WO2014006913A1 - Composé benzodiazaborole, et matériau pour élément électroluminescent organique et élément électroluminescent organique l'utilisant - Google Patents

Composé benzodiazaborole, et matériau pour élément électroluminescent organique et élément électroluminescent organique l'utilisant Download PDF

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WO2014006913A1
WO2014006913A1 PCT/JP2013/004167 JP2013004167W WO2014006913A1 WO 2014006913 A1 WO2014006913 A1 WO 2014006913A1 JP 2013004167 W JP2013004167 W JP 2013004167W WO 2014006913 A1 WO2014006913 A1 WO 2014006913A1
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真樹 沼田
俊裕 岩隈
圭 吉田
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出光興産株式会社
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Definitions

  • the present invention relates to a novel benzodiazaborol compound, an organic electroluminescence element material using the same, and an organic electroluminescence element.
  • an organic EL device if the compound constituting the organic compound layer has poor electrochemical stability, particularly oxidation stability, these compounds decompose in a short time when a charge is applied from the anode and the cathode, and the device The lifetime is short.
  • the voltage is reduced when used as a material in a layer where holes are injected or transported, with excellent electrochemical oxidation stability and a shallow ionization potential. There are several things that can be expected.
  • Patent Documents 1 and 2 various organic compounds have been studied as materials for organic EL devices, and compounds having a 1,3,2-diazaborol ring are disclosed as one of them (Patent Documents 1 and 2).
  • Non-Patent Documents 1 to 5 there are research reports on the optoelectronic properties of compounds having a 1,3,2-benzodiazaborol ring (Non-Patent Documents 1 to 5). Non-Patent Documents 4 and 5 also examine the electrochemical properties.
  • Patent Documents 1 and 2 disclose the use of a benzodiazaborol compound as a material for an organic EL device, but the compounds disclosed therein do not have a substituent on the benzene ring.
  • Patent Document 2 discloses the following compound having a 6-membered ring containing two nitrogen atoms and one boron atom, but these compounds have a triplet energy smaller than that of a 5-membered diazaborol.
  • Non-patent Documents 4 and 5 are examining the electrochemical (oxidation) stability of these compounds in addition to the optoelectronic properties, but pointed out that all of these compounds are electrochemically unstable. ing.
  • any of the compounds having a 1,3,2-benzodiazaborol ring reported so far has poor electrochemical stability and is insufficient as an organic material for an organic EL device.
  • An object of the present invention is to provide a benzodiazaborol compound which is excellent in electrochemical stability, particularly oxidation stability, and is suitable as a material for an organic compound layer of an organic EL device.
  • the present inventor has advanced research on compounds having a 1,3,2-benzodiazaborol ring, and the benzene ring constituting the benzodiazaborol skeleton has sp 2 hybrid orbital properties.
  • a benzodiazaborol compound having a specific substituent bonded by an atom or having a condensed ring and having an aromatic ring group or a heteroaromatic ring group at two nitrogen atoms of the diazaborol ring has been found.
  • the 1,3,2-benzodiazaborol ring has a specific substituent or condensed ring at a predetermined position in this manner, electrochemical oxidation stability is improved. It has been found that by using such a compound in an organic compound layer of an organic EL device, the device life can be improved.
  • the inventor has a skeleton in which two benzodiazaborol skeletons are condensed via a boron atom and a nitrogen atom, and an aromatic ring group or a heterocycle is added to two nitrogen atoms that are not used for the condensation of a diazaborol ring. A novel benzodiazaborol compound having an aromatic ring group has been found.
  • a benzodiazaborol compound represented by formula (1) (Where A 1 and A 2 are each independently A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted silyl group, A substituted or unsubstituted phosphino group, A substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted sulfoxide group, A substituted or unsubstituted sulfone group, or a single bond, A 3 is, A
  • a 1 , A 2 , and A 3 are not bonded to each other to form the following ring in which three diazaborol rings are condensed.
  • Ring Q fused with the diazaborol ring is A substituted or unsubstituted benzene ring, A substituted or unsubstituted benzene ring in which at least one substituted or unsubstituted condensed aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted heterocyclic aromatic ring having 5 to 24 ring atoms is condensed
  • n is an integer from 1 to 6, When n is 1, L does not exist, when n is 2 to 6, L is a linking group that bridges between any of Q, A 1 , A 2 , and A 3 , or a single bond; When n is 2 to 6, n, Q, A 1 , A 2 , and A 3 may be the same as or different from each other.
  • the benzodiazaborol compound excellent in electrochemical stability, especially oxidation stability can be provided.
  • the material for organic EL elements excellent in electrochemical stability, especially oxidation stability can be provided.
  • ADVANTAGE OF THE INVENTION According to this invention, the organic EL element with improved element lifetime can be provided.
  • the benzodiazaborol compound of the present invention is represented by the formula (1).
  • a 1 and A 2 are each independently A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted silyl group, A substituted or unsubstituted phosphino group, A substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted sulfoxide group, It is a substituted or unsubstituted sulfone group, or a single bond.
  • a 3 is, A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or unsubstituted amino group, A substituted or unsubstituted alkyl sulfide group having 1 to 20 carbon atoms, A substituted or unsubstituted arylsulfide group having 6 to 30 ring carbon atoms,
  • a 1 and A 3 , or A 2 and A 3 may be bonded to each other to form a 5- to 7-membered ring including a nitrogen atom and a boron atom of the benzodiazaborol skeleton.
  • a 1 , A 2 , and A 3 are not bonded to each other to form the following ring in which three diazaborol rings are condensed.
  • Ring Q fused with the diazaborol ring is A substituted or unsubstituted benzene ring, A substituted or unsubstituted benzene ring in which at least one substituted or unsubstituted condensed aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted heterocyclic aromatic ring having 5 to 24 ring atoms is condensed And n is an integer of 1 to 6, preferably 1 to 3.
  • n When n is 1, L does not exist, when n is 2 to 6, L is a linking group that bridges between any of Q, A 1 , A 2 , and A 3 , or a single bond; When n is 2 to 6, n, Q, A 1 , A 2 , and A 3 may be the same as or different from each other.
  • the benzodiazaborol compound of the present invention is preferably represented by the following formula (I-1).
  • a 1 and A 2 are each independently A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted silyl group, A substituted or unsubstituted phosphino group, A substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted sulfoxide group, A substituted or unsubstituted sulfone group, or a single bond,
  • a 3 is, A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or unsubstituted amino group, A substituted or unsubstituted alkyl sulfide group having 1 to 20 carbon atoms, A substituted or unsubstituted arylsulfide group having 6 to 30 ring carbon atoms,
  • a 1 and A 3 , or A 2 and A 3 may be bonded to each other to form a 5- to 7-membered ring including a nitrogen atom and a boron atom of the benzodiazaborol skeleton.
  • a 1 and A 3 , or A 2 and A 3 are not bonded to each other to form the following 5-membered ring.
  • a 1 , A 2 , and A 3 are each independently a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms.
  • the ring Q condensed with the diazaborol ring has at least one substituent R, and may further have an optional substituent, a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted ring It is a benzene ring in which at least one heteroaromatic ring is condensed and may further have an arbitrary substituent.
  • Substituent R is A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, a substituted or unsubstituted unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms bonded by an atom having sp 2 hybrid orbital property, a substituted or unsubstituted ring-formed unsaturated aliphatic hydrocarbon ring group having 3 to 20 carbon atoms bonded by an atom having sp 2 hybrid orbital property, A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or unsubstituted amino group, Substituted or unsubsti
  • Examples of the “atom having sp 2 hybrid orbital” include, for example, a carbon atom having a trivalent bonding state in an aromatic ring, a carbon atom having a trivalent bonding state in a heteroaromatic ring, or a nitrogen atom.
  • a carbon atom having a carbon atom, a carbon atom having a trivalent bonding state in a heteroaromatic ring, or a nitrogen atom is preferable.
  • Substituent R is a substituted or unsubstituted phenyl group, a substituted or unsubstituted o-biphenyl group, a substituted or unsubstituted m-biphenyl group, a substituted or unsubstituted p-biphenyl group, a substituted or unsubstituted m- Terphenyl group, substituted or unsubstituted p-terphenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted triphenylenine group, substituted or unsubstituted dibenzofuranyl group , A substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group is preferable.
  • the condensed ring containing the benzene ring is: A condensed aromatic hydrocarbon ring having 9 to 30 ring carbon atoms formed by condensation of 2 or more, preferably 3 or more, 5- to 7-membered hydrocarbon rings, or 1 or more, preferably 2 or more A condensed heteroaromatic ring having 9 to 30 ring atoms formed by condensation of a 5- to 7-membered hydrocarbon ring and one or more 5- to 7-membered heterocyclic rings, And More preferably, it is substituted or unsubstituted phenanthrene, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, or substituted
  • n is an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably 1 or 2.
  • L does not exist
  • L is a linking group that bridges between Q, A 1 , A 2 , and A 3 , or a single bond.
  • Q, A 1 , A 2 , and A 3 may be the same as or different from each other.
  • L is a linking group
  • L is a linking group
  • examples of the case where L is a linking group include an ether group, a thioether group, a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, a substituted or unsubstituted ring atom number of 6 to 30 Heteroaromatic ring groups, and substituted or unsubstituted amino groups, ether groups, substituted or unsubstituted benzene rings, substituted or unsubstituted dibenzofuran rings, dibenzothiophene rings, carbazole rings, substituted or unsubstituted And a n-valent group derived from a substituted or unsubstituted biphenyl.
  • the benzodiazaborol compound represented by the formula (I-1) preferably has a basic skeleton selected from the group consisting of the following structural formulas (I-2) to (I-14).
  • Q is preferably a ring that is condensed with the diazaborol ring in the following structural formulas (I-2) to (I-14).
  • the “basic skeleton” means that the benzene ring of the benzodiazaborol skeleton, the ring condensed to the benzene ring, and the substituent of the benzene ring may have a substituent.
  • a 1 to A 3 , L, and n are as defined in the formula (I-1).
  • X is each independently an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the “basic skeleton” means that the benzene ring condensed to the 6-membered ring formed including the nitrogen atom and boron atom of the benzodiazaborol skeleton may have a substituent. .
  • a 1 , A 2 , Q, L, and n are as defined in the formula (I-1).
  • a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, A substituted or unsubstituted or unsubstituted
  • the aromatic ring group includes a monocyclic aromatic hydrocarbon ring group, a condensed aromatic hydrocarbon ring group in which a plurality of hydrocarbon rings are condensed, and a group in which a plurality of hydrocarbon rings are connected by a single bond.
  • the heteroaromatic ring group includes a monocyclic heteroaromatic ring group, a heterofused aromatic ring group in which a plurality of heteroaromatic rings are condensed, and an aromatic hydrocarbon ring and a heteroaromatic ring are condensed.
  • Ring-forming carbon means a carbon atom constituting a saturated hydrocarbon ring, an unsaturated hydrocarbon ring or an aromatic ring
  • ring-forming atom means an atom constituting a heteroaromatic ring
  • Examples of the aromatic ring group having 6 to 30 ring carbon atoms include phenyl group, tolyl group, xylyl group, mesityl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m- Examples thereof include a terphenyl group, a p-terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, an anthryl group, a phenalenyl group, a fluoranthenyl group, a triphenylenyl group, a naphthacenyl group, a chrycenyl group, and a pyrenyl group.
  • phenyl, o-biphenyl, m-biphenyl, p-biphenyl, m-terphenyl, p-terphenyl, naphthyl, phenanthryl, and triphenylenyl are preferred.
  • Heteroaromatic ring groups having 5 to 30 ring atoms include pyrrolyl, pyrazinyl, pyridinyl, pyrimidinyl, pyridazinyl, triazinyl, indolyl, isoindolyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl Group, azacarbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, triazolyl group, imidazolyl group, benzoimidazolyl group, furyl group, benzofuranyl group, isobenzofuranyl group, Dibenzofuranyl group, dioxanyl group, oxazolyl group, pyranyl group, benzo [c] dibenzofuranyl group dibenzothiophenyl group, thi
  • alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, and n-hexyl group.
  • the alkyl group having 3 to 20 carbon atoms is one obtained by removing the methyl group and the ethyl group from the examples of the alkyl group having 1 to 20 carbon atoms.
  • Examples of the cycloalkyl group having 3 to 20 ring carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group, and the like. Are preferred.
  • alkoxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group and the like, and those having 3 or more carbon atoms are linear, cyclic or branched Among them, those having 1 to 6 carbon atoms are preferable.
  • Examples of the cycloalkoxy group having 3 to 20 carbon atoms include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc. Among them, those having 5 or 6 ring carbon atoms are preferable.
  • Examples of the aryloxy group having 6 to 30 ring carbon atoms include a phenoxy group and a biphenyloxy group, and a phenoxy group is preferable.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms include ethylene group, propylene group, 1-butene group, 2-butene group, 1,3-butadiene group, 2-methylpropene group, 1-pentene group, Examples include 2-pentene group, 1-hexene group, 2-hexene group, 3-hexene group and the like.
  • R when it is the substituent R, it is an unsaturated aliphatic hydrocarbon group bonded to the benzene ring of the benzodiazaborol skeleton by an atom having sp 2 hybrid orbital among the above groups.
  • ethylene group 1-propen-1-yl group, 1-propen-2-yl group, 1-buten-1-yl group, 1-buten-2-yl group, 2-buten-2- Yl group, 1,3-butadiene-1-yl group, 1,3-butadiene-2-yl group, 2-methylpropen-1-yl group, 1-penten-1-yl group, 1-penten-2- Yl, 2-penten-2-yl, 2-penten-3-yl, 1-hexen-1-yl, 1-hexen-2-yl, 2-hexen-2-yl, 2- Examples include a hexen-3-yl group, a 3-hexen-3-yl group, and a 3-hexen-4-yl group.
  • Examples of the unsaturated aliphatic hydrocarbon ring group having 3 to 20 ring carbon atoms include a cyclopropene group, a cyclobutene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, and a cyclooctene group.
  • R when it is the substituent R, it is an unsaturated aliphatic hydrocarbon ring group bonded to the benzene ring of the benzodiazaborol skeleton by an atom having sp 2 hybrid orbital among the above groups.
  • a cyclopropen-1-yl group a cyclobuten-1-yl group, a cyclopenten-1-yl group, a cyclohexen-1-yl group, a cyclohepten-1-yl group, a cycloocten-1-yl group, etc.
  • a cyclopropen-1-yl group a cyclobuten-1-yl group, a cyclopenten-1-yl group, a cyclohexen-1-yl group, a cyclohepten-1-yl group, a cycloocten-1-yl group, etc.
  • the alkyl sulfide group having 1 to 20 carbon atoms is represented by —SX, and X is the above alkyl group having 1 to 20 carbon atoms.
  • An aryl sulfide group having 6 to 30 ring carbon atoms is represented by —SY, and Y is an aromatic ring group having 6 to 30 ring carbon atoms.
  • “Unsubstituted” in “substituted or unsubstituted...” Means that a hydrogen atom is substituted.
  • a hydrogen atom is an isotope having a different neutron number, that is, light hydrogen. (Protium), deuterium, tritium.
  • the compound of the present invention represented by the formula (I-1) can be synthesized by the method described in Examples or a method known to those skilled in the art.
  • the compound of the present invention represented by the formula (I-1) is excellent in electrochemical oxidation stability as compared with the conventional benzodiazaborol compound. This is because the compound of the present invention has a specific substituent or condensed ring bonded to the benzene ring constituting the benzodiazaborol skeleton with an atom having sp 2 hybrid orbital, and two nitrogen atoms of the diazabolol ring This is because it has an aromatic ring group or a heteroaromatic ring group.
  • the electrochemical oxidative stability of the compound can be evaluated by the cyclic voltammetric measurement described in the examples. In addition to the method described in the Examples, those skilled in the art can carry out the cyclic voltammetry by appropriately changing the method based on known knowledge according to the properties of the compound.
  • the compound of the present invention not only improves the electrochemical oxidation stability but also reduces the ionization potential, so that it can be used as a material in a layer into which holes of an organic EL element are injected or transported. Further lower voltage can be expected.
  • the triplet energy of the 1,3,2-diazaborol ring itself is a wide gap
  • the compound having a substituent having sp 2 hybrid orbital property at a predetermined position (I-1) Even in the case of having the structure represented by (I-16), even a person skilled in the art cannot predict that the triplet energy is maintained in a wide gap.
  • the benzodiazaborol compound of the present invention is represented by the following formula (II-1).
  • a 11 and A 12 are each independently A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted silyl group, A substituted or unsubstituted phosphino group, A substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted sulfoxide group, or a substituted or unsubstituted sulfone group,
  • a 11 and A 12 may be bonded to each other to form a 5- to 7-membered ring including a nitrogen atom and a boron atom of the benzodiazaborol skeleton. However, A 11 and A 12 are not bonded to each other to form the following 5-membered ring.
  • Rings Q 1 and Q 2 fused with the diazaborol ring are each independently A substituted or unsubstituted benzene ring, A substituted or unsubstituted benzene ring in which at least one substituted or unsubstituted condensed aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted heterocyclic aromatic ring having 5 to 24 ring atoms is condensed It is.
  • n 2 is an integer of 1 to 6, preferably 1 to 3. When n 2 is 1, L 2 is not present, When n 2 is 2 to 6, L 2 is a linking group that bridges between any of Q 1 , Q 2 , A 11 , and A 12 , or a single bond, When n 2 is 2 to 6, n 2 Q 1 , Q 2 , A 11 , and A 12 may be the same as or different from each other.
  • L 2 is a linking group
  • L 2 is a linking group
  • examples of the case where L 2 is a linking group include, for example, an ether group, a thioether group, a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, a substituted or unsubstituted ring atom number of 6 to 30 heteroaromatic ring groups, and substituted or unsubstituted amino groups, ether groups, substituted or unsubstituted benzene rings, substituted or unsubstituted dibenzofuran rings, dibenzothiophene rings, carbazole rings, substituted or unsubstituted substituted fluorene ring, and a substituted or n 2 divalent group derived from an unsubstituted biphenyl is preferred.
  • Q 1 and Q 2 are fused with at least one substituted or unsubstituted condensed aromatic ring having 10 to 30 ring carbon atoms, or substituted or unsubstituted heteroaromatic ring having 5 to 24 ring atoms.
  • condensed ring containing the benzene ring in the case of a substituted or unsubstituted benzene ring include, for example, substituted or unsubstituted phenanthrene, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorene, substituted or unsubstituted Examples thereof include substituted dibenzofuran, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted carbazole.
  • Q 1 and Q 2 are preferably substituted or unsubstituted benzene rings.
  • the benzodiazaborol compound represented by the above formula (II-1) is preferably a compound represented by the following formula (II-2).
  • R 1 to R 8 are each independently Hydrogen atom, A substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms, A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, a substituted or unsubstituted unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms bonded by an atom having sp 2 hybrid orbital property, a substituted or unsubstituted ring-formed unsaturated aliphatic hydrocarbon ring group having 3 to 20 carbon atoms bonded by an atom having sp 2 hybrid orbital property, A substituted or unsubstituted alkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted silyl group, A substituted or unsubstituted phosphino group, A substituted or unsubstituted
  • atoms having sp 2 hybrid orbital properties for example, carbon atoms having a trivalent bonding states in the aromatic ring, carbon atom or a nitrogen atom having a trivalent bonding states in the heteroaromatic ring , Carbon atom of ethylene group, oxygen atom of ether group, nitrogen atom of amino group, boron atom of boryl group, phosphorus atom of phosphino group, sulfur atom of sulfide group, trivalent bonding state in aromatic ring A carbon atom having a carbon atom, a carbon atom having a trivalent bonding state in a heteroaromatic ring, or a nitrogen atom is preferable.
  • a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or
  • a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms A substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms, A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, A substituted or unsubstituted unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted cycloalkoxy group having 3 to 20 ring carbon atoms, A substituted or unsubstituted or unsubstituted
  • the aromatic ring group includes a monocyclic aromatic hydrocarbon ring group, a condensed aromatic hydrocarbon ring group in which a plurality of hydrocarbon rings are condensed, and a group in which a plurality of hydrocarbon rings are connected by a single bond.
  • the aromatic heterocyclic group includes a monocyclic heteroaromatic ring group, a hetero-fused aromatic ring group in which a plurality of heteroaromatic rings are condensed, and an aromatic hydrocarbon ring and a heteroaromatic ring are condensed.
  • Ring-forming carbon means a carbon atom constituting a saturated hydrocarbon ring, an unsaturated hydrocarbon ring or an aromatic ring
  • ring-forming atom means an atom constituting a heteroaromatic ring
  • Examples of the aromatic ring group having 6 to 30 ring carbon atoms include phenyl group, tolyl group, xylyl group, mesityl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m- Examples thereof include a terphenyl group, a p-terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, an anthryl group, a phenalenyl group, a fluoranthenyl group, a triphenylenyl group, a naphthacenyl group, a chrycenyl group, and a pyrenyl group.
  • phenyl, o-biphenyl, m-biphenyl, p-biphenyl, m-terphenyl, p-terphenyl, naphthyl, phenanthryl, and triphenylenyl are preferred.
  • Heteroaromatic ring groups having 5 to 30 ring atoms include pyrrolyl, pyrazinyl, pyridinyl, pyrimidinyl, pyridazinyl, triazinyl, indolyl, isoindolyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl Group, azacarbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, triazolyl group, imidazolyl group, benzoimidazolyl group, furyl group, benzofuranyl group, isobenzofuranyl group, Dibenzofuranyl, dioxanyl, oxazolyl, pyranyl, benzo [c] dibenzofuranyl, dibenzothiophenyl, thienyl,
  • alkyl group having 1 to 20 carbon atoms examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, and n-hexyl group.
  • the alkyl group having 3 to 20 carbon atoms is one obtained by removing the methyl group and the ethyl group from the examples of the alkyl group having 1 to 20 carbon atoms.
  • Examples of the cycloalkyl group having 3 to 20 ring carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group, and the like. Are preferred.
  • alkoxy group having 1 to 20 carbon atoms examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group and the like, and those having 3 or more carbon atoms are linear, cyclic or branched Among them, those having 1 to 6 carbon atoms are preferable.
  • Examples of the cycloalkoxy group having 3 to 20 carbon atoms include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc. Among them, those having 5 or 6 ring carbon atoms are preferable.
  • Examples of the aryloxy group having 6 to 30 ring carbon atoms include a phenoxy group and a biphenyloxy group, and a phenoxy group is preferable.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms include ethylene group, propylene group, 1-butene group, 2-butene group, 1,3-butadiene group, 2-methylpropene group, 1-pentene group, Examples include 2-pentene group, 1-hexene group, 2-hexene group, 3-hexene group and the like.
  • Examples of the unsaturated aliphatic hydrocarbon ring group having 3 to 20 ring carbon atoms include a cyclopropene group, a cyclobutene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, and a cyclooctene group.
  • the alkyl sulfide group having 1 to 20 carbon atoms is represented by —SX, and X is the above alkyl group having 1 to 20 carbon atoms.
  • An aryl sulfide group having 6 to 30 ring carbon atoms is represented by —SY, and Y is an aromatic ring group having 6 to 30 ring carbon atoms.
  • a 11 and A 12 are each independently It is preferably a substituted or unsubstituted aromatic ring group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heteroaromatic ring group having 5 to 30 ring atoms.
  • a 11 and A 12 are each independently A substituted or unsubstituted phenyl group, A substituted or unsubstituted biphenyl group, A substituted or unsubstituted terphenyl group, A substituted or unsubstituted fluorenyl group, A substituted or unsubstituted pyridinyl group, A substituted or unsubstituted pyrimidinyl group, A substituted or unsubstituted triazinyl group, A substituted or unsubstituted dibenzofuranyl group, A substituted or unsubstituted carbazolyl group, A substituted or unsubstituted dibenzothiophenyl group, A substituted or unsubstituted carbazolyl group, A substituted or unsubstituted azadibenzofuranyl group, A substituted or unsubstituted azadibenzothiophenyl group, A substituted or unsubstituted azacar
  • At least one of R 1 to R 8 is preferably a substituent bonded by an atom having sp 2 property that is not a hydrogen atom.
  • R 1 to R 8 are each independently A substituted or unsubstituted phenyl group, A substituted or unsubstituted biphenyl group, A substituted or unsubstituted terphenyl group, A substituted or unsubstituted fluorenyl group, A substituted or unsubstituted pyridinyl group, A substituted or unsubstituted pyrimidinyl group, A substituted or unsubstituted triazinyl group, A substituted or unsubstituted dibenzofuranyl group, A substituted or unsubstituted carbazolyl group, A substituted or unsubstituted dibenzothiophenyl group, A substituted or unsubstituted carbazolyl group, A substituted or unsubstituted azadibenzofuranyl group, A substituted or unsubstituted azadibenzothiophenyl group, A substituted or unsubstituted
  • “Unsubstituted” in “substituted or unsubstituted...” Means that a hydrogen atom is substituted.
  • a hydrogen atom is an isotope having a different neutron number, that is, light hydrogen. (Protium), deuterium, tritium.
  • Any substituents of Q 1 , Q 2 , A 11 , A 12 , and R 1 to R 8 may further have a substituent.
  • the compound of the present invention represented by the formula (II-1) can be synthesized by the method described in Examples or a method known to those skilled in the art.
  • the compound of the present invention represented by the formula (II-1) is excellent in electrochemical oxidative stability as compared with conventional benzodiazaborol compounds. This effect is obtained when each of the benzene rings constituting the two benzodiazaborol skeletons further has an aromatic ring group or a heteroaromatic ring group at the nitrogen atom of the two diazaborol rings condensed with the compound of the present invention. In particular, it is more prominent when it has a specific substituent or fused ring bonded by an atom having sp 2 hybrid orbital properties.
  • the compound of the present invention represented by the formula (II-1) not only improves the electrochemical oxidation stability, but also has a shallow ionization potential, so that holes of the organic EL element are injected or transported. When used as a material in a layer, a further lower voltage can be expected. Furthermore, although it is known that the triplet energy of the 1,3,2-diazaborol ring itself is a wide gap, it has a skeleton in which two benzodiazaborol skeletons are condensed via a boron atom and a nitrogen atom.
  • the triplet energy has a wide gap even when it has a structure represented by the formula (II-1) having an aromatic ring group or a heteroaromatic ring group at two nitrogen atoms that are not used for the condensation of the diazaborol ring. It will not be anticipated by those skilled in the art that it will be maintained.
  • the material for an organic electroluminescence element (organic EL element) of the present invention includes the compound of the present invention represented by the above formula (1).
  • the material for an organic EL device of the present invention can be suitably used as a material for an organic thin film layer constituting the organic EL device.
  • the organic EL device of the present invention has one or more organic thin film layers including a light emitting layer between an anode and a cathode. And at least 1 layer of an organic thin film layer contains the organic EL element material of this invention.
  • the organic EL device of the present invention has an organic thin film layer containing a light emitting layer between a cathode and an anode, and at least one of the organic thin film layers contains the above-described organic EL device material of the present invention.
  • the life of the organic EL element can be extended.
  • the organic thin film layer containing the organic EL device material of the present invention include a hole transport layer, a light emitting layer, an electron transport layer, a space layer, and a barrier layer, but are not limited thereto. Absent.
  • the material for an organic EL device of the present invention is preferably contained in the light emitting layer, and particularly preferably used as a host material for the light emitting layer. Further, the light emitting layer preferably contains a fluorescent light emitting material or a phosphorescent light emitting material, and particularly preferably contains a phosphorescent light emitting material. Furthermore, the organic EL device material of the present invention is also suitable as an organic layer used in a hole transport zone, It is also suitable as a material added to the hole transport zone.
  • the organic EL element of the present invention may be a fluorescent or phosphorescent monochromatic light emitting element, a fluorescent / phosphorescent hybrid white light emitting element, or a simple type having a single light emitting unit.
  • a tandem type having a plurality of light emitting units may be used, and among them, a phosphorescent type is preferable.
  • the “light emitting unit” refers to a minimum unit that includes one or more organic layers, one of which is a light emitting layer, and can emit light by recombination of injected holes and electrons.
  • typical element configurations of simple organic EL elements include the following element configurations.
  • Anode / light emitting unit / cathode The above light emitting unit may be a laminated type having a plurality of phosphorescent light emitting layers and fluorescent light emitting layers. In that case, the light emitting unit is generated by a phosphorescent light emitting layer between the light emitting layers. In order to prevent the excitons from diffusing into the fluorescent light emitting layer, a space layer may be provided. A typical layer structure of the light emitting unit is shown below.
  • A Hole transport layer / light emitting layer (/ electron transport layer)
  • B Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer (/ electron transport layer)
  • C Hole transport layer / phosphorescent layer / space layer / fluorescent layer (/ electron transport layer)
  • D Hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
  • E Hole transport layer / first phosphorescent light emitting layer / space layer / second phosphorescent light emitting layer / space layer / fluorescent light emitting layer (/ electron transport layer)
  • F Hole transport layer / phosphorescent layer / space layer / first fluorescent layer / second fluorescent layer (/ electron transport layer)
  • G Hole transport layer / electron barrier layer / light emitting layer (/ electron transport layer)
  • H Hole transport layer / light emitting layer / hole barrier layer (
  • Each phosphorescent or fluorescent light-emitting layer may have a different emission color.
  • hole transport layer / first phosphorescent light emitting layer (red light emitting) / second phosphorescent light emitting layer (green light emitting) / space layer / fluorescent light emitting layer (blue light emitting) / Examples include a layer configuration such as an electron transport layer.
  • An electron barrier layer may be appropriately provided between each light emitting layer and the hole transport layer or space layer.
  • a hole blocking layer may be appropriately provided between each light emitting layer and the electron transport layer.
  • the following element structure can be mentioned as a typical element structure of a tandem type organic EL element.
  • the intermediate layer is generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer, and has electrons in the first light emitting unit and holes in the second light emitting unit.
  • a known material structure to be supplied can be used.
  • FIG. 1 is a schematic view showing a layer structure of an embodiment of the organic EL device of the present invention.
  • the organic EL element 1 has a configuration in which an anode 20, a hole transport zone 30, a light emitting layer 40, an electron transport zone 50, and a cathode 60 are laminated on a substrate 10 in this order.
  • the hole transport zone 30 refers to an organic layer sandwiched between the anode 20 and the light emitting layer 40, and means, for example, a hole transport layer, a hole injection layer, an electron barrier layer, or the like.
  • the electron transport zone 50 refers to an organic layer sandwiched between the cathode 60 and the light emitting layer 40, and means, for example, an electron transport layer, an electron injection layer, a hole barrier layer, or the like.
  • the barrier layer can confine electrons and holes in the light emitting layer 40 and increase the probability of exciton generation in the light emitting layer 40. These need not be formed, but preferably one or more layers are formed.
  • the organic thin film layer is each organic layer provided in the hole transport zone 30, each light emitting layer 40, and each organic layer provided in the electron transport zone 50.
  • at least one layer contains the organic EL element material of the present invention.
  • the content of this material with respect to one organic thin film layer containing the organic EL element material of the present invention is preferably 1 to 100% by weight.
  • a host combined with a fluorescent dopant is referred to as a fluorescent host
  • a host combined with a phosphorescent dopant is referred to as a phosphorescent host.
  • the fluorescent host and the phosphorescent host are not distinguished only by the molecular structure. That is, the phosphorescent host means a material constituting a phosphorescent light emitting layer containing a phosphorescent dopant, and does not mean that it cannot be used as a material constituting a fluorescent light emitting layer. The same applies to the fluorescent host.
  • the organic EL element of the present invention is produced on a translucent substrate.
  • the light-transmitting substrate is a substrate that supports the organic EL element, and is preferably a smooth substrate having a light transmittance in the visible region of 400 nm to 700 nm of 50% or more.
  • a glass plate, a polymer plate, etc. are mentioned.
  • the glass plate include those using soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like as raw materials.
  • the polymer plate include those using polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone and the like as raw materials.
  • the anode of the organic EL element plays a role of injecting holes into the hole transport layer or the light emitting layer, and it is effective to use a material having a work function of 4.5 eV or more.
  • Specific examples of the anode material include indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide, gold, silver, platinum, copper, and the like.
  • the anode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. When light emitted from the light emitting layer is extracted from the anode, it is preferable that the transmittance of light in the visible region of the anode is greater than 10%.
  • the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ or less.
  • the film thickness of the anode depends on the material, but is usually selected in the range of 10 nm to 1 ⁇ m, preferably 10 nm to 200 nm.
  • the cathode plays a role of injecting electrons into the electron injection layer, the electron transport layer or the light emitting layer, and is preferably formed of a material having a small work function.
  • the cathode material is not particularly limited, and specifically, indium, aluminum, magnesium, magnesium-indium alloy, magnesium-aluminum alloy, aluminum-lithium alloy, aluminum-scandium-lithium alloy, magnesium-silver alloy and the like can be used.
  • the cathode can be produced by forming a thin film by a method such as vapor deposition or sputtering. Moreover, you may take out light emission from the cathode side as needed.
  • An organic layer having a light emitting function includes a host material and a dopant material.
  • the host material mainly has a function of encouraging recombination of electrons and holes and confining excitons in the light emitting layer, and the dopant material efficiently emits excitons obtained by recombination. It has a function.
  • the host material mainly has a function of confining excitons generated by the dopant in the light emitting layer.
  • the light emitting layer employs, for example, a double host (also referred to as host / cohost) that adjusts the carrier balance in the light emitting layer by combining an electron transporting host and a hole transporting host.
  • the light emitting layer preferably contains a first host material and a second host material, and the first host material is preferably the organic EL device material of the present invention.
  • you may employ adopt the double dopant from which each dopant light-emits by putting in 2 or more types of dopant materials with a high quantum yield. Specifically, a mode in which yellow emission is realized by co-evaporating a host, a red dopant, and a green dopant to make the light emitting layer common is used.
  • the above light-emitting layer is a laminate in which a plurality of light-emitting layers are stacked, so that electrons and holes are accumulated at the light-emitting layer interface, and the recombination region is concentrated at the light-emitting layer interface to improve quantum efficiency. Can do.
  • the ease of injecting holes into the light emitting layer may be different from the ease of injecting electrons, and the hole transport ability and electron transport ability expressed by the mobility of holes and electrons in the light emitting layer may be different. May be different.
  • the light emitting layer can be formed by a known method such as a vapor deposition method, a spin coating method, or an LB method (Langmuir Broadgett method).
  • the light emitting layer can also be formed by thinning a solution obtained by dissolving a binder such as a resin and a material compound in a solvent by a spin coating method or the like.
  • the light emitting layer is preferably a molecular deposited film.
  • the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state.
  • the thin film (molecular accumulation film) formed by the LB method can be classified by the difference in the aggregation structure and the higher-order structure, and the functional difference resulting therefrom.
  • the dopant material is selected from known fluorescent dopants exhibiting fluorescent emission or phosphorescent dopants exhibiting phosphorescent emission.
  • the fluorescent dopant is selected from fluoranthene derivatives, pyrene derivatives, arylacetylene derivatives, fluorene derivatives, boron complexes, perylene derivatives, oxadiazole derivatives, anthracene derivatives, chrysene derivatives, and the like.
  • a fluoranthene derivative, a pyrene derivative, and a boron complex are used.
  • the phosphorescent dopant (phosphorescent material) that forms the light emitting layer is a compound that can emit light from the triplet excited state, and is not particularly limited as long as it emits light from the triplet excited state, but Ir, Pt, Os, Au, Cu, An organometallic complex containing at least one metal selected from Re and Ru and a ligand is preferable.
  • the ligand preferably has an ortho metal bond.
  • a metal complex containing a metal atom selected from Ir, Os and Pt is preferred in that the phosphorescent quantum yield is high and the external quantum efficiency of the light emitting device can be further improved, and an iridium complex, an osmium complex, or a platinum complex.
  • iridium complexes and platinum complexes are more preferable, and orthometalated iridium complexes are particularly preferable.
  • the content of the phosphorescent dopant in the light emitting layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 0.1 to 70% by mass, more preferably 1 to 30% by mass. If the phosphorescent dopant content is 0.1% by mass or more, sufficient light emission can be obtained, and if it is 70% by mass or less, concentration quenching can be avoided.
  • the phosphorescent host is a compound having a function of efficiently emitting the phosphorescent dopant by efficiently confining the triplet energy of the phosphorescent dopant in the light emitting layer.
  • the organic EL device material of the present invention is suitable as a phosphorescent host.
  • the light emitting layer may contain 1 type of organic EL element material of this invention, and may contain 2 or more types of organic EL element material of this invention.
  • the emission wavelength of the phosphorescent dopant material contained in the light emitting layer is not particularly limited.
  • at least one of the phosphorescent dopant materials contained in the light emitting layer preferably has an emission wavelength peak of 430 nm to 700 nm, and more preferably 440 nm to 650 nm.
  • a compound other than the material for the organic EL device of the present invention can be appropriately selected as the phosphorescent host according to the purpose.
  • the organic EL device material of the present invention and other compounds may be used in combination as a phosphorescent host material in the same light emitting layer, and when there are a plurality of light emitting layers, the phosphorescent host of one of the light emitting layers.
  • the material for an organic EL device of the present invention may be used as a material, and a compound other than the material for an organic EL device of the present invention may be used as a phosphorescent host material for another light emitting layer.
  • the organic EL device material of the present invention can be used for organic layers other than the light emitting layer. In that case, a compound other than the organic EL device material of the present invention is used as the phosphorescent host of the light emitting layer. May be.
  • compounds other than the organic EL device material of the present invention and suitable as a phosphorescent host include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, Pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrins Compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidene derivatives And metal complexes of heterocycl
  • the organic EL element material of the present invention is used as the first host material
  • the organic EL element material other than the organic EL element material of the present invention is used as the second host material.
  • a compound may be used.
  • the terms “first host material” and “second host material” mean that the plurality of host materials contained in the light emitting layer have different structures from each other. It is not specified by the material content. It does not specifically limit as said 2nd host material, It is a compound other than the organic EL element material of this invention, and the same thing as the above-mentioned compound as a compound suitable as a phosphorescent host is mentioned.
  • the second host material a compound having no cyano group is preferable.
  • the second host is preferably a carbazole derivative, arylamine derivative, fluorenone derivative, or aromatic tertiary amine compound.
  • the thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and still more preferably 10 to 50 nm.
  • the thickness is 5 nm or more, it is easy to form a light emitting layer, and when the thickness is 50 nm or less, an increase in driving voltage can be avoided.
  • the organic EL device of the present invention preferably has an electron donating dopant in the interface region between the cathode and the light emitting unit. According to such a configuration, it is possible to improve the light emission luminance and extend the life of the organic EL element.
  • the electron donating dopant means a material containing a metal having a work function of 3.8 eV or less, and specific examples thereof include alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earths. Examples thereof include at least one selected from metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and the like.
  • alkali metal examples include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like.
  • a function of 2.9 eV or less is particularly preferable. Of these, K, Rb, and Cs are preferred, Rb and Cs are more preferred, and Cs is most preferred.
  • alkaline earth metals include Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), and the like. The thing below 9 eV is especially preferable.
  • rare earth metals examples include Sc, Y, Ce, Tb, Yb, and the like, and those having a work function of 2.9 eV or less are particularly preferable.
  • alkali metal compound examples include alkali oxides such as Li 2 O, Cs 2 O, and K 2 O, and alkali halides such as LiF, NaF, CsF, and KF, and LiF, Li 2 O, and NaF are preferable.
  • alkaline earth metal compound examples include BaO, SrO, CaO, and Ba x Sr 1-x O (0 ⁇ x ⁇ 1), Ba x Ca 1-x O (0 ⁇ x ⁇ 1) mixed with these. BaO, SrO, and CaO are preferable.
  • the rare earth metal compound, YbF 3, ScF 3, ScO 3, Y 2 O 3, Ce 2 O 3, GdF 3, TbF 3 and the like, YbF 3, ScF 3, TbF 3 are preferable.
  • the alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as each metal ion contains at least one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion.
  • the ligands include quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxydiaryl thiadiazole, hydroxydiaryl thiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, Hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, ⁇ -diketones, azomethines, and derivatives thereof are preferred, but are not limited thereto.
  • the electron donating dopant it is preferable to form a layered or island shape in the interface region.
  • a forming method while depositing an electron donating dopant by resistance heating vapor deposition, an organic compound (light emitting material or electron injecting material) that forms an interface region is simultaneously deposited, and the electron donating dopant is dispersed in the organic compound.
  • the electron donating dopant is formed in a layered form
  • the reducing dopant is vapor-deposited by a resistance heating vapor deposition method. .1 nm to 15 nm.
  • the electron donating dopant is formed in an island shape
  • the electron donating dopant is deposited by resistance heating vapor deposition alone, preferably The island is formed with a thickness of 0.05 nm to 1 nm.
  • the electron transport layer is an organic layer formed between the light emitting layer and the cathode, and has a function of transporting electrons from the cathode to the light emitting layer.
  • an organic layer close to the cathode may be defined as an electron injection layer.
  • the electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit.
  • an aromatic heterocyclic compound containing one or more heteroatoms in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable.
  • the nitrogen-containing ring derivative is preferably an aromatic ring having a nitrogen-containing 6-membered ring or 5-membered ring skeleton, or a condensed aromatic ring compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton.
  • the thickness of the electron transport layer is not particularly limited, but is preferably 1 nm to 100 nm. Moreover, it is preferable to use an insulator or a semiconductor as an inorganic compound in addition to the nitrogen-containing ring derivative as a component of the electron injection layer that can be provided adjacent to the electron transport layer. If the electron injection layer is made of an insulator or a semiconductor, current leakage can be effectively prevented and the electron injection property can be improved.
  • an insulator it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. If the electron injection layer is composed of these alkali metal chalcogenides or the like, it is preferable in that the electron injection property can be further improved.
  • preferable alkali metal chalcogenides include, for example, Li 2 O, K 2 O, Na 2 S, Na 2 Se, and Na 2 O
  • preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS and CaSe.
  • preferable alkali metal halides include, for example, LiF, NaF, KF, LiCl, KCl, and NaCl.
  • preferable alkaline earth metal halides include fluorides such as CaF 2 , BaF 2 , SrF 2 , MgF 2 and BeF 2 , and halides other than fluorides.
  • the inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film. If the electron injection layer is composed of these insulating thin films, a more uniform thin film is formed, and pixel defects such as dark spots can be reduced. Examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides.
  • the preferred thickness of the layer is about 0.1 nm to 15 nm.
  • the electron injection layer in the present invention is preferable even if it contains the above-mentioned electron donating dopant.
  • an organic layer close to the anode may be defined as a hole injection layer.
  • the hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit.
  • the organic EL device material of the present invention is also suitable as a hole injection layer and a hole transport layer.
  • an aromatic amine compound for example, an aromatic amine derivative represented by the following formula (H) is preferably used.
  • Ar 1 ⁇ Ar 4 is a substituted or an aromatic hydrocarbon group or fused aromatic hydrocarbon group unsubstituted ring carbon atoms 6 to 50, a substituted or unsubstituted ring atoms of 5 to 50 aromatic heterocyclic groups or condensed aromatic heterocyclic groups, or a group in which these aromatic hydrocarbon groups or condensed aromatic hydrocarbon groups and aromatic heterocyclic groups or condensed aromatic heterocyclic groups are bonded.
  • L represents a substituted or unsubstituted aromatic hydrocarbon group or condensed aromatic hydrocarbon group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring forming atom number of 5 to 50. Represents an aromatic heterocyclic group or a condensed aromatic heterocyclic group.
  • An aromatic amine represented by the following formula (J) is also preferably used for forming the hole transport layer.
  • the hole transport layer of the organic EL device of the present invention may have a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).
  • the thickness of the hole transport layer is not particularly limited, but is preferably 10 to 200 nm.
  • a layer containing an acceptor material may be bonded to the anode side of the hole transport layer or the first hole transport layer. This is expected to reduce drive voltage and manufacturing costs.
  • the acceptor material a compound represented by the following formula (K) is preferable.
  • R 21 to R 26 may be the same as or different from each other, and each independently represents a cyano group, —CONH 2 , a carboxyl group, or —COOR 27 (R 27 is a group having 1 to 20 carbon atoms) Represents an alkyl group or a cycloalkyl group having 3 to 20 carbon atoms, provided that one or more pairs of R 21 and R 22 , R 23 and R 24 , and R 25 and R 26 are combined together.
  • a group represented by —CO—O—CO— may be formed.
  • R 27 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
  • the thickness of the layer containing the acceptor material is not particularly limited, but is preferably 5 to 20 nm.
  • n doping is a method of doping a metal such as Li or Cs into an electron transport material
  • p doping is F 4 TCNQ (2, 3, 5, 6) as a hole transport material.
  • the space layer is a fluorescent layer for the purpose of adjusting the carrier balance so that excitons generated in the phosphorescent layer are not diffused into the fluorescent layer. It is a layer provided between the layer and the phosphorescent light emitting layer.
  • the space layer can be provided between the plurality of phosphorescent light emitting layers. Since the space layer is provided between the light emitting layers, a material having both electron transport properties and hole transport properties is preferable. In order to prevent diffusion of triplet energy in the adjacent phosphorescent light emitting layer, the triplet energy is preferably 2.6 eV or more. Examples of the material used for the space layer include the same materials as those used for the above-described hole transport layer.
  • the organic EL device of the present invention preferably has a barrier layer such as an electron barrier layer, a hole barrier layer, or a triplet barrier layer in a portion adjacent to the light emitting layer.
  • the electron barrier layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transport layer
  • the hole barrier layer is a layer that prevents holes from leaking from the light emitting layer to the electron transport layer. is there.
  • the triplet barrier layer prevents the triplet excitons generated in the light emitting layer from diffusing into the surrounding layers, and confins the triplet excitons in the light emitting layer, thereby transporting electrons other than the light emitting dopant of the triplet excitons. It has a function of suppressing energy deactivation on the molecules of the layer.
  • the phosphorescent devices When providing the triplet barrier layer, the phosphorescent devices, triplet energy E T d of the phosphorescent dopant in the light emitting layer and the triplet energy of the compound used as a triplet barrier layer and E T TB, E T d ⁇ If the energy magnitude relationship of E T TB is satisfied, the triplet exciton of the phosphorescent dopant is confined (cannot move to other molecules) and the energy deactivation path other than light emission on the dopant is interrupted. It is assumed that light can be emitted with high efficiency.
  • the organic EL element material of the present invention can be used as a triplet barrier layer having a TTF element structure described in International Publication WO2010 / 134350A1.
  • the electron mobility of the material constituting the triplet barrier layer is desirably 10 ⁇ 6 cm 2 / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm.
  • the electron mobility is determined by impedance spectroscopy.
  • the electron injection layer is desirably 10 ⁇ 6 cm 2 / Vs or more in the range of electric field strength of 0.04 to 0.5 MV / cm. This facilitates the injection of electrons from the cathode into the electron transport layer, and also promotes the injection of electrons into the adjacent barrier layer and the light emitting layer, thereby enabling driving at a lower voltage.
  • Cyclic voltammetry was measured using an Electrochemical Analyzer 630B manufactured by ALS as an apparatus under the following conditions and measurement procedures.
  • Electrochemical Analyzer 630B manufactured by ALS as an apparatus under the following conditions and measurement procedures.
  • electrode Working electrode: Glassy carbon Reference electrode: Ag / Ag + Counter electrode: Pt Electrolyte: Tetrabutylammonium perchlorate Measurement solvent: N, N-dimethylformamide Measurement atmosphere: Nitrogen potential Scan rate: Range of 0.005 V / sec to 0.1 V / sec
  • the cyclic voltammetry measurement data of Compound 7 is shown in FIG. From FIG. 2, it can be read that reversible oxidation waves are shown, and it can be seen that Compound 7 has high electrochemical oxidation stability.
  • the cyclic voltammetry measurement data of Comparative Example Compound E1 is shown in FIG. From FIG. 3, it can be seen that an irreversible oxidation wave is shown, and it can be seen that Compound E1 has low electrochemical oxidation stability.
  • Ionization potential A thin film of the measurement compound was formed on the ITO substrate by a vacuum deposition method or a coating method, and the measurement was performed using a commercially available atmospheric photoelectron spectrometer AC-3 (manufactured by Riken Keiki Co., Ltd.).
  • Example 3 A glass substrate with a 130 nm-thick ITO electrode line (manufactured by Geomatec) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes.
  • the glass substrate with the ITO electrode line after the cleaning is mounted on the substrate holder of the vacuum evaporation apparatus, and first, the compound HI1 is formed with a thickness of 20 nm on the surface on which the ITO electrode line is formed so as to cover the ITO electrode line. Subsequently, compound HT1 was deposited by resistance heating with a thickness of 60 nm, and thin films were sequentially formed. The film formation rate was 1 ⁇ / s. These thin films function as a hole injection layer and a hole transport layer, respectively.
  • Compound 7 and Compound BD1 were simultaneously deposited by resistance heating to form a thin film having a thickness of 50 nm.
  • the compound BD1 was vapor-deposited so that the mass ratio was 20% with respect to the total mass of the compound 7 and the compound BD1.
  • the film formation rates were 1.2 ⁇ / s and 0.3 ⁇ / s, respectively.
  • This thin film functions as a phosphorescent light emitting layer, in which the compound 7 functions as a host and the compound BD1 functions as a light emitting dopant.
  • a thin film having a thickness of 10 nm was formed on the phosphorescent light emitting layer by resistance heating vapor deposition of Compound B1. This thin film functions as a hole blocking layer.
  • the film formation rate was 1.2 liter / s.
  • a thin film having a thickness of 10 nm was formed on the hole barrier layer by resistance heating vapor deposition of the compound ET1.
  • the film formation rate was 1 ⁇ / s.
  • This film functions as an electron injection layer.
  • LiF having a film thickness of 1.0 nm was deposited on the electron injection layer at a film formation rate of 0.1 ⁇ / s.
  • metallic aluminum was vapor-deposited on the LiF film at a deposition rate of 8.0 ⁇ / s to form a metal cathode with a film thickness of 80 nm to obtain an organic EL element.
  • the element performance (half life (time until a brightness
  • Comparative Example 4 An organic EL device was prepared and evaluated in the same manner as in Example 3 except that Compound E3 was used as the host of the phosphorescent light emitting layer instead of Compound 7. The results are shown in Table 2. The “half life (relative%)” is a relative ratio when the half life of the element of Example 3 is 100%.
  • Example 4 A glass substrate with a 130 nm-thick ITO electrode line (manufactured by Geomatec) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes.
  • the glass substrate with the ITO electrode line after the cleaning is mounted on the substrate holder of the vacuum evaporation apparatus, and first, the compound HI1 is formed with a thickness of 20 nm on the surface on which the ITO electrode line is formed so as to cover the ITO electrode line. Subsequently, compound HT1 was deposited by resistance heating with a thickness of 60 nm, and thin films were sequentially formed. The film formation rate was 1 ⁇ / s. These thin films function as a hole injection layer and a hole transport layer, respectively.
  • the compound (20) and the compound BD1 were simultaneously deposited by resistance heating to form a thin film having a thickness of 50 nm.
  • the compound BD1 was vapor-deposited so that the mass ratio was 20% with respect to the total mass of the compound (20) and the compound BD1.
  • the film formation rates were 1.2 ⁇ / s and 0.3 ⁇ / s, respectively.
  • This thin film functions as a phosphorescent light emitting layer, in which the compound (20) functions as a host and the compound BD1 functions as a light emitting dopant.
  • a thin film having a thickness of 10 nm was formed on the phosphorescent light emitting layer by resistance heating vapor deposition of Compound B1. This thin film functions as a hole blocking layer.
  • the film formation rate was 1.2 liter / s.
  • a thin film having a thickness of 10 nm was formed on the hole barrier layer by resistance heating vapor deposition of the compound ET1.
  • the film formation rate was 1 ⁇ / s.
  • This film functions as an electron injection layer.
  • LiF having a film thickness of 1.0 nm was deposited on the electron injection layer at a film formation rate of 0.1 ⁇ / s.
  • metallic aluminum was vapor-deposited on the LiF film at a deposition rate of 8.0 ⁇ / s to form a metal cathode with a film thickness of 80 nm to obtain an organic EL element.
  • the element performance (half life (time until a brightness
  • Comparative Example 5 An organic EL device was prepared and evaluated in the same manner as in Example 4 except that compound E3 was used as the host of the phosphorescent light emitting layer instead of compound (20). The results are shown in Table 3. The “half life (relative%)” is a relative ratio when the half life of the element of Example 4 is 100%.
  • Example 8 A glass substrate with a 130 nm-thick ITO electrode line (manufactured by Geomatec) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes.
  • the glass substrate with the ITO electrode line after the cleaning is mounted on the substrate holder of the vacuum evaporation apparatus, and first, the compound HI1 is formed with a thickness of 20 nm on the surface on which the ITO electrode line is formed so as to cover the ITO electrode line. Subsequently, compound HT1 was deposited by resistance heating with a thickness of 60 nm, and thin films were sequentially formed. The film formation rate was 1 ⁇ / s. These thin films function as a hole injection layer and a hole transport layer, respectively.
  • Compound 7 and Compound BD1 were simultaneously deposited by resistance heating to form a thin film having a thickness of 40 nm.
  • the compound BD1 was vapor-deposited so that the mass ratio was 20% with respect to the total mass of the compound 7 and the compound BD1.
  • the film formation rates were 1.2 ⁇ / s and 0.3 ⁇ / s, respectively.
  • This thin film functions as a phosphorescent light emitting layer, in which the compound 7 functions as a host and the compound BD1 functions as a light emitting dopant.
  • a thin film having a thickness of 5 nm was formed on the phosphorescent light emitting layer by resistance heating vapor deposition of Compound 7. This thin film functions as a hole blocking layer.
  • the film formation rate was 1.2 liter / s.
  • a compound having a thickness of 25 nm was formed on the hole barrier layer by resistance heating vapor deposition of the compound ET1.
  • the film formation rate was 1 ⁇ / s.
  • This film functions as an electron injection layer.
  • LiF having a film thickness of 1.0 nm was deposited on the electron injection layer at a film formation rate of 0.1 ⁇ / s.
  • metallic aluminum was vapor-deposited on the LiF film at a deposition rate of 8.0 ⁇ / s to form a metal cathode with a film thickness of 80 nm to obtain an organic EL element.
  • Example 9 An organic EL device was obtained in the same manner as in Example 8, except that Compound 12 was used instead of Compound 7.
  • Example 10 An organic EL device was obtained in the same manner as in Example 8 except that Compound 15 was used instead of Compound 7.
  • Example 11 An organic EL device was obtained in the same manner as in Example 8 except that Compound 73 was used instead of Compound 7.
  • Comparative Example 6 An organic EL device was produced in the same manner as in Example 8 except that Compound E2 was used instead of Compound 7, but E2 had a very low vapor deposition temperature and could not form a uniform thin film. It was not possible to produce an organic EL device capable of measuring Comparative Example 7 An organic EL device was obtained in the same manner as in Example 8 except that Compound E3 was used instead of Compound 7.
  • the obtained organic EL element it was made to light-emit by constant current drive, the brightness
  • Example 12 A glass substrate with a 130 nm-thick ITO electrode line (manufactured by Geomatec) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes.
  • the glass substrate with the ITO electrode line after the cleaning is mounted on the substrate holder of the vacuum evaporation apparatus, and first, the compound HI1 is formed with a thickness of 20 nm on the surface on which the ITO electrode line is formed so as to cover the ITO electrode line. Then, compound HT1 was deposited by resistance heating with a thickness of 50 nm, and a thin film was sequentially formed. The film formation rate was 1 ⁇ / s. These thin films function as a hole injection layer and a first hole transport layer, respectively.
  • a thin film having a thickness of 10 nm was formed on the hole transport layer by resistance heating vapor deposition of compound 73.
  • This thin film functions as a second hole transport layer.
  • Compound B1 and Compound BD1 were simultaneously deposited by resistance heating to form a thin film having a thickness of 40 nm.
  • the compound BD1 was vapor-deposited so that the mass ratio was 20% with respect to the total mass of the compound 7 and the compound BD1.
  • the film formation rates were 1.2 ⁇ / s and 0.3 ⁇ / s, respectively.
  • This thin film functions as a phosphorescent light emitting layer, in which the compound 7 functions as a host and the compound BD1 functions as a light emitting dopant.
  • a thin film having a thickness of 5 nm was formed on the phosphorescent light emitting layer by resistance heating vapor deposition of Compound 7. This thin film functions as a hole blocking layer.
  • the film formation rate was 1.2 liter / s.
  • a compound having a thickness of 25 nm was formed on the hole barrier layer by resistance heating vapor deposition of the compound ET1.
  • the film formation rate was 1 ⁇ / s.
  • This film functions as an electron injection layer.
  • LiF having a film thickness of 1.0 nm was deposited on the electron injection layer at a film formation rate of 0.1 ⁇ / s.
  • metallic aluminum was vapor-deposited on the LiF film at a deposition rate of 8.0 ⁇ / s to form a metal cathode with a film thickness of 80 nm to obtain an organic EL element.
  • Comparative Example 8 An organic EL device was obtained in the same manner as in Example 12 except that the compound E3 was used instead of the compound 73. About the obtained organic EL element, it was made to light-emit by constant current drive, the brightness
  • the compound of the present invention Since the compound of the present invention has high electrochemical oxidation stability, it is extremely useful as a material for organic electronics elements.

Abstract

La présente invention concerne un composé benzodiazaborole représenté par la formule (1) (où le cycle Q qui est fusionné avec un cycle diazaborole est un cycle benzénique substitué ou non substitué, un cycle aromatique fusionné substitué ou non substitué, ou un cycle benzénique substitué ou non substitué avec lequel au moins un cycle hétéroaromatique substitué ou non substitué est fusionné).
PCT/JP2013/004167 2012-07-06 2013-07-04 Composé benzodiazaborole, et matériau pour élément électroluminescent organique et élément électroluminescent organique l'utilisant WO2014006913A1 (fr)

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US9768397B2 (en) 2014-03-31 2017-09-19 Commonwealth Scientific And Industrial Research Organisation Phenylenediamine compounds for phosphorescent diazaborole metal complexes
US9859504B2 (en) 2014-03-31 2018-01-02 Commonwealth Scientific And Industrial Research Organisation Diamine compounds for phosphorescent diazaborole metal complexes and electroluminescent devices
WO2016167491A1 (fr) * 2015-04-13 2016-10-20 덕산네오룩스 주식회사 Composé pour élément électronique organique, élément électronique organique utilisant ce composé, et appareil électronique
JP2020533358A (ja) * 2017-09-12 2020-11-19 メルク パテント ゲーエムベーハー 有機エレクトロルミネッセンスデバイスのための材料
CN109867690A (zh) * 2017-12-01 2019-06-11 元智大学 苯并二氮杂硼杂环戊二烯化合物以及有机发光二极管组件
US11495752B2 (en) 2018-10-08 2022-11-08 Universal Display Corporation Organic electroluminescent materials and devices
CN112390829A (zh) * 2019-08-15 2021-02-23 环球展览公司 有机电致发光材料和装置
US11930699B2 (en) 2019-08-15 2024-03-12 Universal Display Corporation Organic electroluminescent materials and devices
CN111518122A (zh) * 2020-05-29 2020-08-11 南京知研科技有限公司 一种硼氮杂多芳环化合物及其用途
WO2023171231A1 (fr) * 2022-03-07 2023-09-14 キヤノン株式会社 Composé organique et dispositif électroluminescent organique

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