl having 3 to 12 carbons, alkoxy having 1 to 6 carbons or aryloxy having 6 to 16 carbons, and at least one hydrogen in these is aryl having 6 to 16 carbons, having carbons It may be substituted
  • Item 8. The compound according to item 1, represented by the following chemical structural formula.
  • R is independently hydrogen, aryl , Heteroaryl, diaryla
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 30 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in these being aryl , Heteroaryl, alkyl or cycloalkyl, provided that they contain a ring or d ring Acridine system substituents excluded as substituents to, At least one hydrogen in the compound represented by the formula (2) may be substituted with cyano, halogen or deuterium. 5.
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se- or -NR-, wherein R is aryl and at least one hydrogen in R is , Aryl, heteroaryl, alkyl or cycloalkyl, provided that any one or more of Z 1 or Z 2 is —NR—, and the R, R 1 , R 8 , R 9 And / or R 16 is combined with a single bond, —CR 2 —, —O—, —S— or —NR— to form a ring structure, wherein each of R is independently hydrogen, And at least one hydrogen in R may be substituted with aryl, alkyl or cycloalkyl; R 1 to R 16 are each independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these is aryl, heteroaryl, alkyl or cyclo
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 15 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen may be substituted by aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one hydrogen in these may be substituted by aryl, heteroaryl, alkyl or cycloalkyl
  • the acridine-based substituent is removed as a substituent to the ring formed to include the a ring or the d ring
  • At least one hydrogen in the compound represented by the formula (2) may be substituted with cyano, halogen or deuterium. 5.
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se- or -NR-, wherein R is aryl having 6 to 16 carbon atoms, R is At least one hydrogen in the above may be substituted with aryl having 6 to 16 carbons, heteroaryl having 2 to 15 carbons, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 12 carbons, provided that And any one or more of 1 or Z 2 is -NR-, and the R, R 1 , R 8 , R 9 and / or R 16 is a single bond, -CR 2- , -O-, -S- or -NR- combine to form a ring structure, wherein each R independently represents hydrogen, aryl having 6 to 16 carbon atoms, alkyl having 1 to 6 carbons, or 3 to 6 carbon atoms 12 cycloalkyl and at least one hydrogen in R is Aryl having 6 to 16 may be substituted by cycl
  • R 1 to R 4 and R 9 to R 16 are combined to form an aryl ring having 9 to 12 carbon atoms or a heteroaryl having 6 to 10 carbon atoms together with a ring, c ring or d ring.
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 10 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen is aryl having 6 to 16 carbons, heteroaryl having 2 to 15 carbons, diarylamino (wherein aryl is aryl having 6 to 12 carbons), alkyl having 1 to 6 carbons, 3 to 6 carbons 12 cycloalkyl, alkoxy having 1 to 6 carbons or aryloxy having 6 to 16 carbons, and at least one hydrogen in these may be aryl having 6 to 16 carbons, 2 carbons 15 heteroaryl, alkyl substituted with 1 to 6 carbons or cycloalkyl substituted with 3 to 12 carbons, with acridine substitution as a substituent to the ring formed including the a ring or the d ring Groups are removed, At least one hydrogen in the compound represented by the formula (2) may be substituted with cyano, halogen or
  • Z 1 is a single bond, -O-, -S-, -Se- or -NR-, and Z 2 is -NR-, wherein R is aryl having 6 to 16 carbon atoms, R is At least one hydrogen in the above may be substituted with aryl having 6 to 16 carbons, heteroaryl having 2 to 15 carbons, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 12 carbons, Z 2 R in -NR- and R 8 or R 9 are combined with a single bond, -CR 2- , -O-, -S- or -NR- to form a ring structure, where R is And each independently hydrogen, aryl having 6 to 16 carbons, alkyl having 1 to 6 carbons or cycloalkyl having 3 to 12 carbons, Item 12.
  • Item 13 The compound according to item 1, represented by the following chemical structural formula.
  • Item 14 The compound or polymer compound according to any one of Items 1 to 13, wherein at least one of a substituent to a C ring or at least one of R 9 to R 12 is a group represented by the following partial structural formula (TSG1). At least one hydrogen in the group represented by the above formula (TSG1) may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, Y is a single bond, -O-, -S-, -Se-, -NR-,> CR 2 , or> SiR 2 , wherein each of R is independently hydrogen, aryl, hetero The aryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, adjacent groups of R may combine to form an aryl ring having 6 to 15 carbon atoms.
  • TSG1 The group represented by the partial structural formula (TSG1) is a partial structural formula (TSG100), a formula (TSG110), a formula (TSG111), a formula (TSG112), a formula (TSG113), a formula (TSG120) or a formula (TSG121).
  • TSG14 The compound or polymer compound according to item 14, which is a group represented by At least one hydrogen in the above structural formula may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy.
  • Item 16 The compound according to item 14, represented by the following chemical structural formula.
  • Item 17. The compound or polymer compound according to any one of items 14 to 16, which satisfies the following formula. ⁇ E ST ⁇ 0.20 eV
  • Item 18. A material for an organic device, comprising the compound or the polymer compound according to any one of Items 1 to 17.
  • Item 19 The material for an organic device according to Item 18, wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field effect transistor, or a material for an organic thin film solar cell.
  • Item 20 An organic electroluminescent device comprising: a pair of electrodes comprising an anode and a cathode; and an organic layer disposed between the pair of electrodes and containing the material for an organic electroluminescent device according to Item 19.
  • Item 21 Furthermore, it has an electron transport layer and / or an electron injection layer, and at least one of the electron transport layer and the electron injection layer is selected from the group consisting of quinolinol metal complexes, pyridine derivatives, phenanthroline derivatives, borane derivatives and benzimidazole derivatives
  • the electron transport layer and / or the electron injection layer may further be selected from alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, and alkaline earth metals.
  • Item 21. at least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals
  • the organic electroluminescent element as described in.
  • Item 23 It is an organic electroluminescent element which has a light emitting layer, Comprising: The said light emitting layer is At least one host compound as a first component, As a second component, at least one heat-activated delayed phosphor; An organic electroluminescent device comprising a compound represented by the following general formula (1) or a polymer compound having a structure represented by the general formula (1) as a repeating unit as the first component or the second component.
  • Ring A, ring C and ring D are each independently an aryl ring or heteroaryl ring
  • ring B is a heteroaryl ring
  • ring A and ring B and / or ring C and ring D combine
  • the ring structure may be formed, and at least one hydrogen in these rings may be substituted, provided that the acridine-based substituent is removed as a substituent to ring A alone and ring D alone
  • X 1 to X 4 are each independently C or N
  • Item 24 The organic electroluminescent device according to Item 23, which comprises, as the first component, a compound represented by General Formula (1) or a polymer compound having a structure represented by General Formula (1) as a repeating unit.
  • Item 25 The organic electroluminescent device according to Item 23, comprising, as the second component, a compound represented by General Formula (1) or a polymer compound having a structure represented by General Formula (1) as a repeating unit.
  • Item 26 A display comprising the organic electroluminescent device according to any one of items 20 to 25.
  • Item 27 An illuminating device comprising the organic electroluminescent device according to any one of items 20 to 25.
  • a novel compound having a spiro atom of boron, or a polymer compound having the same as a repeating unit which can be used as a material for organic devices such as organic EL elements.
  • An excellent organic EL device can be provided by using these compounds.
  • the compound which makes boron a spiro atom, and its high molecular compound is a high molecular compound which makes a structure denoted by a compound denoted by the following general formula (1) or a general formula (1) as a repeating unit, Preferably, it is a compound represented by the following general formula (2), or a polymer compound having a structure represented by the general formula (2) as a repeating unit.
  • the polymer compound is also collectively referred to simply as the “compound”.
  • the compound represented by the general formula (1) of the present invention utilizes a spiro structure centering on a boron atom or a bridge of a C ring and a D ring by a boron atom to form a donor structure and an acceptor structure in the molecule. It has high triplet energy by being separated.
  • the high triplet energy can be utilized for the peripheral material of a host or a light emitting layer.
  • HOMO and LUMO localize HOMO on the A ring and / or D ring
  • LUMO localize on the B ring and / or C ring centering on the spiro structure centered on the boron atom
  • it may be used as one component of a host compound to be used in combination of two or more types, or may be used as one component of a host compound used in a multi-layered light emitting layer which may be adjacent to each other.
  • DA type TADF compound when it is a thermally activated delayed fluorescence molecule (referred to as “DA type TADF compound”), a TADF light emitting material (emitting dopant) or an assisting dopant in a TAF (TADF Assisting Fluorescence) device
  • HOMO and LUMO utilize a bridge of C ring and D ring by a boron atom, and HOMO is localized on a C ring and / or C ring substituted donor structure, and LUMO is B It takes a molecular orbital localized on the ring, but in the case of LUMO, part of it may exude to the C ring.
  • the emitting dopant and the assisting dopant may be contained in adjacent different layers.
  • fluorescent light emitting compound when it does not have thermally activated delayed fluorescence (referred to as “fluorescent light emitting compound”), it is used as an emitting dopant in TTF (Triplet-Triplet Fusion) light emitting material (dopant) or TAF (TADF Assisting Fluorescence) device can do.
  • TTF Triplet-Triplet Fusion
  • dopant light emitting material
  • TAF TADF Assisting Fluorescence
  • a substituent in which Z 1 and / or Z 2 has a cyclic structure with A ring, B ring, C ring and / or D ring, etc., and HOMO and LUMO are partially compared Take molecular orbitals that overlap
  • the emitting dopant and the assisting dopant may be contained in adjacent different layers.
  • Ring A, ring C and ring D are each independently an aryl ring or heteroaryl ring
  • ring B is a heteroaryl ring
  • ring A and ring B and / or ring C and ring D combine
  • the ring structure may be formed, and at least one hydrogen in these rings may be substituted, provided that the acridine-based substituent is removed as a substituent to ring A alone and ring D alone
  • X 1 to X 4 are each independently C or N
  • Z 1 and Z 2 are each independently a single bond, -O-, -S-, -Se-, -NR- or 1,2-phenylene, wherein R is hydrogen, aryl , Heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, at least one hydrogen in R is aryl, heteroaryl, alkyl or cycloalkyl
  • Z 1 and Z 2 can not simultaneously be a single bond
  • R 1 to R 16 each independently represent hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy; At least one hydrogen may be substituted with aryl, heteroaryl, alkyl
  • the ring may be formed, and adjacent groups among R 5 to R 8 may be combined to form a heteroaryl ring having 6 to 30 carbon atoms together with the b ring, in the formed ring
  • At least one hydrogen may be substituted with aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, at least one hydrogen in these being aryl , Heteroaryl, alkyl or cycloalkyl, provided that they contain a ring or d ring Acridine system substituents excluded as substituents to, At least one hydrogen in the compound represented by formula (2) may be substituted with cyano, halogen or deuterium.
  • Ring A, ring C and ring D are each independently an aryl ring or a heteroaryl ring.
  • Ring B is a heteroaryl ring containing at least one nitrogen.
  • aryl ring examples include an aryl ring having 6 to 30 carbon atoms, preferably an aryl ring having 6 to 16 carbon atoms, and an aryl ring having 6 to 12 carbon atoms Is more preferable, and an aryl ring having 6 to 10 carbon atoms is particularly preferable.
  • aryl ring adjacent groups among “R 1 to R 4 and R 9 to R 16 defined in the general formula (2) are bonded together to form a ring, c ring or d ring Corresponding to the formed aryl ring having 9 to 30 carbon atoms, and the a ring (or c ring, d ring) is already composed of a benzene ring having 6 carbon atoms, a 5-membered ring is condensed thereto The total carbon number 9 of the fused rings is the lower limit carbon number.
  • aryl ring examples include a benzene ring which is a monocyclic ring, a biphenyl ring which is a bicyclic ring, a naphthalene ring which is a fused bicyclic ring, and a terphenyl ring which is a tricyclic ring (m-terphenyl, o -Terphenyl, p-terphenyl), fused tricyclic ring system, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic ring triphenylene ring, pyrene ring, naphthacene ring, benzofluorene ring, fused five ring system Examples include ring systems such as perylene ring and pentacene ring.
  • the fluorene ring and the benzofluorene ring also include structures in which a fluorene ring
  • heteroaryl ring examples include a heteroaryl ring having 2 to 30 carbon atoms, preferably a heteroaryl ring having 2 to 25 carbon atoms, and heteroaryl having 2 to 20 carbon atoms.
  • a ring is more preferable, a C 2-15 heteroaryl ring is more preferable, and a C 2-10 heteroaryl ring is particularly preferable.
  • the “heteroaryl ring” for example, a heterocyclic ring containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituting atom can be mentioned.
  • heteroaryl ring examples include a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring (unsubstituted, alkyl-substituted such as methyl or aryl-substituted such as phenyl), oxa Diazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole ring, benzoxazole ring , Benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquino
  • Ring A and ring B and / or ring C and ring D may be combined to form a ring structure, and the linking group in this case includes the same groups as Z 1 and Z 2, and may be a single bond Good.
  • At least one hydrogen in the ring structure formed by combining the "aryl ring” or “heteroaryl ring” as ring A to ring D, ring A with ring B and / or ring C with ring D is a first ring.
  • the substituent may be substituted, and the first substituent may be further substituted by a second substituent.
  • the first substituent includes aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy or aryloxy, etc., and the second substituent And aryl, heteroaryl, alkyl or cycloalkyl and the like.
  • the substituents “R 1 to R 16 ” and “adjacent groups among R 1 to R 16 are bonded to each other to form a ring, b ring, c ring or It also corresponds to a substituent to "an aryl ring or heteroaryl ring formed with ring d", and the second substituent also corresponds to a further substituent to these.
  • aryl and the “aryl” and the “heteroaryl” as the second substituent include the monovalent groups of the “aryl ring” and the “heteroaryl ring” described above.
  • alkyl as the first and second substituents may be either linear or branched, and examples thereof include linear alkyl having 1 to 24 carbon atoms and branched alkyl having 3 to 24 carbon atoms. .
  • Alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons) is preferable, alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons) is more preferable, and alkyl having 1 to 6 carbons (C3-C6 branched alkyl) is more preferable, and C1-C4 alkyl (C3-C4 branched alkyl) is particularly preferable.
  • alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl and 1-methyl Pentyl, 4-methyl-2-pentyl, 3, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl,
  • cycloalkyl As the “cycloalkyl” as the first and second substituents, a cycloalkyl consisting of one ring, a cycloalkyl consisting of a plurality of rings, a cycloalkyl containing a double bond which is not conjugated in the ring, and an exocyclic branch
  • cycloalkyl having 3 to 20 carbon atoms For example, cycloalkyl having 3 to 14 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 10 carbon atoms, or 6 carbon atoms may be used. And the like.
  • cycloalkyl having 5 to 10 carbon atoms is preferable, and cycloalkyl having 6 to 10 carbon atoms is more preferable.
  • cycloalkyl cyclopropyl, methylcyclopropyl, cyclobutyl, methylcyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, methylcyclooctyl, cyclononyl, methylcyclononyl , Cyclodecyl, methylcyclodecyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3 .0.1] hexyl, bicyclo [2.2.1] heptyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, decahydronaphthyl, a
  • alkynyl as the first substituent include groups in which one or more of —CH 2 —CH 2 — in the above “alkyl” is substituted with —C ⁇ C—, preferably one or more groups. Groups in which two are substituted, more preferably one are mentioned.
  • alkoxy examples include straight-chain having 1 to 24 carbon atoms and branched alkoxy having 3 to 24 carbon atoms.
  • C1-C18 alkoxy branched alkoxy having 3 to 18 carbon atoms
  • alkoxy having 1 to 12 carbons branched alkoxy having 3 to 12 carbon atoms
  • C1 to 6 carbons are preferable.
  • alkoxy examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
  • acridine based substituents are excluded.
  • the acridine-based substituent is a monovalent group of acridine and an acridine derivative.
  • the acridine derivative is acridine having a substituent, and examples of the substituent include an alkyl group and an aryl group.
  • substituents to A ring (a ring) alone and D ring (d ring) alone preferably, it is a substituent having not only an acridine substituent but also a nitrogen atom, and the nitrogen atom is a ring ( Groups which are directly bonded to a ring a) and ring D directly (such as an amino group) are also removed, and more preferably, substituents having a nitrogen atom are also removed.
  • At least one of a substituent to ring C or at least one of R 9 to R 12 be a group represented by the following partial structural formula (TSG 1).
  • At least one hydrogen in the group represented by the above formula (TSG1) may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and for details of these groups, Descriptions of the first and second substituents described above can be cited.
  • Y in the group represented by the above formula (TSG1) is a single bond, -O-, -S-, -Se-, -NR-,> CR 2 or> SiR 2 , where R is , Each independently hydrogen, aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and for details of these groups, the descriptions of the first and second substituents described above are cited can do.
  • adjacent groups of R may be bonded to each other to form an aryl ring having 6 to 15 carbon atoms, and for the details of the aryl ring, the description of the ring A to ring D described above is cited. be able to.
  • TSG1 Specific examples of the group represented by the partial structural formula (TSG1) include the following partial structural formula (TSG100), formula (TSG110), formula (TSG111), formula (TSG112), formula (TSG113), formula (TSG120) or The group represented by formula (TSG121) is mentioned.
  • Me in the formula is a methyl group.
  • At least one hydrogen in the above structural formula may be substituted with aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and for details of these groups, the first and second as described above. Descriptions of the substituents of can be cited.
  • Alkylene, alkenylene, alkynylene or arylene as Z 1 and Z 2 includes the “alkyl”, “alkenyl”, “alkynyl” or “aryl” divalent group described above as the monovalent group.
  • the description of these groups can refer to the description of the first and second substituents described above.
  • R and A ring, B ring, C ring and / or D ring (a ring, b ring, c ring and / or D ring) are adjacent to each other, they are combined to form a ring structure.
  • R preferably R of "-NR-" and R 1 , R 8 , R 9 and / or R 16 are a single bond, -CR 2- , -O-, -S- or -NR- combines with each other to form a ring structure, wherein each R independently represents hydrogen, aryl, alkyl or cycloalkyl (for the description of these groups, the first and second substituents described above And at least one hydrogen in R may be aryl, alkyl or cycloalkyl (for descriptions of these groups, reference may be made to the descriptions of the first and second substituents described above). Can be substituted).
  • the specific ring structure formed will be described later.
  • Z 1 and Z 2 are not simultaneously a single bond.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine or chlorine.
  • the compound of the present invention comprises a fused ring moiety containing A ring and D ring (a ring and d ring) and a fused ring moiety containing B ring and C ring (b ring and c ring) It is a compound in which boron is spiro bonded as a spiro atom.
  • a substituent may be bonded to each ring or Z 1 and Z 2 , first, the basic skeleton of the spiro compound will be described below.
  • the boron “B” which is a spiro atom is a carbon in ring A, ring C and ring D (formula In particular, it is bonded to “C” (not shown) and coordinated to one nitrogen “N” in ring B.
  • X 1 to X 4 are each independently C (carbon) or N (nitrogen)
  • Z 1 is a linking group of ring A and ring D
  • Z 2 is a linking group of ring B and ring C.
  • the following general formula (1-C) is a structural formula in which X 1 to X 4 are C (carbon), and the general formula (1-N) has a structure in which X 1 to X 4 is N (nitrogen) It is a formula.
  • Each of X 1 to X 4 can be independently selected from C or N, and forms other than the following structural formula may be possible.
  • Z 1 and Z 2 include the following partial structural formulas (a) to (v).
  • R in the partial structural formula is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one of them is Hydrogen may be substituted by aryl, heteroaryl, alkyl or cycloalkyl.
  • Z 1 is the formula (g), the formula (q) or the formula (u), preferably the formula (g) or the formula (u), more preferably the formula (g) .
  • Examples of ring A, ring C and ring D include partial structural formulas (P) to (Xb) shown below.
  • the bond interrupted by a wavy line indicates a binding site to the spiro atom “B” or Z 1 or Z 2 in the general formula (1).
  • the partial structural formulas in the general formula (1) are preferably all the same partial structure, but may be different types of partial structures. Also in the following partial structural formulas, illustration of substituents is omitted.
  • R in the partial structural formula is each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy or aryloxy, and at least one of them is Hydrogen may be substituted by aryl, heteroaryl, alkyl or cycloalkyl.
  • the ring B includes, for example, a pyridine ring, a pyridazine ring, a pyrimidine ring or a triazine ring, and in these rings, one nitrogen is coordinated to the spiro atom "B".
  • structural formulas containing such a ring B include, for example, the following general formulas (10) to (145) as modified examples of the above-mentioned formula (1-C). The same applies to the case where the above formulas (1-N) or X 1 to X 4 are other combinations.
  • the structural formula is preferably formula (10), formula (15) or formula (135), and more preferably formula (10).
  • Ring A, ring C and ring D may have the same structure or may be different.
  • ring A, ring C and ring D may have different structures, they are represented by the following general formula.
  • Z 1 and Z 2 may have the same structure or may be different. Examples of Z 1 and Z 2 independently selected from partial structural formulas (a) to (v) are listed below.
  • Z 1 and Z 2 may have different structures, and they may be represented by the general formula (10P-Z-1), the formula (12P-Z-1), the formula (13P-Z-1), the formula (14P-Z-1), the formula 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1)
  • the case where the ether bond of partial structural formula (g) and the amine bond of formula (q) are selected as Z 1 and Z 2 in the formula (145P-Z-1) is shown below.
  • Z 1 and Z 2 may have different structures, and they may be represented by the general formula (10P-Z-1), the formula (12P-Z-1), the formula (13P-Z-1), the formula (14P-Z-1), the formula 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1)
  • the case where an ether bond of partial structural formula (g) and a single bond of formula (u) are selected as Z 1 and Z 2 in the formula (145P-Z-1) is shown below.
  • Z 1 and Z 2 may have different structures, and they may be represented by the general formula (10P-Z-1), the formula (12P-Z-1), the formula (13P-Z-1), the formula (14P-Z-1), the formula 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) Or (145P-Z-1), a case where a single bond of partial structural formula (u) and an ether bond of formula (g) are selected as Z 1 and Z 2 is shown below.
  • Z 1 and Z 2 may have different structures, and they may be represented by the general formula (10P-Z-1), the formula (12P-Z-1), the formula (13P-Z-1), the formula (14P-Z-1), the formula 15P-Z-1), formula (123P-Z-1), formula (124P-Z-1), formula (125P-Z-1), formula (134P-Z-1), formula (135P-Z-1) Or (145P-Z-1), a case where a single bond of partial structural formula (u) and an amine bond of formula (q) are selected as Z 1 and Z 2 is shown below.
  • J1 partial structural formula (J1) to J74).
  • Me is a methyl group
  • tBu is a t-butyl group.
  • partial structural formula (J1) to formula (J3), formula (J11), formula (J12), formula (J38) or formula (J41) to formula (J44) are preferable, and more preferably J1), formula (J3), formula (J11), formula (J12), formula (J41) or formula (J44), and more preferably formula (J11).
  • the general formula (10P-j-1), formula (10P-k-1), formula (10P-p-1) or formula (10P-q-1) in the Z 1 and Z 2 as a partial structural formula (j Formula (k), formula (p) or formula (q) is selected, and R in this partial structural formula is hydrogen, partial structural formula (J1), formula (J3), formula (J6), formula ( When it is J9), Formula (J11), or Formula (J21), it is represented by following Structural formula.
  • “Me” is a methyl group
  • tBu is a t-butyl group
  • partial structure (q) is selected as and Z 2
  • R in this partial structure is hydrogen, partial structure (J1), formula (J3), formula (J6), formula (J9), formula (J11) Or when it is a formula (J21), it represents with following Structural formula.
  • a partial structural formula (q) is selected as Z 2 in the general formula (10P-gq-1), the formula (10P-q-1) or the formula (10P-uq-1), and in the partial structural formula
  • R is a partial structural formula (J11) and adjacent R and B ring (b ring) are bonded to form a ring structure, they are represented by the following structural formula.
  • a partial structural formula (q) is selected as Z 2 in the general formula (10P-gq-1), the formula (10P-q-1) or the formula (10P-uq-1), and in the partial structural formula
  • R is a partial structural formula (J11) and adjacent R and C rings (c rings) are bonded to form a ring structure, they are represented by the following structural formula.
  • a partial structural formula (q) is selected as Z 2 in the general formula (10P-gq-1), the formula (10P-q-1) or the formula (10P-uq-1), and in the partial structural formula
  • R is a partial structural formula (J11) and adjacent R, B ring (b ring) and C ring (c ring) combine to form a ring structure, they are represented by the following structural formula.
  • partial structural formula (q) is selected as Z 1 in general formula (10P-q-1) or formula (10P-qg-1), and R in this partial structural formula is a partial structural formula (J11) When adjacent R and A ring (a ring) or D ring (d ring) combine to form a ring structure, they are represented by the following structural formula.
  • partial structural formula (q) is selected as Z 1 in general formula (10P-q-1) or formula (10P-qg-1), and R in this partial structural formula is a partial structural formula (J11) When adjacent R and A ring (a ring) and D ring (d ring) combine to form a ring structure, they are represented by the following structural formula.
  • the partial structural formula (J11) is selected as the partial structural formula (q) as Z 1 or Z 2 in the general formula (10P-Z-1) and the partial structural formula (J11) as R in the partial structural formula (q)
  • a general formula (10P-gq-21-J11), Formula (10P-gq-22-J11), Formula (10P-gq-23-J11), Formula (10P-gq-24-J11), Formula (10P-gq-25) -J11 formula (10P-q-21-J11), formula (10P-q-22-J11), formula (10P-q-23-J11), formula (10P-q-24-J11), formula (10P-q-24-J11) 10P-q-25-J11), formula (10P-uq-21-J11), formula (10P-uq-22-J11),
  • partial structural formula (J1) to formula (J3), formula (J11), formula (J12), formula (J38) or formula (J41) to formula (J44) are preferable, and more preferably J1), formula (J3), formula (J11), formula (J12), formula (J41) or formula (J44), and more preferably formula (J11).
  • a ring and a ring are selected.
  • substructures (J81) to (J91) are used as substituents of HO, HOMO and LUMO can be separated between the a and d rings and the substituents for the a and d rings.
  • substructures (J32) to (J46) are used as substituents for the b ring and c ring, HOMO and LUMO are selected between the b ring and c ring and the substituents for the b ring and c ring. It can be separated.
  • a part of hydrogen atoms in ring a and ring d in General Formula (10P-g-1) may be substituted, or adjacent substituents may be combined to form an aryl ring or a heteroaryl ring together with ring a or ring d.
  • it is represented by the following structural formula. It lists with the unsubstituted compound of Formula (10P-g-100).
  • “Me” is a methyl group
  • tBu is a t-butyl group
  • the hydrogen atoms in rings a to d in general formula (10P-g-1) may be each independently substituted with the same structure or a different structure. For example, it is represented by the following structural formula.
  • part of the hydrogen atoms in ring a and ring d in General Formula (10P-gq-1) are substituted, or adjacent substituents are combined to form an aryl ring or heteroaryl together with ring a or ring d.
  • a ring is formed, it is represented by the following structural formula. It lists with the unsubstituted compound of a formula (10P-gq-100).
  • the hydrogen atoms in rings a to d in general formula (10P-gq-1) may be each independently substituted with the same structure or a different structure. For example, it is represented by the following structural formula.
  • R in the general formula (10P-gq-1) is the formula (J11), it is represented by the following structural formula.
  • the hydrogen atom in ring a to d in the general formula (10P-gq-21-J11) and the hydrogen atom of phenyl which is R in NR are each independently substituted with the same or different structure. It is also good. Substituents to phenyl which is R in b ring, c ring and N—R are preferably substituted so as to be symmetrical with respect to b ring —Z 2 bond from the viewpoint of easiness of synthesis. For example, it is represented by the following structural formula.
  • the hydrogen atom in ring a to d in the general formula (10P-gq-23-J11) and the hydrogen atom of phenyl which is R in NR are each independently substituted with the same or different structure. It is also good.
  • Substituents to phenyl which is R in b ring, c ring and N—R are preferably substituted so as to be symmetrical with respect to b ring —Z 2 bond from the viewpoint of easiness of synthesis. For example, it is represented by the following structural formula.
  • the hydrogen atom in ring a to d in the general formula (10P-gq-25-J11) and the hydrogen atom of phenyl which is R in NR are each independently substituted with the same or different structure. It is also good.
  • Substituents to phenyl which is R in b ring, c ring and N—R are preferably substituted so as to be symmetrical with respect to b ring —Z 2 bond from the viewpoint of easiness of synthesis. For example, it is represented by the following structural formula.
  • a part of hydrogen atoms in ring a and ring d in General Formula (10P-gu-1) are substituted, or adjacent substituents are combined to form an aryl ring or a heteroaryl ring together with ring a or ring d.
  • it is represented by the following structural formula. It lists with the unsubstituted compound of a formula (10P-gu-100).
  • the hydrogen atoms in rings a to d in general formula (10P-gu-1) may be each independently substituted with the same structure or a different structure. For example, it is represented by the following structural formula.
  • a part of hydrogen atoms in ring a and ring d in General Formula (10P-ug-1) may be substituted, or adjacent substituents may be combined to form an aryl ring or a heteroaryl ring together with ring a or ring d.
  • it is represented by the following structural formula. It lists with the unsubstituted compound of a formula (10P-ug-100).
  • the hydrogen atoms in rings a to d in general formula (10P-ug-1) may be each independently substituted with the same structure or a different structure. For example, it is represented by the following structural formula.
  • a part of hydrogen atoms in ring a and ring d in General Formula (10P-uq-1) are substituted, or adjacent substituents are combined to form an aryl ring or heteroaryl together with ring a or ring d.
  • a ring is formed, it is represented by the following structural formula. It lists with the unsubstituted compound of a formula (10P-uq-100).
  • the hydrogen atoms in rings a to d in general formula (10P-uq-1) may be each independently substituted with the same or different structure. For example, it is represented by the following structural formula.
  • Ring A, ring C and ring D in the general formula (10) may independently have the same structure or different structures, and a hydrogen atom in ring A, ring C, ring D and ring b is Each may be independently substituted with groups having the same structure or different structures. For example, it is represented by the following structural formula.
  • E S Singlet excitation energy
  • E T 1240 / B from the maximum emission wavelength B of the fluorescence spectrum (nm).
  • ⁇ E ST is, for example, “Purely organic electroluminescent material realizing 100% conversion from electricity to light”, H. Kaji, H. Suzuki, T. Fukushima, K. Shizu, K. Katsuaki, S. Kubo, T. Komino It can also be calculated by the method described in H. Oiwa, F. Suzuki, A. Wakamiya, Y. Murata, C. Adachi, Nat. Commun. 2015, 6, 8476.
  • “Thermally activated delayed fluorescent substance” absorbs thermal energy to cause an inverse intersystem crossing from an excited triplet state to an excited singlet state, and is radiatively deactivated from the excited singlet state to give delayed fluorescence. It means a compound that can emit radiation.
  • “thermally activated delayed fluorescence” also includes those that undergo high-order triplets in the process of excitation from an excitation triplet state to an excitation singlet state. For example, the article by Monkman et al. Of Durham University (NATURE COMMUNICATIONS, 7: 13680, DOI: 10.1038 / ncomms 13680), the article by Hoseki et al.
  • the compounds represented by the general formulas (1) and (2) have, first, an A ring (a ring), a D ring (d ring), a B ring (b ring) and a C ring (c ring) Is linked by a linking group (a group containing Z 1 and Z 2 ) to produce an intermediate (first reaction), and then A ring (a ring), B ring (b ring), C ring (c)
  • the final product can be prepared by bonding the ring) and the D ring (d ring) with a boron atom (second reaction) (Scheme (1) and Scheme (2)).
  • first reaction for example, in the case of an etherification reaction, general reactions such as a nucleophilic substitution reaction and an Ullmann reaction can be used, and in the case of an amination reaction, a general reaction such as a Buchwald-Hartwig reaction can be used.
  • second reaction metal-boron transmetallation can be used.
  • the second reaction is a reaction in which the A ring (a ring), the B ring (b ring), the C ring (c ring) and the D ring (d ring) are linked by introducing a boron atom, and the scheme (1)
  • intermediates substituted with halogen (Hal) such as chlorine, bromine and iodine are shown as intermediates.
  • the intermediate (1-C) or ((C) is obtained by orthometalating the halogen atom of the dihalogen compound intermediate (1-A) or (2-A) with n-butyllithium, sec-butyllithium or t-butyllithium, etc.
  • 2-C) (wherein M is a metal such as lithium).
  • the intermediates (1-B) and (2-B), which are halogen compounds, are first metallized with n-butyllithium, sec-butyllithium, t-butyllithium or the like, and then boron trichloride or triolum Boron fluoride or the like is added, and metal-boron metal exchange is performed to obtain intermediates (1-D) and (2-D). Then, the intermediate (1-C) or (2-C) prepared above is added and metal-boron is exchanged with the intermediate (1-D) or (2-D) to give a compound of the general formula The compounds of 1) or (2) can be obtained.
  • the compound represented by the general formula (1) or (2) is an intermediate in which a halogen atom is not introduced by selective metallation. Can be manufactured (Scheme (3), Scheme (4)).
  • the orthometalation reagents used in the above Schemes (1) to (4) include alkyllithiums such as methyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, lithium diisopropylamide, lithium tetramethyl Organic alkali compounds such as piperidid, lithium hexamethyl disilazide, potassium hexamethyl disilazide and the like can be mentioned.
  • a coordination additive can be added during metallation to dissociate the association, thereby improving the reactivity.
  • N, N ', N, N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoramide (HMPA), dimethylpropyleneurea (DMPU) and the like can be mentioned.
  • boron trifluoride boron trichloride, boron tribromide, boron tribromide, and other halides of boron such as boron triiodide are used.
  • alkoxy borane compounds such as trimethyl borate and the like, boron, and alkoxy borane compounds such as 4,4,5,5-tetramethyl-1,3,2-dioxaborolane; and aryloxy compounds such as triphenyl borate.
  • the polymer compound (I) is a polymer compound which is formed by sharing a part of the structure of the formula (1) (for example, any one of the ring A to the ring D) with each other,
  • the polymer compound (II) is a polymer compound obtained by linking the structure of the formula (1) via the crosslinked structure XL, provided that EC is a terminal structure
  • the polymer compound (III) is a polymer compound having a structure of the formula (1) as a side chain of a linear polymer, provided that EC is a terminal structure and MU is a monomer unit in which a polymerizable group is polymerized
  • the dimer (i) is a dimer formed by sharing a part of the structure of the formula (1) (for example, any of ring A to ring D) with one another.
  • the dimer (ii) is a dimer formed by linking the structure of the formula (1) via the crosslinked structure XL.
  • the form in which the partial structure of the formula (1), the cross-linked structure XL, the terminal structure EC and the monomer unit MU are bonded is described above.
  • a form in which they are bonded by a single bond an alkylene group having 1 to 3 carbon atoms, a phenylene group, a naphthalene group or the like may be used.
  • the a ring in the partial structure of the formula (10P-gq-100-J11) and the d ring in the partial structure of the formula (10P-g-100) are dimers (crosslinking structure XL (single bond)) as a linking group
  • ii crosslinking structure XL (single bond)
  • a dimer (ii) with the cross-linked structure XL (single bond) as a linking group it is represented by the following formula (ii-2).
  • the terminal structure EC in the polymer compound (II) is hydrogen or a monovalent aryl ring or heteroaryl ring having 6 to 30 carbon atoms, preferably hydrogen or a monovalent aryl ring having 6 to 18 carbon atoms .
  • the crosslinked structure XL in the polymer compound (II) and the dimer (ii) is a single bond or a divalent aryl ring or heteroaryl ring having 6 to 30 carbon atoms, preferably a single bond or 6 to carbon atoms It is an 18 divalent aryl ring, more preferably a single bond or a divalent aryl ring having 6 to 12 carbon atoms.
  • aryl rings in the structures EC and XL include a benzene ring which is a single ring system, a biphenyl ring which is a bicyclic system, a naphthalene ring which is a fused bicyclic system, and a terphenyl ring which is a three-ring system -Terphenyl, o-terphenyl, p-terphenyl), fused tricyclic ring system, acenaphthylene ring, fluorene ring, phenalene ring, phenanthrene ring, fused tetracyclic ring triphenylene ring, pyrene ring, naphthacene ring, benzo ring Examples thereof include a fluorene ring, a condensed pentacyclic ring system perylene ring, and a pentacene ring.
  • the fluorene ring and the benzofluorene ring also include
  • heteroaryl rings in the structures EC and XL include, for example, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring (unsubstituted, alkyl-substituted such as methyl, phenyl and the like) Aryl substituted), oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, 1H-indazole ring, benzimidazole Ring, benzoxazole ring, benzothiazole ring, 1H-benzotriazole ring, quinoline ring, isoquinoline ring, c
  • the A ring (a ring) -Z 1 -D is used as in the synthesis method of Schemes (1) to (4).
  • the ring, the halogenation reaction, or the boroxidation reaction can be appropriately combined and synthesized.
  • a (meth) acrylate derivative of the structure of the formula (1) a meta (acrylamide) derivative, an epoxy derivative, an oxetane derivative, a norbornene derivative, a dicyclopentadiene derivative using a known method
  • they can be synthesized using radical polymerization, cationic polymerization, anionic polymerization, ring-opening metathesis polymerization, etc., using an indene derivative as a starting material.
  • the reactive functional group of the halide and boronic acid derivative in Suzuki-Miyaura coupling may be replaced as appropriate, and the same applies to Kumada-Tamao-Coliue coupling and Negishi coupling.
  • the functional groups involved in these reactions may be interchanged.
  • you may replace metal magnesium and an isopropyl Grignard reagent suitably.
  • the boronic acid ester may be used as it is or may be hydrolyzed with an acid and used as a boronic acid.
  • alkyl groups other than those exemplified can also be used as the alkyl group of the ester moiety.
  • the palladium catalyst used in the coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh 3 ) 4 , bis (triphenylphosphine) palladium (II) dichloride: PdCl 2 (PPh 3 ) 2, palladium (II): Pd (OAc) 2, tris (dibenzylideneacetone) dipalladium (0): Pd 2 (dba) 3, tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd 2 ( dba) 3 ⁇ CHCl 3 , bis (dibenzylideneacetone) palladium (0): Pd (dba) 2 , bis (tri t-butylphosphino) palladium (0): Pd (t-Bu 3 P) 2 , [1 , 1′-Bis (diphenylphosphino) ferrocene] dichlor
  • a phosphine compound may be optionally added to the palladium catalyst.
  • the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N-dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1'-bis (di-t-butylphos) Fino) ferrocene, 2,2'-bis (di-t-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2 '-(di-t-butylphosphino)
  • the base used in the coupling reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, Examples include potassium acetate, tripotassium phosphate, and potassium fluoride.
  • the base may be added as an aqueous solution and reacted in a two-phase system.
  • a phase transfer catalyst such as a quaternary ammonium salt may be added, if necessary.
  • the radically polymerizable, cationically polymerizable or anionically polymerizable polymerizable group used for the synthesis of the polymer compound (III) there may be mentioned (meth) acrylic group, allyl group, vinyl group, epoxide group, oxetane and the like.
  • a radical generator is preferably used in the case of radical polymerization, and an acid generator and a base generator are preferably used in the case of cationic polymerization and anionic polymerization.
  • the polymerization initiator may be one type of compound or a mixture of two or more types of compounds.
  • the ring-opened metathesis polymerizable polymerizable group used for the synthesis of the polymer compound (III) includes a cyclic alkene structure and a cyclic alkyne structure, and specifically, a norbornene structure, a dicyclopentadiene structure, an indene structure And cyclopentene structures.
  • a catalyst used for ring-opening metathesis polymerization complexes such as ruthenium, molybdenum, and tungsten are used, and examples thereof include Grubbs catalyst.
  • solvent used in the coupling reaction and the polymerization reaction include benzene, toluene, xylene, 1,2,4-trimethylbenzene, anisole, acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, tetrahydrofuran, Examples thereof include diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, ethanol, t-butyl alcohol, cyclopentyl methyl ether and isopropyl alcohol. These solvents can be selected appropriately, and may be used alone or as a mixed solvent.
  • a polymer compound When producing a polymer compound, it may be produced in one step or may be produced through multiple steps. Alternatively, it may be carried out by a batch polymerization method in which the raw materials are all put in the reaction vessel and then the reaction is started, or may be carried out by the drop polymerization method in which the raw materials are dropped and added. It may carry out by the precipitation polymerization method which precipitates with it, and it can synthesize
  • the desired product is obtained by conducting the reaction in a state where the partial structural compound of the formula (1) having a polymerizable group and the compound having a terminal structure (EC) are added to a reaction vessel.
  • a compound having a terminal structure (EC) is added and reacted to obtain a target product.
  • the primary structure of the polymer can be controlled by selecting the polymerizable group of the monomer unit (MU). For example, as shown in Scheme (1) to (3), a polymer having a random primary structure (1 in Scheme (5)), a polymer having a regular primary structure (2 and 3 in Scheme (5)), etc. Can be synthesized, and can be used in appropriate combination according to the object.
  • MU monomer unit
  • dimers (i) and (ii) it is preferable that the dipole moment formed by each of the partial structure of the two formulas (1) and the linking group (XL) cancel each other.
  • dimers (i) and (ii) have high symmetry.
  • Organic Device The compound according to the present invention and the polymer compound thereof can be used as a material for an organic device.
  • an organic device an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell etc. are mentioned, for example.
  • FIG. 1 is a schematic cross-sectional view showing the organic EL element according to the present embodiment.
  • the organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. Provided on the light emitting layer 105 provided on the hole transport layer 104, the electron transport layer 106 provided on the light emitting layer 105, and the electron transport layer 106 provided on the light emitting layer 105. And the cathode 108 provided on the electron injection layer 107.
  • the organic electroluminescent device 100 is, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer in reverse manufacturing order.
  • An electron transport layer 106 provided on the light emitting layer 107, a light emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light emitting layer 105, and a hole transport layer 104;
  • the hole injection layer 103 provided thereover and the anode 102 provided on the hole injection layer 103 may be provided.
  • the minimum structural unit is configured of the anode 102, the light emitting layer 105 and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, the electron injection
  • the layer 107 is an optional layer.
  • Each of the layers may be a single layer or a plurality of layers.
  • the layer which comprises an organic electroluminescent element other than the structure aspect of "substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode” mentioned above, "Substrate / anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode", “substrate / Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode "," substrate / Anode / light emitting layer / electron transport layer / electron injection layer / cathode "," substrate / anode / light emitting
  • the substrate 101 is a support of the organic electroluminescent device 100, and usually, quartz, glass, metal, plastic or the like is used.
  • the substrate 101 is formed in a plate shape, a film shape, or a sheet shape according to the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used.
  • a glass plate and a plate made of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate or polysulfone are preferable.
  • soda lime glass, alkali-free glass, or the like may be used, and the thickness may be sufficient to maintain mechanical strength.
  • the upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less.
  • alkali-free glass is preferable because less elution ions from glass is preferable, but soda lime glass with a barrier coat such as SiO 2 may also be commercially available. it can.
  • the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side in order to enhance the gas barrier properties, and a plate, a film or a sheet made of a synthetic resin having particularly low gas barrier properties is used as the substrate 101 When using it, it is preferable to provide a gas barrier film.
  • the anode 102 plays a role of injecting holes into the light emitting layer 105.
  • the hole injection layer 103 and / or the hole transport layer 104 is provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 via these. .
  • Materials forming the anode 102 include inorganic compounds and organic compounds.
  • the inorganic compound for example, metal (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxide (oxide of indium, oxide of tin, indium-tin oxide (ITO), indium-zinc oxide Substances (IZO etc.), metal halides (copper iodide etc.), copper sulfide, carbon black, ITO glass, Nesa glass etc.
  • the organic compound include polythiophenes such as poly (3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, it can select suitably from the substances used as an anode of an organic electroluminescent element, and can use it.
  • the resistance of the transparent electrode is not limited as long as a current sufficient for light emission of the light emitting element can be supplied, and the resistance of the transparent electrode is not limited in view of the power consumption of the light emitting element.
  • an ITO substrate of 300 ⁇ / sq or less functions as a device electrode, but at present it is also possible to supply a substrate of about 10 ⁇ / sq, for example 100 to 5 ⁇ / sq, preferably 50 to 5 ⁇ It is particularly desirable to use a low resistance product of / ⁇ .
  • the thickness of ITO can be arbitrarily selected according to the resistance value, but usually it is often used in the range of 50 to 300 nm.
  • the hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or into the hole transport layer 104.
  • the hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 via the hole injection layer 103 to the light emitting layer 105.
  • the hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one or two or more hole injecting / transporting materials, or a mixture of a hole injecting / transporting material and a polymer binder. Be done.
  • an inorganic salt such as iron (III) chloride may be added to the hole injecting / transporting material to form a layer.
  • the hole injecting / transporting substance As the hole injecting / transporting substance, it is necessary to efficiently inject / transport holes from the positive electrode between the electrodes given an electric field, the hole injection efficiency is high, and the injected holes are efficiently transported. It is desirable to do.
  • the substance has a small ionization potential, a large hole mobility, and a high stability, and is a substance which hardly generates an impurity serving as a trap during production and use.
  • the compound according to the present invention and the polymer compound thereof can be used as materials for forming the hole injection layer 103 and the hole transport layer 104.
  • photoconductive materials compounds conventionally used as charge transport materials for holes, p-type semiconductors, and known compounds used for hole injection layer and hole transport layer of organic electroluminescent device And any compound can be selected and used.
  • carbazole derivatives N-phenylcarbazole, polyvinylcarbazole and the like
  • biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole)
  • triarylamine derivatives aromatic tertiary Polymer having amino in the main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 , 4'-Diaminobiphenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, N, N'-diphenyl-N, N'-di (3-methylphenyl) -4 4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl-N, N'-
  • polycarbonates or styrene derivatives having the above-mentioned monomer in the side chain polyvinylcarbazole, polysilane etc. It is not particularly limited as long as it is a compound capable of forming a thin film necessary for manufacturing a device, injecting holes from the anode, and transporting holes.
  • Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property.
  • Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donors.
  • TCNQ tetracyanoquinone dimethane
  • F4TCNQ 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane
  • the light emitting layer 105 is a layer that emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied.
  • the material for forming the light emitting layer 105 may be a compound (light emitting compound) that emits light by being excited by the recombination of holes and electrons, and can form a stable thin film shape, and a solid state Preferably, they are compounds that exhibit strong luminescence (fluorescence) efficiency.
  • the compound according to the present invention and the polymer compound thereof can be used as the material for the light emitting layer.
  • the light emitting layer may be a single layer or a plurality of layers, and is formed of the material for the light emitting layer (host material, dopant material).
  • the host material and the dopant material may be of one type or a combination of two or more.
  • the dopant material may be contained in the entire host material, partially contained or may be contained. As a doping method, it can be formed by co-evaporation with a host material, but it may be simultaneously vapor-deposited after being previously mixed with the host material.
  • the amount of host material used varies depending on the type of host material, and may be determined in accordance with the characteristics of the host material.
  • the standard of the amount of host material used is preferably 50 to 99.999% by weight of the entire light emitting layer material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight It is.
  • the compound according to the present invention and the polymer compound thereof can also be used as a host material.
  • the amount of dopant material used varies depending on the type of dopant material, and may be determined in accordance with the characteristics of the dopant material.
  • the standard for the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight of the entire light emitting layer material. is there.
  • the above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.
  • the compounds according to the invention and their macromolecular compounds can also be used as dopant materials.
  • the amount of the dopant material used is preferably low, because the concentration quenching phenomenon can be prevented, but the amount of the dopant material used is high
  • the concentration is preferable in terms of the efficiency of the heat activation delayed fluorescence mechanism.
  • the amount used be low.
  • the indication of the usage of the host material, assist dopant material and dopant material is 40 to 99.999% by weight, 59 to 1% by weight and 20 to 20% by weight of the entire light emitting layer material. It is 0.001 wt%, preferably 60 to 99.99 wt%, 39 to 5 wt% and 10 to 0.01 wt%, respectively, more preferably 70 to 99.95 wt%, 29 to 10 % By weight and 5 to 0.05% by weight.
  • the compound according to the present invention and the polymer compound thereof can also be used as an assist dopant material.
  • condensed ring derivatives such as anthracene and pyrene, which have been known as light emitters, bisstyrylanthracene derivatives and distyrylbenzene derivatives, etc.
  • Bisstyryl derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives and the like can be mentioned.
  • the dopant material to be used in combination with the compound according to the present invention and the polymer compound thereof is not particularly limited, and known compounds can be used, and among various materials depending on the desired emission color It can be selected.
  • fused ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene and chrysene
  • benzoxazole derivatives benzothiazole derivatives, benzoimidazole derivatives, benzotriazole derivatives, oxazoles Derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenyl butadiene derivatives, cyclopentadiene derivatives, bis st
  • blue to blue-green dopant materials include, for example, naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perphenylene, fluorene, indene, chrysene and the like, and aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, Aromatic complexes such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene, etc.
  • Aromatic complexes such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzo
  • Ring compounds and derivatives thereof distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiasia Azole derivatives such as carbazole, carbazole, oxazole, oxadiazole and triazole and metal complexes thereof and N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diphenyl-1, Aromatic amine derivatives represented by 1'-diamine may, for example, be mentioned.
  • green to yellow dopant materials examples include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, naphthacene derivatives such as rubrene, etc.
  • Preferred examples of the blue-green dopant material include compounds introduced with a substituent capable of achieving longer wavelength such as aryl, heteroaryl, arylvinyl, amino and cyano.
  • naphthalimide derivatives such as bis (diisopropylphenyl) perylene tetracarboximide, perinone derivatives, rare earth complexes such as Eu complex having acetylacetone or benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and analogs thereof, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridones Derivative, phenoxazine derivative, oxazine derivative, quinazoline derivative, pyrrolopyridine derivative, squarylium derivative, biolanthrone derivative, phenazine derivative, fenoxazo Derivatives, thiadiazolopyrene derivatives and
  • a dopant it can be used suitably selected from the chemical compounds etc. which are described in Chemical Industry 2004 June issue page 13 and the reference etc. which were given to it.
  • amines having a stilbene structure perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives are particularly preferable.
  • An amine having a stilbene structure is represented by, for example, the following formula.
  • Ar 1 is an m-valent group derived from aryl having 6 to 30 carbon atoms
  • Ar 2 and Ar 3 are each independently aryl having 6 to 30 carbon atoms, but Ar 1 to Ar At least one of 3 has a stilbene structure, Ar 1 to Ar 3 may be substituted, and m is an integer of 1 to 4.
  • the amine having a stilbene structure is more preferably diaminostilbene represented by the following formula.
  • Ar 2 and Ar 3 are each independently an aryl having 6 to 30 carbon atoms, and Ar 2 and Ar 3 may be substituted.
  • aryl having 6 to 30 carbon atoms are benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, stilbene, distyrylbenzene, distyrylbiphenyl, distyryl. And fluorene.
  • amines having stilbene structure are N, N, N ', N'-tetra (4-biphenylyl) -4,4'-diaminostilbene, N, N, N', N'-tetra (1-naphthyl) ) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (2-naphthyl) -4,4′-diaminostilbene, N, N′-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) styryl] -biphenyl, 1,4-bis [4'-bis (diphenylamino) styryl]
  • perylene derivatives include, for example, 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene 3- (9'-anthryl) -8,11-di (t-butyl) perylene, 3,3'-bis (8,11-di (t-butyl) perylenyl) and the like.
  • JP-A-11-97178, JP-A-2000-133457, JP-A-2000-26324, JP-A-2001-267079, JP-A-2001-267078, JP-A-2001-267076, Perylene derivatives described in JP-A-2000-34234, JP-A-2001-267075, and JP-A-2001-217077 may be used.
  • borane derivatives include 1,8-diphenyl-10- (dimesitylboryl) anthracene, 9-phenyl-10- (dimesitylboryl) anthracene, 4- (9'-anthryl) dimesitylborylnaphthalene, 4- (10 ') -Phenyl-9'-anthryl) dimesitylborylnaphthalene, 9- (dimesitylboryl) anthracene, 9- (4'-biphenylyl) -10- (dimesitylboryl) anthracene, 9- (4 '-(N-carbazolyl) phenyl) And -10- (dimesitylboryl) anthracene.
  • borane derivatives described in WO 2000/40586 and the like may be used.
  • the aromatic amine derivative is represented, for example, by the following formula.
  • Ar 4 is an n-valent group derived from aryl having 6 to 30 carbon atoms
  • Ar 5 and Ar 6 are each independently aryl having 6 to 30 carbon atoms
  • Ar 4 to Ar 6 are It may be substituted
  • n is an integer of 1 to 4.
  • Ar 4 is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene
  • Ar 5 and Ar 6 are each independently aryl having 6 to 30 carbon atoms
  • n is 2 and aromatic amine derivatives are more preferred.
  • aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, pentacene and the like.
  • aromatic amine derivative as a chrysene type, for example, N, N, N ', N'-tetraphenyl chrysene-6,12-diamine, N, N, N', N'-tetra (p-tolyl) Chrysene-6,12-diamine, N, N, N ', N'-tetra (m-tolyl) chrysene-6,12-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) chrysene -6,12-diamine, N, N, N ', N'-tetra (naphthalen-2-yl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl ) Chrysene-6,12-diamine, N, N'-diphenyl-N, N'-di (p-
  • N, N, N ', N'-tetraphenylpyrene-1,6-diamine N, N, N', N'-tetra (p-tolyl) pyrene-1,6 -Diamine
  • N, N, N ', N'-tetra (m-tolyl) pyrene-1,6-diamine N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamines
  • anthracene type for example, N, N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N ', N'-tetra (p-tolyl) anthracene-9,10-diamine N, N, N ', N'-tetra (m-tolyl) anthracene-9, 10-diamine, N, N, N ', N'- tetrakis (4-isopropylphenyl) anthracene-9, 10- diamine, N, N'-diphenyl-N, N'-di (p-tolyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine
  • Examples of coumarin derivatives include coumarin-6, coumarin-334 and the like.
  • coumarin derivatives described in JP-A-2004-43646, JP-A-2001-76876, and JP-A-6-298758 may be used.
  • Examples of pyran derivatives include the following DCM and DCJTB.
  • the electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or into the electron transport layer 106.
  • the electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105.
  • the electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials, or a mixture of an electron transport / injection material and a polymer binder.
  • the electron injecting / transporting layer is a layer that injects electrons from the cathode and is responsible for transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are efficiently transported. For this purpose, it is preferable that the substance has a large electron affinity, a large electron mobility, and is excellent in stability and in which impurities serving as traps are less likely to be generated during production and use. However, considering the transport balance of holes and electrons, the electron transport capacity is so large when it mainly plays a role of being able to efficiently block the flow of holes from the anode to the cathode side without recombination.
  • the electron injecting / transporting layer in the present embodiment may also include the function of a layer capable of efficiently blocking the movement of holes.
  • the compound according to the present invention and the polymer compound thereof can be used as a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107.
  • the photoconductive material can be optionally selected from compounds conventionally used conventionally as an electron transfer compound, and known compounds used in the electron injection layer and the electron transport layer of the organic electroluminescent device. .
  • compounds comprising an aromatic ring or heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, pyrrole derivatives And at least one selected from a fused ring derivative thereof and a metal complex having an electron accepting nitrogen.
  • fused ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives and indole derivatives.
  • metal complexes having an electron accepting nitrogen include hydroxyazole complexes such as hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes and benzoquinoline metal complexes. These materials may be used alone or in combination with different materials.
  • pyridine derivatives naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazoles Derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-) Triazole etc.), thiadiazole derivative, metal complex of oxine derivative, quinolinol metal complex, quinoxaline derivative, polymer of quinoxaline derivative, benzazole compound, gallium complex, pyrazole derivative, perfluorinated fluoride Nylene derivatives
  • metal complexes having an electron accepting nitrogen can also be used, for example, hydroxyazole complexes such as quinolinol metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, benzoquinoline metal complexes, etc. can give.
  • hydroxyazole complexes such as quinolinol metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, benzoquinoline metal complexes, etc. can give.
  • quinolinol metal complexes quinolinol metal complexes, bipyridine derivatives, phenanthroline derivatives or borane derivatives are preferable.
  • the quinolinol metal complex is a compound represented by the following general formula (E-1).
  • R 1 to R 6 are hydrogen or a substituent
  • M is Li, Al, Ga, Be or Zn
  • n is an integer of 1 to 3.
  • quinolinol metal complexes include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3) , 4-Dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( (Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolate) aluminum, bis (2-methyl-8-) Quinolinolate) (4- Tylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis
  • the bipyridine derivative is a compound represented by the following general formula (E-2).
  • G represents a simple bond or an n-valent linking group, and n is an integer of 2 to 8.
  • carbon not used for binding of pyridine-pyridine or pyridine-G may be substituted.
  • G in formula (E-2) examples include the following structural formulas.
  • each R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenylyl or terphenylyl.
  • pyridine derivative examples include 2,5-bis (2,2'-pyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2'-) Pyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilol, 2,5-bis (2,2'-pyridin-5-yl) -1,1-dimethyl-3,4- Diphenylsilole, 2,5-bis (2,2'-pyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilol, 9,10-di (2,2'-pyridine-6) -Yl) anthracene, 9,10-di (2,2'-pyridin-5-yl) anthracene, 9,10-di (2,3'-pyridin-6-yl) anthracene, 9,10-di (2 , 3'-Pyridin-5-yl,
  • the phenanthroline derivative is a compound represented by the following general formula (E-3-1) or (E- 3-2).
  • R 1 to R 8 are hydrogen or a substituent, and adjacent groups may be bonded to each other to form a fused ring
  • G represents a simple bond or an n-valent linking group
  • n is 2 It is an integer of ⁇ 8.
  • G in the general formula (E-3-2) for example, the same structural formula as G described in the section of bipyridine derivative can be mentioned.
  • phenanthroline derivative examples include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline- 2-yl) anthracene, 2,6-di (1,10-phenanthrolin-5-yl) pyridine, 1,3,5-tri (1,10-phenanthrolin-5-yl) benzene, 9,9'-difluoro And -bis (1,10-phenanthrolin-5-yl), vasocuproin and 1,3-bis (2-phenyl-1,10-phenanthrolin-9-yl) benzene.
  • a phenanthroline derivative is used for the electron transporting layer and the electron injecting layer.
  • the substituent itself has a three-dimensional steric structure, or with a phenanthroline skeleton or A derivative having a three-dimensional steric structure by steric repulsion with an adjacent substituent or a derivative in which a plurality of phenanthroline skeletons are linked is preferable.
  • a compound including a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in a linking unit is more preferable.
  • the borane derivative is a compound represented by the following general formula (E-4), and is disclosed in detail in JP-A-2007-27587.
  • each of R 11 and R 12 independently represents at least one of hydrogen, alkyl, aryl which may be substituted, silyl which is substituted, nitrogen-containing heterocycle which may be substituted, or cyano
  • R 13 to R 16 each independently represent optionally substituted alkyl or optionally substituted aryl
  • X is optionally substituted arylene
  • Y is An optionally substituted aryl having 16 or less carbon atoms, a substituted boryl, or an optionally substituted carbazolyl
  • n is each independently an integer of 0 to 3.
  • each of R 11 and R 12 independently represents at least one of hydrogen, alkyl, aryl which may be substituted, silyl which is substituted, nitrogen-containing heterocycle which may be substituted, or cyano
  • R 13 to R 16 each independently represent optionally substituted alkyl or optionally substituted aryl
  • each of R 21 and R 22 independently represents hydrogen, alkyl, At least one of optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano
  • X 1 is an optionally substituted arylene having a carbon number of 20 or less
  • n is each independently an integer of 0 to 3
  • m is each independently an integer of 0 to 4.
  • R 31 to R 34 each independently represent either methyl, isopropyl or phenyl
  • R 35 and R 36 each independently represent any of hydrogen, methyl, isopropyl or phenyl It is.
  • each of R 11 and R 12 independently represents at least one of hydrogen, alkyl, aryl which may be substituted, silyl which is substituted, nitrogen-containing heterocycle which may be substituted, or cyano R 13 to R 16 each independently represent optionally substituted alkyl or optionally substituted aryl, and X 1 represents an optionally substituted arylene having a carbon number of 20 or less And n is each independently an integer of 0 to 3.
  • R 31 to R 34 are each independently any of methyl, isopropyl or phenyl
  • R 35 and R 36 are each independently any of hydrogen, methyl, isopropyl or phenyl It is.
  • each of R 11 and R 12 independently represents at least one of hydrogen, alkyl, aryl which may be substituted, silyl which is substituted, nitrogen-containing heterocycle which may be substituted, or cyano
  • R 13 to R 16 each independently represent optionally substituted alkyl or optionally substituted aryl
  • X 1 represents an optionally substituted arylene having 10 or less carbon atoms
  • Y 1 is an optionally substituted aryl having 14 or less carbon atoms
  • n is each independently an integer of 0 to 3.
  • R 31 to R 34 each independently represent either methyl, isopropyl or phenyl
  • R 35 and R 36 each independently represent any of hydrogen, methyl, isopropyl or phenyl It is.
  • the benzimidazole derivative is a compound represented by the following general formula (E-5).
  • Ar 1 to Ar 3 are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. Particularly preferred is a benzimidazole derivative in which Ar 1 is anthryl which may be substituted.
  • aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthyl-1-yl, acenaphthyl-3-yl, acenaphthyl-4-yl, acenaphthyl-5-yl, and fluorene-1-l.
  • benzimidazole derivatives are 1-phenyl-2- (4- (10-phenylanthracene-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalene-2) -Yl) anthracene-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracene-9-yl) phenyl) -1-l Phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracene-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4- (10) -(Naphthalen-2-yl) anthracene-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9- (9
  • the electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer.
  • a substance capable of reducing the material forming the electron transport layer or the electron injection layer various materials can be used as long as the material has a certain reducibility, for example, alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, alkali From the group consisting of oxides of earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals At least one selected can be suitably used.
  • alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), Ca (1.2. And alkaline earth metals such as 9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and materials having a work function of 2.9 eV or less are particularly preferable.
  • more preferable reducing substances are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs.
  • alkali metals are particularly high in reducing ability, and the addition of a relatively small amount to the material forming the electron transport layer or the electron injection layer can improve the emission luminance and prolong the life of the organic EL element.
  • a combination of two or more alkali metals is also preferable as a reducing substance having a work function of 2.9 eV or less, and in particular, a combination containing Cs, such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • Cs By including Cs, the reduction ability can be efficiently exhibited, and by addition to the material for forming the electron transport layer or the electron injection layer, the emission luminance in the organic EL element can be improved and the lifetime can be prolonged.
  • the cathode 108 plays a role of injecting electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.
  • the material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as the material for forming the anode 102 can be used.
  • metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or alloys thereof (magnesium-silver alloy, magnesium Indium alloy, aluminum-lithium alloy such as lithium fluoride / aluminum, etc. are preferable.
  • Lithium, sodium, potassium, cesium, calcium, magnesium or alloys containing these low work function metals are effective for enhancing the electron injection efficiency to improve the device characteristics.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals for electrode protection, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride It is preferable to stack a hydrocarbon-based polymer compound or the like as a preferred example.
  • the method for producing these electrodes is also not particularly limited as long as conduction can be taken, such as resistance heating evaporation, electron beam evaporation, sputtering, ion plating and coating.
  • ⁇ Binder which may be used in each layer>
  • the materials used for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer described above can form each layer independently, but polyvinyl chloride, polycarbonate, or the like as a polymer binder Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS resin, polyurethane resin Etc., and can be used by dispersing it in a solvent-soluble resin such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. is there.
  • a solvent-soluble resin such as phenol resin, xylene
  • Each layer constituting the organic electroluminescent element is formed of a material to be constituted of each layer by a method such as evaporation, resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination, printing, spin coating or casting, or the like. It can be formed by using a thin film. There is no particular limitation on the film thickness of each layer formed in this way, and it can be appropriately set according to the property of the material, but it is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured by a crystal oscillation type film thickness measuring device or the like.
  • the vapor deposition conditions differ depending on the type of material, the desired crystal structure and association structure of the film, and the like.
  • the deposition conditions are generally: boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁇ 6 to 10 ⁇ 3 Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature ⁇ 150 to + 300 ° C., film thickness 2 nm to 5 ⁇ m It is preferable to set appropriately in the range.
  • an organic electric field comprising a light emitting layer / electron transport layer / electron injection layer / cathode comprising anode / hole injection layer / hole transport layer / host material and dopant material
  • a method for manufacturing a light emitting element is described. After forming a thin film of an anode material on a suitable substrate by vapor deposition or the like to prepare an anode, thin films of a hole injection layer and a hole transport layer are formed on the anode.
  • a host material and a dopant material are co-deposited thereon to form a thin film to form a light emitting layer, an electron transporting layer and an electron injecting layer are formed on the light emitting layer, and a thin film made of a cathode material is deposited by evaporation or the like.
  • the intended organic electroluminescent element is obtained by forming it as a cathode.
  • the anode When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode may be applied as + and the cathode may be applied as-polarity, and when a voltage of about 2 to 40 V is applied, it is transparent or semitransparent. Luminescence can be observed from the electrode side (anode or cathode, and both).
  • the organic electroluminescent device also emits light when a pulse current or an alternating current is applied.
  • the waveform of the alternating current to apply may be arbitrary.
  • the present invention can also be applied to a display device provided with an organic electroluminescent device or a lighting device provided with an organic electroluminescent device.
  • the display device or the illumination device provided with the organic electroluminescent device can be manufactured by a known method such as connecting the organic electroluminescent device according to the present embodiment and a known drive device, and can be DC drive, pulse drive, AC It can drive, using suitably well-known drive methods, such as a drive.
  • Examples of the display device include a panel display such as a color flat panel display, a flexible display such as a flexible color organic electroluminescent (EL) display, and the like (for example, Japanese Patent Application Laid-Open Nos. 10-335066 and 2003-321546). See Japanese Patent Laid-Open Publication No. 2004-281086 etc.
  • a display method of a display a matrix and / or a segment system etc. are mentioned, for example.
  • the matrix display and the segment display may coexist in the same panel.
  • pixels for display are two-dimensionally arranged in a lattice shape, a mosaic shape, or the like, and a character or an image is displayed by a set of pixels.
  • the shape and size of the pixels depend on the application. For example, for displaying images and characters on personal computers, monitors, and televisions, square pixels with one side of 300 ⁇ m or less are usually used, and in the case of a large display such as a display panel, pixels with one side of mm order become.
  • monochrome display pixels of the same color may be arranged, but in color display, red, green and blue pixels are displayed side by side. In this case, there are typically delta types and stripe types.
  • a line sequential driving method or an active matrix may be used.
  • the line-sequential drive has an advantage that the structure is simple, in consideration of the operation characteristics, the active matrix may be superior in some cases, so it is necessary to use this in accordance with the application.
  • a pattern is formed so as to display predetermined information, and a predetermined area is made to emit light.
  • predetermined information For example, time and temperature displays on digital watches and thermometers, operation status displays on audio devices and induction cookers, and panel displays on automobiles can be mentioned.
  • the lighting device examples include a lighting device such as interior lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, and JP 2004-119211 A). Etc.).
  • Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit light themselves, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display boards, signs, and the like.
  • backlights for liquid crystal display devices particularly for personal computer applications where thinning is an issue, considering that thinning is difficult because the conventional method is composed of a fluorescent lamp and a light guide plate
  • the backlight using the light emitting element according to is characterized by being thin and lightweight.
  • the compound according to the present invention and the polymer compound thereof can be used for the production of an organic field effect transistor, an organic thin film solar cell, etc. in addition to the above-described organic electroluminescent device.
  • An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and a gate electrode is provided in addition to a source electrode and a drain electrode. When a voltage is applied to the gate electrode, an electric field is generated, and the flow of electrons (or holes) flowing between the source electrode and the drain electrode can be arbitrarily blocked to control the current.
  • a field effect transistor is easier to miniaturize than a simple transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.
  • a source electrode and a drain electrode are provided in contact with the organic semiconductor active layer formed using the compound according to the present invention and the polymer compound thereof, and further the organic semiconductor active layer
  • the gate electrode may be provided with the insulating layer (dielectric layer) in contact with the gate electrode.
  • Examples of the element structure include the following structures.
  • the organic field effect transistor configured in this way is The present invention can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display.
  • the organic thin film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass.
  • the photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side.
  • the compound according to the present invention and the polymer compound thereof can be used as a material of a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer depending on the physical properties.
  • the compound according to the present invention and the polymer compound thereof can function as a hole transport material or an electron transport material in an organic thin film solar cell.
  • the organic thin film solar cell may be appropriately provided with a hole block layer, an electron block layer, an electron injection layer, a hole injection layer, a smoothing layer and the like in addition to the above.
  • known materials used for the organic thin film solar cell can be appropriately selected and used in combination.
  • Step 1 To di-para-tolyl ether (10.1 g) and dimethylformamide (200 ml), add 1,3-dibromo-5,5-dimethylhydantoin (DBH: 55.9 g, 200 mmol), Heated and stirred for time. The reaction solution was cooled to room temperature, water (500 ml) was added, and then extracted with toluene (200 ml ⁇ 5 times). The solvent was distilled off by distillation at 140 ° C. under normal pressure. The crude product was filtered through a silica gel short path column, and the solvent was evaporated under reduced pressure to obtain a crude product. Thereafter, the residue was washed with hexane to give 1,1′-oxybis (2-bromo-4-methylbenzene) as a white solid (10.8 g, yield 61%).
  • DBH 1,3-dibromo-5,5-dimethylhydantoin
  • Step 3 Add butyllithium (245 ml, 3.9 mmol) to 2- (2-bromophenoxy) pyridine (0.971 g, 3.9 mmol) and toluene (50 ml) at -78 ° C. under a nitrogen atmosphere, and then at 0 ° C. Stir for 1 hour. Furthermore, boron tribromide (0.380 ml, 0.50 mmol) was added at ⁇ 78 ° C., and the boron intermediate was prepared by stirring at 0 ° C. for 15 minutes. Also at the same time, butyllithium (4.90 ml) at ⁇ 78 ° C.
  • Synthesis example (2) Synthesis of the compound of formula (10P-g-101) (alternative method) The yield is improved by performing the second and third steps of the synthesis example (1) by the following method.
  • Step 3 Butyllithium (6.00 ml) at ⁇ 78 ° C. under nitrogen atmosphere to 1,1′-oxybis (2-bromo-4-methylbenzene) (1.70 g, 4.8 mmol) and diethyl ether (30 ml)
  • the lithium intermediate was prepared by adding 9.6 mmol) and stirring at 0 ° C. for 1 hour. Meanwhile, boron tribromide (0.451 ml, 4.8 mmol) was added to 2-phenoxypyridine (0.812 g, 4.8 mmol) and toluene (20 ml) at room temperature under a nitrogen atmosphere, and the mixture was heated and stirred at 90 ° C.
  • the boron intermediate was prepared by This was added to the reaction solution containing a lithium intermediate at ⁇ 78 ° C., and stirred at 0 ° C. for 1 hour.
  • the reaction solution was filtered through a silica gel short pass column, and the solvent was evaporated under reduced pressure to obtain a crude product. After that, washing with hexane gave the compound of the formula (10P-g-101) as a yellow solid (0.710 g, yield 40%).
  • reaction solution was cooled to room temperature, filtered through a silica gel short pass column, and the solvent was evaporated under reduced pressure to give a crude product. After that, washing with hexane gave N, N-diphenylpyridin-2-amine as a white solid (6.52 g, yield 88%).
  • boron tribromide (0.285 ml, 3.0 mmol) was added to N, N-diphenylpyridin-2-amine (0.724 g, 2.9 mmol) and toluene (20 ml) at room temperature under a nitrogen atmosphere, and 90 After preparing a boron intermediate by heating and stirring at 1 ° C.
  • reaction solution was concentrated under reduced pressure until the volume of the reaction solution became about two thirds of the whole. This was added to the reaction solution containing a lithium intermediate at ⁇ 78 ° C., and stirred at 0 ° C. for 1 hour.
  • the reaction solution was filtered through a silica gel short pass column, and the solvent was evaporated under reduced pressure to obtain a crude product. Then, the compound was washed with hexane to give the compound of the formula (10P-gq-101-J11) as a yellow solid (0.813 mg, yield 61%).
  • Step 1 2-bromophenol (6.30 ml, 59.7 mmol), potassium carbonate (10.3 g, 77.4 mmol) and 1,3-dimethyl-2-imidazolidinone (DMI: 150 ml) under a nitrogen atmosphere, At room temperature, 1-bromo-2-fluorobenzene (5.50 ml, 50.3 mmol) was added, and the mixture was heated and stirred at 200 ° C. for 24 hours. The reaction solution was cooled to room temperature, toluene (200 ml) was added, and then extracted with water (150 ml ⁇ 3 times). The crude product was distilled at 70 ° C. under 4.6 ⁇ 10 ⁇ 2 Pa to obtain 2,2′-oxybis (bromobenzene) as a colorless liquid (3.46 g, 23% yield).
  • DMI 1,3-dimethyl-2-imidazolidinone
  • Second Step Add butyl lithium (14.0 ml) to 2,2′-oxybis (bromobenzene) (3.52 g, 10.7 mmol) and diethyl ether (30 ml) at ⁇ 78 ° C. under a nitrogen atmosphere, and at 0 ° C.
  • the lithium intermediate was prepared by stirring for 1 hour.
  • boron tribromide (1.02 ml, 10.7 mmol) is added to 2-phenoxypyridine (1.75 g, 10.2 mmol) and toluene (30 ml) at room temperature under a nitrogen atmosphere, and stirred at 90 ° C. for 1 hour
  • the reaction solution was concentrated under reduced pressure until the volume of the reaction solution became about two thirds of the whole.
  • Phenylboronic acid (2.93 g, 24 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh 3 ) 4 : 1.74 g, 1.5 mmol), potassium carbonate (8.30 g, 60 mmol), water ( 5-bromo-2-chloropyridine (3.87 g, 20 mmol) was added to 80 ml) and 1,4-dioxane (80 ml) at room temperature under nitrogen atmosphere, and stirred at room temperature for 45 hours. The solvent of the reaction solution was evaporated under reduced pressure, and then extracted with toluene (100 ml ⁇ 3 times), and the solvent was evaporated under reduced pressure to obtain a crude product. Thereafter, the residue was washed with hexane and purified by silica gel short path column to obtain 2-chloro-5-phenylpyridine as a white solid (1.69 g, yield 44%).
  • reaction solution containing the lithium intermediate at ⁇ 78 ° C., stirred at 0 ° C. for 1 hour and at room temperature for 19 hours.
  • the reaction solution was filtered through a silica gel short path column, and the solvent was evaporated under reduced pressure to obtain a crude product. Thereafter, the residue was purified by silica gel short path column to obtain a compound of formula (10P-gq-342-J11) as a pale yellow solid (0.548 g, yield 21%).
  • reaction solution was concentrated under reduced pressure until the volume of the reaction solution became about two thirds of the whole. This was added to the reaction solution containing a lithium intermediate at ⁇ 78 ° C., and stirred at 0 ° C. for 1 hour. The reaction solution was filtered through a silica gel short pass column, and the solvent was evaporated under reduced pressure to give a crude product. After that, washing with hexane gave the compound of the formula (10P-gq-23-J11) as a yellow solid (3.30 g, yield 75%).
  • the compound according to the present invention and the polymer compound according to the present invention can be synthesized by a method according to the above-described synthesis example by appropriately changing the compound of the raw material.
  • the compound When evaluating the absorption characteristics and the emission characteristics (fluorescence and phosphorescence) of the compound to be evaluated, the compound may be dissolved in a solvent and evaluated in a solvent or in a thin film state. Furthermore, when evaluating in the thin film state, depending on the mode of use of the compound in the organic EL element, when thin filming only the compound is to be evaluated (single component vapor deposition film) and the compound dispersed in an appropriate matrix material (Co-deposited film) may be evaluated.
  • PMMA polymethyl methacrylate
  • a thin film sample dispersed in PMMA is prepared, for example, by dissolving PMMA and a compound to be evaluated in toluene, and then forming a thin film on a transparent support substrate (10 mm ⁇ 10 mm) made of quartz by a spin coating method.
  • a transparent support substrate (10 mm ⁇ 10 mm) made of quartz by a spin coating method.
  • a method of producing a single component vapor deposited film is described below.
  • a transparent support substrate made of quartz or glass is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum deposition boat containing a compound to be evaluated is mounted.
  • the vacuum tank is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and the deposition boat containing the compound is heated to deposit an appropriate film thickness to form a single component deposition film.
  • a method of preparing a thin film sample when the matrix material is a host material is described below.
  • a transparent support substrate made of quartz or glass is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum deposition boat containing a host material, a molybdenum deposition boat containing a dopant material Wear
  • the vacuum chamber is depressurized to 5 ⁇ 10 -4 Pa, and the deposition boat containing the host material and the deposition boat containing the dopant material are simultaneously heated to obtain an appropriate film thickness.
  • Form a mixed film of material and dopant material is controlled in accordance with the set weight ratio of the host material and the dopant material.
  • Example 1 A transparent support substrate made of ITO vapor-deposited glass and a molybdenum evaporation boat containing the compound (10P-gq-101-J11) are fixed to a commercially available evaporation system (manufactured by Showa Vacuum Co., Ltd.), and the vacuum chamber is The pressure was reduced to 5 ⁇ 10 ⁇ 4 Pa, and the compound (10 P-gq-101-J11) was heated and evaporated to a film thickness of 50 nm to form a single-component deposited film. The photoelectron yield spectrum, the absorption spectrum in the visible region, the fluorescence spectrum and the phosphorescence spectrum of the obtained single component vapor deposition film were measured.
  • the results are shown as differences with respect to the compound mCBP used in Comparative Example 1 (Table 1).
  • singlet energy (S 1 ) and triplet energy (T 1 ) are first excited singlet energy and first excited triplet energy unless otherwise noted.
  • ⁇ E ST is the difference between singlet energy and triplet energy.
  • Example 2 A single-component deposited film was produced by the method according to Example 1 except that the compound (10P-gq-101-J11) was changed to the compound (10P-g-101), and each spectrum was measured. Moreover, ionization potential (Ip) etc. were calculated
  • Comparative Example 1 A single-component deposited film was prepared by the method according to Example 1, except that the compound (10P-gq-101-J11) was changed to the compound mCBP (3,3'-di (9H-carbazolyl-9-yl) biphenyl). And each spectrum was measured. Moreover, ionization potential (Ip) etc. were calculated
  • Comparative Example 2 A single-component deposited film was produced by the method according to Example 1 except that the compound (10P-gq-101-J11) was changed to the compound CBP, and each spectrum was measured. Moreover, ionization potential (Ip) etc. were calculated
  • organic EL elements according to Example 3, Example 4 and Comparative Example 3 can be produced with the layer configuration shown in Table 2.
  • HAT-CN is 1,4,5,8,9,12- Hexaazatriphenylene hexa-carbonitrile
  • TB is N 4, N 4, N 4 ', N 4' - tetra ([ 1,1'-biphenyl] -4-yl)-[1,1'-biphenyl] -4,4'-diamine
  • TcTa is tris (4-carbazolyl-9-ylphenyl) amine
  • CBP is 4,4'-di (9H-carbazolyl-9-yl) -1,1'-biphenyl
  • Ir (PPy) 3 is tris (2-phenylpyridine) iridium (III)
  • TBi is 1,3 5,5-tris (1-phenyl-1H-benzo [d] imidazol-2-yl) benzene.
  • the chemical structure is shown below.
  • Example 3 ⁇ Device using compound (10P-g-101) as host material of light emitting layer> A 26 mm ⁇ 28 mm ⁇ 0.7 mm glass substrate (Opto Science Co., Ltd.) obtained by polishing an ITO film formed by sputtering to 50 nm is used as a transparent support substrate.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (Choshu Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, compound (10P-g-101), Ir (PPy) 3 , TPBi and LiF Attach a crucible for vapor deposition made of tantalum and a crucible for vapor deposition made of aluminum nitride containing aluminum.
  • a commercially available vapor deposition apparatus Choshu Sangyo Co., Ltd.
  • HAT-CN, TBB, TcTa compound (10P-g-101), Ir (PPy) 3 , TPBi and LiF Attach a crucible for vapor deposition made of tantalum and a crucible for vapor deposition made of aluminum nitride containing aluminum.
  • the following layers are sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber is depressurized to 2.0 ⁇ 10 -4 Pa, first, HAT-CN is heated to deposit to a film thickness of 5 nm, and then TBB is heated to deposit a film thickness to 65 nm. Further, TcTa is heated and evaporated to a film thickness of 10 nm to form a three-layer hole injection layer and a hole transport layer. Next, the compound (10P-g-101) and Ir (PPy) 3 are simultaneously heated and evaporated to a film thickness of 30 nm to form a light emitting layer. The deposition rate is adjusted so that the weight ratio of compound (10P-g-101) to Ir (PPy) 3 is approximately 95 to 5.
  • TPBi is heated and evaporated to a film thickness of 50 nm to form an electron transport layer.
  • the deposition rate of each layer so far is 0.01 to 1 nm / second.
  • LiF is heated to deposit 1 nm in film thickness at a deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to 100 nm in thickness to 0.1 to 2 nm / nm. It vapor-deposits with the vapor deposition rate of second, and forms a cathode, and an organic EL element is obtained.
  • Green light emission can be obtained by applying a DC voltage with the ITO electrode as an anode and the LiF / aluminum electrode as a cathode.
  • Example 4 ⁇ Element using Compound (10P-gq-101-J11) as host material of light emitting layer>
  • An organic EL device can be obtained by the method according to Example 3 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced with the compound (10P-gq-101-J11).
  • light emission can be obtained by applying a DC voltage.
  • Comparative Example 3 ⁇ Device using compound CBP as host material of light emitting layer> An organic EL device can be obtained by the method according to Example 3, except that the compound (10P-g-101), which is the host material of the light emitting layer, is replaced with the compound CBP.
  • organic EL elements according to Example 5 and Example 6 can be manufactured with the layer configuration shown in Table 3.
  • Example 5 ⁇ Device using compound (10P-g-101) for electron transport layer>
  • This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (Choshu Sangyo Co., Ltd.), and HAT-CN, TBB, TcTa, CBP, Ir (PPy) 3 , compound (10P-g-101) and LiF Attach a crucible for vapor deposition made of tantalum and a crucible for vapor deposition made of aluminum nitride containing aluminum.
  • the following layers are sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber is depressurized to 2.0 ⁇ 10 -4 Pa, first, HAT-CN is heated to deposit to a film thickness of 10 nm, and then TBB is heated to deposit a film to a thickness of 20 nm Further, TcTa is heated and evaporated to a film thickness of 10 nm to form a three-layer hole injection layer and a hole transport layer. Next, CBP and Ir (PPy) 3 are simultaneously heated and evaporated to a film thickness of 30 nm to form a light emitting layer. The deposition rate is adjusted so that the weight ratio of CBP to Ir (PPy) 3 is approximately 95 to 5.
  • the compound (10P-g-101) is heated and evaporated to a film thickness of 50 nm to form an electron transport layer.
  • the deposition rate of each layer so far is 0.01 to 1 nm / second.
  • LiF is heated to deposit 1 nm in film thickness at a deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to 100 nm in thickness to 0.1 to 2 nm / nm. It vapor-deposits with the vapor deposition rate of second, and forms a cathode, and an organic EL element is obtained.
  • Green light emission can be obtained by applying a DC voltage with the ITO electrode as an anode and the LiF / aluminum electrode as a cathode.
  • Example 6 ⁇ Device using compound (10P-gq-101-J11) for the electron transport layer>
  • An organic EL device can be obtained by the method according to Example 5 except that the compound (10P-g-101) in the electron transport layer is changed to the compound (10P-gq-101-J11).
  • light emission can be obtained by applying a DC voltage.
  • organic EL elements according to Example 7, Example 8 and Comparative Example 4 can be manufactured with the layer configuration shown in Table 4.
  • Firpic is bis [2- (4,6-difluorophenyl) pyridinato-N, C2] (picolinato) iridium (III). The chemical structure is shown below.
  • Example 7 ⁇ Device using compound (10P-g-101) as host material of light emitting layer> A 26 mm ⁇ 28 mm ⁇ 0.7 mm glass substrate (Opto Science Co., Ltd.) obtained by polishing an ITO film formed by sputtering to 50 nm is used as a transparent support substrate.
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Choshu Sangyo Co., Ltd.), and each of HAT-CN, TBB, TcTa, compound (10P-g-101), Firpic, TPBi and LiF was loaded A tantalum evaporation crucible and an aluminum nitride evaporation crucible containing aluminum are mounted.
  • the following layers are sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber is depressurized to 2.0 ⁇ 10 -4 Pa, first, HAT-CN is heated to deposit to a film thickness of 5 nm, and then TBB is heated to deposit a film thickness to 65 nm. Further, TcTa is heated and evaporated to a film thickness of 10 nm to form a three-layer hole injection layer and a hole transport layer. Next, the compound (10P-g-101) and Firpic are simultaneously heated to deposit a film thickness of 30 nm to form a light emitting layer. The deposition rate is adjusted so that the weight ratio of the compound (10P-g-101) to the Firpic is approximately 95 to 5.
  • TPBi is heated and evaporated to a film thickness of 50 nm to form an electron transport layer.
  • the deposition rate of each layer is 0.01 to 1 nm / second.
  • LiF is heated to deposit 1 nm in film thickness at a deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to 100 nm in thickness to 0.1 to 2 nm / nm. It vapor-deposits with the vapor deposition rate of second, and forms a cathode, and an organic EL element is obtained.
  • Example 8 ⁇ Element using Compound (10P-gq-101-J11) as host material of light emitting layer>
  • An organic EL device can be obtained by the method according to Example 7 except that the compound (10P-g-101) which is the host material of the light emitting layer is changed to the compound (10P-gq-101-J11). Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Comparative Example 4 ⁇ Device using compound mCBP as host material of light emitting layer>
  • An organic EL device can be obtained by the method according to Example 7 except that the compound (10P-g-101) as the host material of the light emitting layer is changed to the compound mCBP. Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • organic EL elements according to Examples 9 to 16 and Comparative Examples 5 to 8 were produced with the layer configurations shown in Table 5.
  • NPD N, N′-bis (naphthylene-1-yl) -N, N′-bis (phenyl) benzene
  • mCP 1,3-bis (carbazolyl-9-yl) Benzene
  • DBNA2 is 9-([1,1′-biphenyl] -3-yl-N, N, 5,11-tetraphenyl-5,9-dihydro-5,9-diaza-13b-boranaphtho [3 , 2,1-de] anthracene-3-amine
  • DBNA3 is N, N, 5,9-tetraphenyl-5,9-dihydro-5,9-diaza-13b-boranaphtho [3,2,1- "4CzIPN” is a dimer which shares one benzene ring of each other of de] anthracene-7-amine, "2,4,5,6-tetra (9H-carbazol
  • Example 9 ⁇ Device using compound (10P-g-101) as host and DABNA2 as dopant> A 26 mm ⁇ 28 mm ⁇ 0.7 mm glass substrate (Opto Science Co., Ltd.) obtained by polishing an ITO film formed by sputtering to 50 nm was used as a transparent support substrate.
  • This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (Choshu Sangyo Co., Ltd.) and made of tantalum containing NPD, TcTa, mCP, compound (10P-g-101), DABNA2, TSPO1 and LiF.
  • An evaporation crucible and an aluminum nitride evaporation crucible containing aluminum were mounted.
  • the following layers were formed sequentially on the ITO film of the transparent support substrate.
  • the vacuum chamber is depressurized to 2.0 ⁇ 10 -4 Pa, first, NPD is heated to deposit 40 nm thick, and then TcTa is heated to deposit 15 nm thick, The mCP was heated and evaporated to a film thickness of 15 nm to form a three-layer hole injection layer and a hole transport layer.
  • the compound (10P-g-101) and DABNA2 were simultaneously heated and vapor deposited to a film thickness of 20 nm to form a light emitting layer.
  • the deposition rate was adjusted so that the weight ratio of the compound (10P-g-101) to DABNA2 was about 98: 2.
  • TSPO1 was heated and vapor deposited to a film thickness of 40 nm to form an electron transport layer.
  • the deposition rate of each layer was 0.01 to 1 nm / second.
  • LiF is heated to deposit 1 nm thick at a deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to a thickness of 100 nm to 0.1 to 2 nm / It vapor-deposited at the vapor deposition rate of second, the cathode was formed, and the organic EL element was obtained.
  • Example 10 ⁇ Device using compound (10P-gq-101-J1) as host and DABNA2 as dopant>
  • An organic EL device was obtained by the method according to Example 9, except that the compound (10P-g-101) as the host material of the light emitting layer was changed to the compound (10P-gq-101-J11). Blue light emission was obtained when a DC voltage was applied to both electrodes. The light emission luminance was 10 cd / m 2 at a drive voltage of 3.82 V and a current density of 0.04 mA / cm 2 , and the external quantum efficiency at this time was 22.6%.
  • the light emission luminance was 100 cd / m 2 at a drive voltage of 4.70 V and a current density of 0.66 mA / cm 2 , and the external quantum efficiency at this time was 15.3%.
  • the external quantum efficiencies at 10 cd / m 2 and 100 cd / m 2 were both superior to those of Comparative Example 5.
  • Comparative Example 5 ⁇ Device using compound mCBP as host and DABNA2 as dopant> An organic EL device was obtained by the method according to Example 5, except that the compound (10P-g-101) as the host material of the light emitting layer was changed to the compound mCBP.
  • the compound (10P-g-101) as the host material of the light emitting layer was changed to the compound mCBP.
  • blue emission having a peak top at about 467 nm was obtained.
  • the light emission luminance was 10 cd / m 2 at a drive voltage of 3.65 V and a current density of 0.06 mA / cm 2 , and the external quantum efficiency at this time was 18.2%.
  • the light emission luminance was 100 cd / m 2 at a drive voltage of 5.13 V and a current density of 0.92 mA / cm 2 , and the external quantum efficiency at this time was 11.4%.
  • Example 11 ⁇ Device using compound (10P-g-101) as host and DABNA3 as dopant> An organic EL element is obtained by the method according to Example 9 except that the compound DABNA2 which is a dopant material of the light emitting layer is changed to the compound DABNA3. Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Example 12 ⁇ Device using compound (10P-gq-101-J11) as host and DABNA3 as dopant> Method according to Example 9 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced by the compound (10P-gq-101-J11) and the compound DABNA2 which is the dopant material is replaced by the compound DABNA3
  • the organic EL element is obtained by Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Comparative Example 6 ⁇ Device using compound mCBP as host and DABNA3 as dopant> An organic EL device is obtained by the method according to Example 9 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced with the compound mCBP and the compound DABNA2 which is the dopant material is replaced with the compound DABNA3. Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Example 13 ⁇ Device using compound (10P-g-101) as host and 4CzIPN as dopant> An organic EL element is obtained by the method according to Example 9 except that the compound DABNA2 which is a dopant material of the light emitting layer is changed to the compound 4CzIPN. Green light emission can be obtained by applying a DC voltage to both electrodes.
  • Example 14 ⁇ Device using compound (10P-gq-101-J11) as host and 4CzIPN as dopant> Method according to Example 9 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced by the compound (10P-gq-101-J11) and the compound DABNA2 which is the dopant material is replaced by the compound 4CzIPN
  • the organic EL element is obtained by Green light emission can be obtained by applying a DC voltage to both electrodes.
  • Comparative Example 7 ⁇ Device using compound mCBP as host and 4CzIPN as dopant>
  • An organic EL element is obtained by the method according to Example 9 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced with the compound mCBP and the compound DABNA2 which is the dopant material is replaced with the compound 4CzIPN.
  • Green light emission can be obtained by applying a DC voltage to both electrodes.
  • Example 15 ⁇ Device using compound (10P-g-101) as host and CzBPCN as dopant> An organic EL device is obtained by the method according to Example 9, except that the compound DABNA2 which is a dopant material of the light emitting layer is changed to the compound CzBPCN. Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Example 16 ⁇ Device using compound (10P-gq-101-J11) as host and CzBPCN as dopant> Method according to Example 9 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced by the compound (10P-gq-101-J11) and the compound DABNA2 which is the dopant material is replaced by the compound CzBPCN
  • the organic EL element is obtained by Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Comparative Example 8 ⁇ Device using compound mCBP as host and CzBPCN as dopant> An organic EL device is obtained by the method according to Example 9 except that the compound (10P-g-101) which is the host material of the light emitting layer is replaced by the compound mCBP and the compound DABNA2 which is the dopant material is replaced by the compound CzBPCN. Blue light emission is obtained when a DC voltage is applied to both electrodes.
  • Example 17 ⁇ Device using compound (10P-gq-100-J11) as host and DABNA2 as dopant>
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Choshu Sangyo Co., Ltd.), and each of NPD, TcTa, mCP, compound (10P-gq-100-J11), DABNA2, TSPO1 and LiF was loaded.
  • a tantalum evaporation crucible and an aluminum nitride evaporation crucible containing aluminum were mounted.
  • the following layers were formed sequentially on the ITO film of the transparent support substrate.
  • the vacuum chamber is depressurized to 2.0 ⁇ 10 -4 Pa, first, NPD is heated to deposit 40 nm thick, and then TcTa is heated to deposit 15 nm thick, The mCP was heated and evaporated to a film thickness of 15 nm to form a three-layer hole injection layer and a hole transport layer.
  • the compound (10P-gq-100-J11) and DABNA2 were simultaneously heated and vapor deposited to a film thickness of 20 nm to form a light emitting layer.
  • the deposition rate was adjusted so that the weight ratio of the compound (10P-gq-100-J11) to DABNA2 was about 98: 2.
  • TSPO1 was heated and vapor deposited to a film thickness of 40 nm to form an electron transport layer.
  • the deposition rate of each layer was 0.01 to 1 nm / second.
  • LiF is heated to deposit 1 nm thick at a deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to a thickness of 100 nm to 0.1 to 2 nm / It vapor-deposited at the vapor deposition rate of second, the cathode was formed, and the organic EL element was obtained.
  • the light emission luminance was 10 cd / m 2 at a drive voltage of 4.00 V and a current density of 0.04 mA / cm 2 , and the external quantum efficiency at this time was 25.0%.
  • the light emission luminance was 100 cd / m 2 at a drive voltage of 4.84 V and a current density of 0.48 mA / cm 2 , and the external quantum efficiency at this time was 21.0%.
  • organic EL elements according to Examples 18, 19 and Comparative Examples 9, 10 were produced with the layer configurations shown in Table 7.
  • Example 18 ⁇ Device using compound (10P-gq-100-J11) as host and DABNA2 as dopant>
  • This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (Choshu Sangyo Co., Ltd.), and each of NPD, TcTa, mCP, compound (10P-gq-100-J11), DABNA2, TSPO1 and LiF was loaded.
  • a tantalum evaporation crucible and an aluminum nitride evaporation crucible containing aluminum were mounted.
  • the following layers were formed sequentially on the ITO film of the transparent support substrate.
  • the vacuum chamber is depressurized to 2.0 ⁇ 10 -4 Pa, first, NPD is heated to deposit 40 nm thick, and then TcTa is heated to deposit 15 nm thick, The mCP was heated and evaporated to a film thickness of 15 nm to form a three-layer hole injection layer and a hole transport layer.
  • the compound (10P-gq-100-J11) and DABNA2 were simultaneously heated and vapor deposited to a film thickness of 20 nm to form a light emitting layer.
  • the deposition rate was adjusted so that the weight ratio of the compound (10P-gq-100-J11) to DABNA2 was about 98: 2.
  • TSPO1 was heated and vapor deposited to a film thickness of 30 nm to form an electron transport layer.
  • the deposition rate of each layer was 0.01 to 1 nm / second.
  • LiF is heated to deposit 1 nm thick at a deposition rate of 0.01 to 0.1 nm / sec, and then aluminum is heated to a thickness of 100 nm to 0.1 to 2 nm / It vapor-deposited at the vapor deposition rate of second, the cathode was formed, and the organic EL element was obtained.
  • Comparative Example 9 ⁇ Device using compound mCBP as host and DABNA2 as dopant> An organic EL device was obtained by the method according to Example 18 except that the compound (10P-gq-100-J11) as the host material of the light emitting layer was changed to the compound mCBP.
  • the compound (10P-gq-100-J11) as the host material of the light emitting layer was changed to the compound mCBP.
  • blue emission having a peak top at about 467 nm was obtained.
  • the light emission luminance was 10 cd / m 2 at a drive voltage of 4.50 V and a current density of 0.06 mA / cm 2 , and the external quantum efficiency at this time was 17.6%.
  • the light emission luminance was 100 cd / m 2 at a drive voltage of 5.38 V and a current density of 0.83 mA / cm 2 , and the external quantum efficiency at this time was 12.4%.
  • Example 19 ⁇ Device using compound (10P-gq-100-J11) as host and DABNA3 as dopant>
  • An organic EL device was obtained by the method according to Example 18 except that DABNA3 was used as the dopant material of the light emitting layer.
  • DABNA3 was used as the dopant material of the light emitting layer.
  • blue emission having a peak top at about 472 nm was obtained.
  • the light emission luminance was 10 cd / m 2 at a drive voltage of 4.00 V and a current density of 0.03 mA / cm 2 , and the external quantum efficiency at this time was 34.5%.
  • the emission luminance was 100 cd / m 2 at a drive voltage of 5.38 V and a current density of 0.34 mA / cm 2 , and the external quantum efficiency at this time was 32.7%.
  • the external quantum efficiency at 10 cd / m 2 and 100 cd / m 2 were both excellent.
  • the S 1 excitation energy calculated using the PBE 0 / 6-31 G (d) method was 18 nm shorter than the emission wavelength obtained by the measurement, and ⁇ E ST was about 10 times smaller. Moreover, although the value of the calculated oscillator strength was very small, the actually measured PLQY was very high.
  • the compound is a TADF-active fluorescent material under the assumption that the calculated values and the comparative example 1 have a similar tendency.
  • the actual emission wavelength may be shorter than the calculation result of the S 1 excitation energy
  • the actually measured ⁇ E ST may be larger than the calculation result
  • the PLQY also has a large oscillator strength. It was assumed that there is a large possibility compared to the calculation results. Therefore, it is considered that those with ⁇ E ST calculated less than 0.20 eV can be used as TADF fluorescent materials, and those smaller than 0.02 eV can be used more effectively as TADF fluorescent materials.
  • the oscillator strength is 0.0002 or more, high PLQY can be obtained, and when it is smaller than 0.0002, low PLQY can be obtained. Also, it is assumed that the actual emission wavelength is close to the calculation result of the S 1 excitation energy but may shift somewhat.
  • the choice of materials for organic devices such as organic EL elements can be increased by providing a novel compound in which boron is a spiro atom. Further, by using a novel compound in which boron is a spiro atom as a material for an organic EL element, it is possible to provide an excellent organic EL element, a display device including the same, a lighting device including the same, and the like.
  • organic electroluminescent device 101 substrate 102 anode 103 hole injection layer 104 hole transport layer 105 light emitting layer 106 electron transport layer 107 electron injection layer 108 cathode

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