WO2021131766A1 - 有機電界発光素子 - Google Patents

有機電界発光素子 Download PDF

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WO2021131766A1
WO2021131766A1 PCT/JP2020/046173 JP2020046173W WO2021131766A1 WO 2021131766 A1 WO2021131766 A1 WO 2021131766A1 JP 2020046173 W JP2020046173 W JP 2020046173W WO 2021131766 A1 WO2021131766 A1 WO 2021131766A1
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carbon atoms
substituted
group
unsubstituted
hydrocarbon group
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French (fr)
Japanese (ja)
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匡志 多田
棟智 井上
智 浮海
絢香 寺田
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority to KR1020227017006A priority Critical patent/KR102781807B1/ko
Priority to CN202080086843.1A priority patent/CN114830366B/zh
Priority to JP2021567219A priority patent/JP7554209B2/ja
Priority to EP20907187.7A priority patent/EP4083033B1/en
Priority to US17/775,465 priority patent/US20230023388A1/en
Publication of WO2021131766A1 publication Critical patent/WO2021131766A1/ja
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    • 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
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • H10K2101/20—Delayed fluorescence emission
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    • H10K2101/90—Multiple hosts in the emissive layer

Definitions

  • the present invention relates to an organic electroluminescent device (referred to as an organic EL device).
  • the phosphorescent organic EL element that uses light emission by triplet excitons can increase the internal quantum efficiency to 100% when intersystem crossing is efficiently performed from the singlet excitons. Has been done. However, extending the life of a blue phosphorescent organic EL device has become a technical issue.
  • Patent Document 1 discloses an organic EL device using a TTF (Triplet-Triplet Fusion) mechanism, which is one of the delayed fluorescence mechanisms.
  • TTF Triplet-Triplet Fusion
  • the TTF mechanism utilizes the phenomenon that singlet excitons are generated by the collision of two triplet excitons, and it is theoretically thought that the internal quantum efficiency can be increased to 40%.
  • Patent Document 2 discloses an organic EL device using a TADF (Thermally Activated Delayed Fluorescence) mechanism.
  • the TADF mechanism utilizes the phenomenon that inverse intersystem crossing from triplet excitons to singlet excitons occurs in materials with a small energy difference between singlet and triplet levels, and theoretically determines the internal quantum efficiency. It is believed that it can be increased to 100%. However, as with the phosphorescent element, further improvement in life characteristics is required.
  • Patent Document 3 and Patent Document 4 disclose an organic EL element using a TADF material composed of a polycyclic aromatic compound represented by the following compound as a light emitting dopant.
  • An object of the present invention is to provide a practically useful organic EL device having high efficiency and high drive stability while having a low drive voltage.
  • an organic electroluminescent element including one or more light emitting layers between an opposing anode and a cathode
  • at least one light emitting layer has an excitation singlet energy (S1) and an excitation triplet energy (T1).
  • S1 excitation singlet energy
  • T1 excitation triplet energy
  • It contains an organic luminescent material having a difference ( ⁇ EST) of 0.20 eV or less as a luminescent dopant, and is represented by a first host selected from compounds represented by the following general formula (1) and the following general formula (2).
  • ⁇ EST difference
  • X 1 represents O, S, or N-Ar 1 .
  • Ar 1 contains an independently substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or 2 to 8 of these aromatic rings. Represents a substituted or unsubstituted linked aromatic group composed of linked pieces.
  • R 1 is independently a heavy hydrogen, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 substituted or unsubstituted carbon atoms, or an aromatic hydrocarbon group having 3 to 17 carbon atoms substituted or unsubstituted.
  • a and d represent an integer of 0 to 4
  • b and c represent an integer of 0 to 3.
  • X 2 represents an N or C-H independently represent at least two X 2 is N.
  • Ar 2 is composed of a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or 2 to 8 of these aromatic rings linked together.
  • R 2 is independently a heavy hydrogen, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 3 to 17 carbon atoms.
  • e, f, g, and h represent integers from 0 to 4.
  • a preferred embodiment of the organic light emitting material is a boron-containing polycyclic aromatic compound represented by the following general formula (3) or (4), and the following general formula (4) is more preferable.
  • X 3 represents N-Ar 3 , O, or S, but at least one X 3 represents N-Ar 3 .
  • Ar 3 is an independently substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms, or 2 to 8 aromatic rings thereof. Represents a substituted or unsubstituted linked aromatic group formed by linking.
  • R 3 is independently a cyano group, deuterium, diarylamino group having 12 to 44 carbon atoms, aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group substituted or unsubstituted 6 to 18 carbon atoms, Alternatively, it represents a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms.
  • i and j represent an integer of 0 to 4, and k represents an integer of 0 to 3.
  • X 4 represents N-Ar 4 , O, or S, but at least one X 4 represents N-Ar 4 .
  • Ar 4 has independently substituted or unsubstituted aromatic hydrocarbon groups having 6 to 18 carbon atoms, substituted or unsubstituted aromatic heterocyclic groups having 3 to 17 carbon atoms, or 2 to 8 aromatic rings thereof. Represents a substituted or unsubstituted linked aromatic group formed by linking.
  • R 4 is independently a cyano group, deuterium, Jiriruamino group having 12 to 44 carbon atoms, aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group substituted or unsubstituted 6 to 18 carbon atoms, or Represents a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms.
  • m and n represent integers of 0 to 4
  • o and p represent integers of 0 to 3
  • q represents integers of 0 to 2.
  • X 4 in the general formula (4) is N-Ar 4.
  • X 1 in the general formula (1) is N-Ar 1.
  • a preferred embodiment of the compound represented by the general formula (1) is a compound represented by the general formula (5).
  • Ar 1 has the same meaning as Ar 1 in the general formula (1).
  • the ⁇ EST of the organic light emitting material is 0.10 eV or less.
  • the host contains 99.1 to 90 wt% with respect to 0.1 to 10 wt% of the luminescent dopant, and the host contains 10 to 90 wt% of the first host and 90 to 10 wt% of the second host.
  • the organic EL device of the present invention can be an organic EL device having a low driving voltage, high luminous efficiency, and a long life by containing a specific luminescent dopant and a plurality of specific host materials in the light emitting layer.
  • the organic EL element of the present invention has one or more light emitting layers between the opposing anode and cathode, and at least one light emitting layer has an excitation singlet energy (S1) and an excitation triplet energy (T1).
  • An organic light emitting material having a difference ( ⁇ EST) of 0.20 eV or less is contained as a luminescent dopant, and is represented by a first host selected from compounds represented by the following general formula (1) and the following general formula (2). Contains a second host selected from the following compounds.
  • the organic light emitting material used as a light emitting dopant in the organic EL device of the present invention has a ⁇ EST of 0.20 eV or less. It is preferably 0.15 eV or less, and more preferably 0.10 eV.
  • ⁇ EST represents the difference between the excited singlet energy (S1) and the excited triplet energy (T1).
  • S1 and T1 are measured as follows.
  • a sample compound is deposited on a quartz substrate by a vacuum vapor deposition method under the conditions of a vacuum degree of 10 -4 Pa or less to form a thin-film deposition film with a thickness of 100 nm.
  • S1 measures the emission spectrum of this vapor-deposited film, draws a tangent to the rising edge of the emission spectrum on the short wavelength side, and formulates the wavelength value ⁇ edge [nm] at the intersection of the tangent and the horizontal axis by the following equation ( Substitute in i) to calculate S1.
  • S1 [eV] 1239.85 / ⁇ edge (i)
  • T1 measures the phosphorescence spectrum of the above-mentioned vapor deposition film, draws a tangent line with respect to the rising edge of the phosphorescence spectrum on the short wavelength side, and sets the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis with equation (ii). Substitute in to calculate T1.
  • T1 [eV] 1239.85 / ⁇ edge (ii)
  • X 1 represents O, S, or N-Ar 1 . It preferably represents O or N-Ar 1 , and more preferably N-Ar 1 .
  • a more preferable mode of the general formula (1) is the general formula (5).
  • the common symbols have the same meaning.
  • Ar 1 contains independently substituted or unsubstituted aromatic hydrocarbon groups having 6 to 18 carbon atoms, substituted or unsubstituted aromatic heterocyclic groups having 3 to 17 carbon atoms, or these aromatic rings having 2 to 8 carbon atoms.
  • unsubstituted Ar 1 examples include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo [a] anthracene, pyridine, pyrimidine, triazine, thiophene, isothiazole, Thiazol, pyridazine, pyrrol, pyrazole, imidazole, triazole, thiazazole, pyrazine, furan, isoxazole, quinoline, isoquinoline, quinoxalin, quinazoline, thiazilazole, phthalazine, tetrazole, indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benz One from imidazole,
  • Examples include groups produced by taking hydrogen.
  • benzene, naphthalene, acenaphthene, acenaphthylene, azulene, or a group formed by taking one hydrogen from a compound composed of 2 to 4 linkages thereof can be mentioned. More preferably, there is a group formed by taking one hydrogen from benzene or a compound composed of two or three linkages thereof.
  • Each of these aromatic hydrocarbon groups, aromatic heterocyclic groups or linked aromatic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • R 1 is independently a heavy hydrogen, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 substituted or unsubstituted carbon atoms, or an aromatic hydrocarbon group having 3 to 17 carbon atoms substituted or unsubstituted.
  • it is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms. is there.
  • a and d represent integers from 0 to 4
  • b and c represent integers from 0 to 3.
  • R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • Preferred include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl.
  • R 1 is an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms include benzene, naphthalene, acenaphthene, and acenaphthylene.
  • Kinolin isoquinolin, quinoxalin, quinazoline, thiadiazole, phthalazine, tetrazole, indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazyl, purine, pyranone, coumarin, isocmarin.
  • Each of these aromatic hydrocarbon groups or aromatic heterocyclic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • X 2 represents an N or C-H independently represent at least two X 2 is N. Preferably three X 2 represents N.
  • Ar 2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted or unsubstituted, an aromatic heterocyclic group having 3 to 17 carbon atoms substituted or unsubstituted, or 2 to 8 of these aromatic rings linked together.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms, or 2 to 6 of these aromatic rings are linked to each other.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms, or 2 to 4 of these aromatic rings are linked.
  • unsubstituted Ar 2 examples include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo [a] anthracenepyridine, pyrimidine, triazine, thiophene, isothiazole, and thiazole.
  • Tetrazole indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazole, purine, pyranone, coumarin, isocmarin, chromone, or a combination of 2 to 4 of these. Examples thereof include a group formed by taking one hydrogen from the compound to be produced.
  • Each of these aromatic hydrocarbon groups, aromatic heterocyclic groups or linked aromatic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a diarylamino group having 12 to 44 carbon atoms, or a triphenylsilyl group.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • R 2 is independently a heavy hydrogen, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 18 substituted or unsubstituted carbon atoms, or an aromatic hydrocarbon group having 3 to 17 carbon atoms substituted or unsubstituted.
  • it is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 15 carbon atoms. More preferably, it is an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • e, f, g, h represent integers from 0 to 4.
  • R 2 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 2 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 2 represents an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms includes benzene, naphthalene, acenaphthene, and acenaphthylene.
  • Kinolin isoquinolin, quinoxalin, quinazoline, thiadiazole, phthalazine, tetrazole, indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazyl, purine, pyranone, coumarin, isocmarin.
  • Each of these aromatic hydrocarbon groups or aromatic heterocyclic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • a preferred embodiment of the organic light emitting material used for the organic EL element of the present invention is a boron-containing polycyclic aromatic compound represented by the following general formula (3) or (4), which is represented by the general formula (4). It is more preferable that it is a boron-containing polycyclic aromatic compound.
  • the boron-containing polycyclic aromatic compound represented by the general formula (3) will be described.
  • X 3 represents O, S, or N-Ar 3 , but at least one X 3 represents N-Ar 3 . It preferably represents O or N-Ar 3 , and more preferably N-Ar 3 .
  • Ar 3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted or unsubstituted, an aromatic heterocyclic group having 3 to 17 carbon atoms substituted or unsubstituted, or 2 to 8 of these aromatic rings linked together.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms, or 2 to 6 of these aromatic rings are linked to each other.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms, or 2 to 4 of these aromatic rings are linked.
  • unsubstituted Ar 3 examples include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo [a] anthracenepyridine, pyrimidine, triazine, thiophene, isothiazole, and thiazole.
  • Tetrazole indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazole, purine, pyranone, coumarin, isocmarin, chromone, or a combination of 2 to 4 of these. Examples thereof include a group formed by taking one hydrogen from the compound to be produced.
  • Each of these aromatic hydrocarbon groups, aromatic heterocyclic groups or linked aromatic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • R 3 is independently a cyano group, a hydrocarbon, a diarylamino group having 12 to 44 carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, Alternatively, it represents a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms.
  • it is a diarylamino group having 12 to 36 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an substituted or unsubstituted aromatic heterocycle having 3 to 15 carbon atoms.
  • ⁇ is a diarylamino group having 12 to 24 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms.
  • .. i and j represent an integer of 0 to 4, and k represents an integer of 0 to 3.
  • R 3 represents a diarylamino group having 12 to 44 carbon atoms and an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • R 3 represents a diarylamino group having 12 to 44 carbon atoms and an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • Preferred examples thereof include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino, diphenanthrenylamino and dipyrenylamino. More preferably, diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino and dinaphthylamino can be mentioned.
  • R 3 represents an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms includes benzene, naphthalene, acenaphthene, and acenaphthylene.
  • Kinolin isoquinolin, quinoxalin, quinazoline, thiadiazole, phthalazine, tetrazole, indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazyl, purine, pyranone, coumarin, isocmarin.
  • Each of these aromatic hydrocarbon groups or aromatic heterocyclic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, and BR> W naphthylamino and dianthranylamino. Examples thereof include diphenylenylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • the boron-containing polycyclic aromatic compound represented by the general formula (4) will be described.
  • X 4 represents O, S, or N-Ar 4 , but at least one X 4 represents N-Ar 4 . It preferably represents O or N-Ar 3 , and more preferably N-Ar 3 .
  • Ar 4 contains an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted or unsubstituted, an aromatic heterocyclic group having 3 to 17 carbon atoms substituted or unsubstituted, or 2 to 8 linked aromatic rings thereof.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 12 carbon atoms, or 2 to 6 of these aromatic rings are linked to each other.
  • a substituted or unsubstituted aromatic hydrocarbon group having 6 to 10 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 3 to 10 carbon atoms, or 2 to 4 of these aromatic rings are linked.
  • unsubstituted Ar 4 examples include benzene, naphthalene, acenaphthene, acenaphthylene, azulene, anthracene, chrysene, pyrene, phenanthrene, triphenylene, fluorene, benzo [a] anthracenepyridine, pyrimidine, triazine, thiophene, isothiazole, and thiazole.
  • Tetrazole indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazole, purine, pyranone, coumarin, isocmarin, chromone, or a combination of 2 to 4 of these. Examples thereof include a group formed by taking one hydrogen from the compound to be produced.
  • Each of these aromatic hydrocarbon groups, aromatic heterocyclic groups or linked aromatic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • R 4 is independently a cyano group, a hydrocarbon, a diarylamino group having 12 to 44 carbon atoms, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, Alternatively, it represents a substituted or unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms.
  • it is a diarylamino group having 12 to 36 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, or an substituted or unsubstituted aromatic heterocycle having 3 to 15 carbon atoms.
  • n represent integers from 0 to 4
  • o and p represent integers from 0 to 3
  • q represents integers from 0 to 2.
  • R 4 represents a diarylamino group having 12 to 44 carbon atoms and an aliphatic hydrocarbon group having 1 to 10 carbon atoms
  • examples thereof include amino, dianthranylamino, diphenanthrenylamino, dipyrenylamino, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl.
  • Preferred examples thereof include diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino, diphenanthrenylamino and dipyrenylamino. More preferably, diphenylamino, dibiphenylamino, phenylbiphenylamino, naphthylphenylamino and dinaphthylamino can be mentioned.
  • R 4 represents an unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an unsubstituted aromatic heterocyclic group having 3 to 17 carbon atoms includes benzene, naphthalene, acenaphthene, and acenaphthylene.
  • Kinolin isoquinolin, quinoxalin, quinazoline, thiadiazole, phthalazine, tetrazole, indol, benzofuran, benzothiophene, benzoxazole, benzothiazole, indazole, benzimidazole, benzotriazole, benzoisothiazole, benzothiazyl, purine, pyranone, coumarin, isocmarin.
  • Each of these aromatic hydrocarbon groups or aromatic heterocyclic groups may have a substituent.
  • the substituent is a cyano group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a diarylamino group having 12 to 44 carbon atoms.
  • the number of substituents is 0 to 5, preferably 0 to 2.
  • the carbon number calculation does not include the carbon number of the substituent. However, it is preferable that the total number of carbon atoms including the number of carbon atoms of the substituent satisfies the above range.
  • substituents include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, diphenylamino, naphthylphenylamino, dinaphthylamino, dianthranylamino and diphenan. Examples thereof include threnylamino and dipyrenylamino.
  • Preferred include cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, diphenylamino, naphthylphenylamino, or dinaphthylamino.
  • a material selected from the compounds represented by the general formula (3) or (4) is used as a luminescent dopant, and a material selected from the compounds represented by the general formula (1) is used as the first host, and the general.
  • An excellent organic EL device can be provided by using a material selected from the compound represented by the formula (2) as the second host.
  • FIG. 1 is a cross-sectional view showing a structural example of a general organic EL device used in the present invention, in which 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, and 5 is a light emitting layer. , 6 represent an electron transport layer, and 7 represents a cathode.
  • the organic EL device of the present invention may have an exciton blocking layer adjacent to the light emitting layer, or may have an electron blocking layer between the light emitting layer and the hole injection layer.
  • the exciton blocking layer can be inserted into either the anode side or the cathode side of the light emitting layer, and both can be inserted at the same time.
  • the organic EL device of the present invention has an anode, a light emitting layer, and a cathode as essential layers, but it is preferable to have a hole injection transport layer and an electron injection transport layer in addition to the essential layers, and further, a light emitting layer and electron injection. It is preferable to have a hole blocking layer between the transport layers.
  • the hole injection transport layer means either or both of the hole injection layer and the hole transport layer
  • the electron injection transport layer means either or both of the electron injection layer and the electron transport layer.
  • the structure opposite to that of FIG. 1, that is, the cathode 7, the electron transport layer 6, the light emitting layer 5, the hole transport layer 4, and the anode 2 can be laminated in this order on the substrate 1, and in this case as well, the layers can be laminated in this order. It can be added or omitted.
  • the organic EL device of the present invention is preferably supported by a substrate.
  • the substrate is not particularly limited as long as it is conventionally used for an organic EL element, and for example, a substrate made of glass, transparent plastic, quartz or the like can be used.
  • anode material in the organic EL device a material having a large work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2, and ZnO.
  • conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2, and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3- ZnO) capable of producing a transparent conductive film may be used.
  • a thin film may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and a pattern of a desired shape may be formed by a photolithography method, or when pattern accuracy is not required so much (about 100 ⁇ m or more). May form a pattern through a mask having a desired shape during vapor deposition or sputtering of the electrode material.
  • a coatable substance such as an organic conductive compound
  • a wet film forming method such as a printing method or a coating method can also be used.
  • the transmittance is larger than 10%, and the sheet resistance as the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
  • the cathode material a material having a small work function (4 eV or less) (referred to as an electron-injectable metal), an alloy, an electrically conductive compound, or a mixture thereof is used.
  • an electron-injectable metal a material having a small work function (4 eV or less)
  • an alloy an electrically conductive compound, or a mixture thereof.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O). 3 ) Examples thereof include a mixture, an indium, a lithium / aluminum mixture, and a rare earth metal.
  • a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this for example, magnesium / silver mixture, magnesium / Aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) mixture, lithium / aluminum mixture, aluminum and the like are suitable.
  • the cathode can be produced by forming a thin film of these cathode materials by a method such as vapor deposition or sputtering.
  • the sheet resistance of the cathode is preferably several hundred ⁇ / ⁇ or less, and the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the emission brightness is improved, which is convenient.
  • a transparent or translucent cathode can be produced by forming the above metal on the cathode with a thickness of 1 to 20 nm and then forming the conductive transparent material mentioned in the description of the anode on the cathode. By applying this, it is possible to manufacture an element in which both the anode and the cathode are transparent.
  • the light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and cathode, and the light emitting layer contains a light emitting dopant and a host.
  • the luminescent dopant and the host can be used, for example, at 99.9 to 90 wt% of the host with respect to 0.1 to 10 wt% of the luminescent dopant.
  • the luminescent dopant is 1 to 5 wt% and the host is 99 to 95 wt%, and more preferably the luminescent dopant is 1 to 3 wt% and the host is 99 to 97 wt%.
  • a first host represented by the general formula (1) and a second host represented by the general formula (2) are used.
  • the first host and the second host can be used, for example, with 10 to 90 wt% of the first host and 90 to 10 wt% of the second host.
  • the first host is 30 to 70 wt%
  • the second host is 70 to 30 wt%
  • more preferably the first host is 40 to 60 wt% and the second host is 60 to 40 wt%.
  • one or a plurality of known hosts may be used in combination, but the amount used may be 50 wt% or less, preferably 25 wt% or less, based on the total amount of the host materials.
  • the compound has a hole transporting ability and an electron transporting ability, and has a high glass transition temperature, and has T1 larger than T1 of the luminescent dopant.
  • hosts are known from a large number of patent documents, etc., they can be selected from them.
  • Specific examples of the host are not particularly limited, but are indol derivative, carbazole derivative, indolocarbazole derivative, triazole derivative, oxazole derivative, oxadiazole derivative, imidazole derivative, phenylenediamine derivative, arylamine derivative, and styryl.
  • Anthracene derivatives fluorenone derivatives, stylben derivatives, triphenylene derivatives, carborane derivatives, porphyrin derivatives, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives and metal phthalocyanine, various metal complexes represented by metal complexes of benzoxazole and benzothiazole derivatives, poly Examples thereof include polymer compounds such as (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives.
  • polymer compounds such as (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives.
  • each host can be vapor-deposited from different vapor deposition sources, or multiple types of hosts can be vapor-deposited from one vapor deposition source at the same time by premixing them before vapor deposition to form a premixture. ..
  • a method capable of mixing as uniformly as possible is desirable, and examples thereof include pulverization and mixing, a method of heating and melting under reduced pressure or an atmosphere of an inert gas such as nitrogen, and sublimation. It is not limited to the method.
  • an organic light emitting material having a difference ( ⁇ EST) between the excited singlet energy (S1) and the excited triplet energy (T1) of 0.20 eV or less is used.
  • ⁇ EST the excited singlet energy
  • T1 the excited triplet energy
  • a compound represented by the general formula (3) or (4) is preferable.
  • Only one type of organic light emitting dopant may be contained in the light emitting layer, or two or more types may be contained.
  • the content of the organic light emitting dopant is preferably 0.1 to 50 wt%, more preferably 1 to 40 wt% with respect to the host material.
  • the organic light-emitting dopant and the first host or the second host are vapor-deposited from different vapor deposition sources, or premixed before vapor deposition to form a premixture, whereby the light-emitting dopant and the first host can be deposited from one vapor deposition source.
  • the second host can be vapor-deposited at the same time.
  • the injection layer is a layer provided between the electrode and the organic layer in order to reduce the driving voltage and improve the emission brightness.
  • the injection layer can be provided as needed.
  • the hole blocking layer has the function of an electron transporting layer in a broad sense, and is made of a hole blocking material having a function of transporting electrons and a significantly small ability to transport holes. It is possible to improve the recombination probability of electrons and holes in the light emitting layer by blocking the above.
  • a known hole blocking material can be used for the hole blocking layer.
  • the material used as the second host can also be used as the material of the hole blocking layer. Further, a plurality of types of hole blocking materials may be used in combination.
  • the electron blocking layer has a function of a hole transporting layer in a broad sense, and by blocking electrons while transporting holes, the probability of recombination of electrons and holes in the light emitting layer can be improved. ..
  • As the material of the electron blocking layer a known electron blocking layer material can be used. In order to bring out the characteristics of the luminescent dopant, the material used as the first host can also be used as the material of the electron blocking layer.
  • the film thickness of the electron blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.
  • the exciton blocking layer is a layer for blocking excitons generated by the recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer, and the excitons are inserted by inserting this layer. It is possible to efficiently confine it in the light emitting layer, and it is possible to improve the light emitting efficiency of the element.
  • the exciton blocking layer can be inserted between two adjacent light emitting layers in an element in which two or more light emitting layers are adjacent to each other.
  • a known exciton blocking layer material can be used as the material of the exciton blocking layer.
  • Examples of the layer adjacent to the light emitting layer include a hole blocking layer, an electron blocking layer, an exciton blocking layer, and the like, but if these layers are not provided, the hole transport layer, the electron transport layer, and the like are the adjacent layers. Become.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer may be provided as a single layer or a plurality of layers.
  • the hole transporting material has any of hole injection, transport, and electron barrier properties, and may be either an organic substance or an inorganic substance. Any compound can be selected and used for the hole transport layer from conventionally known compounds. Examples of such hole transport materials include porphyrin derivatives, arylamine derivatives, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, and styrylanthracene.
  • Derivatives fluorenone derivatives, hydrazone derivatives, stylben derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, especially thiophene oligomers, etc. can be mentioned, but porphyrin derivatives, arylamine derivatives and styrylamine derivatives can be used. It is preferable to use an arylamine compound, and it is more preferable to use an arylamine compound.
  • the electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer may be provided with a single layer or a plurality of layers.
  • the electron transporting material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer.
  • any conventionally known compound can be selected and used.
  • a polycyclic aromatic derivative such as naphthalene, anthracene or phenanthroline, tris (8-quinolinolate) aluminum (III).
  • Derivatives phosphine oxide derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide, freolenidene methane derivatives, anthracinodimethane and antron derivatives, bipyridine derivatives, quinoline derivatives, oxadiazole derivatives, benzoimidazole Derivatives, benzothiazole derivatives, indolocarbazole derivatives and the like can be mentioned. Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • the film forming method for each layer is not particularly limited, and it may be manufactured by either a dry process or a wet process.
  • S1 and T1 were measured as follows.
  • Compounds (3-2) or (4-2) are co-deposited from different vapor deposition sources on a quartz substrate by vacuum deposition using BH1 as a host and a luminescent dopant under conditions of a vacuum degree of 10-4 Pa or less.
  • a thin film was formed with a thickness of 100 nm.
  • S1 measures the emission spectrum of this vapor-deposited film, draws a tangent to the rising edge of the emission spectrum on the short wavelength side, and formulates the wavelength value ⁇ edge [nm] at the intersection of the tangent and the horizontal axis by the following equation ( Substitute in i) to calculate S1.
  • S1 [eV] 1239.85 / ⁇ edge (i)
  • T1 measures the phosphorescence spectrum of the above-mentioned vapor deposition film, draws a tangent line with respect to the rising edge of the phosphorescence spectrum on the short wavelength side, and sets the wavelength value ⁇ edge [nm] at the intersection of the tangent line and the horizontal axis with equation (ii). Substitute in to calculate T1.
  • T1 [eV] 1239.85 / ⁇ edge (ii)
  • Example 1 Each thin film was laminated with a vacuum degree of 4.0 ⁇ 10 -5 Pa by vacuum deposition on a glass substrate on which an anode made of ITO with a film thickness of 70 nm was formed.
  • HAT-CN was formed on the ITO to a thickness of 10 nm as a hole injection layer, and then HT-1 was formed to a thickness of 25 nm as a hole transport layer.
  • compound (1-77) was formed to a thickness of 5 nm as an electron blocking layer.
  • compound (1-77) was co-deposited as the first host
  • compound (2-1) was co-deposited as the second host
  • compound (4-2) was co-deposited as a luminescent dopant from different deposition sources to produce 30 nm
  • a light emitting layer was formed to a thickness.
  • co-deposited under the vapor deposition conditions where the concentration of the compound (4-2) was 2 wt% and the weight ratio between the first host and the second host was 50:50.
  • compound (2-1) was formed to a thickness of 5 nm as a hole blocking layer.
  • ET-1 was formed to a thickness of 40 nm as an electron transport layer.
  • lithium fluoride (LiF) was formed on the electron transport layer as an electron injection layer to a thickness of 1 nm.
  • aluminum (Al) was formed as a cathode on the electron injection layer to a thickness of 70 nm to fabricate an organic EL device.
  • Examples 2-10 An organic EL device was produced in the same manner as in Example 1 except that the luminescent dopant, the first host, the second host, and the weight ratio of the first host to the second host were the compounds shown in Table 2.
  • Comparative Example 1 Each thin film was laminated with a vacuum degree of 4.0 ⁇ 10 -5 Pa by vacuum deposition on a glass substrate on which an anode made of ITO with a film thickness of 70 nm was formed.
  • HAT-CN was formed on the ITO to a thickness of 10 nm as a hole injection layer, and then HT-1 was formed to a thickness of 25 nm as a hole transport layer.
  • compound (1-77) was formed to a thickness of 5 nm as an electron blocking layer.
  • compound (1-77) as the first host and compound (4-2) as the luminescent dopant were co-deposited from different deposition sources to form a light emitting layer to a thickness of 30 nm.
  • compound (2-1) was formed to a thickness of 5 nm as a hole blocking layer.
  • ET-1 was formed to a thickness of 40 nm as an electron transport layer.
  • lithium fluoride (LiF) was formed on the electron transport layer as an electron injection layer to a thickness of 1 nm.
  • aluminum (Al) was formed as a cathode on the electron injection layer to a thickness of 70 nm to fabricate an organic EL device.
  • Comparative Examples 2, 3, 5, 6, 7 An organic EL device was produced in the same manner as in Comparative Example 1 except that the luminescent dopant and the first host (without the second host) were the compounds shown in Table 2.
  • Comparative Examples 4 and 8 An organic EL device was produced in the same manner as in Example 1 except that the luminescent dopant, the first host, and the second host were the compounds shown in Table 2.
  • Table 3 shows the voltage of the organic EL device produced in Examples and Comparative Examples, the maximum emission wavelength of the emission spectrum, the external quantum efficiency, and the lifetime.
  • the voltage, maximum emission wavelength, and external quantum efficiency are the values when the brightness is 500 cd / m 2 , which are the initial characteristics.
  • the life was measured by measuring the time until the brightness attenuated to 50% of the initial brightness at an initial brightness of 500 cd / m 2.
  • the compound represented by the general formula (1) is used as the first host, the compound represented by the general formula (2) is used as the second host, and the compound represented by the general formula (3) or (4) is used. It can be seen that the organic EL element using the compound as a luminescent dopant emits blue light from the maximum emission wavelength, and has characteristics of low voltage, high efficiency, and long life.
  • the organic EL element of the present invention has characteristics of low drive voltage, high luminous efficiency, and long life, it can be practically used as a display element such as a flat panel display or a light source.

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