WO2011152466A1 - Composé de carbazole présentant un groupe substituant comprenant un hétéroaryle acceptant les électrons contenant de l'azote et élément organique électroluminescent - Google Patents

Composé de carbazole présentant un groupe substituant comprenant un hétéroaryle acceptant les électrons contenant de l'azote et élément organique électroluminescent Download PDF

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WO2011152466A1
WO2011152466A1 PCT/JP2011/062620 JP2011062620W WO2011152466A1 WO 2011152466 A1 WO2011152466 A1 WO 2011152466A1 JP 2011062620 W JP2011062620 W JP 2011062620W WO 2011152466 A1 WO2011152466 A1 WO 2011152466A1
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carbons
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bis
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洋平 小野
国防 王
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Jnc株式会社
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Priority to KR1020127031124A priority patent/KR101864902B1/ko
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • the present invention relates to a carbazole compound having a substituent containing an electron-accepting nitrogen-containing heteroaryl, an electron transport material, an organic electroluminescent element, a display device, and a lighting device using the same.
  • the present inventors have made an organic electroluminescent device comprising an organic layer containing a compound represented by the following formula (1) as an electron transporting material, in particular, the device.
  • the present inventors have found that an organic electroluminescent device having an excellent lifetime and a well-balanced driving voltage can be obtained. That is, the present invention provides the following carbazole compounds.
  • a carbazole compound represented by the following formula (1-1) is aryl having 6 to 24 carbons or heteroaryl having 2 to 24 carbons, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons;
  • Hy 1 and Hy 2 are each independently an electron-accepting nitrogen-containing heteroaryl having 2 to 24 carbon atoms, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • Ar 1 and Ar 2 are each independently aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons; At least one hydrogen atom in the carbazole compound represented by the formula (1-1) may be substituted with deuterium.
  • R is phenyl, biphenylyl, terphenylyl, quaterphenyl, naphthyl, phenyl-substituted naphthyl, phenanthrolinyl optionally substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons , Pyridyl, bipyridyl, terpyridyl, quinolinyl, isoquinolinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl, Hy 1 and Hy 2 are each independently pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaind, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • Lydinyl benzoimidazolyl, benzothiazolyl, benzoxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl
  • Ar 1 and Ar 2 are each independently benzene, naphthalene, anthracene, naphthacene, pentacene, biphenyl, acenaphthylene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons,
  • R is phenyl, biphenylyl, terphenylyl, quaterphenyl, naphthyl, phenyl-substituted naphthyl, phenanthrolinyl optionally substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons
  • a group selected from the group consisting of pyridyl, quinolinyl and isoquinolinyl, Hy 1 and Hy 2 are each independently pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaind, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • Ar 1 and Ar 2 are each independently benzene, naphthalene, anthracene, pyrene, triphenylene, fluorene, biphenyl, which may be substituted with alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, and
  • R is a group represented by the following formulas (R-1) to (R-20), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • a group selected from the group consisting of Hy 1 and Hy 2 are each independently groups represented by the following formulas (Hy-1-1) to (Hy-1-3), and the following formulas (Hy-2-1) to (Hy-2-).
  • Ar 1 and Ar 2 each independently represents a divalent structure selected from the group consisting of benzene and naphthalene, which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons Which is the basis of The carbazole compound described in [1] above.
  • R is a group represented by the above formulas (R-1) to (R-14), which may be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • a group selected from the group consisting of Hy 1 and Hy 2 are each independently groups represented by the above formulas (Hy-1-1) to (Hy-1-3), and the above formulas (Hy-2-1) to (Hy-2-).
  • Ar 1 and Ar 2 are each independently 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6- A divalent group selected from the group consisting of naphthalene-diyl and 2,7-naphthalene-diyl, The carbazole compound described in [1] above.
  • a pair of electrodes including an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the above [9] disposed between the cathode and the light emitting layer.
  • An organic electroluminescent device having an electron transport layer and / or an electron injection layer.
  • At least one of the electron transport layer and the electron injection layer further includes at least one selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a bipyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.
  • a quinolinol-based metal complex a pyridine derivative, a bipyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.
  • At least one of the electron transport layer and the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one selected from the group consisting of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes
  • alkaline earth metal halides At least one selected from the group consisting of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes
  • a display device comprising the organic electroluminescent element according to any one of [10] to [12].
  • an organic electroluminescent element excellent in the lifetime of the light emitting element can be obtained.
  • the preferred electron transport material of the present invention is particularly suitable for a blue light emitting element, and according to this electron transport material, a blue light emitting element having an element life comparable to a red or green light emitting element can be produced. Can do.
  • a high-performance display device such as a full-color display can be obtained.
  • Carbazole Compound Represented by Formula (1) The carbazole compound having a substituent containing an electron-accepting nitrogen-containing heteroaryl according to the present invention will be described in detail.
  • the carbazole compound of the present invention is a compound represented by the following formula (1).
  • a 0 or 1
  • b 0 or 1
  • R is aryl having 6 to 24 carbon atoms or heteroaryl having 2 to 24 carbon atoms.
  • Hy 1 and Hy 2 are each independently an electron-accepting nitrogen-containing heteroaryl having 2 to 24 carbon atoms, and may be the same or different.
  • R, Hy 1 , Hy 2 , Ar 1 and Ar 2 may each independently be substituted with alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
  • alkyl having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, Examples thereof include 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl and 2-ethylbutyl.
  • methyl, isopropyl or t-butyl is preferable, and t-butyl is particularly preferable.
  • the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl and dimethylcyclohexyl.
  • the number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
  • the “aryl having 6 to 24 carbon atoms” in R is preferably an aryl having 6 to 16 carbon atoms, and more preferably an aryl having 6 to 12 carbon atoms.
  • aryl include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl.
  • Terphenylyl which is a tricyclic aryl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o -Terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl -2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, o-terpheny
  • the number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
  • phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, phenylnaphthyl and those substituted with alkyl having 1 to 6 carbon atoms or cyclohexyl having 3 to 6 carbon atoms are preferable.
  • heteroaryl having 2 to 24 carbon atoms in R is preferably a heteroaryl having 2 to 20 carbon atoms, more preferably a heteroaryl having 2 to 15 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Of heteroaryl. Examples of the “heteroaryl” include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.
  • heteroaryl examples include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H -Indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolinyl, isoquinolinyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, a
  • R include groups represented by the following formulas (R-1) to (R-20). Of these, groups represented by the following formulas (R-1) to (R-14), and groups represented by the following formulas (R-1) to (R-9) are particularly preferable. .
  • Hy 1 and Hy 2 are each independently an electron-accepting nitrogen-containing heteroaryl, and the electron-accepting nitrogen represents a nitrogen atom that forms a double bond with an adjacent atom.
  • Examples of the electron-accepting nitrogen-containing heteroaryl include pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolidinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, indazolyl, purinyl, carbolinyl, naphthyridinyl, quinoxalinyl, quinolinyl, isoquinolinyl, Examples include pyridylquinolinyl, pyridylisoquinolinyl, acridinyl, phenanthrolinyl, phenazinyl and imidazopyridinyl.
  • pyridyl preferred are pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyrazinyl, triazinyl, azaindolizinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, pyridylquinolinyl, pyridylisoquinolinyl and imidazopyridinyl. Particularly preferred are pyridyl and bipyridyl.
  • Hy 1 or Hy 2 is preferably a group represented by the following formulas (Hy-1-1) to (Hy-1-3), or the following formulas (Hy-2-1) to (Hy-2-). 18), and groups represented by the following formulas (Hy-3-1) to (Hy-3-27).
  • Hy 1 or Hy 2 More preferred as Hy 1 or Hy 2 are groups represented by the above formulas (Hy-1-1) to (Hy-1-3), and the above formulas (Hy-2-1) to (Hy-2-18). It is group represented by these.
  • arylene a divalent group derived from an aromatic hydrocarbon group such as benzene, naphthalene, anthracene, naphthacene, pentacene, acenaphthylene, phenalene, phenanthrene, pyrene, triphenylene, fluorene, biphenyl, and perylene can be used.
  • a divalent group derived from naphthalene is preferred.
  • Divalent groups derived from benzene or naphthalene include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthalene-diyl, 1,5-naphthalene-diyl, 2,6- And naphthalene-diyl and 2,7-naphthalene-diyl.
  • the specific aryl of Ar 2 includes the groups exemplified in the above description of R, and the groups represented by the above formulas (R-1) to (R-9) are preferable. Particularly preferred are groups represented by the above formula (R-1), formula (R-6) and formula (R-7).
  • Hy 1 and Hy 2 may be the same or different, but are preferably the same, and Ar 1 and Ar 2 are also the same. Or may be different, but preferably the same.
  • Specific examples of the compound represented by the above formula (1) include, for example, the following formulas (1-1-1) to (1-1-1458) belonging to the compound represented by the above formula (1-1). ), Compounds represented by the following formulas (1-2-1) to (1-2-629) belonging to the compounds represented by the above formula (1-2), the above formula (1) -3) belonging to the compound represented by the following formulas (1-3-1) to (1-3-924), belonging to the compound represented by the above formula (1-4), Examples thereof include compounds represented by the following formulas (1-4-1) to (1-4-561).
  • the carbazole compound of the present invention basically comprises a known compound and a known synthesis method such as Suzuki coupling reaction or Negishi coupling reaction (for example, “Metal-Catalyzed Cross-Coupling Reactions—Second, Completely Revised”). and Enlarged Edition ”). It can also be synthesized by combining both reactions.
  • a scheme for synthesizing the carbazole compound represented by the formula (1) by Suzuki coupling reaction or Negishi coupling reaction is illustrated below.
  • Hy 1- (Ar 1 ) a ” and “(Hy 2 ) b —Ar 2 ” mean groups bonded to the 2nd and 7th positions of the carbazole skeleton of the compound represented by the formula (1). , A and b are 0 or 1.
  • the palladium catalyst used in the Suzuki coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh 3 ) 4 , bis (triphenylphosphine) palladium (II) dichloride: PdCl 2 (PPh 3 ) 2 , palladium (II) acetate: 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 , PdCl 2 ⁇ P (t-Bu) 2- (p-NMe 2 -Ph) ⁇ 2 , palladium bis ( Dibenzylidene).
  • a phosphine compound may be added to these palladium compounds in some cases.
  • 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) -1,1′-binaphthy
  • bases used in the Suzuki coupling reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate. , Tripotassium phosphate, or potassium fluoride.
  • solvent used in the Suzuki coupling reaction examples include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1 1,4-dioxane, methanol, ethanol, cyclopentyl methyl ether or isopropyl alcohol.
  • solvents can be appropriately selected and may be used alone or as a mixed solvent.
  • the palladium catalyst used in the Negishi coupling reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh 3 ) 4 , bis (triphenylphosphine) palladium (II) dichloride: PdCl 2 (PPh 3 ) 2 , palladium (II) acetate: 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), or (1,1′-bis (diphenylphosphine) Fino) ferrocene) dichlor
  • solvent used in the Negishi coupling reaction examples include benzene, toluene, xylene, 1,2,4-trimethylbenzene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, cyclopentyl. Examples include methyl ether or 1,4-dioxane. These solvents can be appropriately selected and may be used alone or as a mixed solvent.
  • ZnCl 2 ⁇ TMEDA is a tetramethylethylenediamine complex of zinc chloride.
  • R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • Also illustrated here is a method for synthesizing 2- (4-bromophenyl) pyridine and 2- (4-bromonaphthalen-1-yl) pyridine using 1,4-dibromobenzene or 1,4-dibromonaphthalene as raw materials.
  • 1,3-dibromobenzene, 2,6-dibromonaphthalene or 2,7-dibromonaphthalene as a raw material, dichloro, diiodo, bis (trifluoromethanesulfonate)
  • a mixture of them for example: 1-bromo-4-iodobenzene, etc.
  • the corresponding target product ie, 2- (3-bromophenyl) pyridine, 2- (6-bromonaphthalen-2-yl) ) Pyridine and 2- (7-bromonaphthalen-2-yl) pyridine can be obtained. Kill.
  • a similar target product can be obtained by reacting pyridylboronic acid or pyridylboronic acid ester (coupling reaction).
  • R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine may be lithiated using an organolithium reagent, or magnesium Or an organomagnesium reagent to form a Grignard reagent and react with bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane to produce other 4- (pyridine-2- Yl) phenylboronic acid esters and 4- (pyridin-2-yl) naphthalen-1-ylboronic acid esters can be synthesized.
  • 2- (4-bromophenyl) pyridine or 2- (4-bromonaphthalen-1-yl) pyridine and bis (pinacolato) diboron or 4,4,5 The same 4- (pyridin-2-yl) phenylboronic acid ester and 4- (pyridine) can also be obtained by coupling reaction of 5-tetramethyl-1,3,2-dioxaborolane with a palladium catalyst and a base. -2-yl) naphthalen-1-ylboronic acid ester can be synthesized.
  • R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the carbazole compound of the present invention has a “Hy 1- (Ar 1 ) a —” group and a “(Hy 2 ) b —Ar 2 —” group at the 2nd and 7th positions of the carbazole skeleton as described above.
  • “Ar 1 (or Ar 2 )” and “Hy 1 (or Hy 2 )” may be bonded in order to the carbazole skeleton as follows.
  • Cz-R-ArOR "is synthesized. Next, demethylation is performed using boron tribromide, pyridine hydrochloride, or the like to synthesize a compound represented by “Cz—R—ArOH”. Thereafter, a compound represented by “Cz—R—ArOTf” is obtained by reacting with trifluoromethanesulfonic anhydride.
  • R which is an alkyl part of alkoxy and R which is a substituent bonded to the 9-position of carbazole are represented by the same symbol, but they may be the same or different.
  • the compounds of the present invention include those in which at least a part of the hydrogen atoms are substituted with deuterium.
  • a compound can be obtained by using a raw material in which a desired position is deuterated. It can be synthesized in the same way.
  • FIG. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to this embodiment.
  • An 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.
  • the cathode 108 provided on the electron injection layer 107.
  • the organic electroluminescent element 100 is manufactured in the reverse order, 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.
  • a structure including the hole injection layer 103 provided above and the anode 102 provided on the hole injection layer 103 may be employed.
  • each said layer may consist of a single layer, respectively, and may consist of multiple layers.
  • the substrate 101 serves as a support for the organic electroluminescent device 100, and usually quartz, glass, metal, plastic, or the like is used.
  • the substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose.
  • a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used.
  • glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable.
  • soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength.
  • the upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less.
  • the glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass.
  • soda lime glass with a barrier coat such as SiO 2 is also commercially available, so it can be used. it can.
  • the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.
  • the anode 102 serves to inject holes into the light emitting layer 105.
  • the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .
  • Examples of the material for forming the anode 102 include inorganic compounds and organic compounds.
  • Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide) Products (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, and the like.
  • Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances currently used as an anode of an organic electroluminescent element, and can use it.
  • the resistance of the transparent electrode is not particularly limited as long as a current sufficient for light emission of the light emitting element can be supplied, but it is desirable that the resistance is low from the viewpoint of power consumption of the light emitting element.
  • an ITO substrate of 300 ⁇ / ⁇ or less functions as an element electrode, but at present, since it is possible to supply a substrate of about 10 ⁇ / ⁇ , for example, 100 to 5 ⁇ / ⁇ , 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 is usually used in a range of 100 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 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 through 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 kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done.
  • an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.
  • a hole injection / transport material As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.
  • a compound conventionally used as a charge transport material for holes, a p-type semiconductor, and a hole injection of an organic electroluminescent element are used.
  • Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class).
  • Styrene derivatives polyvinyl carbazole, polysilane, and the like are preferable, but there is no particular limitation as long as it is a compound that forms a thin film necessary for manufacturing a light-emitting element, can inject holes from the anode, and can further transport holes. .
  • organic semiconductors are strongly influenced by the doping.
  • 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 donor materials.
  • TCNQ tetracyanoquinone dimethane
  • F4TCNQ 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane
  • the light emitting layer 105 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 that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a high emission (fluorescence and / or phosphorescence) efficiency.
  • the light emitting layer may be either a single layer or a plurality of layers, each formed of a light emitting material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations.
  • the dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.
  • the amount of host material used depends on the type of host material and can be determined according to the characteristics of the host material.
  • the amount of the host material used is preferably 50 to 99.999% by weight of the entire light emitting material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight. .
  • the amount of dopant material used depends on the type of dopant material, and can be determined according to the characteristics of the dopant material.
  • the standard of the amount of dopant used is preferably 0.001 to 50% by weight of the entire light emitting material, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight.
  • the above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.
  • the light emitting material of the light emitting device according to this embodiment may be either fluorescent or phosphorescent.
  • the host material is not particularly limited, but has previously been known as a phosphor, fused ring derivatives such as anthracene and pyrene, metal chelated oxinoid compounds such as tris (8-quinolinolato) aluminum, bis Bisstyryl derivatives such as styryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, pyrrolopyrrole
  • fluorene derivatives, benzofluorene derivatives, and polymer systems polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives are preferably used.
  • the dopant material is not particularly limited, and a known compound can be used, and can be selected from various materials according to a desired emission color.
  • condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene, and chrysene
  • benzoxazole derivatives benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives
  • Bisstyryl such as oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and dist
  • blue to blue-green dopant materials include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene, chrysene and other aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, Aromatic complex such as silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene Ring compounds and their derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazo
  • green to yellow dopant material examples include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene.
  • a compound in which a substituent capable of increasing the wavelength such as aryl, heteroaryl, arylvinyl, amino, and cyano is introduced into the compound exemplified as the blue to blue-green dopant material is also a suitable example.
  • orange to red dopant materials include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazo Derivatives, thi
  • a compound into which a group is introduced is also a suitable example.
  • a phosphorescent metal complex having iridium or platinum represented by tris (2-phenylpyridine) iridium (III) as a central metal is also a suitable example.
  • the dopant can be appropriately selected from compounds described in Chemical Industry, June 2004, page 13, and references cited therein.
  • perylene derivatives perylene derivatives, borane derivatives, amine-containing styryl derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, iridium complexes, or platinum complexes are particularly preferable.
  • perylene derivatives examples include 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 No. 2000-34234, JP-A No. 2001-267075, JP-A No. 2001-217077 and the like may be used.
  • borane derivatives examples 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.
  • amine-containing styryl derivatives include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl).
  • aromatic amine derivative examples include N, N, N, N-tetraphenylanthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, and 9,10-bis (4- Di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p-tolylamino-1) -Naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene, [4- (4-diphenyl) Amino-phenyl) naphthalen-1-yl
  • Examples of coumarin derivatives include coumarin-6 and coumarin-334. Moreover, you may use the coumarin derivative described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, and Unexamined-Japanese-Patent No. 6-298758.
  • Examples of the pyran derivative include the following DCM and DCJTB. Also, JP 2005-126399, JP 2005-097283, JP 2002-234892, JP 2001-220577, JP 2001-081090, and JP 2001-052869. Alternatively, pyran derivatives described in the above may be used.
  • iridium complex examples include Ir (ppy) 3 described below. Further, the iridium complexes described in JP-A-2006-089398, JP-A-2006-080419, JP-A-2005-298483, JP-A-2005-097263, JP-A-2004-111379, etc. It may be used.
  • platinum complex examples include the following PtOEP. Further, the platinum complexes described in JP-A-2006-190718, JP-A-2006-128634, JP-A-2006-093542, JP-A-2004-335122, JP-A-2004-331508, etc. It may be used.
  • the electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or 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 through 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 the electron transport / injection material and the polymer binder.
  • the electron injection / transport layer is a layer that is responsible for injecting electrons from the cathode and further transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.
  • a compound represented by the above formula (1) can be used as the material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107.
  • a compound represented by the above formula (1) can be used as the material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107.
  • the content of the compound represented by the above formula (1) in the electron transport layer 106 or the electron injection layer 107 differs depending on the type of the compound and may be determined according to the characteristics of the compound.
  • the standard for the content of the compound represented by the formula (1) is preferably 1 to 100% by weight, more preferably 10 to 100% by weight, based on the whole electron transport layer material (or electron injection layer material). More preferably, it is 50 to 100% by weight, and particularly preferably 80 to 100% by weight.
  • the compound represented by the formula (1) is not used alone (100% by weight), other materials described in detail below may be mixed.
  • Other materials for forming the electron transport layer or electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and known materials used for electron injection layers and electron transport layers of organic electroluminescent devices. Any of these compounds can be selected and used.
  • condensed 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, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives other than the compound represented by the above formula (1), and indole derivatives.
  • metal complexes having electron-accepting nitrogen examples include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials.
  • anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene, styryl aromatic ring derivatives such as 4,4′-bis (diphenylethenyl) biphenyl, 4,4′-bis (N-carbazolyl) biphenyl
  • a carbazole derivative such as 1,3,5-tris (N-carbazolyl) benzene is preferably used from the viewpoint of durability.
  • pyridine derivatives other than the compound represented by the above formula (1) naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives represented by the formula (1) , Naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (such as 1,3-bis [(4-tert-butylphenyl) 1,3,4-oxadiazolyl] phenylene), thiophene Derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole Compound
  • metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. Is given.
  • the above-mentioned materials can be used alone, but they may be mixed with different materials.
  • quinolinol metal complexes bipyridine derivatives, phenanthroline derivatives, borane derivatives or benzimidazole derivatives are preferable.
  • the quinolinol-based 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 Al, Ga, Be, or Zn
  • n is an integer of 2 or 3.
  • quinolinol-based metal complexes include 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-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (4- Methyl phenolate) Aluminum Bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (4-Phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenol
  • 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. Further, carbon not used for bonding of pyridine-pyridine or pyridine-G may be substituted.
  • G in the general 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′-bipyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Bipyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-bipyridin-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-bipyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilole 9,10-di (2,2′-bipyridine-6- Yl) anthracene, 9,10-di (2,2′-bipyridin-5-yl) anthracene, 9,10-di (2,3′-bipyridin-6-yl) anthracene, 9,10-di (2, 3′-b
  • 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, adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or an n-valent linking group, and n represents 2 It is an integer of ⁇ 8.
  • Examples of G in the general formula (E-3-2) include the same ones as described in the bipyridine derivative column.
  • phenanthroline derivatives 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-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthroline-5-yl) benzene, 9,9′-difluor -Bis (1,10-phenanthroline-5-yl), bathocuproin, 1,3-bis (2-phenyl-1,10-phenanthroline-9-yl) benzene and the like.
  • a phenanthroline derivative is used for the electron transport layer and the electron injection layer.
  • the substituent itself has a three-dimensional structure, or a phenanthroline skeleton or Those having a three-dimensional structure by steric repulsion with an adjacent substituent or those having a plurality of phenanthroline skeletons linked to each other are preferred.
  • a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the 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.
  • R 11 and R 12 are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl
  • X is an optionally substituted arylene
  • Y is a substituted Aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazole
  • each n is independently an integer of 0 to 3.
  • the compound represented by -1-4) is preferred. Specific examples include 9- [4- (4-Dimesitylborylnaphthalen-1-yl) phenyl] carbazole, 9- [4- (4-Dimesitylborylnaphthalen-1-yl) naphthalen-1-yl. Carbazole and the like.
  • R 11 and R 12 are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl
  • R 21 and R 22 are each independently hydrogen, alkyl, or substituted.
  • X 1 is an optionally substituted arylene having 20 or less carbon atoms
  • n is each Each independently represents an integer of 0 to 3, and each m independently represents an integer of 0 to 4;
  • R 31 to R 34 are each independently methyl, isopropyl or phenyl
  • R 35 and R 36 are each independently hydrogen, methyl, isopropyl or phenyl. It is.
  • R 11 and R 12 are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl
  • X 1 is an optionally substituted arylene having 20 or less carbon atoms
  • N is an integer of 0 to 3 independently.
  • 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.
  • R 11 and R 12 are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano
  • R 13 to R 16 are each independently an optionally substituted alkyl or an optionally substituted aryl
  • X 1 is 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 are each independently methyl, isopropyl or phenyl
  • R 35 and R 36 are each independently 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.
  • a benzimidazole derivative which is anthryl optionally substituted with Ar 1 is preferable.
  • aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene-3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, and fluorene-1- Yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, phenalen-1-yl, phenalen-2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthen-1-yl, fluoranthen-2-yl, fluoranthen-3-yl, fluoranthen-7-yl, fluoranthen-8-yl, Triphenylene-1-yl, 2-
  • benzimidazole derivative examples include 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H-benzo [d] imidazole, 2- (4- (10- (naphthalene-2) -Yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1- Phenyl-1H-benzo [d] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1,2-diphenyl-1H-benzo [d] imidazole, 1- (4- (10 -(Naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-benzo [d] imidazole, 2- (4- (9,10-di (n)-
  • 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 substances can be used as long as they have a certain reducing ability.
  • alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali Group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes, and rare earth metal organic complexes At least one selected from can be preferably used.
  • Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV), and Ca (2. 9eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and alkaline earth metals such as those having a work function of 2.9 eV or less are particularly preferable.
  • a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs.
  • alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.
  • a reducing substance having a work function of 2.9 eV or less a combination of two or more alkali metals is also preferable.
  • 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 such as Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred.
  • the cathode 108 serves to inject electrons into the light emitting layer 105 through 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 is a substance that can efficiently inject electrons into the organic layer, but the same material as that for forming the anode 102 can be used.
  • metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium or their alloys (magnesium-silver Alloys, magnesium-indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum) and the like are preferred.
  • lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective.
  • metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, or alloys using these metals, and inorganic substances such as silica, titania, and silicon nitride, polyvinyl alcohol, Preferred examples include laminating vinyl chloride, hydrocarbon polymer compounds and the like.
  • the method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating.
  • the materials used for the above hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate , 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 Can be used by being dispersed in solvent-soluble resins such as resins, and curable resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicone resins.
  • solvent-soluble resins such as resins
  • curable resins such as phenol resins, xylene resins,
  • Each layer constituting the organic electroluminescent element is formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method, casting method, or coating method.
  • the film can be formed by forming a thin film.
  • the film thickness of each layer thus formed is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like.
  • the vapor deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, and the like.
  • Deposition conditions generally include boat heating temperature +50 to + 400 ° C., vacuum degree 10 ⁇ 6 to 10 ⁇ 3 Pa, deposition rate 0.01 to 50 nm / second, substrate temperature ⁇ 150 to + 300 ° C., film thickness 2 nm to 5 ⁇ m. It is preferable to set appropriately within the range.
  • an organic electric field composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode.
  • a method for manufacturing a light-emitting element will be described.
  • a thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode.
  • a host material and a dopant material are co-evaporated to form a thin film to form a light emitting layer.
  • An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a desired organic electroluminescent element can be obtained.
  • the order of preparation may be reversed, and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode may be fabricated in this order. Is possible.
  • the anode When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, the organic electroluminescent device is transparent or translucent. Luminescence can be observed from the electrode side (anode or cathode, and both). The organic electroluminescence device emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.
  • the present invention can also be applied to a display device provided with an organic electroluminescent element or a lighting device provided with an organic electroluminescent element.
  • a display device or an illuminating device including an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.
  • Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, JP-A-2004-281086, etc.).
  • Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.
  • a matrix is a pixel in which pixels for display are arranged two-dimensionally, such as a grid or mosaic, and displays characters and images as a set of pixels.
  • the shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 ⁇ m or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become.
  • monochrome display pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type.
  • the matrix driving method may be either a line sequential driving method or an active matrix.
  • the line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.
  • a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light.
  • a predetermined region is caused to emit light.
  • the time and temperature display in a digital clock or a thermometer, the operation status display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be given.
  • the illuminating device examples include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A).
  • the backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like.
  • a backlight for liquid crystal display devices especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness.
  • the backlight using the light emitting element according to the embodiment is thin and lightweight.
  • the reaction solution was cooled to room temperature, water was added, and washing operation was performed.
  • the reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration.
  • EDTA ethylenediaminetetraacetic acid
  • the obtained solid was washed with methanol, dissolved in heated chlorobenzene, and filtered while hot using a Kiriyama funnel covered with activated alumina. Crystals precipitated by gradually distilling off the obtained filtrate under reduced pressure were collected by suction filtration, and 2,7-bis (4-ethoxynaphthalen-1-yl) -9-phenyl-9H-carbazole (21 0.8 g) was obtained.
  • reaction solution was cooled to room temperature and washed repeatedly with water and methanol warmed to about 75 ° C., whereby 4,4 ′-(9-phenyl-9H-carbazole-2,7-diyl) bis (naphthalene-1- All) (19.3 g) was obtained.
  • the resulting precipitate was washed with water and then with methanol. Further, it was purified by activated alumina column chromatography (developing solution: toluene), and (9-phenyl-9H-carbazole-2,7-diyl) bis (naphthalene-4,1-diyl) bis (trifluoromethanesulfonate) (18 0.5 g) was obtained.
  • the reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration. The obtained precipitate was washed with methanol, dissolved in heated chlorobenzene, and filtered while hot.
  • EDTA ethylenediaminetetraacetic acid
  • the reaction solution was cooled to room temperature, an ethylenediaminetetraacetic acid (EDTA) aqueous solution was added, and the precipitate was collected by suction filtration.
  • the compound represented was 9-phenyl-2,7-bis (4- (pyridin-4-yl) naphthalen-1-yl) -9H-carbazole (0.4 g).
  • reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added for liquid separation.
  • EDTA ethylenediaminetetraacetic acid
  • the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution: toluene). Methanol was added to the oil obtained by distilling off the solvent under reduced pressure to perform reprecipitation, and 9-([1 , 1 ′: 3 ′, 1 ′′ -terphenyl] -5′-yl) -2,7-bis (3-methoxyphenyl) -9H-carbazole (11.5 g).
  • the compounds of the present invention include those in which at least a part of the hydrogen atoms are substituted with deuterium.
  • Such a compound can be obtained by using a raw material in which a desired position is deuterated. It can be synthesized in the same way.
  • Example 1 The electroluminescent elements according to Example 1 and Comparative Example 1 were manufactured, the driving start voltage (V) in the constant current driving test, the time (h) for maintaining the luminance of 90% (1800 cd / m 2 ) or more of the initial luminance, and The external quantum efficiency at 1000 cd / m 2 was measured.
  • V driving start voltage
  • h time for maintaining the luminance of 90% (1800 cd / m 2 ) or more of the initial luminance
  • the external quantum efficiency at 1000 cd / m 2 was measured.
  • the quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency.
  • the ratio of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is converted into photons purely. What is shown is the internal quantum efficiency.
  • the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element.
  • the external quantum efficiency is lower than the internal quantum efficiency because it is continuously reflected and is not emitted outside the light emitting element.
  • the external quantum efficiency is measured as follows.
  • a voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m 2 to cause the element to emit light.
  • a spectral radiance meter SR-2A manufactured by TOPCON the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by ⁇ is the number of photons at each wavelength.
  • the value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.
  • Table 1 below shows the material structure of each layer in the electroluminescent devices according to the manufactured Example 1 and Comparative Example 1.
  • CuPc copper phthalocyanine
  • NPD N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl
  • compound (A) is 9-phenyl-10- [6 -(1,1 ′; 3,1 ′′) terphenyl-5′-yl] naphthalen-2-ylanthracene
  • compound (B) is N 5 , N 5 , N 9 , N 9 -7,7-hexaphenyl -7H-benzo [c] fluorene-5,9-diamine
  • compound (C) is 9,10-bis (4- (pyridin-4-yl) phenyl) anthracene
  • Liq is 8-quinolinol lithium .
  • the chemical structure is shown below.
  • Example 1 ⁇ Device Using Compound (1-1-856) for Electron Transport Layer>
  • a glass substrate of 26 mm ⁇ 28 mm ⁇ 0.7 mm obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 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 (manufactured by Vacuum Kiko Co., Ltd.), and a molybdenum vapor deposition boat containing CuPc, a molybdenum vapor deposition boat containing NPD, and a compound (A) are placed therein.
  • Molybdenum deposition boat molybdenum deposition boat containing compound (B), molybdenum deposition boat containing compound represented by formula (1-1-856), molybdenum deposition boat containing Liq A boat, a molybdenum boat containing magnesium, and a tungsten evaporation boat containing silver were installed.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was depressurized to 5 ⁇ 10 ⁇ 4 Pa, first, the vapor deposition boat containing CuPc was heated to deposit to a film thickness of 50 nm to form a hole injection layer, and then NPD was contained. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm.
  • the deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5.
  • the evaporation boat containing the compound represented by the formula (1-1-856) was heated and evaporated to a thickness of 15 nm to form an electron transport layer.
  • the deposition rate of each layer was 0.01 to 1 nm / second.
  • the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm.
  • a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode.
  • the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was from 0.1 nm to 10 nm to obtain an organic electroluminescent device.
  • Electroluminescent devices according to Examples 2 to 9 and Comparative Examples 2 to 4 were manufactured, and the driving start voltage (V) in the constant current driving test and the luminance of 80% (1600 cd / m 2 ) or more of the initial luminance were maintained. Measurement of the external quantum efficiency at a time (h) and 1000 cd / m 2 .
  • V driving start voltage
  • h time
  • 1000 cd / m 2
  • Table 3 below shows the material structure of each layer in the devices according to Examples 2 to 9 and Comparative Examples 2 to 4.
  • HI refers to N 4 , N 4 ′ -diphenyl-N 4 , N 4 ′ -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine
  • compound (D) is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene
  • compound (E) is 2,7-di ([2,4′-bipyridine] -6- Yl) -9-phenyl-9H-carbazole
  • compound (F) is 9,10-bis (4- (pyridin-4-yl) naphthalen-1-yl) anthracene
  • compound (G) is 9,10-bis ( 4- (Pyridin-2-yl) phenyl) anthracene.
  • Example 2 ⁇ Device Using Compound (1-1-854) for Electron Transport Layer>
  • a glass substrate of 26 mm ⁇ 28 mm ⁇ 0.7 mm obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 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 (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and compound (D) are placed therein.
  • Molybdenum deposition boat molybdenum deposition boat containing compound (B), molybdenum deposition boat containing compound (1-1-854), molybdenum deposition boat containing Liq, magnesium A molybdenum boat and a tungsten evaporation boat containing silver were installed.
  • the following layers were sequentially formed on the ITO film of the transparent support substrate.
  • the vacuum chamber was depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI was heated and vapor-deposited to a film thickness of 40 nm to form a hole injection layer, and then NPD was contained. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (D) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm.
  • the deposition rate was adjusted so that the weight ratio of compound (D) to compound (B) was approximately 95 to 5.
  • the evaporation boat containing the compound (1-1-854) was heated and evaporated to a thickness of 20 nm to form an electron transport layer.
  • the deposition rate of each layer was 0.01 to 1 nm / second.
  • the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm.
  • a boat containing magnesium and a boat containing silver were heated at the same time to form a cathode with a thickness of 100 nm.
  • the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was from 0.1 nm to 10 nm to obtain an organic electroluminescent device.
  • Example 3 ⁇ Device Using Compound (1-1-855) for Electron Transport Layer> An organic EL device was obtained in the same manner as in Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-855).
  • a constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 .
  • the drive test start voltage was 5.16 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 321 hours.
  • the external quantum efficiency of this device at 1000 cd / m 2 was 6.79%.
  • Example 4 ⁇ Device Using Compound (1-1-856) for Electron Transport Layer> An organic EL device was obtained in the same manner as in Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-856). A constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 . The driving test starting voltage was 4.84 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 198 hours. In addition, the external quantum efficiency of this device at 1000 cd / m 2 was 5.29%.
  • Example 5 ⁇ Device Using Compound (1-1-851) for Electron Transport Layer> An organic EL device was obtained in the same manner as in Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-851). A constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 .
  • the driving test start voltage was 4.83 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 334 hours.
  • the external quantum efficiency in 1000 cd / m ⁇ 2 > of this element was 5.01%.
  • Example 6> ⁇ Device Using Compound (1-1-852) for Electron Transport Layer> An organic EL device was obtained in the same manner as in Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-852). A constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 .
  • the driving test start voltage was 5.08 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 289 hours.
  • the external quantum efficiency of this device at 1000 cd / m 2 was 6.59%.
  • Example 7 ⁇ Device Using Compound (1-1-853) for Electron Transport Layer> An organic EL device was obtained in the same manner as in Example 2, except that the compound (1-1-854) was replaced with the compound (1-1-853). A constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 . The drive test starting voltage was 4.03 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 229 hours. In addition, the external quantum efficiency of this device at 1000 cd / m 2 was 6.89%.
  • Example 8> ⁇ Device Using Compound (1-1-98) for Electron Transport Layer>
  • An organic EL device was obtained in the same manner as in Example 2 except that the compound (1-1-854) was changed to the compound (1-1-98).
  • a constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 .
  • the drive test start voltage was 5.51 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 235 hours.
  • the external quantum efficiency of this device at 1000 cd / m 2 was 5.95%.
  • Example 9 ⁇ Device Using Compound (1-1-99) for Electron Transport Layer> An organic EL device was obtained in the same manner as in Example 2 except that the compound (1-1-854) was replaced with the compound (1-1-99). A constant current driving test was performed using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 . The driving test start voltage was 6.35 V, and the time for maintaining the luminance of 80% or more of the initial luminance was 186 hours. In addition, the external quantum efficiency of this device at 1000 cd / m 2 was 4.91%.
  • an organic electroluminescent element that improves the lifetime of the light emitting element and has an excellent balance with the driving voltage, a display device including the organic electroluminescent element, and a lighting device including the organic electroluminescent element. it can.

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Abstract

Le but de la présente invention réside dans la mise à disposition d'un élément organique électroluminescent dans lequel la tension de commande et la longévité de l'élément électroluminescent sont excellentes. Un composé de carbazole représenté par la formule (1-1) est utilisé comme matériau de transport d'électrons pour préparer un élément organique électroluminescent. (Dans la formule (1-1), R représente aryle ou hétéroaryle, Hy1 et Hy2 représentent chacun des hétéroaryles en C2-24 acceptant des électrons contenant de l'azote, et Ar1 et Ar2 représentent chacun des C6-24-arylènes.)
PCT/JP2011/062620 2010-06-02 2011-06-01 Composé de carbazole présentant un groupe substituant comprenant un hétéroaryle acceptant les électrons contenant de l'azote et élément organique électroluminescent WO2011152466A1 (fr)

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JP2009173642A (ja) * 2007-12-27 2009-08-06 Chisso Corp ピリジルフェニル基を有するアントラセン誘導体化合物及び有機電界発光素子
JP2010168363A (ja) * 2008-12-25 2010-08-05 Chisso Corp ピリジルナフチル基を有するアントラセン誘導体及び有機電界発光素子

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WO2014002871A1 (fr) * 2012-06-28 2014-01-03 Jnc株式会社 Matériau transporteur d'électrons et élément électroluminescent organique l'utilisant
CN104379572A (zh) * 2012-06-28 2015-02-25 捷恩智株式会社 电子输送材料及使用其的有机电场发光元件
JPWO2014002871A1 (ja) * 2012-06-28 2016-05-30 Jnc株式会社 電子輸送材料およびこれを用いた有機電界発光素子
CN104379572B (zh) * 2012-06-28 2016-09-21 捷恩智株式会社 苯并[a]咔唑化合物、电子输送材料及使用其的有机电场发光元件
JP2015051966A (ja) * 2013-08-07 2015-03-19 Jnc株式会社 電子輸送材料およびこれを用いた有機電界発光素子

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KR101864902B1 (ko) 2018-06-05
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