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  • 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
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/82—Carbazoles; Hydrogenated carbazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • 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
  • C07D401/02—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 two hetero rings
  • C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
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  • 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
  • C07D401/02—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 two hetero rings
  • C07D401/10—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 two hetero rings linked by a carbon chain containing aromatic rings
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  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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  • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
  • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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  • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
  • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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  • 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

Definitions

• the present invention relates to a novel electron transport material having a pyridyl group, an organic electroluminescence device using the electron transport material (hereinafter, sometimes abbreviated as an organic EL device or simply a device), and the like.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2003-123983 discloses that an organic EL device can be driven at a low voltage by using a 2,2′-bipyridyl compound, which is a phenanthroline derivative or an analog thereof, as an electron transport material. It is stated that it can be done.
• An object of the present invention is to provide an electron transport material that contributes to high luminous efficiency and long life of an organic EL element. Furthermore, this invention makes it a subject to provide the organic EL element using this electron transport material.
• a benzo [a] carbazole compound represented by the following formula (1) represented by the following formula (1).
• a, b, c, and d are independently 1 or 0, but a and b are not 0 at the same time;
• Py 1 and Py 2 are independently pyridyl or bipyridyl, and any hydrogen of the pyridyl or bipyridyl is alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or Optionally substituted with heteroaryl having 2 to 12 carbons;
• Ar 1 is hydrogen or aryl having 6 to 20 carbon atoms when a is 0;
• Ar 1 is arylene having 6 to 20 carbon atoms when a is 1;
• Ar 2 is hydrogen or carbon when b is 0
• Py 1 and Py 2 are independently groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) One selected from the group of Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
• Ar 1 and Ar 2 are independently phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups is replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl May be;
• A is phenyl, naphthyl or phenanthryl, and any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cycl
• Py 2 is selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) And Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
• Ar 1 is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrycenyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
• Ar 2 is phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t
• Py 1 is selected from the group of groups represented by the following formulas (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2-18) And Any hydrogen in these groups may be replaced by methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, or pyridyl;
• Ar 1 is phenylene, naphthalenediyl, anthracenediyl, or chrysenediyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, or naphthyl;
• Ar 2 is hydrogen, phenyl, naphthyl, anthryl, phenanthryl, or chrysenyl, and any hydrogen in these groups may be replaced with methyl, ethyl, isopropyl, t
• Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2- 2), (Py-2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11) And any one of the groups represented by (Py-2-12), wherein any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl Often; Ar 1 and Ar 2 are independently 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7 -Diyl, or anthracene-9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or
• Py 2 is represented by the formula (Py-1-1), (Py-1-2), (Py-l-3), (Py-2-1), (Py-2-2), (Py- 2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and (Py-2) -12) is one selected from the group of groups, and any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
• Ar 1 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl, and any hydrogen in these groups may be replaced by methyl, t-butyl, or phenyl;
• Ar 2 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-
• Py 1 is represented by the formula (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-1), (Py-2-2), (Py- 2-3), (Py-2-7), (Py-2-8), (Py-2-9), (Py-2-10), (Py-2-11), and (Py-2) -12) is one selected from the group of groups, and any hydrogen of these groups may be replaced by methyl, t-butyl, phenyl, naphthyl, or pyridyl;
• Ar 1 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-1,6-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene- 9,10-diyl, any hydrogen of these groups may be replaced by methyl, t-butyl, or phenyl;
• Ar 2 is
• Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2- 3) one selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
• Ar 1 and Ar 2 are independently 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9, 10-diyl;
• A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
• R 1 to R 8 are all hydrogen; and
• Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2- 3) one selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
• Ar 1 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
• Ar 2 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
• A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naph
• Py 1 and Py 2 are independently represented by the formulas (Py-1-1), (Py-1-2), (Py-1-3), (Py-2-2), (Py-2- 3) one selected from the group of groups represented by (Py-2-8), (Py-2-9), (Py-2-11), and (Py-2-12);
• Ar 1 is 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, or anthracene-9,10-diyl;
• Ar 2 is hydrogen, phenyl, 1-naphthyl, 2-naphthyl, or 9-phenanthryl;
• A is phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, 1-naphthyl, 2-naph
• a pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the item [22], disposed between the cathode and the light emitting layer.
• An organic electroluminescent device having an electron transport layer and / or an electron injection layer containing
• At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a bipyridine derivative, a phenanthroline derivative, and a borane derivative, [23]
• a quinolinol-based metal complex a bipyridine derivative, a phenanthroline derivative, and a borane 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, or alkaline earth. Containing at least one selected from the group consisting of 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 The organic electroluminescence device as described in the item [23].
• the compound of the present invention is stable even when a voltage is applied in a thin film state and has a feature of high charge transport capability.
• the compound of the present invention is suitable as a charge transport material in an organic EL device.
• an organic EL device having high luminous efficiency and a long lifetime can be obtained.
• a high-performance display device such as full-color display can be created.
• arbitrary used in the definition of a compound may mean “can be freely selected not only by position but also by number”.
• the expression “any hydrogen of phenyl may be substituted with alkyl having 1 to 6 carbon atoms” not only means “one hydrogen may be substituted with alkyl”, but also “ It may also mean “same alkyl, or each may be replaced by a different alkyl”.
• the symbols Me, Et, i-Pr, t-Bu, Cy, and Ph used in the structural formulas, chemical reaction formulas, and the like of this specification represent methyl, ethyl, isopropyl, tertiary butyl, cyclohexyl, and phenyl, respectively. .
• a first invention of the present application is a benzo [a] carbazole compound having pyridyl or bipyridyl represented by the following formula (1).
• a, b, c and d are independently 1 or 0, but a and b are not 0 at the same time.
• pyridyl or bipyridyl is linked to the 3rd and 9th positions of benzo [a] carbazole directly or via arylene.
• the LUMO level is lowered, and the injection of electrons from the cathode to the electron transport layer or the electron injection layer is likely to occur. It is thought to bring about effects such as lowering.
• a structure of the formula (1-1) in which pyridyl or bipyridyl is connected to both ends of the molecule is more preferable. Even if arylene is interposed between benzo [a] carbazole and pyridyl or bipyridyl, there is no significant characteristic variation, and c and d in the formula may be 0 or 1.
• a compound in which bipyridyl is directly linked to benzo [a] carbazole has limitations on the intermediate materials that can be used, and thus the production methods that can be selected are limited.
• the side to which bipyridyl is linked is preferably via arylene.
• pyridyl or bipyridyl is linked to the 9-position of benzo [a] carbazole directly or via arylene.
• pyridyl or bipyridyl is linked to the 3-position of benzo [a] carbazole directly or via arylene.
• a compound having pyridyl or bipyridyl linked to one end of these molecules is preferable next to the compound represented by the above formula (1-1) as a material used for the electron transport layer or the electron injection layer.
• the position of benzo [a] carbazole to which pyridyl and bipyridyl are linked may be the 3rd position or the 9th position.
• Py 1 and Py 2 are independently pyridyl or bipyridyl.
• pyridyl is 2-pyridyl, 3-pyridyl and 4-pyridyl represented by the following formulas (Py-1-1), (Py-1-2) and (Py-1-3).
• Bipyridyl is specifically a group represented by the following formulas (Py-2-1) to (Py-2-30).
• Any hydrogen of this pyridyl or bipyridyl may be replaced by alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 12 carbons .
• 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.
• alkyl having 1 to 6 carbon atoms examples 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, 2-ethylbutyl and the like. Among these, methyl, ethyl, isopropyl, and t-butyl are preferable, methyl and t-butyl are more preferable, and methyl is particularly preferable.
• Examples of the cycloalkyl having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Among these, cyclohexyl is preferable because of easy availability of raw materials and ease of production.
• aryl having 6 to 14 carbon atoms examples include phenyl, naphthyl, anthryl, phenanthryl and the like. Among these, phenyl and naphthyl are preferable, and phenyl is more preferable because of easy availability of raw materials and ease of production.
• heteroaryl having 2 to 12 carbon atoms include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.
• Py 1 and Py 2 may be the same or different groups, but are preferably the same in terms of ease of production of the compound. Whether Py 1 and Py 2 are the same or different, (Py-1-1) to (Py-1-3) and (Py-2-1) to (Py-2- 18) is preferably selected from the group of groups represented by (Py-1-1) to (Py-1-3), (Py-2-1) to (Py-2-3) and (Py It is more preferably selected from the group of groups represented by -2-7) to (Py-2-12).
• Py 1 or Py 2 is (Py-1-1) to (Py-1-3) and (Py-2-1).
• Py-1-1) to (Py-1-3) and (Py-2-1) are preferably selected from the group of groups represented by (Py-1-1) to (Py-1-3), (Py-2-1) to (Py--). It is more preferable that the group is selected from the group of groups represented by 2-3) and (Py-2-7) to (Py-2-12).
• Ar 1 is hydrogen or aryl having 6 to 20 carbon atoms, preferably aryl having 6 to 20 carbon atoms
• Ar 2 is arylene having 6 to 20 carbon atoms. is there.
• Ar 1 is arylene having 6 to 20 carbon atoms
• Ar 2 is hydrogen or aryl having 6 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms preferable.
• aryl having 6 to 20 carbon atoms examples include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrycenyl, naphthacenyl, perylenyl and the like.
• phenyl, naphthyl, anthryl, and phenanthryl are preferable, and phenyl, naphthyl, and anthryl are more preferable.
• Examples of the arylene having 6 to 20 carbon atoms include phenylene, naphthalenediyl, anthracenediyl, phenanthrene diyl, pyrenediyl, chrysenediyl, naphthacene diyl, perylene diyl and the like.
• phenylene, naphthalenediyl, anthracenediyl and chrysenediyl are preferable, and phenylene, naphthalenediyl and anthracenediyl are more preferable.
• Any hydrogen in the above aryl or arylene may be replaced with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, or aryl having 6 to 14 carbon atoms.
• substituents include those exemplified as the above-mentioned pyridyl or bipyridyl substituents, and methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl, naphthyl, anthryl and phenanthryl are preferred, and methyl, ethyl , Isopropyl, t-butyl, cyclohexyl, phenyl, and naphthyl are more preferable, and methyl, t-butyl, and phenyl are more preferable.
• 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.
• Ar 1 and Ar 2 are aryl, including aryl having a substituent, phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5 ′ -Iyl and 9-phenanthryl are preferred, with phenyl, 1-naphthyl, 2-naphthyl, 3-biphenylyl, and m-terphenyl-5'-yl being more preferred.
• Ar 1 and Ar 2 are arylene, 1,4-phenylene, 1,3-phenylene, 1,4-naphthalenediyl, 2,7-naphthalenediyl, and 9,10-anthracenediyl are preferred, 4-phenylene, 1,4-naphthalenediyl and 9,10-anthracenediyl are more preferred.
• A is aryl having 6 to 20 carbon atoms, and any hydrogen of the aryl is alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or aryl having 6 to 14 carbon atoms. It may be replaced.
• Examples of the aryl having 6 to 20 carbon atoms include the groups exemplified for Ar 1 and Ar 2 above.
• Examples of the substituents of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, and aryl having 6 to 14 carbon atoms include the groups exemplified as the substituents for the above-mentioned pyridyl or bipyridyl.
• A is preferably phenyl, 1-naphthyl, 2-naphthyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, m-terphenyl-5′-yl, and 9-phenanthryl, including aryl having a substituent. More preferred are phenyl, 1-naphthyl, 2-naphthyl, 3-biphenylyl, and 4-biphenylyl.
• R 1 to R 8 are independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, aryl having 6 to 14 carbons, or heteroaryl having 2 to 10 carbons.
• Aryl, and any hydrogen of the aryl or heteroaryl may be replaced by alkyl having 1 to 6 carbons or cycloalkyl having 3 to 6 carbons.
• Examples of the alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 14 carbon atoms, and heteroaryl having 2 to 10 carbon atoms include the groups exemplified as the substituents for the above-mentioned pyridyl or bipyridyl. .
• R 1 to R 8 are preferably hydrogen, methyl, ethyl, isopropyl, t-butyl, cyclohexyl and phenyl, more preferably hydrogen, methyl, t-butyl, cyclohexyl and phenyl, and even more preferably all hydrogen.
• Specific examples of the compound represented by the formula (1-1) in the embodiment of the present invention include the following compounds (1-1-1) to (1-1-861) and (1-1-871) to ( 1-1-1019).
• preferred compounds are (1-1-1) to (1-1-56), (1-1-65) to (1-1-67), (1-1-71) to (1-1 -76), (1-1-86) to (1-1-88), (1-1-92) to (1-1-97), (1-1-102) to (1-1-104) ), (1-1-108) to (1-1-113), (1-1-118), (1-1-119), (1-1-123) to (1-1-133), (1-1-137) to (1-1-141), (1-1-145) to (1-1-150), (1-1-154) to (1-1-159), (1 -1-163) to (1-1-177), (1-1-181) to (1-1-183), (1-1-205), (1-1-206), (1-1 -208) to (1-1-213), (1-1-215) to (1 1-220), (1-1-222) to (1-1-227), (1-1-230) to (1
• Specific examples of the compound represented by the formula (1-2) in the embodiment of the present invention include the following compounds (1-2-1) to (1-2-365) and (1-2-381) to ( 1-2-656). Of these, preferred compounds are (1-2-1) to (1-2-146), (1-2-149), (1-2-150), (1-2-153) to (1-2).
• Specific examples of the compound represented by the formula (1-3) in the embodiment of the present invention include the following compounds (1-3-1) to (1-3-352) and (1-3-361) to ( 1-3-654).
• preferred compounds are (1-3-1) to (1-3-132), (1-136) to (1-3-141), (1-3-144) to (1-3 -161), (1-3-165) to (1-3-170), (1-3-173), (1-3-174), (1-3-177) to (1-3-179) ), (1-3-183) to (1-3-189), (1-3-193) to (1-3-198), (1-3-201), (1-3-202), (1-3-205) to (1-3-207), (1-3-211) to (1-3-214), (1-3-225) to (1-3-352), and ( 1-3-479) to (1-3-620).
• the compound represented by Formula (1) can be manufactured using a known synthesis method. For example, it can be synthesized by following the routes shown in the following reactions 1 to 8. It can also be synthesized by following the routes shown in the following reactions 9 to 17.
• reaction 2 the nitro group of compound (a-1) is reductively cyclized with triphenylphosphine: PPh 3 or triethoxyphosphine: P (OEt) 3 to synthesize compound (a-2).
• Reaction 3 using a palladium catalyst or a copper catalyst, compound (a-2) is reacted with bromide or iodide of A in the presence of a base and a reaction accelerator to synthesize compound (a-3).
• a in the formula is the same as described above including the following.
• compound (a-5) is synthesized by reacting compound (a-4) with trifluoromethanesulfonic anhydride in the presence of a base.
• compound (a-6) is synthesized by reacting compound (a-5) with bis (pinacolato) diboron in the presence of a base using a palladium catalyst.
• Reaction 7 is the final step.
• Compound (a-6) obtained in Reaction 6 is subjected to Suzuki coupling reaction with 2 moles of pyridyl, bipyridyl halide or pyridylaryl (A 0 ) halide or triflate, and the compound represented by Formula (1) Is synthesized.
• the compound (a-5) obtained in Reaction 5 was added to a boronic acid of 2-fold moles of pyridyl, bipyridyl or pyridylaryl (A 0 ) in the presence of a base using a palladium catalyst or A boronic ester can also be subjected to a Suzuki coupling reaction to synthesize a compound represented by the formula (1).
• a 0 is 2-pyridyl or bipyridyl
• the reaction 7 is preferred in view of the stability of the reaction intermediate.
• compound (b-3) is synthesized by reacting compound (b-2) with a bromide or iodide of A in the presence of a base and a reaction accelerator using a palladium catalyst or a copper catalyst.
• a in the formula is the same as described above including the following.
• compound (b-3) is reacted with boronic acid or boronic acid ester of pyridylaryl or aryl (A 02 ) in the presence of a base to synthesize compound (b-4). To do.
• This reaction can be used even when A 02 is pyridyl or bipyridyl.
• Y of compound (b-3) is lithiated or used as a Grignard reagent, and then a boronic ester is used according to a conventional method.
• compound (b-7) is synthesized by reacting compound (b-6) with bis (pinacolato) diboron in the presence of a base using a palladium catalyst.
• Reaction 16 is the final step.
• the compound (b-7) obtained in Reaction 15 is subjected to Suzuki coupling reaction with a pyridyl, bipyridyl, pyridylaryl, or aryl (A 01 ) halide or triflate to synthesize a compound represented by Formula (1). .
• the compound (b-6) obtained in the reaction 14 was subjected to a Suzuki coupling reaction with a boronic acid or boronic acid ester of pyridylaryl or aryl (A 01 ) in the presence of a base using a palladium catalyst to obtain a compound of the formula
• the compound represented by (1) can also be synthesized. This reaction can be used even when A 01 is pyridyl or bipyridyl, but reaction 16 is preferred in view of the stability of the reaction intermediate.
• a method for synthesizing a compound in which Ar 1 in formula (1-2) is hydrogen will be described.
• naphthalen-2-ylboronic acid in which the 6-position of the naphthalene ring is hydrogen is used. do it.
• synthesizing via the route of reactions 9 to 17 in place of (6-methoxynaphthalen-2-yl) boronic acid used in reaction 9, naphthalen-2-ylboronic acid in which the 6-position of the naphthalene ring is hydrogen is used. do it.
• a method for synthesizing a compound of formula (1-3) in which Ar 2 is hydrogen will be described.
• a compound in which the 4-position of the benzene ring is hydrogen may be used.
• a halide or triflate in which Y of nitrobenzene, which is the starting material of reaction 9 is hydrogen may be used.
• the compound represented by the formula (1) can be synthesized by a route other than the above route.
• 2-nitrohalobenzene or triflate previously substituted at the 4-position with pyridyl, bipyridyl, pyridylaryl, aryl (A 02 ), etc., and the 6-position previously substituted with pyridyl, bipyridyl, pyridylaryl, aryl (A 01 ), etc.
• Naphthalen-2-ylboronic acid is synthesized, respectively, and subjected to Suzuki coupling reaction according to a conventional method.
• the nitro group is reductively cyclized using PPh 3 or P (OEt) 3 to obtain an 11H-benzo [a] carbazole derivative.
• 11H-benzo [a] carbazole derivative with bromide or iodide of A using a palladium catalyst or a copper catalyst in the presence of a base and a reaction accelerator, the formula (1) of the present invention Can be synthesized.
• This reaction route is suitable for synthesizing a compound in which the 3-position and 9-position groups of benzo [c] carbazole are different, but can also be applied to a compound in which the 3-position and 9-position groups are the same. In either case, when a compound in which pyridyl or bipyridyl is linked to the 9-position of benzo [c] carbazole is synthesized, it is preferable to go through this reaction route.
• the palladium catalyst used in the above-described Suzuki coupling reaction is tetrakis (triphenylphosphine) palladium (0): Pd (PPh 3 ) 4 , bis ( Triphenylphosphine) dichloropalladium (II): PdCl 2 (PPh 3 ) 2 , palladium acetate (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 (P ( t-Bu) 3) 2 or [1,
• a phosphine compound may be added to these palladium compounds in some cases.
• the phosphine compound include tri (t-butyl) phosphine: t-Bu 3 P, tricyclohexylphosphine: PCy 3 , 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-butylphosphino) ferrocene, 2,2'-bis (di-t-butylphosphino) -1,1'-binaphthyl, 2-methoxy-2 '-(di-(di-)
• bases used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphorus
• bases used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphorus
• Examples include tripotassium acid: K 3 PO 4 , and potassium fluoride.
• Solvents used in the reaction include benzene, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, ethanol, Examples thereof include isopropyl alcohol and cyclopentyl methyl ether. These solvents may be used alone or as a mixed solvent.
• the reaction is usually carried out in the temperature range of 50 to 180 ° C, more preferably 70 to 130 ° C.
• reaction solvent used in Reaction 2 and Reaction 10 examples include toluene, xylene, chlorobenzene, o-dichlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, and 1-methyl-2-pyrrolidone.
• a solvent may be used independently and may be used as a mixed solvent.
• the reaction temperature is usually in the range of 100 ° C to 220 ° C. More preferably, it is 130 to 190 ° C.
• a copper catalyst When a copper catalyst is used in Reaction 3 and Reaction 11, copper powder, copper oxide, copper halide, or the like is used.
• the base used at the same time is potassium carbonate, sodium carbonate, sodium bicarbonate, sodium hydride and the like, and the reaction accelerator is crown ether (for example, 18-crown-6-ether), polyethylene glycol (PEG), polyethylene glycol dialkyl. And ether (PEGDM).
• the reaction solvent N, N-dimethylformamide, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like are used.
• the reaction temperature is 160 to 250 ° C. However, when the reactivity of the substrate is low, a higher temperature reaction may be performed using an autoclave or the like.
• the bases used at the same time are lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydride, alkoxy potassium (for example, methoxy potassium, ethoxy potassium, normal propoxy potassium, isopropoxy potassium, n- Butoxy potassium, etc.), and alkoxy sodium (eg, methoxy sodium, ethoxy sodium, normal propoxy sodium, isopropoxy sodium, n-butoxy sodium, and t-butoxy sodium).
• alkoxy potassium for example, methoxy potassium, ethoxy potassium, normal propoxy potassium, isopropoxy potassium, n- Butoxy potassium, etc.
• alkoxy sodium eg, methoxy sodium, ethoxy sodium, normal propoxy sodium, isopropoxy sodium, n-butoxy sodium, and t-butoxy sodium.
• the reaction accelerator is 2,2 ′-(diphenylphosphino) -1,1′-binaphthyl, 1,1 ′-(diphenylphosphino) ferrocene, dicyclohexylphosphinobiphenyl, di-t-butylphosphinobiphenyl, tri ( t-butyl) phosphine: t-Bu 3 P, 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-butylphosphino) ferrocene, 1,1'-bis (di-t-butylphosphin
• reaction solvent an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or mesitylene is used.
• a solvent may be used independently and may be used as a mixed solvent.
• the reaction temperature is usually 50 to 200 ° C., more preferably 80 to 140 ° C.
• reaction solvent used in Reaction 4 and Reaction 13 examples include 1-methyl-2-pyrrolidone, N, N-dimethylacetamide, nitrobenzene, dimethyl sulfoxide, dichlorobenzene, quinoline and the like.
• a solvent may be used independently and may be used as a mixed solvent. In some cases, the reaction may be performed without a solvent.
• the reaction is usually carried out in a temperature range of 150 to 220 ° C, more preferably 180 to 200 ° C.
• Examples of the solvent used in Reaction 5 and Reaction 14 include pyridine, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, CH 2 Cl 2 , CHCl 3 , and CH 3 CN. These solvents may be used alone or as a mixed solvent.
• the reaction is usually carried out in the temperature range of ⁇ 10 to 50 ° C., more preferably 0 to 30 ° C.
• the phosphine compound includes tri (t-butyl) phosphine: t-Bu 3 P, tricyclohexylphosphine: PCy 3 , 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-butylphosphino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino)
• the bases used in Reaction 6 and Reaction 15 are sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, potassium acetate. : KOAc, tripotassium phosphate: K 3 PO 4 , potassium fluoride and the like.
• Solvents used in Reaction 6 and Reaction 15 are benzene, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4-dioxane, methanol, Ethanol, isopropyl alcohol, cyclopentyl methyl ether and the like. These solvents may be used alone or as a mixed solvent.
• the reaction temperature is usually 50 to 180 ° C, more preferably 70 to 130 ° C.
• the Suzuki coupling reaction is used in the step of bonding rings such as aryl and heteroaryl, but Negishi coupling reaction can be used depending on the types of available raw materials and reagents.
• the compound of the present invention When the compound of the present invention is used for an electron injection layer or an electron transport layer in an organic EL device, it is stable when an electric field is applied. These represent that the compound of the present invention is excellent as an electron injecting material or an electron transporting material for an electroluminescent device.
• the electron injection layer mentioned here is a layer for receiving electrons from the cathode to the organic layer
• the electron transport layer is a layer for transporting the injected electrons to the light emitting layer.
• the electron transport layer can also serve as the electron injection layer.
• the material used for each layer is referred to as an electron injection material and an electron transport material.
• 2nd invention of this application is an organic EL element containing the compound represented by Formula (1) of this invention in an electron injection layer or an electron carrying layer.
• the organic EL element of the present invention has a low driving voltage and high durability during driving.
• the structure of the organic EL device of the present invention has various modes, it is basically a multilayer structure in which at least a hole transport layer, a light emitting layer, and an electron transport layer are sandwiched between an anode and a cathode.
• Examples of the specific configuration of the device are (1) anode / hole transport layer / light emitting layer / electron transport layer / cathode, (2) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer. / Cathode, (3) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, etc.
• the compound of the present invention Since the compound of the present invention has high electron injecting property and electron transporting property, it can be used for an electron injecting layer or an electron transporting layer alone or in combination with other materials.
• the organic EL device of the present invention emits blue, green, red and white light by combining a hole injection layer, a hole transport layer, a light emitting layer, etc. using other materials with the electron transport material of the present invention. It can also be obtained.
• the light-emitting material or light-emitting dopant that can be used in the organic EL device of the present invention is daylight fluorescence as described in the Polymer Society of Japan, Polymer Functional Materials Series “Optical Functional Materials”, Joint Publication (1991), P236. Materials, fluorescent brighteners, laser dyes, organic scintillators, various fluorescent analysis reagents and other luminescent materials, supervised by Koji Koji, “Organic EL materials and displays” published by CMMC (2001) P155-156 And a light emitting material of a triplet material as described in P170 to 172.
• the compounds that can be used as the light emitting material or the light emitting dopant are polycyclic aromatic compounds, heteroaromatic compounds, organometallic complexes, dyes, polymer light emitting materials, styryl derivatives, aromatic amine derivatives, coumarin derivatives, borane derivatives, oxazines. Derivatives, compounds having a spiro ring, oxadiazole derivatives, fluorene derivatives and the like.
• Examples of the polycyclic aromatic compound are anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, rubrene derivatives, and the like.
• heteroaromatic compounds are oxadiazole derivatives having a dialkylamino group or diarylamino group, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, silole derivatives, thiophene derivatives having a triphenylamino group, quinacridone derivatives Etc.
• organometallic complexes examples include zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold, etc., quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, A complex with a benzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, or the like.
• dyes are xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyril derivatives, perylene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazoles And pigments such as derivatives.
• the polymer light-emitting material are polyparaphenyl vinylene derivatives, polythiophene derivatives, polyvinyl carbazole derivatives, polysilane derivatives, polyfluorene derivatives, polyparaphenylene derivatives, and the like.
• styryl derivatives are amine-containing styryl derivatives, styrylarylene derivatives, and the like.
• electron transport materials used in the organic EL device of the present invention are arbitrarily selected from compounds that can be used as electron transport compounds in photoconductive materials and compounds that can be used in the electron transport layer and electron injection layer of organic EL devices. Can be used.
• electron transport materials include quinolinol metal complexes, 2,2′-bipyridyl derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, oxine derivatives.
• a compound conventionally used as a charge transport material for holes or a hole injection of an organic EL device is used in a photoconductive material.
• Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof are carbazole derivatives, triarylamine derivatives, phthalocyanine derivatives and the like.
• Each layer constituting the organic EL element of the present invention can be formed by forming a material to constitute each layer into a thin film by a method such as a vapor deposition method, a spin coating method, or a casting method.
• 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.
• a vapor deposition method as a method of thinning the light emitting material from the standpoint that a homogeneous film can be easily obtained and pinholes are hardly generated.
• the vapor deposition conditions differ depending on the type of the light emitting material of the present invention.
• 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 5 nm to 5 ⁇ m. It is preferable to set appropriately within the range.
• the organic EL device of the present invention is preferably supported by a substrate in any of the structures described above.
• the substrate only needs to have mechanical strength, thermal stability, and transparency, and glass, a transparent plastic film, and the like can be used.
• the anode material metals, alloys, electrically conductive compounds and mixtures thereof having a work function larger than 4 eV can be used. Specific examples thereof include metals such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO 2 , ZnO, and the like.
• Cathode materials can use metals, alloys, electrically conductive compounds, and mixtures thereof with work functions of less than 4 eV. Specific examples thereof are aluminum, calcium, magnesium, lithium, magnesium alloy, aluminum alloy and the like. Specific examples of the alloy include aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, and magnesium / indium. In order to efficiently extract light emitted from the organic EL element, it is desirable that at least one of the electrodes has a light transmittance of 10% or more.
• the sheet resistance as the electrode is preferably several hundred ⁇ / ⁇ or less.
• the film thickness depends on the properties of the electrode material, it is usually set in the range of 10 nm to 1 ⁇ m, preferably 10 to 400 nm.
• Such an electrode can be produced by forming a thin film by a method such as vapor deposition or sputtering using the electrode material described above.
• the organic material comprising the above-mentioned anode / hole injection layer / hole transport layer / light emitting layer / electron transport material of the present invention / cathode
• a method for creating an EL element will be described.
• a thin film of an anode material is formed on a suitable substrate by vapor deposition 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 light emitting layer thin film is formed thereon.
• the electron transport material of this invention is vacuum-deposited, a thin film is formed, and it is set as an electron carrying layer.
• the target organic EL element is obtained by forming the thin film which consists of a substance for cathodes by a vapor deposition method, and making it a cathode.
• the production order can be reversed, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order.
• the anode When a DC voltage is applied to the organic EL 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, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode and both). The organic EL element also emits light when an alternating voltage is applied.
• the alternating current waveform to be applied may be arbitrary.
• reaction solution was cooled and 150 ml of pure water was added.
• the reaction mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, the desiccant was removed, the solvent was distilled off under reduced pressure, and the resulting crude product was purified with a silica gel short column (solvent: toluene). did. Further, reprecipitation was performed with heptane, and intermediate compound (a-6a): 11-phenyl-3,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2- Yl) -11H-benzo [a] carbazole (12 g, yield: 87%) was obtained.
• the product is recrystallized from toluene and further purified by sublimation to obtain the target compound (1-2-8): 3-([naphthalen-2-yl) -11-phenyl-9- (pyridin-3-yl). ) -11H-benzo [a] carbazole 0.8 g (yield: 38%) was obtained.
• the structure of the compound (1-2-8) was confirmed by MS spectrum and NMR measurement.
• the target compound (1-3-300) 9-([1,1′-biphenyl] -3-yl) -11-phenyl-3- (3- (pyridin-3-yl) phenyl) -11H -1.29 g (yield: 64%) of benzo [a] carbazole was obtained.
• the structure of the compound (1-3-300) was confirmed by MS spectrum and NMR measurement.
• 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. Using a voltage / current generator R6144 manufactured by Advantest, a current was applied so that the luminance of the device was 1000 cd / m 2 , and the device was caused to emit light. Using a spectral radiance meter SR-3AR 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 configuration of each layer in the manufactured organic EL elements according to Examples 1 to 3 and Comparative Examples 1 to 3.
• 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
• HT is N 4 , N 4 , N 4 ′ , N 4 ′ -tetra [1,1′-biphenyl] -4-yl)-[1,1′-biphenyl] -4,4 '-Diamine
• BH1 is 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene
• BH2 is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene
• BD1 4,4 ′-((7,7-diphenyl-7H-benzo [c] fluorene-5,9-diyl) bis (phenylazanezyl
• Example 1 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-66) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) was used as a transparent support substrate.
• This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and a molybdenum vapor vessel containing BH1.
• Vapor deposition boat molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing compound (1-1-66) of the present invention, molybdenum vapor deposition boat containing quinolinol lithium (Liq), and aluminum A tungsten vapor deposition boat was 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 HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then HT entered. 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 BH1 and the vapor deposition boat containing BD1 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 BH1 to BD1 was approximately 95: 5.
• an evaporation boat containing the compound (1-1-66) and an evaporation boat containing Liq were simultaneously heated to evaporate to a thickness of 20 nm to form an electron transport layer.
• the deposition rate was adjusted so that the weight ratio of the compound (1-1-66) and Liq was approximately 1: 1.
• 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 vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.
• the characteristics at 1000 cd / m 2 emission were measured. It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 77% (1540 cd / m 2 ) or more of the initial value was 321 hours.
• Example 1 An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-66) in the electron transport layer was changed to the compound (ET1). Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 5.5 V and the external quantum efficiency was 3.2% (blue emission with a wavelength of about 451 nm). there were.
• the time for maintaining the luminance of 77% (1540 cd / m 2 ) or more of the initial value was 63 hours.
• Example 2 The compound (BH1), which is the host material of the device light emitting layer using the compound (1-1-758) for the electron transport layer, is replaced with the compound (BH2), and the compound (BD1) which is the dopant material of the light emitting layer ) Was replaced with compound (BD2), and compound (1-1-66), which was an electron transport material for the electron transport layer, was replaced with compound (1-1-758).
• An organic EL device was obtained. Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 5.8 V and the external quantum efficiency was 5.1% (blue emission with a wavelength of about 455 nm). there were.
• the time for maintaining the luminance of 77% (1540 cd / m 2 ) or more of the initial value was 170 hours.
• Example 3 Device using compound (1-1-66) as an electron transport layer
• the same transparent support substrate as used in Example 1 was used as a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.).
• Molybdenum deposition boat with HI and fixed, molybdenum deposition boat with HT, molybdenum deposition boat with BH1, molybdenum deposition boat with BD1, compound of the present invention (1- A molybdenum vapor deposition boat containing 1-66), a molybdenum vapor deposition boat containing Liq, and a tungsten vapor deposition boat containing aluminum were mounted.
• 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 to deposit to a film thickness of 40 nm to form a hole injection layer, and then HT entered.
• the vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer.
• the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 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 BH1 to BD1 was approximately 95: 5.
• the vapor deposition boat containing the compound (1-1-66) was heated and vapor-deposited to a film 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 vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 3.7 V and the external quantum efficiency was 4.5% (blue emission with a wavelength of about 451 nm). It was.
• the time for maintaining the luminance of 77% (1540 cd / m 2 ) or more of the initial value was 345 hours.
• Example 2 An organic EL device was obtained in the same manner as in Example 3, except that the compound (1-1-66), which was the electron transport material for the electron transport layer, was changed to the compound (ET1). Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. there were. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 77% (1540 cd / m 2 ) or more of the initial value was 0.5 hours. It was.
• Example 3 An organic EL device was obtained in the same manner as in Example 3 except that the compound (1-1-66), which was the electron transport material for the electron transport layer, was changed to the compound (ET2). Using the ITO electrode as the anode and the quinolinol lithium / aluminum electrode as the cathode, measuring the characteristics at 1000 cd / m 2 emission, the drive voltage is 5.4 V, the external quantum efficiency is 2.2% (blue emission with a wavelength of about 453 nm) there were.
• the time for maintaining the luminance of 77% (1540 cd / m 2 ) or more of the initial value was 22 hours.
• Table 3 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 4 to 8 and Comparative Examples 4 to 7.
• HI2 is 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile
• E3 is 5,9-di ( [2,3′-bipyridin] -6-yl) -7-phenyl-7H-benzo [c] carbazole
• E4 is 3- (6- (10-phenylanthracen-9-yl) naphthalen-2-yl ) Pyridine
• E5 is 2-([1,1′-biphenyl] -3-yl) -7-([2,3′-bipyridin] -6-yl) -9-phenyl-9H-carbazole
• “ET6” is 9-phenyl-2,7-bis (4- (pyridin-4-yl) naphthalen-1-yl) -9H-carbazole.
• the chemical structure is shown below.
• Example 4 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-66) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the vapor deposition boat containing the compound (1-1-66) and the vapor deposition boat containing Liq were heated at the same time so as to have a film thickness of 30 nm to form an electron transport layer.
• the deposition rate was adjusted so that the weight ratio of the compound (1-1-66) and Liq was approximately 1: 1.
• 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 vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 3.8 V and the external quantum efficiency was 5.1% (blue emission with a wavelength of about 454 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 396 hours.
• Example 4 An organic EL device was obtained in the same manner as in Example 4 except that the compound (1-1-66) in the electron transport layer was changed to the compound (ET3). Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 4.0 V and the external quantum efficiency was 4.6% (blue emission with a wavelength of about 458 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 279 hours.
• Example 5 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-2-125) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the vapor deposition boat containing the compound (1-2-125) and the vapor deposition boat containing Liq were heated at the same time to be vapor-deposited to a film thickness of 30 nm to form an electron transport layer.
• the deposition rate was adjusted so that the weight ratio of the compound (1-2-125) and Liq was approximately 1: 1.
• 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 vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and an organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 3.8 V and the external quantum efficiency was 6.0% (blue emission with a wavelength of about 458 nm). Met.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 220 hours.
• Example 5 An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-2-125) in the electron transport layer was changed to the compound (ET4). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, measuring the characteristics at 1000 cd / m 2 emission, the drive voltage is 3.5 V, the external quantum efficiency is 5.5% (blue emission with a wavelength of about 454 nm) Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 170 hours.
• Example 6 Example 5 except that the compound (1-2-125) in the device electron transport layer was changed to the compound (1-3-206) using the compound (1-3-206) in the electron transport layer.
• An organic EL device was obtained by a method according to the above. Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 5.3% (blue emission with a wavelength of about 455 nm). Met.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 307 hours.
• Example 6 An organic EL device was obtained by the method according to Example 5 except that the compound (1-2-125) in the electron transport layer was changed to the compound (ET5). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 3.9 V and the external quantum efficiency was 4.4% (blue emission with a wavelength of about 456 nm). Met. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 201 hours.
• Example 7 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-893) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the evaporation boat containing the compound (1-1-893) was heated and evaporated to a thickness of 30 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 vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and an organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.
• the drive voltage is 3.3 V
• the external quantum efficiency is 3.6% (blue emission with a wavelength of about 456 nm) Met.
• the time for maintaining the luminance of 90% (1800 cd / m 2 ) or more of the initial value was 56 hours.
• An organic EL device was obtained by a method according to the above. Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 4.2 V and the external quantum efficiency was 4.8% (blue emission with a wavelength of about 456 nm). Met.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 80 hours.
• Example 7 An organic EL device was obtained in the same manner as in Example 7 except that the compound (1-1-893) in the electron transport layer was changed to the compound (ET6). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 5.6 V and the external quantum efficiency was 4.8% (blue emission with a wavelength of about 455 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 35 hours.
• Table 5 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 9 and 10 and Comparative Examples 8 and 9.
• E7 is 2-phenyl-9,10-di ([2,2′-bipyridin] -5-yl) anthracene
• E8 is 7-phenyl-5,9-bis (3- ( Pyridin-4-yl) phenyl) -7H-benzo [c] carbazole
• E9 is 9- (4 ′-(dimesitylboryl)-[1,1′-binaphthalene] -4-yl) -9H-carbazole
• “ET10” is 4,4 ′-((2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine.
• the chemical structure is shown below.
• Example 9 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm by element sputtering using the compound (1-1-765) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• LiF lithium fluoride
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the vapor deposition boat containing the compound (1-1-765) is heated and vapor-deposited to a film thickness of 20 nm to form the first electron transport layer, and further the vapor deposition boat containing ET7 was heated to a thickness of 10 nm to form a second electron transport layer.
• the deposition rate of each layer was 0.01 to 1 nm / second.
• the evaporation boat containing LiF 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 vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 3.8 V and the external quantum efficiency was 5.3% (blue emission with a wavelength of about 456 nm). It was.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 107 hours.
• Example 8 An organic EL device was obtained in the same manner as in Example 9 except that the compound (1-1-765) in the electron transport layer was changed to the compound (ET8). Using the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 5.3 V and the external quantum efficiency was 4.3% (blue emission with a wavelength of about 455 nm). It was. In addition, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 48 hours.
• Example 10 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-1-973) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• Vapor deposition boat molybdenum vapor deposition boat containing BH2, molybdenum vapor deposition boat containing BD2, molybdenum vapor deposition boat containing ET9, molybdenum product containing the compound of the present invention (1-1973)
• a vapor deposition boat, a molybdenum vapor deposition boat containing lithium fluoride (LiF), and a tungsten vapor deposition boat containing aluminum were mounted.
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the vapor deposition boat containing the compound (ET9) was heated and vapor-deposited to a film thickness of 20 nm to form the first electron transport layer, and the compound (1-1-973) was further contained.
• a vapor deposition boat was heated and vapor-deposited to a film thickness of 10 nm to form a second electron transport layer.
• the deposition rate of each layer was 0.01 to 1 nm / second.
• the evaporation boat containing LiF 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 vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 4.3 V and the external quantum efficiency was 5.9% (blue emission with a wavelength of about 457 nm). It was.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 338 hours.
• Example 9 An organic EL device was obtained by a method according to Example 10 except that the compound (1-1 to 973) in the electron transport layer was changed to the compound (ET10). Using the ITO electrode as the anode and the LiF / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 4.3 V and the external quantum efficiency was 5.4% (blue emission with a wavelength of about 455 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 200 hours.
• Table 7 below shows the material structure of each layer in the organic EL elements according to Examples 11 to 15 thus manufactured.
• Example 11 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-1-765) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the vapor deposition boat containing the compound (1-1-765) and the vapor deposition boat containing Liq were heated at the same time to form a 20 nm-thick film, thereby forming an electron transport layer.
• the deposition rate was adjusted so that the weight ratio of the compound (1-1-765) and Liq was approximately 1: 1.
• 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 vapor deposition boat containing aluminum was heated, and aluminum was deposited at a deposition rate of 0.01 to 2 nm / second so as to have a film thickness of 100 nm to form a cathode, thereby obtaining an organic EL device.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 3.7 V and the external quantum efficiency was 7.4% (blue emission with a wavelength of about 456 nm). It was. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 243 hours.
• Example 12 An organic EL device was obtained in the same manner as in Example 11 except that the compound (1-1-765) in the electron transport layer was changed to the compound (1-2-125). Using the ITO electrode as the anode and the Liq / aluminum electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 4.3 V and the external quantum efficiency was 6.2% (blue emission with a wavelength of about 456 nm). It was.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 223 hours.
• Example 13 A glass substrate (26 mm x 28 mm x 0.7 mm) obtained by polishing ITO having a thickness of 180 nm formed by element sputtering using the compound (1-1-2) as an electron transport layer to 150 nm (( Opt Science Co., Ltd.) 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.), a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT.
• the vacuum chamber is depressurized to 5 ⁇ 10 ⁇ 4 Pa, and first, a vapor deposition boat containing HI is heated and vapor-deposited to a film thickness of 40 nm to form a first hole injection layer. Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH2 and the vapor deposition boat containing BD2 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm.
• the deposition rate was adjusted so that the weight ratio of BH2 to BD2 was approximately 95: 5.
• the vapor deposition boat containing the compound (1-1-2) and the vapor deposition boat containing Liq were heated at the same time so as to have a film thickness of 20 nm, thereby forming an electron transport layer.
• the deposition rate was adjusted so that the weight ratio of compound (1-1-2) to Liq was approximately 1: 1.
• 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 vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and an organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.
• the characteristics at 1000 cd / m 2 emission were measured.
• the drive voltage was 3.9 V and the external quantum efficiency was 6.2% (blue emission with a wavelength of about 458 nm). Met.
• the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 150 hours.
• Example 14 An organic EL device was obtained in the same manner as in Example 13 except that the compound (1-1-2) in the electron transport layer was changed to the compound (1-1-765). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 3.5 V and the external quantum efficiency was 6.7% (blue emission with a wavelength of about 457 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 210 hours.
• Example 15 An organic EL device was obtained by a method according to Example 13 except that the compound (1-1-2) in the electron transport layer was changed to the compound (1-1-973). Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m 2 emission were measured. The drive voltage was 3.8 V and the external quantum efficiency was 6.7% (blue emission with a wavelength of about 455 nm). Met. Further, as a result of conducting a constant current driving test with a current density for obtaining an initial luminance of 2000 cd / m 2 , the time for maintaining the luminance of 80% (1600 cd / m 2 ) or more of the initial value was 170 hours.
• an organic electroluminescent element having excellent luminous efficiency and element lifetime, a display device including the same, a lighting device including the display device, and the like.

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