WO2013146942A1 - Nouveau composé, matériau pour élément électroluminescent organique, et élément électroluminescent organique - Google Patents

Nouveau composé, matériau pour élément électroluminescent organique, et élément électroluminescent organique Download PDF

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WO2013146942A1
WO2013146942A1 PCT/JP2013/059127 JP2013059127W WO2013146942A1 WO 2013146942 A1 WO2013146942 A1 WO 2013146942A1 JP 2013059127 W JP2013059127 W JP 2013059127W WO 2013146942 A1 WO2013146942 A1 WO 2013146942A1
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substituted
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carbon atoms
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井上　哲也
由美子 水木
伸浩 藪ノ内
西村　和樹
茎子 日比野
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Idemitsu Kosan Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • 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
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—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 two hetero rings
    • C07D403/10—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 two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to a novel compound, a material for an organic electroluminescence element, and an organic electroluminescence element.
  • an organic electroluminescence element (hereinafter also referred to as an organic EL element)
  • holes from the anode and electrons from the cathode are injected into the light emitting layer.
  • the injected holes and electrons are recombined to form excitons.
  • singlet excitons and triplet excitons are generated at a ratio of 25%: 75% according to the statistical rule of electron spin.
  • the fluorescence type uses light emitted from singlet excitons, and therefore the internal quantum efficiency of the organic EL element is said to be limited to 25%.
  • the phosphorescent type since light emission by triplet excitons is used, it is known that the internal quantum efficiency can be increased to 100% when intersystem crossing is efficiently performed from singlet excitons.
  • an optimal element design has been made according to a light emission mechanism of a fluorescent type and a phosphorescent type.
  • phosphorescent organic EL elements cannot obtain high-performance elements by simple diversion of fluorescent element technology because of their light emission characteristics.
  • the reason is generally considered as follows.
  • phosphorescence emission is emission using triplet excitons
  • the energy gap of the compound used for the light emitting layer must be large. This is because the value of the singlet energy of a compound (the energy difference between the lowest excited singlet state and the ground state) is usually the triplet energy of the compound (the energy between the lowest excited triplet state and the ground state). This is because it is larger than the value of the difference.
  • a host material having a triplet energy larger than the triplet energy of the phosphorescent dopant material must be used for the light emitting layer. I must.
  • a compound having a triplet energy larger than that of the phosphorescent dopant material must be used for the electron transport layer and the hole transport layer.
  • a compound having a larger energy gap is used for the phosphorescent organic EL element as compared with the compound used for the fluorescent organic EL element. Connected. As a result, the driving voltage of the entire phosphorescent organic EL element increases.
  • hydrocarbon compounds having high oxidation resistance and reduction resistance which are useful in fluorescent organic EL devices, have a large energy gap due to a large ⁇ electron cloud spread. Therefore, in a phosphorescent organic EL element, such a hydrocarbon compound is difficult to select, and an organic compound containing a hetero atom such as oxygen or nitrogen is selected.
  • a phosphorescent organic EL element using an organic compound containing a hetero atom for a light emitting layer has a problem that its lifetime is shorter than that of a fluorescent organic EL element.
  • the exciton relaxation rate of the triplet exciton of the phosphorescent dopant material is much longer than that of the singlet exciton also greatly affects the device performance. That is, since light emitted from singlet excitons has a high relaxation rate that leads to light emission, the diffusion of excitons to the peripheral layers of the light-emitting layer (for example, a hole transport layer or an electron transport layer) hardly occurs and is efficient. Light emission is expected. On the other hand, light emission from triplet excitons is light emission based on spin-forbidden transition and has a slow relaxation rate. Therefore, excitons are easily diffused to the peripheral layer of the light emitting layer, and thermal energy deactivation occurs from other than the specific phosphorescent compound.
  • the light-emitting layer for example, a hole transport layer or an electron transport layer
  • the phosphorescent organic EL element it is more important to control the recombination region of electrons and holes than the fluorescent organic EL element. For the above reasons, in order to improve the performance of phosphorescent organic EL elements, it is necessary to select materials and design elements different from those of fluorescent organic EL elements.
  • a carbazole derivative is known as a compound used in a phosphorescent organic EL device.
  • a carbazole derivative has a carbazole skeleton which shows high triplet energy and is known as a main skeleton of a hole transporting material.
  • Carbazole derivatives have been used as useful phosphorescent host materials.
  • Patent Documents 1 and 2 disclose that a compound in which two carbazole rings are bonded via a linking group is used as a material for an organic EL device. However, it is still required to improve the light emission efficiency of the organic EL element, and development of a compound capable of improving the light emission efficiency and a material for the organic EL element containing the compound is desired.
  • An object of the present invention is to provide a novel compound capable of lowering the driving voltage of an organic electroluminescence element and improving luminous efficiency, and a material for an organic electroluminescence element containing the compound. Furthermore, the objective of this invention is aiming at the reduction in the drive voltage of an organic electroluminescent element, and the improvement of luminous efficiency using the said compound or the said material for organic electroluminescent elements.
  • the present inventors have found that in a biscarbazole derivative in which two carbazoles or azacarbazoles (hereinafter referred to as carbazole derivatives) are linked, two carbazole derivatives And a substituted or unsubstituted 6-membered condensed polycyclic aromatic hydrocarbon having 3 to 6 ring atoms directly or directly to at least one of the two linked carbazole derivatives. It has been found that by connecting through another linking group, the driving voltage of the organic electroluminescence device using the biscarbazole derivative can be lowered and the luminous efficiency can be improved. The present inventors have completed the present invention based on such findings.
  • the compound of the present invention is represented by the following general formula (1).
  • a 1 and A 2 each independently represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms.
  • Y 1 to Y 16 each independently represent CR or a nitrogen atom. However, among Y 5 to Y 12 , those bonded to L 3 are carbon atoms.
  • R are independent of each other, Hydrogen atom, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, A substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms, A substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, A substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted haloalkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, A substituted
  • L 1 and L 2 each independently represent a single bond or a linking group. However, at least one of A 1 , A 2 and R represents a substituted or unsubstituted condensed polycyclic aromatic hydrocarbon group having 3 to 6 ring members.
  • L 3 is a linking group represented by any of the following general formulas (2) to (4), or a linking group represented by the following general formulas (2) to (4). Represents a combined linking group.
  • Y 17 to Y 34 each independently represents CH or a nitrogen atom.
  • n, m and p each independently represent an integer of 1 to 5.
  • L 3 is a composite linking group in which the linking groups represented by the general formulas (2) to (4) are combined, n + m + p is an integer of 1 to 5.
  • Y 17 to Y 34 are preferably CH.
  • the substituted or unsubstituted condensed polycyclic aromatic hydrocarbon group having 6 to 6 ring members in at least one of A 1 , A 2 and R in the general formula (1) is a substituted or unsubstituted fluorane.
  • the general formula (1) is preferably represented by any one of the following general formulas (5) to (7).
  • a 1 , A 2 , Y 1 to Y 5 , Y 7 to Y 10 , Y 12 to Y 16 , L 1 , L 2 and L 3 are each represented by the general formula (1)
  • Y 6 and Y 11 represent a carbon atom.
  • a 1 , A 2 , Y 1 to Y 5 , Y 7 to Y 9 , Y 11 to Y 16 , L 1 , L 2 and L 3 are respectively represented by the general formula (1) and Synonymous, Y 6 and Y 10 represent a carbon atom.
  • a 1 , A 2 , Y 1 to Y 6 , Y 8 to Y 9 , Y 11 to Y 16 , L 1 , L 2 and L 3 are respectively represented by the general formula (1) and Y 7 and Y 10 are synonymous and represent a carbon atom.
  • those bonded to L 3 are preferably carbon atoms, and other Y 5 to Y 12 are preferably CH.
  • Any one of A 1 and A 2 in the general formula (1) and the general formulas (5) to (7) is a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted triphenylenyl group, substituted or unsubstituted Substituted benzophenanthrenyl group, substituted or unsubstituted benzotriphenylenyl group, substituted or unsubstituted dibenzotriphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted benzochrysenyl group, substituted or unsubstituted Selected from the group consisting of a substituted picenyl group, a substituted or unsubstituted benzofluoranthenyl group, and a substituted or unsubstituted phenanthrenyl group;
  • the other of A 1 and A 2 is a substituted or unsubstituted
  • n in the general formula (2), m in the general formula (3), and p in the general formula (4) each independently represent an integer of 1 to 3.
  • L 3 in the general formula (1) is preferably a linking group represented by the general formula (2).
  • the organic electroluminescent element material of the present invention contains any of the compounds of the present invention.
  • the organic electroluminescence element of the present invention is A cathode, The anode, One or more organic thin film layers including a light emitting layer disposed between the cathode and the anode; Have At least one of the organic thin film layers contains the compound.
  • the light emitting layer preferably contains the compound.
  • the light emitting layer preferably contains a phosphorescent material.
  • the phosphorescent material is preferably an orthometalated complex of metal atoms selected from iridium (Ir), osmium (Os), and platinum (Pt).
  • the light emitting layer preferably contains a compound represented by the following general formula (21).
  • Z 1 represents a ring structure represented by the following general formula (21-1) or (21-2) condensed in a.
  • Z 2 represents a ring structure represented by the following general formula (21-1) or (21-2) condensed at b.
  • M is a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group having 5 to 30 ring atoms
  • L 11 is A single bond or a linking group,
  • q is 1 or 2.
  • R 11 and R 31 are each independently Hydrogen atom, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, A substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms, A substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
  • R 11 may be bonded to each other to form a ring.
  • X 3 is a sulfur atom, an oxygen atom, N—R 32 , or C (R 32 ) 2 ; R 32 has the same meaning as R 11 and R 31 above. ]
  • the compound represented by the general formula (21) is preferably represented by the following general formula (22).
  • Z 1 represents a ring structure represented by the general formula (21-1) or (21-2) condensed in a.
  • Z 2 represents a ring structure represented by the general formula (21-1) or (21-2) condensed at b.
  • L 11 has the same meaning as L 11 in the general formula (21).
  • X 1 is a nitrogen atom or C—R 10 , and at least one of the plurality of X 1 is a nitrogen atom.
  • R 1 and R 10 have the same meaning as R 11 in the general formula (21-1).
  • q and r each independently represents 1 or 2.
  • c represents condensation in a or b in the general formula (21).
  • any one of d, e, and f represents condensation in a or b in the general formula (21).
  • the compound represented by the general formula (21) is preferably represented by the following general formula (23).
  • L 11 has the same meaning as L 11 in the general formula (21).
  • X 1 is a nitrogen atom or C—R 10 , and at least one of the plurality of X 1 is a nitrogen atom.
  • R 1 , R 10 and R 11 have the same meaning as R 11 in the general formula (21-1).
  • q and r each independently represents 1 or 2.
  • the compound represented by the general formula (21) is preferably represented by the following general formula (24).
  • L 11 is the same meaning as L 11, R 1 in the general formula (21), R 11 is the same as defined in the general formula (21-1).
  • L 13 and L 14 have the same meaning as L 11 in the general formula (21).
  • X 1 is a nitrogen atom or C—R 10 , and at least one of the plurality of X 1 is a nitrogen atom.
  • R 10 has the same meaning as R 11 in formula (21-1).
  • r represents 1 or 2.
  • M 3 is, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms.
  • h and k are each independently an integer of 0 to 4, and
  • i and j are each independently an integer of 0 to 3.
  • the present invention it is possible to provide a novel compound capable of lowering the driving voltage of an organic electroluminescence element and improving the light emission efficiency, and a material for an organic electroluminescence element containing the compound. Furthermore, according to the present invention, the driving voltage of the organic electroluminescent element can be lowered and the luminous efficiency can be improved by using the compound or the material for the organic electroluminescent element.
  • FIG. 2 is a diagram showing a chemical formula of Compound A.
  • FIG. It is a figure which shows the molecular orbital diagram of the compound A shown to FIG. 1A.
  • 2 is a view showing a chemical formula of Compound B.
  • FIG. It is a figure which shows the molecular orbital diagram of the compound B shown to FIG. 2A.
  • a 1 and A 2 are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring forming carbon number 1 to 30 aromatic heterocyclic groups are represented.
  • Y 1 to Y 16 each independently represent CR or a nitrogen atom. However, among Y 5 to Y 12 , those bonded to L 3 are carbon atoms.
  • the CR is a compound in which R is bonded to a carbon atom (C).
  • each R independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms.
  • Kill diarylsilyl group a substituted or unsubstituted triarylsilyl group having a carbon number of 18-60, a halogen atom, a cyano group, a hydroxyl group, a nitro group, or a carboxy group.
  • the plurality of R are the same or different.
  • two adjacent ones of Y 1 to Y 16 are CR, a part of R in adjacent CRs may be bonded to form a ring structure.
  • At least one of A 1 , A 2 and R represents a condensed polycyclic aromatic hydrocarbon group having 6 to 6 ring members.
  • the substituted or unsubstituted condensed polycyclic aromatic hydrocarbon group having 3 to 6 ring members in at least one of A 1 , A 2 and R in the general formula (1) is substituted.
  • At least one of A 1 and A 2 in the general formula (1) is preferably a substituted or unsubstituted condensed polycyclic aromatic hydrocarbon group having 3 to 6 ring members.
  • one of A 1 and A 2 in the general formula (1) is substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted triphenylenyl group, substituted or unsubstituted benzophenanthrenyl group, substituted or Unsubstituted benzotriphenylenyl group, substituted or unsubstituted dibenzotriphenylenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted benzochrysenyl group, substituted or unsubstituted picenyl group, substituted or unsubstituted benzo Selected from the group consisting of a fluoranthenyl group and a substituted or unsubstituted phenanthrenyl
  • a 1 in the general formula (1) is a group selected from the substituent group A, and A 2 in the general formula (1) is a substituted or unsubstituted ring-forming carbon number of 6 to 30 An aromatic hydrocarbon group,
  • a 2 in the general formula (1) is a group selected from the substituent group A, and A 1 in the general formula (1) is a substituted or unsubstituted ring carbon having 6 to 30 carbon atoms.
  • a 1 and A 2 may be the same or different from each other.
  • the substituent group A is preferably a group consisting of a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted triphenylenyl group, and a substituted or unsubstituted phenanthrenyl group.
  • At least one of A 1 , A 2 and R, more preferably at least one of A 1 and A 2 is substituted or unsubstituted 6-membered ring number 3
  • the charge transporting property of the compound represented by the general formula (1) is improved, and it has an appropriate triplet energy as a phosphorescent host material.
  • the charge transport property is lowered.
  • the triplet energy becomes too small and energy cannot be transmitted to the phosphorescent dopant material.
  • L 1 and L 2 each independently represent a single bond or a linking group.
  • the linking group in L 1 and L 2 of the general formula (1) include a divalent group derived from a substituted or unsubstituted aromatic hydrocarbon compound having 6 to 30 ring carbon atoms, or a substituted or unsubstituted group. And a divalent group derived from an aromatic heterocyclic compound having 1 to 30 ring carbon atoms.
  • At least one of L 1 and L 2 is a divalent group derived from a substituted or unsubstituted aromatic hydrocarbon compound having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring forming carbon number 1 to 30
  • the divalent group is derived from the aromatic heterocyclic compound, the electron transport property tends to be improved. Therefore, it is desirable to appropriately select L 1 and L 2 for the purpose of adjusting the balance of carrier transport properties of the compound represented by the general formula (1).
  • the selection of L 1 and L 2 as appropriate is also effective when the compound of the present invention represented by the general formula (1) is used as a host material for the light emitting layer in the organic EL device.
  • examples of the substituent include groups obtained by removing a hydrogen atom from the groups listed for R in the CR.
  • L 3 is a linking group represented by any of the following general formulas (2) to (4), or a linking group represented by the following general formulas (2) to (4). Represents a combined linking group.
  • Y 17 to Y 34 each independently represent CH or a nitrogen atom.
  • This CH represents one in which a hydrogen atom (H) is bonded to a carbon atom (C).
  • n, m and p each independently represent an integer of 1 to 5.
  • L 3 is a composite linking group in which the linking groups represented by the general formulas (2) to (4) are combined
  • n + m + p is an integer of 1 to 5 (preferably 2 to 5, more preferably 2 to 4, more preferably 2 or 3).
  • the composite linking group can be constituted by arbitrarily combining the linking groups represented by the general formulas (2) to (4).
  • Preferred examples of the composite linking group include the following combinations of structures.
  • Y 17 to Y 34 are preferably CH, and are represented by the following general formulas (2A) to (4A), respectively.
  • Y 17 to Y 34 are preferably CH, and examples thereof include the following structures.
  • n in the general formula (2), m in the general formula (3), and p in the general formula (4) each independently represent an integer of 1 to 3.
  • L 3 in the general formula (1) is preferably a linking group represented by the general formula (2), and more preferably a linking group represented by the general formula (2A).
  • n is more preferably 1 or 2, and n is particularly preferably 1.
  • any one of Y 5 to Y 8 is bonded to L 3
  • any one of Y 9 to Y 12 is bonded to L 3 .
  • the bonding position is Y 6 -L 3 -Y 11 , Y 6 -L 3 -Y 10 , Y 6 -L 3 -Y 12 , Y 6 -L 3 -Y 9 , Y 7 -L.
  • the compound represented by the general formula (1) is preferably represented by any one of the following general formulas (5) to (7).
  • a 1 , A 2 , Y 1 to Y 5 , Y 7 to Y 10 , Y 12 to Y 16 , L 1 , L 2, and L 3 are respectively represented by the general formula (1) and Synonymous, Y 6 and Y 11 represent a carbon atom.
  • a 1 , A 2 , Y 1 to Y 5 , Y 7 to Y 9 , Y 11 to Y 16 , L 1 , L 2 and L 3 are respectively represented by the general formula (1) and Synonymous, Y 6 and Y 10 represent a carbon atom.
  • a 1 , A 2 , Y 1 to Y 6 , Y 8 to Y 9 , Y 11 to Y 16 , L 1 , L 2 and L 3 are respectively represented by the general formula (1) and Y 7 and Y 10 are synonymous and represent a carbon atom.
  • the general formula (1) it is preferable that among Y 5 to Y 12 , those bonded to L 3 are carbon atoms, and other Y 5 to Y 12 are CH.
  • the general formulas (5) to (7) are represented by the following general formulas (5A) to (7A).
  • Examples of the aromatic hydrocarbon group having 6 to 30 ring carbon atoms in the general formulas (1) and (5) to (7) include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 1-anthryl group.
  • the aromatic hydrocarbon group preferably has 6 to 20 ring-forming carbon atoms, and more preferably 6 to 12 carbon atoms.
  • a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a terphenyl group, a fluorenyl group, and a triphenylenyl group are particularly preferable.
  • the substituted or unsubstituted carbon in the above general formulas (1), (5) to (7) is attached to the 9-position carbon atom. It is preferable that an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 ring carbon atoms is substituted.
  • Examples of the aromatic heterocyclic group having 1 to 30 ring carbon atoms in the general formulas (1) and (5) to (7) include, for example, a pyrrolyl group, a pyrazinyl group, a pyridinyl group, an indolyl group, an isoindolyl group, and an imidazolyl group.
  • Furyl group benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, dibenzothiophenyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, Phenazinyl group, phenothiazinyl group, phenoxazinyl group, oxazolyl group, oxadiazolyl group, furazanyl group, thienyl group, benzothiophenyl group, and pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine Ring, pyrrolidine ring, Oxan ring, piperidine ring, morpholine ring, piperazine ring, carbazo
  • the aromatic heterocyclic group preferably has 1 to 20 ring carbon atoms, and more preferably 1 to 14 carbon atoms.
  • the alkyl group having 1 to 30 carbon atoms in the general formulas (1) and (5) to (7) may be linear, branched or cyclic.
  • Examples of the linear or branched alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n- Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- Hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpenty
  • cyclic alkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and 2- And norbornyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the linear or branched alkyl groups methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group Is preferred.
  • the cycloalkyl group preferably has 3 to 10 ring carbon atoms, and more preferably 5 to 8 carbon atoms.
  • a cyclopentyl group and a cyclohexyl group are preferable.
  • Examples of the haloalkyl group having 1 to 30 carbon atoms in the general formulas (1) and (5) to (7) include those in which the alkyl group having 1 to 30 carbon atoms is substituted with one or more halogen atoms. It is done. Specific examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, and a trifluoromethylmethyl group.
  • the alkenyl group having 2 to 30 carbon atoms in the general formulas (1) and (5) to (7) may be linear, branched or cyclic, for example, vinyl, propenyl, butenyl, oleyl Eicosapentaenyl, docosahexaenyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl and the like.
  • a vinyl group is preferable.
  • the alkynyl group having 2 to 30 carbon atoms in the general formulas (1) and (5) to (7) may be linear, branched or cyclic, and examples thereof include ethynyl, propynyl and 2-phenyl. And ethynyl. Of the alkynyl groups described above, an ethynyl group is preferred.
  • Examples of the alkylsilyl group having 3 to 30 carbon atoms in the general formulas (1) and (5) to (7) include trialkylsilyl groups having an alkyl group exemplified as the alkyl group having 1 to 30 carbon atoms.
  • the three alkyl groups in the trialkylsilyl group may be the same or different.
  • the dialkylarylsilyl group having 8 to 40 carbon atoms in the general formulas (1) and (5) to (7) has, for example, two alkyl groups exemplified as the above alkyl group having 1 to 30 carbon atoms, Examples thereof include a dialkylarylsilyl group having one aromatic hydrocarbon group having 6 to 30 ring carbon atoms.
  • the carbon number of the dialkylarylsilyl group is preferably 8-30.
  • the two alkyl groups in the dialkylarylsilyl group may be the same or different.
  • the alkyldiarylsilyl group having 13 to 50 carbon atoms in the general formulas (1) and (5) to (7) has, for example, one alkyl group exemplified as the alkyl group having 1 to 30 carbon atoms, Examples thereof include an alkyldiarylsilyl group having two aromatic hydrocarbon groups having 6 to 30 ring carbon atoms.
  • the alkyldiarylsilyl group preferably has 13 to 30 carbon atoms.
  • the two aryl groups may be the same or different from each other.
  • Examples of the triarylsilyl group having 18 to 60 carbon atoms in the general formulas (1) and (5) to (7) include, for example, triaryl having three aromatic hydrocarbon groups having 6 to 30 ring carbon atoms. A silyl group is mentioned. The carbon number of the triarylsilyl group is preferably 18-30. In the triarylsilyl group, the three aromatic hydrocarbon groups may be the same or different.
  • the alkoxy group having 1 to 30 carbon atoms in the general formulas (1) and (5) to (7) is represented as —OY 1 .
  • Y 1 include the alkyl group having 1 to 30 carbon atoms.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
  • Examples of the haloalkoxy group having 1 to 30 carbon atoms in the general formulas (1) and (5) to (7) include those in which the alkoxy group having 1 to 30 carbon atoms is substituted with one or more halogen groups. Can be mentioned.
  • the aralkyl group having 7 to 30 carbon atoms in the general formulas (1) and (5) to (7) is represented as —Y 2 —Z 2 .
  • Y 2 include an alkylene group corresponding to the alkyl group having 1 to 30 carbon atoms.
  • Z 2 include the above aromatic hydrocarbon groups having 6 to 30 ring carbon atoms.
  • the aromatic hydrocarbon group moiety has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the alkyl group moiety has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
  • Examples of the aralkyl group include benzyl group, 2-phenylpropan-2-yl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, and phenyl-t-butyl.
  • ⁇ -naphthylmethyl group 1- ⁇ -naphthylethyl group, 2- ⁇ -naphthylethyl group, 1- ⁇ -naphthylisopropyl group, 2- ⁇ -naphthylisopropyl group, ⁇ -naphthylmethyl group, 1- ⁇ - Naphthylethyl group, 2- ⁇ -naphthylethyl group, 1- ⁇ -naphthylisopropyl group, 2- ⁇ -naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, m -Methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromine Benzyl group, m
  • the aryloxy group having 6 to 30 ring carbon atoms in the general formulas (1) and (5) to (7) is represented by —OZ 3 .
  • this Z 3 include the above aromatic hydrocarbon groups having 6 to 30 ring carbon atoms, or monocyclic groups and condensed ring groups described later.
  • Examples of the aryloxy group include a phenoxy group.
  • halogen atom in the general formulas (1), (5) to (7) examples include fluorine, chlorine, bromine, iodine and the like, preferably a fluorine atom.
  • ring-forming carbon means a carbon atom constituting a saturated ring, an unsaturated ring, or an aromatic ring.
  • Ring-forming atom means a carbon atom and a hetero atom constituting a hetero ring (including a saturated ring, an unsaturated ring, and an aromatic ring).
  • hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (triuterium), and tritium.
  • substituents include the aromatic hydrocarbon group, aromatic heterocyclic group, alkyl group (straight chain or branched chain alkyl group, cycloalkyl group, haloalkyl group). Group), alkoxy group, aryloxy group, aralkyl group, haloalkoxy group, alkylsilyl group, dialkylarylsilyl group, alkyldiarylsilyl group, triarylsilyl group, halogen atom, cyano group, hydroxyl group, nitro group, and carboxy group Groups.
  • an alkenyl group and an alkynyl group are also included.
  • an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkyl group, a halogen atom, an alkylsilyl group, an arylsilyl group, and a cyano group are preferable. Further, in the description of each substituent, Specific substituents that are preferred are preferred.
  • the term “unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the substituent. In the compound described below or a partial structure thereof, the case of “substituted or unsubstituted” is the same as described above.
  • the compounds represented by the general formulas (1) and (5) to (7) may be abbreviated as Cz, which is two carbazoles or azacarbazoles. Are linked by a linking group represented by L 3 or a composite linking group.
  • L 3 does not have a substituent, and two Cz are bonded at a specific position of L 3 . Therefore, in the biscarbazole derivative, the steric hindrance between L 3 and Cz is small, the planarity between L 3 and Cz is maintained, and the ⁇ -conjugated system can be expanded at the Cz-L 3 -Cz moiety.
  • HOMO highest occupied molecular orbital
  • FIG. 1B shows a molecular orbital diagram of the compound A.
  • compound B is described.
  • the other Cz is bonded at the m-position (meta-position) of the phenylene group to the site to which one Cz is bonded.
  • FIG. 2B shows a molecular orbital diagram of this compound B. Comparing the molecular orbital diagrams of Compound A and Compound B, in Compound B, as shown in FIG. 2B, the ⁇ -electron conjugation is broken at the positions of the 2nd and 5th carbon atoms of the phenylene group. . On the other hand, in the compound A, as shown in FIG. 1B, conjugation of ⁇ electrons is expanded in the phenylene group.
  • the biscarbazole derivative has an appropriate triplet energy as a phosphorescent host material because it is linked by L 3 having a specific structure represented by any one of the general formulas (2) to (4). Therefore, the biscarbazole derivative is suitable as a phosphorescent host material, and in particular, becomes a phosphorescent host material suitable for a phosphorescent dopant material that emits red, yellow, and green light.
  • Patent Document 1 the following compound is described in Patent Document 1 described above, but in these compounds, two Cz are bonded by anthracene or pyrene.
  • Anthracene and pyrene are condensed polycyclic aromatic hydrocarbon groups having a relatively small triplet energy, and compounds having anthracene or pyrene as a linking group between two carbazoles have sufficient triplet energy as a phosphorescent host material. Absent.
  • Examples of specific structures of the compounds represented by the general formulas (1), (5) to (7) of the present invention include the following. However, the present invention is not limited to compounds having these structures.
  • the method for producing the compounds represented by the general formulas (1), (5) to (7) is not particularly limited, and may be produced by a known method.
  • a copper catalyst described in “Tetrahedron, Volume 40 (1984), P. 1435-1456” or “Journal of American Chemical Society” (Journal of the American Chemical Society), 123 (2001), P. 7727 to 7729 ” can be used for the production by a coupling reaction using a palladium catalyst.
  • the compound of the present invention can be used as a material for an organic EL device.
  • the organic EL device material of the present invention can be used for forming an organic thin film layer of an organic EL device.
  • the material for an organic EL device of the present invention may contain any of the compounds represented by the general formulas (1) and (5) to (7), or the general formulas (1) and ( In addition to any of the compounds represented by 5) to (7), other compounds may be contained.
  • the organic EL element in the first embodiment of the present invention has a cathode, an anode, and an organic thin film layer disposed between the cathode and the anode.
  • the organic thin film layer is composed of one layer or a plurality of layers.
  • at least one of the organic thin film layers is a light emitting layer. Therefore, the organic thin film layer may be composed of, for example, a single light emitting layer, such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole barrier layer, an electron barrier layer, etc. You may have the layer employ
  • the organic thin film layer may contain an inorganic compound.
  • the compound of the present invention is contained in an organic thin film layer. If there are a plurality of organic thin film layers, at least one of the layers contains the compound of the present invention alone or as a component of a mixture.
  • the light emitting layer contains the compound of the present invention. In this case, the light emitting layer preferably includes the compound of the present invention as a host material and further includes a dopant material.
  • the “light emitting layer” is an organic layer having a light emitting function, and includes a host material and a dopant material when a doping system is employed.
  • 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.
  • hole injection / transport layer means “at least one of a hole injection layer and a hole transport layer”
  • electron injection / transport layer means “an electron injection layer and an electron transport layer”. "At least one of them”.
  • the positive hole injection layer is provided in the anode side.
  • the electron injection layer refers to an organic layer having the highest electron mobility among the organic layers in the electron transport region existing between the light emitting layer and the cathode.
  • the layer is an electron transport layer.
  • a barrier layer that does not necessarily have high electron mobility is used to prevent diffusion of excitation energy generated in the light emitting layer.
  • the organic layer adjacent to the light emitting layer does not necessarily correspond to the electron transport layer.
  • FIG. 3 schematic structure of an example of the organic EL element in embodiment of this invention is shown.
  • An organic EL element 1 shown in FIG. 3 includes a transparent substrate 2, an anode 3, a cathode 4, and an organic thin film layer 10 disposed between the anode 3 and the cathode 4.
  • the organic thin film layer 10 includes a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and an electron injection layer 9 in order from the anode 3 side.
  • the organic EL element of the present invention is produced on a light-transmitting 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 injection layer, the hole transport layer, or the light emitting layer, and it is effective to have 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.
  • the light transmittance in the visible region of the anode be greater than 10%.
  • the sheet resistance of the anode is preferably several hundred ⁇ / ⁇ (ohm / square) 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 a material having a small work function is preferable for the purpose of injecting electrons into the electron injection layer, the electron transport layer, or the light emitting layer.
  • 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.
  • the aspect which takes out light emission from a cathode side is also employable.
  • the light emitting layer of the organic EL element provides a field for recombination of electrons and holes, and has a function of connecting this to light emission.
  • 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.
  • a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coating method or the like.
  • a light emitting layer can be formed.
  • the host material is preferably the compound of the present invention or the material for an organic EL device of the present invention containing the compound of the present invention.
  • the biscarbazole derivative which is the compound of the present invention is formed and stacked in the organic thin film layer of the organic EL element, the overlap of ⁇ electrons between the molecules of the biscarbazole derivative increases, and the organic thin film layer The charge transport property of the is improved.
  • the compound of the present invention has charge transport properties when at least one of A 1 and A 2 is a condensed polycyclic aromatic hydrocarbon.
  • the compound of the present invention in the light emitting layer of the organic EL device, the charge balance in the light emitting layer can be improved, and the voltage of the organic EL device can be lowered and the efficiency can be increased.
  • the compound of the present invention since the HOMO at the Cz-L 3 -Cz portion and the LUMO of the polycyclic fused aromatic hydrocarbon group can be separated, the compound of the present invention has resistance to holes and electrons. It is considered excellent. Therefore, the lifetime of the organic EL device can be improved by including the compound of the present invention in the organic thin film layer.
  • the light emitting layer may further contain another host material as a host material.
  • the dopant material is selected from a known fluorescent material exhibiting fluorescence emission or a phosphorescent material exhibiting phosphorescence emission.
  • Fluorescent materials used as dopant materials include fluoranthene derivatives, pyrene derivatives, arylacetylene derivatives, fluorene derivatives, boron complexes, perylene derivatives, oxadiazole derivatives, anthracene derivatives, chrysene Selected from derivatives and the like.
  • a fluoranthene derivative, a pyrene derivative, and a boron complex are used.
  • a phosphorescent material used as a dopant material preferably contains a metal complex.
  • the metal complex has a metal atom selected from iridium (Ir), platinum (Pt), osmium (Os), gold (Au), rhenium (Re), and ruthenium (Ru) and a ligand. Is preferred.
  • an orthometalated complex in which a ligand and a metal atom form an orthometal bond is preferable.
  • the phosphorescent dopant material contains a metal selected from iridium (Ir), osmium (Os) and platinum (Pt) in that the phosphorescent quantum yield is high and the external quantum efficiency of the light emitting device can be further improved.
  • Ortho-metalated complexes are preferred. From the viewpoint of luminous efficiency, a metal complex composed of a ligand selected from phenylquinoline, phenylisoquinoline, phenylpyridine, phenylpyrimidine, phenylpyrazine and phenylimidazole is preferable.
  • the biscarbazole derivative which is the compound of the present invention has a suitable triplet energy as a phosphorescent host material. Therefore, it is suitable as a phosphorescent host material, and in particular, a phosphorescent host material suitable for a phosphorescent dopant material that emits light in red, yellow, and green.
  • a phosphorescent dopant material may be used independently and may use 2 or more types together.
  • the emission wavelength of the phosphorescent dopant material contained in the light emitting layer is not particularly limited, but at least one of the phosphorescent dopant materials contained in the light emitting layer preferably has a peak emission wavelength of 490 nm to 700 nm. More preferably, it is 650 nm or less.
  • red, yellow, and green are preferable, for example.
  • the compound of the present invention as the host material and doping the phosphorescent dopant material having such an emission wavelength to form the light emitting layer, an organic EL device having a low driving voltage, high efficiency and long life can be obtained.
  • the hole injection layer and the hole transport layer are layers that assist hole injection into the light emitting layer and transport to the light emitting region, and a compound that has high hole mobility and low ionization energy is used.
  • a material for forming the hole injection layer and the hole transport layer a material that transports holes to the light emitting layer with lower electric field strength is preferable.
  • an aromatic amine compound is preferably used.
  • a porphyrin compound an aromatic tertiary amine compound or a styrylamine compound.
  • an aromatic tertiary amine compound such as hexacyanohexaazatriphenylene (HAT) is used. It is preferable to use it.
  • the electron injection layer and the electron transport layer are layers that assist injection of electrons into the light emitting layer and transport to the light emitting region, and a compound having a high electron mobility is used.
  • a compound having a high electron mobility is used as the compound used for the electron injection layer and the electron transport layer.
  • an aromatic heterocyclic compound containing one or more hetero atoms in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable.
  • a nitrogen-containing ring derivative a heterocyclic compound having a nitrogen-containing 6-membered ring or 5-membered ring skeleton is preferable.
  • the organic thin film layers such as a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and a barrier layer other than the light emitting layer are conventionally used in addition to the compounds exemplified above.
  • Arbitrary compounds can be selected and used from well-known compounds used in the organic EL device.
  • the hole injection / transport layer is a layer that assists hole injection into the light emitting layer and transports it to the light emitting region, and has a high hole mobility and a low ionization energy.
  • the hole injection / transport layer may be constituted by a hole injection layer or a hole transport layer, or may be constituted by laminating a hole injection layer and a hole transport layer.
  • a material for forming the hole injecting / transporting layer a material that transports holes to the light emitting layer with lower electric field strength is preferable, and an aromatic amine compound, for example, an aromatic amine derivative represented by the following general formula (A1) Are preferably used.
  • Ar 1 to Ar 4 are each independently An aromatic hydrocarbon group having 6 to 50 ring carbon atoms, An aromatic heterocyclic group having 2 to 40 ring carbon atoms, It represents a group in which these aromatic hydrocarbon groups and these aromatic heterocyclic groups are bonded, or a group in which these aromatic hydrocarbon groups and these aromatic heterocyclic groups are bonded.
  • the aromatic hydrocarbon group and aromatic heterocyclic group mentioned here may have a substituent.
  • L is a linking group, A divalent aromatic hydrocarbon group having 6 to 50 ring carbon atoms, A divalent aromatic heterocyclic group having 5 to 50 ring carbon atoms, A single bond of two or more aromatic hydrocarbon groups or aromatic heterocyclic groups, Ether bond, Thioether bond, An alkylene group having 1 to 20 carbon atoms, An alkenylene group having 2 to 20 carbon atoms, or a divalent group obtained by bonding with an amino group, Represents.
  • the divalent aromatic hydrocarbon group and divalent aromatic heterocyclic group mentioned here may have a substituent.
  • An aromatic amine represented by the following general formula (A2) is also preferably used for forming the hole injection / transport layer.
  • the electron injection / transport layer is a layer that assists injection of electrons into the light emitting layer, and has a high electron mobility.
  • the electron injection layer is provided to adjust the energy level, for example, to alleviate a sudden change in the energy level.
  • the electron injection / transport layer includes at least one of an electron injection layer and an electron transport layer.
  • the electron injection layer may be a layer that functions as an electron transport layer. “As a main component” means that the electron injection layer contains 50% by mass or more of a nitrogen-containing ring derivative.
  • an aromatic heterocyclic compound containing one or more hetero atoms such as nitrogen, oxygen, sulfur and phosphorus in the molecule is preferably used, and a nitrogen-containing ring derivative is particularly preferable.
  • a nitrogen-containing ring derivative the aromatic ring compound which has a nitrogen-containing 6-membered ring or 5-membered ring skeleton is preferable.
  • this nitrogen-containing ring derivative for example, a nitrogen-containing ring metal chelate complex represented by the following general formula (B1) is preferable.
  • R 2 to R 7 in the general formula (B1) are each independently Hydrogen atom, A halogen atom, An oxy group, An amino group, A hydrocarbon group having 1 to 40 carbon atoms, An alkoxy group, An aryloxy group, An alkoxycarbonyl group, or An aromatic heterocyclic group, These may have a substituent.
  • the halogen atom include fluorine, chlorine, bromine and iodine.
  • the optionally substituted amino group include an alkylamino group, an arylamino group, and an aralkylamino group.
  • the alkoxycarbonyl group is represented as —COOY ′, and examples of Y ′ include the same as the alkyl group.
  • the alkylamino group and the aralkylamino group are represented as —NQ 1 Q 2 .
  • Specific examples of Q 1 and Q 2 are the same as those described above for the alkyl group and the aralkyl group (a group in which a hydrogen atom of an alkyl group is substituted with an aryl group). Preferred examples Is the same.
  • One of Q 1 and Q 2 may be a hydrogen atom.
  • the aralkyl group is a group in which a hydrogen atom of the alkyl group is substituted with the aryl group.
  • the arylamino group is represented as —NAr 1 Ar 2, and specific examples of Ar 1 and Ar 2 are the same as those described for the aromatic hydrocarbon group independently.
  • One of Ar 1 and Ar 2 may be a hydrogen atom.
  • M in the general formula (B1) is aluminum (Al), gallium (Ga), or indium (In), and is preferably In.
  • L in the general formula (B1) is a group represented by the following general formula (B2) or (B3).
  • R 8 to R 12 are each independently A hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, and groups adjacent to each other may form a cyclic structure. This hydrocarbon group may have a substituent.
  • R 13 to R 27 are each independently A hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, Adjacent groups may form a cyclic structure. This hydrocarbon group may have a substituent. Examples of the hydrocarbon group having 1 to 40 carbon atoms represented by R 8 to R 12 and R 13 to R 27 in the general formula (B2) and the general formula (B3) include those in the general formula (B1). those from R 2 similar to the specific examples to R 7 can be exemplified.
  • divalent group when the groups adjacent to each other from R 8 to R 12 in the general formula (B2) and R 13 to R 27 in the general formula (B3) form a cyclic structure, Examples include a tetramethylene group, a pentamethylene group, a hexamethylene group, a diphenylmethane-2,2′-diyl group, a diphenylethane-3,3′-diyl group, and a diphenylpropane-4,4′-diyl group.
  • the electron transport layer preferably contains at least one of nitrogen-containing heterocyclic derivatives represented by the following general formulas (B4) to (B6).
  • R is Hydrogen atom, An aromatic hydrocarbon group having 6 to 60 ring carbon atoms, Pyridyl group, A quinolyl group, An alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • n is an integer of 0 or more and 4 or less.
  • R 1 is Aromatic hydrocarbon group having 6 to 60 ring carbon atoms, pyridyl group, A quinolyl group, An alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • R 2 and R 3 are each independently Hydrogen atom, Aromatic hydrocarbon group having 6 to 60 ring carbon atoms, pyridyl group, A quinolyl group, An alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • L is An aromatic hydrocarbon group having 6 to 60 ring carbon atoms, a pyridinylene group, It is a quinolinylene group or a fluorenylene group.
  • Ar 1 is An aromatic hydrocarbon group having 6 to 60 ring carbon atoms, a pyridinylene group, It is a quinolinylene group.
  • Ar 2 is Aromatic hydrocarbon group having 6 to 60 ring carbon atoms, pyridyl group, A quinolyl group, An alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • Ar 3 is Aromatic hydrocarbon group having 6 to 60 ring carbon atoms, pyridyl group, A quinolyl group, An alkyl group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, or a group represented by “—Ar 1 —Ar 2 ” (Ar 1 and Ar 2 are the same as defined above), respectively.
  • 8-hydroxyquinoline or a metal complex of its derivative, an oxadiazole derivative, or a nitrogen-containing heterocyclic derivative is preferable.
  • a metal chelate oxinoid compound containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), for example, tris (8-quinolinol) aluminum is used.
  • 8-quinolinol or 8-hydroxyquinoline for example, tris (8-quinolinol
  • Ar 17 , Ar 18 , Ar 19 , Ar 21 , Ar 22 and Ar 25 are aromatic hydrocarbon groups having 6 to 40 ring carbon atoms.
  • the aromatic hydrocarbon group mentioned here may have a substituent.
  • Ar 17 and Ar 18 , Ar 19 and Ar 21 , Ar 22 and Ar 25 may be the same as or different from each other.
  • the aromatic hydrocarbon group mentioned here include a phenyl group, a naphthyl group, a biphenyl group, an anthranyl group, a perylenyl group, and a pyrenyl group.
  • a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, etc. are mentioned.
  • Ar 20 , Ar 23 and Ar 24 are A divalent aromatic hydrocarbon group having 6 to 40 ring carbon atoms.
  • the aromatic hydrocarbon group mentioned here may have a substituent.
  • Ar 23 and Ar 24 may be the same as or different from each other.
  • the divalent aromatic hydrocarbon group mentioned here include a phenylene group, a naphthylene group, a biphenylene group, an anthranylene group, a peryleneylene group, and a pyrenylene group.
  • a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, etc. are mentioned.
  • electron transfer compounds those having good thin film forming properties are preferably used.
  • Specific examples of these electron transfer compounds include the following.
  • the nitrogen-containing heterocyclic derivative as the electron transfer compound is a nitrogen-containing heterocyclic derivative composed of an organic compound having the following general formula, and includes a nitrogen-containing compound that is not a metal complex.
  • a 5-membered or 6-membered ring containing a skeleton represented by the following general formula (B7) and a structure represented by the following general formula (B8) can be given.
  • X represents a carbon atom or a nitrogen atom.
  • Z 1 and Z 2 each independently represents an atomic group capable of forming a nitrogen-containing heterocycle.
  • the nitrogen-containing heterocyclic derivative is more preferably an organic compound having a nitrogen-containing aromatic polycyclic group consisting of a 5-membered ring or a 6-membered ring. Further, in the case of such a nitrogen-containing aromatic polycyclic group having a plurality of nitrogen atoms, a skeleton combining the above general formulas (B7) and (B8) or the above general formula (B7) and the following general formula (B9) is used.
  • the nitrogen-containing aromatic polycyclic organic compound having is preferable.
  • the nitrogen-containing group of the nitrogen-containing aromatic polycyclic organic compound is selected from, for example, nitrogen-containing heterocyclic groups represented by the following general formula.
  • R is An aromatic hydrocarbon group having 6 to 40 ring carbon atoms, An aromatic heterocyclic group having 2 to 40 ring carbon atoms, An alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
  • n is an integer of 0 or more and 5 or less, and when n is an integer of 2 or more, a plurality of R may be the same or different from each other.
  • preferred specific compounds include nitrogen-containing heterocyclic derivatives represented by the following general formula (B10).
  • HAr-L 1 -Ar 1 -Ar 2 (B10)
  • HAr is A nitrogen-containing heterocyclic group having 1 to 40 ring carbon atoms.
  • L 1 is Single bond, An aromatic hydrocarbon group having 6 to 40 ring carbon atoms or an aromatic heterocyclic group having 2 to 40 ring carbon atoms.
  • Ar 1 is a divalent aromatic hydrocarbon group having 6 to 40 ring carbon atoms.
  • Ar 2 is An aromatic hydrocarbon group having 6 to 40 ring carbon atoms or an aromatic heterocyclic group having 2 to 40 ring carbon atoms.
  • the nitrogen-containing heterocyclic group, aromatic hydrocarbon group, and aromatic heterocyclic group mentioned in the description of HAr, L 1 , Ar 1 , and Ar 2 in the general formula (B10) are substituents. You may have.
  • HAr in the formula of the general formula (B10) is selected from the following group, for example.
  • L 1 in the formula (B10) is, for example, selected from the following group.
  • Ar 1 in the formula (B10) is, for example, selected from the following arylanthranyl groups.
  • R 1 to R 14 are each independently Hydrogen atom, A halogen atom, An alkyl group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 40 ring carbon atoms, An aromatic hydrocarbon group having 6 to 40 ring carbon atoms or an aromatic heterocyclic group having 2 to 40 ring carbon atoms.
  • Ar 3 is An aromatic hydrocarbon group having 6 to 40 ring carbon atoms or an aromatic heterocyclic group having 2 to 40 ring carbon atoms.
  • R 1 to R 14 in the general formula of the arylanthranyl group, and the aromatic hydrocarbon group and aromatic heterocyclic group mentioned in the description of Ar 3 may have a substituent.
  • any of R 1 to R 8 may be a nitrogen-containing heterocyclic derivative which is a hydrogen atom.
  • Ar 2 is selected from the following group, for example.
  • nitrogen-containing aromatic polycyclic organic compound as the electron transporting compound, a compound represented by the following general formula (B11) (see JP-A-9-3448) is also preferably used.
  • R 1 to R 4 are each independently Hydrogen atom, Aliphatic groups, An aliphatic cyclic group, Represents a carbocyclic aromatic ring group or a heterocyclic group. However, the aliphatic group, aliphatic cyclic group, carbocyclic aromatic ring group, and heterocyclic group mentioned here may have a substituent.
  • X 1 and X 2 each independently represent an oxygen atom, a sulfur atom, or a dicyanomethylene group.
  • the electron transport compound a compound represented by the following general formula (B12) (see JP-A No. 2000-173774) is also preferably used.
  • R 1 , R 2 , R 3 and R 4 are the same or different groups, and are an aromatic hydrocarbon group or a condensed aromatic group represented by the following general formula (B12-1) It is a hydrocarbon group.
  • R 5 , R 6 , R 7 , R 8 and R 9 are the same or different groups, and a hydrogen atom or at least one of them is a saturated or unsaturated alkoxyl group , An alkyl group, an amino group, or an alkylamino group.
  • the electron transfer compound may be a polymer compound containing the nitrogen-containing heterocyclic group or the nitrogen-containing heterocyclic derivative.
  • the thickness of the electron injection layer or the electron transport layer is not particularly limited, but is preferably 1 nm or more and 100 nm or less. Moreover, as a constituent component of the electron injection layer, it is preferable to use an insulator or a semiconductor as an inorganic compound in addition to the nitrogen-containing ring derivative. 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.
  • alkali metal chalcogenides include, for example, lithium oxide (Li 2 O), potassium oxide (K 2 O), sodium sulfide (Na 2 S), sodium selenide (Na 2 Se), and sodium oxide (Na 2 O).
  • Preferred alkaline earth metal chalcogenides include, for example, calcium oxide (CaO), barium oxide (BaO), strontium oxide (SrO), beryllium oxide (BeO), barium sulfide (BaS), and calcium selenide (CaSe).
  • Examples of preferable alkali metal halides include lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), lithium chloride (LiCl), potassium chloride (KCl), and sodium chloride (NaCl). ) And the like.
  • Examples of preferable alkaline earth metal halides include calcium fluoride (CaF 2 ), barium fluoride (BaF 2 ), strontium fluoride (SrF 2 ), magnesium fluoride (MgF 2 ), and beryllium fluoride. Examples thereof include fluorides such as (BeF 2 ) and halides other than fluorides.
  • the inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film.
  • the electron injection layer is composed of these insulating thin films, a more uniform thin film is formed, so that pixel defects such as dark spots can be reduced.
  • inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides.
  • the preferable thickness of the layer is about 0.1 nm to 15 nm.
  • the electron injection layer in this invention contains the above-mentioned reducing dopant, it is preferable.
  • the organic EL device of the present invention preferably has at least one of an electron donating dopant and an organometallic complex in an interface region between the cathode and the organic thin film layer. 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 include at least one selected from alkali metals, alkali metal compounds, alkaline earth metals, alkaline earth metal compounds, rare earth metals, rare earth metal compounds, and the like.
  • the organometallic complex include at least one selected from an organometallic complex containing an alkali metal, an organometallic complex containing an alkaline earth metal, an organometallic complex containing a rare earth metal, and the like.
  • alkali metal examples include lithium (Li) (work function: 2.93 eV), sodium (Na) (work function: 2.36 eV), potassium (K) (work function: 2.28 eV), rubidium (Rb) (work Function: 2.16 eV), cesium (Cs) (work function: 1.95 eV) and the like, and those having a work function of 2.9 eV or less are particularly preferable.
  • K, Rb, and Cs are preferred, Rb or Cs is more preferred, and Cs is most preferred.
  • alkaline earth metal examples include calcium (Ca) (work function: 2.9 eV), strontium (Sr) (work function: 2.0 eV to 2.5 eV), barium (Ba) (work function: 2.52 eV).
  • a work function of 2.9 eV or less is particularly preferable.
  • the rare earth metal examples include scandium (Sc), yttrium (Y), cerium (Ce), terbium (Tb), ytterbium (Yb) and the like, and those having a work function of 2.9 eV or less are particularly preferable.
  • preferred metals are particularly high in reducing ability, and by adding a relatively small amount to the electron injection region, it is possible to improve the light emission luminance and extend the life of the organic EL element.
  • alkali metal compound examples include lithium oxide (Li 2 O), cesium oxide (Cs 2 O), alkali oxides such as potassium oxide (K 2 O), lithium fluoride (LiF), sodium fluoride (NaF), fluorine.
  • alkali halides such as cesium fluoride (CsF) and potassium fluoride (KF), and lithium fluoride (LiF), lithium oxide (Li 2 O), and sodium fluoride (NaF) are preferable.
  • alkaline earth metal compound examples include barium oxide (BaO), strontium oxide (SrO), calcium oxide (CaO), and barium strontium oxide (Ba x Sr 1-x O) (0 ⁇ x ⁇ 1), Examples thereof include barium calcium oxide (Ba x Ca 1-x O) (0 ⁇ x ⁇ 1), and BaO, SrO, and CaO are preferable.
  • the rare earth metal compound ytterbium fluoride (YbF 3), scandium fluoride (ScF 3), scandium oxide (ScO 3), yttrium oxide (Y 2 O 3), cerium oxide (Ce 2 O 3), gadolinium fluoride (GdF 3), such as terbium fluoride (TbF 3) can be mentioned, YbF 3, ScF 3, TbF 3 are preferable.
  • the organometallic complex is not particularly limited as long as it contains at least one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion as a metal ion as described above.
  • the ligand includes quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxydiaryl oxadiazole, hydroxydiaryl thiadiazole, hydroxyphenyl pyridine, hydroxyphenyl benzimidazole, hydroxybenzotriazole, Hydroxyfulborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, ⁇ -diketones, azomethines, and derivatives thereof are preferred, but not limited thereto.
  • the addition form of the electron donating dopant and the organometallic complex is preferably formed in a layered or island shape in the interface region.
  • a forming method while depositing at least one of an electron donating dopant and an organometallic complex by a resistance heating vapor deposition method, an organic material which is a light-emitting material or an electron injection material for forming an interface region is vapor-deposited at the same time.
  • a method of dispersing at least one of a donor dopant and an organometallic complex reducing dopant is preferable.
  • At least one of the electron donating dopant and the organometallic complex in a layered form, after forming the light emitting material or the electron injecting material as the organic layer at the interface in a layered form, at least one of the electron donating dopant and the organometallic complex is formed.
  • These are vapor-deposited by a resistance heating vapor deposition method alone, preferably with a layer thickness of 0.1 nm to 15 nm.
  • the electron donating dopant and the organometallic complex is formed in an island shape
  • the electron donating dopant and the organometallic complex At least one of them is vapor-deposited by a resistance heating vapor deposition method, preferably with an island thickness of 0.05 nm to 1 nm.
  • each layer of the organic EL element of the present invention is not particularly limited. Conventionally known methods such as vacuum deposition and spin coating can be used.
  • the organic thin film layer used in the organic EL device of the present invention can be formed by vacuum deposition, molecular beam deposition (MBE, MBE; Molecular Beam Epitaxy) or a solution dipping method in a solvent, spin coating method, casting method, bar It can be formed by a known method such as a coating method or a roll coating method.
  • the thickness of the light emitting layer is preferably 5 nm to 50 nm, more preferably 7 nm to 50 nm, and most preferably 10 nm to 50 nm.
  • the thickness of each of the other organic thin film layers is not particularly limited, but is usually preferably in the range of several nm to 1 ⁇ m.
  • the organic EL device according to the second embodiment of the present invention contains the organic EL device according to the first embodiment and another material that functions as a host material in addition to the compound of the present invention in the light emitting layer. It is.
  • materials contained in addition to the compound of the present invention will be described in detail.
  • 2nd embodiment has the structure similar to above-described 1st embodiment in another structure.
  • the material contained in addition to the compound of the present invention is preferably a compound represented by the following general formula (21).
  • the compound represented by the following general formula (21) functions as a host material in the light emitting layer.
  • Z 1 represents a ring structure represented by the following general formula (21-1) or (21-2) condensed in a.
  • Z 2 represents a ring structure represented by the following general formula (21-1) or (21-2) condensed at b.
  • M is a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group having 5 to 30 ring atoms
  • L 11 is A single bond or a linking group,
  • q is 1 or 2.
  • R 11 and R 31 are each independently Hydrogen atom, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, A substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms, A substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, A substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms,
  • R 11 may be bonded to each other to form a ring.
  • X 3 is a sulfur atom, an oxygen atom, N—R 32 , or C (R 32 ) 2 ; R 32 has the same meaning as R 11 and R 31 above. ]
  • the “nitrogen-containing aromatic heterocyclic group” represented by M in the general formula (21) includes an azine ring.
  • Examples of the nitrogen-containing aromatic heterocyclic group represented by M in the general formula (21) include pyridine, pyrimidine, pyrazine, triazine, aziridine, azaindolizine, indolizine, imidazole, indole, isoindole, indazole, purine, Examples include pteridine, ⁇ -carboline, naphthyridine, quinoxaline, terpyridine, bipyridine, acridine, phenanthroline, phenazine, and imidazopyridine.
  • pyridine, pyrimidine, and triazine are preferable, and the compound represented by the general formula (21) is preferably represented by the following general formula (22).
  • Z 1 represents a ring structure represented by the general formula (21-1) or (21-2) condensed in a.
  • Z 2 represents a ring structure represented by the general formula (21-1) or (21-2) condensed at b.
  • L 11 has the same meaning as L 11 in the general formula (21).
  • X 1 is a nitrogen atom or C—R 10 , and at least one of the plurality of X 1 is a nitrogen atom.
  • R 1 and R 10 have the same meaning as R 11 in the general formula (21-1).
  • q and r each represent 1 or 2.
  • c represents condensation in a or b in the general formula (21).
  • any one of d, e, and f represents condensation in a or b in the general formula (21).
  • examples of the compound in which the general formulas (21-1) and (22-2) are condensed in a and b in the general formula (22) include those represented by the following general formula.
  • the compounds represented by the general formulas (21) and (22) are more preferably represented by the following general formula (23), and particularly preferably represented by the following general formula (24).
  • L 11 has the same meaning as L 11 in the general formula (21).
  • X 1 is a nitrogen atom or C—R 10 , and at least one of the plurality of X 1 is a nitrogen atom.
  • R 1 , R 10 and R 11 have the same meaning as R 11 in the general formula (21-1).
  • q and r each represent 1 or 2.
  • L 11 is the same meaning as L 11, R 1 in the general formula (21), R 11 is the same as defined in the general formula (21-1).
  • L 13 and L 14 have the same meaning as L 11 in the general formula (21).
  • X 1 is a nitrogen atom or C—R 10 , and at least one of the plurality of X 1 is a nitrogen atom.
  • R 10 has the same meaning as R 11 in formula (21-1).
  • r represents 1 or 2.
  • M 3 is, A substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 1 to 30 ring carbon atoms.
  • h and k are each independently an integer of 0 to 4, and
  • i and j are each independently an integer of 0 to 3.
  • each of the groups represented by R 1 , R 10 to R 11 and R 31 to R 32 has the above general formula ( 1) The groups described in the compounds represented by (5) to (7).
  • Aromatic hydrocarbon groups having 6 to 30 ring carbon atoms and aromatic heterocyclic groups having 1 to 30 ring carbon atoms represented by L 11 , L 13 and L 14 in the general formulas (21) to (24) As examples thereof, groups corresponding to the divalent groups described for the compounds represented by the general formulas (1), (5) to (7) can be given.
  • Examples of the compound represented by any one of the general formulas (21) to (24) include the following.
  • a bond having no chemical formula (CN, benzene ring, or the like) at its end represents a methyl group.
  • the compound of the present invention represented by any one of the above general formulas (1), (5) to (7) and the compound represented by the above general formulas (21) to (24) The content ratio in the light emitting layer is not particularly limited. Inclusion of the compound of the present invention represented by any one of the general formulas (1), (5) to (7) and the compound represented by the general formulas (21) to (24) in the light emitting layer The ratio is preferably in the range of 1: 100 to 100: 1 by mass ratio.
  • the light-emitting layer is represented by the compound of the present invention represented by any one of the above general formulas (1), (5) to (7) and the above general formulas (21) to (24). In addition to the compound represented, it may further contain other host materials.
  • the compound represented by any one of the general formulas (21) to (24) may be included in the organic EL device material of the present invention.
  • the configuration of the organic EL element is not limited to the configuration example of the organic EL element 1 shown in FIG.
  • an electron barrier layer may be provided on the anode side of the light emitting layer, and a hole barrier layer may be provided on the cathode side of the light emitting layer.
  • the light emitting layer is not limited to one layer, and a plurality of light emitting layers may be stacked.
  • the organic EL device has a plurality of light emitting layers, it is preferable that at least one light emitting layer contains the compound of the present invention or the material for the organic EL device.
  • these light emitting layers may be provided adjacent to each other, or may be laminated via other layers (for example, charge generation layers).
  • the compound of the present invention represented by any one of the above general formulas (1), (5) to (7) is contained in at least one organic thin film layer other than the light emitting layer. It may be.
  • the compound of the present invention may be contained in an organic thin film layer other than the light emitting layer, and the compounds represented by the general formulas (21) to (24) may be contained in the light emitting layer.
  • Synthesis Example (1-1) Synthesis of Intermediate 1 First, a method for synthesizing Intermediate 1 will be described. A synthesis scheme of Intermediate 1 is shown below.
  • Synthesis Example (1-2) Synthesis of Intermediate 2 Next, a method for synthesizing Intermediate 2 will be described. A synthesis scheme of Intermediate 2 is shown below.
  • intermediate 3 (1.6 g, 3.9 mmol), 2-bromotriphenylene (1.2 g, 3.9 mmol), tris (dibenzylideneacetone) dipalladium (0.071 g, 0.078 mmol), tri -T-Butylphosphonium tetrafluoroborate (0.091 g, 0.31 mmol), t-butoxy sodium (0.53 g, 5.5 mmol), and anhydrous toluene (20 mL) were sequentially added, and the mixture was heated to reflux for 8 hours. After cooling the reaction solution to room temperature, the organic layer was separated, and the organic solvent was distilled off under reduced pressure.
  • Synthesis Example 3 (Synthesis of Compound GH2-3) Synthesis Example (3-1): Synthesis of Intermediate 4 A synthesis scheme of Intermediate 4 is shown below.
  • Intermediate 4 was synthesized in the same manner as Intermediate 4 except that 3-bromofluoranthene was used instead of 3-bromotriphenylene.
  • the powder was identified as Intermediate 6 by FD-MS analysis.
  • Example 1 A glass substrate with an ITO transparent electrode of 25 mm ⁇ 75 mm ⁇ thickness 1.1 mm (manufactured by Geomatic Co., Ltd.) was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes and then UV ozone cleaning for 30 minutes.
  • the glass substrate with the transparent electrode line after washing is mounted on a substrate holder of a vacuum deposition apparatus, and the electron-accepting compound (HA- 1) was vapor-deposited to form a 5 nm thick HA-1 film.
  • the aromatic amine derivative (HT-3) was deposited as a first hole transport material to form a first hole transport layer having a thickness of 50 nm.
  • the aromatic amine derivative (HT-4) was deposited as a second hole transport material to form a second hole transport layer having a thickness of 60 nm. Further, a compound GH2-5 was vapor-deposited on the second hole transport layer to form a light emitting layer having a thickness of 45 nm.
  • Ir (piq) 3 was co-evaporated as a phosphorescent material. The concentration of Ir (piq) 3 was 8.0% by mass. This co-deposited film functions as a light emitting layer.
  • the compound (ET-3) was formed to a thickness of 30 nm. This ET-3 film functions as an electron transport layer.
  • the film thickness was set to 1 nm at a film forming rate of 0.1 angstrom / min.
  • Metal Al was vapor-deposited on this LiF film, and a metal cathode was formed with a film thickness of 80 nm to produce an organic EL device.
  • Examples 2 to 3 and Comparative Examples 1 to 3 An organic EL device was produced in the same manner as in Example 1 except that the light emitting layer was formed using the compounds shown in Table 1 instead of GH2-5.
  • Table 1 shows the results of measuring the luminance 2000 cd / m 2 of the organic EL devices obtained in Examples 1 to 3 and Comparative Examples 1 to 3, luminous efficiency (cd / A) at room temperature and DC constant current driving. In addition, the half life of light emission at an initial luminance of 5000 cd / m 2 , room temperature, and DC constant current driving was measured. The results are shown in Table 1.
  • the organic EL elements of Examples 1 to 3 showed a tendency toward higher efficiency and lower voltage than Comparative Examples 1 to 3.
  • Compound H-4 used for the organic EL device of Comparative Example 1 and Compound H-5 used for the organic EL device of Comparative Example 2 both have a phenyl group or naphthalene substituent at the 9-position (N-position) of the carbazole group It is a group. Since these substituents have lower electron transport properties than the condensed polycyclic aromatic hydrocarbon group having 3 to 6 ring members of the present invention, the balance between holes and electrons in the light emitting layer is lost. Conceivable.
  • Example 4 A glass substrate (manufactured by Geomatic Co., Ltd.) with an ITO transparent electrode (anode) of 25 mm ⁇ 75 mm ⁇ thickness 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes.
  • a glass substrate with a transparent electrode (anode) after cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and firstly compound HA-1 is deposited so as to cover the transparent electrode on the surface where the transparent electrode line is formed. Then, an HA-1 film having a thickness of 5 nm was formed. This HA-1 film functions as a hole injection layer.
  • a compound HT-1 was vapor-deposited on this HA-1 film to form an HT-1 film having a thickness of 65 nm.
  • This HT-1 film functions as a first hole transport layer.
  • the compound HT-2 was vapor-deposited on the HT-1 film to form a 10 nm-thick HT-2 film.
  • This GHT-2 film functions as a second hole transport layer.
  • compound GH1-1 as the first host material
  • compound GH2-1 as the second host material
  • Ir (bzq) 3 as the phosphorescent dopant material were co-evaporated. This formed the 25-nm-thick light emitting layer which shows yellow light emission.
  • concentration of a phosphorescent dopant material were 10 mass%, and the remainder was made into the 1st host material.
  • the compound ET-1 was vapor-deposited on the hole blocking layer to form a first electron transport layer having a thickness of 35 nm.
  • a compound ET-2 was vapor-deposited on the first electron transport layer to form a second electron transport layer having a thickness of 30 nm.
  • LiF was deposited on the electron transport layer at a rate of 1 kg / min to form an electron injection layer having a thickness of 1 nm.
  • metal Al was vapor-deposited on the electron injecting cathode to form a cathode having a thickness of 80 nm.
  • Examples 5 to 9 and Comparative Examples 4 to 7 The organic EL elements of Examples 5 to 9 and Comparative Examples 4 to 7 emit light using the materials shown in Table 2 as the first host material and the second host material of the light emitting layer in Example 4. An organic EL device was produced in the same manner as in Example 4 except that the layer was formed.
  • Compound H-1 used in the organic EL device of Comparative Example 4 has a structure in which two carbazoles are linked by a phenylene group.
  • the other carbazole is bonded at the m-position of the phenylene group to the site to which one carbazole is bonded. Therefore, in compound H-1, the conjugation between two carbazoles is cleaved, the ⁇ -conjugated system does not expand, and HOMO does not expand.
  • the compound H-1 used in the organic EL device of Comparative Example 5 has a structure in which two carbazoles are connected by a phenylene group having a substituent.
  • this substituent sterically affects carbazole, and twisting occurs between the plane of the phenylene group and the plane of carbazole. For this reason, in Compound H-2, the conjugation between the two carbazoles is cleaved, the ⁇ -conjugated system does not expand, and HOMO does not expand.
  • the compound H-2 did not exhibit sufficient hole transport properties, and the driving voltage was high and the light emission efficiency was low as compared with the devices of Examples 4 to 9.
  • the 9-position (N-position) substituent of carbazole is a phenyl group, and a condensed polycyclic aromatic having 6 to 6 ring members. Since the electron transport property is lower than that of a hydrocarbon group, the balance between holes and electrons in the light emitting layer is lost, and it is considered that the voltage is increased.
  • the organic EL element using the material for an organic EL element of the present invention can be used as a light emitting element in a display device or a lighting device.
  • SYMBOLS 1 Organic EL element, 2 ... Substrate, 3 ... Anode, 4 ... Cathode, 5 ... Hole injection layer, 6 ... Hole transport layer, 7 ... Light emitting layer, 8 ... Electron transport layer, 9 ... Electron injection layer, 10 ... Organic thin film layer.

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Abstract

Composé exprimé par la formule générale (1). Dans la formule générale (1), Y1 à Y16 représentent chacun indépendamment CR ou un atome d'azote. Au moins un des A1, A2, et R représente un groupe hydrocarbure aromatique polycyclique condensé, substitué ou non. L'élément électroluminescent organique selon l'invention est doté d'une couche organique en film mince entre une électrode positive et une électrode négative, et la couche organique en film mince comprend le composé précité.
PCT/JP2013/059127 2012-03-28 2013-03-27 Nouveau composé, matériau pour élément électroluminescent organique, et élément électroluminescent organique Ceased WO2013146942A1 (fr)

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