Arylamine compound, organic electroluminescence element, and electronic device

Abstract

The object of the present invention is to provide an organic compound having excellent properties such as excellent hole injection / transport performance, electron blocking ability, and high stability in a thin film state as a material for highly efficient and durable organic EL devices, and further to provide a highly efficient and durable organic EL device by using this compound. The arylamine compound of the present invention has excellent heat resistance and good hole transporting ability. Organic EL devices using the compound in the hole transport layer, electron blocking layer, light emitting layer and hole injection layer of the organic EL device showed good device characteristics.

Description

[Technical field]

[0001] The present invention relates to a compound and an element suitable for an organic electroluminescence element (hereinafter abbreviated as organic EL element), which is a self-luminous element suitable for various display devices, and more particularly to an arylamine compound and an organic EL element using the compound. [Background technology]

[0002] Organic EL elements are self-luminous elements, and therefore are brighter and have better visibility than liquid crystal elements, enabling clearer displays, and therefore have been the subject of vigorous research.

[0003] In 1987, C.W. Tang and his colleagues at Eastman Kodak Company made organic EL devices practical by developing a layered structure element in which various roles are assigned to each material. They layered a phosphor capable of transporting electrons and an organic material capable of transporting holes, and emitted light by injecting both charges into the phosphor layer, achieving an luminance of 1000cd / m at a voltage of 10V or less. 2 The above-mentioned high brightness has been obtained (for example, see Patent Documents 1 and 2).

[0004] To date, many improvements have been made to the practical application of organic EL elements, and the various roles of the laminated structure have been further subdivided to achieve high efficiency and durability using electroluminescent elements in which an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in that order on a substrate (see, for example, Non-Patent Document 1).

[0005] Also, in order to further improve the luminous efficiency, the use of triplet excitons has been attempted, and the use of phosphorescent compounds has been considered (for example, see Non-Patent Document 2). Furthermore, elements that utilize luminescence due to thermally activated delayed fluorescence (TADF) have also been developed, and in 2011, Adachi et al. of Kyushu University achieved an external quantum efficiency of 5.3% with an element that uses a thermally activated delayed fluorescence material (for example, see Non-Patent Document 3).

[0006] The light-emitting layer can also be prepared by doping a charge-transporting compound, generally called a host material, with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence. As described in the above non-patent literature, the selection of organic materials in an organic EL element has a significant effect on various properties such as the efficiency and durability of the element (for example, see Non-Patent Literature 2).

[0007] In an organic EL element, the charges injected from both electrodes are recombined in the light-emitting layer to emit light, but how efficiently the charges of holes and electrons are transferred to the light-emitting layer is important, and it is necessary to make the element excellent in carrier balance. Therefore, by using a material that has the characteristics of increasing the hole injection property that supplies holes injected from the anode to the light-emitting layer and increasing the electron blocking property that blocks electrons injected from the cathode, the probability of holes and electrons recombining in the light-emitting layer can be improved, and further, high luminous efficiency can be obtained by confining the excitons generated in the light-emitting layer. For this purpose, the role played by the hole transport material is important, and a hole transport material that has high hole injection property, high hole mobility, high electron blocking property, and high durability against electrons is required.

[0008] Furthermore, the heat resistance and amorphous nature of the material are also important for the lifespan of the element. With materials that have low heat resistance, the heat generated when the element is in operation can cause thermal decomposition even at low temperatures, resulting in material degradation. With materials that have low amorphous nature, thin film crystallization can occur even in a short period of time, causing the element to deteriorate. For this reason, the materials used must have high heat resistance and good amorphous nature.

[0009] Hole transport materials that have been used in organic EL devices so far include N,N'-diphenyl-N,N'-di(α-naphthyl)benzidine (NPD) and various aromatic amine derivatives (see, for example, Patent Document 1 and Patent Document 2). However, although NPD has good hole transport ability, its glass transition point (Tg), which is an index of heat resistance, is low at 96°C, and crystallization occurs under high temperature conditions, causing a deterioration in device characteristics (see, for example, Non-Patent Document 4).

[0010] In addition, among the aromatic amine derivatives described in the above patent documents, the hole mobility is 10 -3 cm 2 Although there are compounds with excellent mobility of 1000 times or more than 1000 times the charge transporting layer (see, for example, Patent Document 1 and Patent Document 2), their electron blocking properties are insufficient, so that some of the electrons pass through the light-emitting layer, and improvement in light-emitting efficiency cannot be expected. To achieve further efficiency improvement, materials with higher electron blocking properties, more stable thin films, and high heat resistance are required. In addition, aromatic amine derivatives with high durability have been reported (see, for example, Patent Document 3), but these were used as charge transport materials for electrophotographic photoreceptors, and there have been no examples of their use in organic EL devices.

[0011] In order to solve this problem, substituted carbazole structures and arylamine compounds have been proposed as compounds with improved properties such as heat resistance and hole injection properties (see, for example, Patent Documents 4 and 5). However, in devices using these compounds in the hole injection layer or hole transport layer, improvements have been made in the device life and luminous efficiency, but these improvements are still insufficient, and there is a demand for further lowering of the driving voltage, higher luminous efficiency, and longer device life. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Pat. No. 5,792,557 [Patent Document 2] U.S. Pat. No. 5,639,914 [Patent Document 3] U.S. Patent No. 7,759,030 [Patent Document 4] JP4589223B2 [Patent Document 5] JP6674892B2 [Patent Document 6] European Patent No. 2684932 [Patent Document 7] JP6748335B1 [Patent Document 8] KR102288034B1 [Non-patent literature]

[0013] [Non-Patent Document 1] Proceedings of the 9th Seminar of the Japan Society of Applied Physics, pp. 55-61 (2001) [Non-Patent Document 2] Proceedings of the 9th Seminar of the Japan Society of Applied Physics, pp. 23-31 (2001) [Non-Patent Document 3] Appl.Phys.Let.,98,083302(2011) [Non-Patent Document 4] Proceedings of the 3rd Regular Meeting of the Organic EL Symposium, pages 13-14 (2006) Summary of the Invention [Problem to be solved by the invention]

[0014] An object of the present invention is to provide a material for highly efficient and durable organic EL devices, which has (1) excellent hole injection and transport performance, (2) electron blocking ability, (3) high stability in a thin film state, and (4) excellent durability.

[0015] By using the material of the present invention, it is possible to provide an organic EL element which has (1) high luminous efficiency and power efficiency, (2) low luminous onset voltage and low practical driving voltage, and (3) long life. [Means for solving the problem]

[0016] In order to achieve the above object, the inventors focused on the excellent hole injection / transport capability, thin film stability and durability of arylamine compounds, and pursued the introduction of phenanthrenyl and naphthylene groups and optimization of the substituents, resulting in a dramatic improvement in the properties of the material. In organic EL devices, the performance of luminous efficiency and power efficiency has been improved, the light emission start voltage and practical driving voltage can be suppressed, and a longer life than conventional devices has been realized, leading to the completion of the present invention.

[0017] 1) That is, the present invention provides an arylamine compound represented by the following general formula (a) or (b):

[0018] [ka]

[0019] [ka]

[0020] In the above general formula (a) or (b), A represents a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group, L1 represents a divalent group obtained by removing two hydrogen atoms from unsubstituted benzene or a divalent group obtained by removing two hydrogen atoms from unsubstituted biphenyl, L2 represents a divalent group obtained by removing two hydrogen atoms from unsubstituted benzene. R1 and R2 may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

[0021] 2) The present invention also relates to an arylamine compound according to 1) above, which is represented by the following general formula (c), (d), (e) or (f).

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] [ka]

[0026] In the above general formula (c), (d), (e) or (f), A, L1, L2, R1 and R2 are defined the same as in the above general formula (a) or (b).

[0027] 3) The present invention also relates to a compound represented by the general formula (c), (d), (e) or (f). The arylamine compound is as described in 1) or 2) above, wherein L2 is a 1,4-phenylene group.

[0028] 4) The present invention also relates to a compound represented by the general formula (c), (d), (e) or (f). A is an unsubstituted dibenzofuranyl group or an unsubstituted dibenzothienyl group. The arylamine compound is described in any one of 1) to 3) above.

[0029] 5) The present invention also relates to a compound represented by the general formula (c), (d), (e) or (f). The arylamine compound according to any one of the above items 1) to 4), wherein A is an unsubstituted dibenzofuranyl group.

[0030] 6) The present invention also relates to a compound represented by the general formula (c), (d), (e) or (f). The arylamine compound according to any one of the above items 1) to 5), wherein A is an unsubstituted 3-dibenzofuranyl group or an unsubstituted 4-dibenzofuranyl group.

[0031] 7) The present invention also relates to an organic EL device having a pair of electrodes and at least one organic layer sandwiched between them, the organic layer comprising the arylamine compound according to any one of 1) to 6) above.

[0032] 8) The present invention also provides the organic EL device according to the above 7), wherein the organic layer is a hole transport layer.

[0033] 9) The present invention also provides the organic EL device according to the above 7), wherein the organic layer is an electron blocking layer.

[0034] 10) The present invention also provides the organic EL device according to the above 7), wherein the organic layer is a hole-injection layer.

[0035] 11) The present invention also provides the organic EL device according to the above item 7), wherein the organic layer is a light-emitting layer.

[0036] 12) The present invention also relates to an electronic device having a pair of electrodes and at least one organic layer sandwiched between them, the organic layer comprising the arylamine compound according to any one of 1) to 6) above.

[0037] Represented by R1 and R2 in general formula (a) or (b) "Substituted or unsubstituted aromatic hydrocarbon group", "Substituted or unsubstituted aromatic heterocyclic group" or in the "substituted or unsubstituted condensed polycyclic aromatic group" The "aromatic hydrocarbon group", "aromatic heterocyclic group" or "condensed polycyclic aromatic group" includes Specifically, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a fluorenyl group, a spirofluorenyl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a furyl group, a pyrrolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzophenyl ... Examples of the alkyl group include an aryl group, a benzothiazolyl group, an azafluorenyl group, a diazafluorenyl group, an azaspirobifluorenyl group, a diazaspirobifluorenyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, an acridinyl group, and a carbolinyl group, as well as an aryl group having 6 to 30 carbon atoms and a heteroaryl group having 2 to 20 carbon atoms.

[0038] Represented by R1 and R2 in general formula (a) or (b) The "substituent" in the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" or "substituted fused polycyclic aromatic group" includes, Specifically, deuterium atoms, cyano groups, nitro groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; silyl groups such as trimethylsilyl groups and triphenylsilyl groups; linear or branched alkyl groups having 1 to 6 carbon atoms such as methyl groups, ethyl groups, and propyl groups; linear or branched alkyloxy groups having 1 to 6 carbon atoms such as methyloxy groups, ethyloxy groups, and propyloxy groups; alkenyl groups such as vinyl groups and allyl groups; aryloxy groups such as phenyloxy groups and tolyloxy groups; arylalkyloxy groups such as benzyloxy groups and phenethyloxy groups; phenyl groups, biphenyl groups, terphenyl groups, naphthyl groups, anthracene groups, Examples of the aromatic hydrocarbon group or condensed polycyclic aromatic group include pyridyl group, thienyl group, furyl group, pyrrolyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, and aromatic heterocyclic group such as carbolinyl group, and these substituents may be further substituted with the above-mentioned substituents.In addition, the benzene ring substituted with these substituents, or the substituents substituted on the same benzene ring may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

[0039] The "substituent" in the "substituted dibenzofuranyl group" or "substituted dibenzothienyl group" represented by A in the general formula (a) or (b) is, Represented by R1 and R2 in general formula (a) or (b) Examples of the "substituent" in the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group", or "substituted fused polycyclic aromatic group" include the same as those exemplified as the "substituent", and possible embodiments thereof are also the same.

[0040] As L1 in the general formula (a) or (b), a phenylene group is preferable, and a 1,4-phenylene group is more preferable.

[0041] As A in the general formula (a) or (b), a 3-dibenzofuranyl group or a 4-dibenzofuranyl group is preferable, and a 4-dibenzofuranyl group is more preferable.

[0042] In general formula (a) or (b), R1 and R2 are preferably a hydrogen atom, a phenyl group, a biphenylyl group, a naphthyl group, a phenanthrenyl group, or a carbazolyl group, and more preferably a hydrogen atom, a phenyl group, or a biphenyl group.

[0043] The arylamine compound represented by the general formula (a) or (b) and suitable for use in the organic EL device of the present invention is preferably used as a constituent material of the hole injection layer, hole transport layer, electron blocking layer or light emitting layer of the organic EL device, and more preferably used as a constituent material of the hole transport layer or electron blocking layer. Effect of the Invention

[0044] The arylamine compounds of the present invention have properties such as (1) better hole injection properties, (2) higher hole mobility, (3) superior electron blocking ability, (4) higher electron resistance, (5) stable existence in a thin film state, and (6) superior heat resistance, compared to conventional hole transport materials. By using the arylamine compounds of the present invention in organic EL devices, properties such as (7) higher luminous efficiency, (8) lower luminescence onset voltage, (9) lower practical driving voltage, and (10) longer life can be obtained.

[0045] The arylamine compound of the present invention is excellent in hole injection / transport performance, thin film stability and durability. As a result, an organic EL device having a hole injection layer and / or hole transport layer produced using the compound as a hole injection material and / or hole transport material has improved hole transport efficiency to the light emitting layer, improved luminous efficiency, and improved durability of the device due to a reduced driving voltage, and can obtain characteristics of high efficiency, low driving voltage and long life.

[0046] The arylamine compound of the present invention has excellent electron blocking ability, high electron resistance, and is stable even in a thin film state, and has the characteristic of confining excitons generated in the light-emitting layer. As a result, an organic EL device having an electron blocking layer prepared using the compound as an electron blocking material has high luminous efficiency because the probability of recombination of holes and electrons is improved and thermal deactivation is suppressed, and the maximum luminous brightness is improved by reducing the driving voltage and improving current resistance.

[0047] The arylamine compound of the present invention has excellent hole transport properties and a wide band gap, and therefore, an organic EL device having an emission layer prepared using the compound as a host material can have a lower driving voltage and improved luminous efficiency by forming the emission layer by supporting a fluorescent emitter, a phosphorescent emitter, or a delayed fluorescent emitter called a dopant.

[0048] Therefore, the arylamine compound of the present invention is useful as a material for a hole injection layer, a hole transport layer, an electron blocking layer or a light emitting layer of an organic EL device, and can improve the luminous efficiency, driving voltage and durability of conventional organic EL devices.

[0049] In addition, the arylamine compound of the present invention can be used not only in organic EL devices but also in the field of electronic devices such as electrophotographic photoreceptors, image sensors, photoelectric conversion elements, and solar cells. [Brief description of the drawings]

[0050] [Figure 1]FIG. 1 shows compounds (1) to (12) as specific preferred examples of the arylamine compound represented by general formula (a) or (b). [Diagram 2] FIG. 1 shows compounds (13) to (24) as specific preferred examples of the arylamine compound represented by general formula (a) or (b). [Diagram 3] FIG. 1 shows compounds (25) to (36) as specific preferred examples of the arylamine compound represented by general formula (a) or (b). [Figure 4] FIG. 1 shows compounds (37) to (48) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Diagram 5] FIG. 1 shows compounds (49) to (60) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 6] FIG. 1 shows compounds (61) to (72) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 7] FIG. 1 shows compounds (73) to (84) as specific preferred examples of the arylamine compounds represented by general formula (a) or (b). [Figure 8] FIG. 1 shows compounds (85) to (96) as specific preferred examples of the arylamine compound represented by general formula (a) or (b). [Figure 9] FIG. 1 shows compounds (97) to (111) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 10] FIG. 1 shows compounds (112) to (123) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 11] FIG. 1 shows compounds (124) to (138) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 12]FIG. 1 shows compounds (139) to (150) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 13] FIG. 1 shows compounds (151) to (165) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 14] FIG. 1 shows compounds (166) to (177) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 15] FIG. 1 shows compounds (178) to (190) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 16] FIG. 1 shows compounds (191) to (203) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 17] FIG. 2 shows compounds (204) to (215) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 18] FIG. 2 shows compounds (216) to (220) as preferred specific examples of the arylamine compounds represented by general formula (a) or (b). [Figure 19] FIG. 1 shows the configurations of the organic EL elements of Examples 19 to 34 and Comparative Examples 1 and 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0051] Although the arylamine compounds of the present invention are novel compounds, these compounds can be synthesized according to methods known per se.

[0052] Among the arylamine compounds represented by the general formula (a) or (b) that can be suitably used in the organic EL device of the present invention, specific preferred compounds are shown in Figs. 1 to 18, but the compounds are not limited to these.

[0053] The arylamine compound represented by the general formula (a) or (b) can be purified by known methods such as purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, and sublimation purification. The compound can be identified by NMR analysis. Examples of physical property values ​​include measurements of melting point, glass transition point (Tg), and work function. The melting point is an index of vapor deposition properties, the glass transition point (Tg) is an index of stability in a thin film state, and the work function is an index of hole injection properties, hole transport properties, or electron blocking properties.

[0054] The melting point and the glass transition point (Tg) can be measured, for example, by a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS) using a powder.

[0055] The work function can be determined, for example, by forming a 100 nm thin film on an ITO substrate and using an ionization potential measuring device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).

[0056] The structure of the organic EL element of the present invention includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode, which are arranged in this order on a substrate, an electron blocking layer between the hole transport layer and the light emitting layer, and a hole blocking layer between the light emitting layer and the electron transport layer. In these multilayer structures, one organic layer can serve several roles, for example, one organic layer can serve both as a hole injection layer and a hole transport layer, or as an electron injection layer and an electron transport layer. In addition, two or more organic layers having the same function can be laminated, and examples of such structures include a structure in which two hole transport layers are laminated, a structure in which two light emitting layers are laminated, and a structure in which two electron transport layers are laminated.

[0057] As the anode of the organic EL device of the present invention, an electrode material with a large work function such as ITO or gold is used. As the material of the hole injection layer of the organic EL device of the present invention, a porphyrin compound represented by copper phthalocyanine, a starburst type triphenylamine derivative, an arylamine compound having two or more triphenylamine structures or carbazolyl structures in the molecule, each of which is linked by a single bond or a divalent group not containing a hetero atom, an acceptor heterocyclic compound such as hexacyanoazatriphenylene, and a coating type polymer material can be used. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an inkjet method.

[0058] As materials for the hole injection layer and hole transport layer of the organic EL device of the present invention, in addition to the arylamine compound of the present invention, benzidine derivatives such as N,N'-diphenyl-N,N'-di(m-tolyl)-benzidine (TPD), N,N'-diphenyl-N,N'-di(α-naphthyl)-benzidine (NPD), N,N,N',N'-tetrabiphenylylbenzidine, 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), and arylamine compounds having two or more triphenylamine structures or carbazolyl structures in the molecule, each of which is linked by a single bond or a divalent group not containing a hetero atom, can be used. These materials may be used alone to form a film, or may be used in combination to form a film, and each of them can be used as a single layer. In addition, the layer structure may be a layer structure of layers formed by solely depositing these materials, a layer structure of layers formed by mixing these materials, or a layer structure of layers formed by solely depositing these materials and layers formed by mixing a plurality of types of these materials. In addition, a coating type polymer material such as poly(3,4-ethylenedioxythiophene) (PEDOT) / poly(styrenesulfonate) (PSS) can be used as the material for the hole injection / transport layer. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet.

[0059] For the hole injection layer or the hole transport layer, materials that are typically used for these layers can be doped with P such as trisbromophenylaminehexachloroantimony or radialene derivatives (see, for example, Patent Document 6), or polymer compounds having a structure of a benzidine derivative such as TPD in its partial structure.

[0060] In addition to the arylamine compound of the present invention, compounds having an electron blocking effect such as carbazole derivatives such as 4,4',4''-tri(N-carbazolyl)triphenylamine (TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), and 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz), and compounds having a triphenylsilyl group and a triarylamine structure such as 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene can be used as the material for the electron blocking layer of the organic EL device of the present invention. These materials may be used as the material for the hole transport layer. These materials may be used to form a film alone or in a mixture of a plurality of types, and each of them may be used as a single layer. In addition, the laminated structure may be a laminated structure of layers formed from these materials alone, a laminated structure of layers formed from a mixture of these materials, or a laminated structure of a layer formed from a layer formed from a single material and a layer formed from a mixture of a plurality of types of these materials. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet printing.

[0061] As the material for the light-emitting layer of the organic EL device of the present invention, in addition to the arylamine compound of the present invention, metal complexes of quinolinol derivatives such as tris(8-quinolinolato)aluminum (Alq3), various metal complexes, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylenevinylene derivatives, etc. can be used. The light-emitting layer may be composed of a host material and a dopant material, and anthracene derivatives are preferably used as the host material. In addition to the light-emitting materials such as the arylamine compound of the present invention, heterocyclic compounds having an indole ring as a partial structure of a condensed ring, heterocyclic compounds having a carbazole ring as a partial structure of a condensed ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, and polydialkylfluorene derivatives can be used. As the dopant material, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, and aminostyryl derivatives can be used. These materials may be formed as a single layer, or may be formed as a mixture of a plurality of materials, and each of them may be used as a single layer. In addition, these materials may be used as a laminated structure of layers formed as a single layer, a laminated structure of layers formed as a mixture, or a laminated structure of layers formed as a single layer and layers formed as a mixture of a plurality of materials. These materials can be formed into a thin film by known methods such as vapor deposition, spin coating, and inkjet.

[0062] It is also possible to use a phosphorescent emitter as the light-emitting material. As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. For example, green phosphorescent emitters such as Ir(ppy)3, blue phosphorescent emitters such as FIrpic and FIr6, and red phosphorescent emitters such as Btp2Ir(acac) can be mentioned. In this case, as the host material, hole injection / transport host materials include carbazole derivatives such as 4,4'-di(N-carbazolyl)biphenyl (CBP), TCTA, and mCP, as well as the arylamine compound of the present invention, and electron transport host materials include p-bis(triphenylsilyl)benzene (UGH2) and 2,2',2''-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (TPBI). By using such materials, a high-performance organic EL device can be manufactured.

[0063] In order to avoid concentration quenching, the phosphorescent light-emitting material is preferably doped into the host material by co-evaporation in a range of 1 to 30 weight percent based on the entire light-emitting layer.

[0064] In addition, materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, can also be used as light-emitting materials (see, for example, Non-Patent Document 3). These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and ink-jet methods.

[0065] As the material of the hole blocking layer of the organic EL device of the present invention, compounds having a hole blocking effect, such as phenanthroline derivatives such as bathocuproine (BCP), metal complexes of quinolinol derivatives such as bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives, can be used. These materials may also serve as materials for the electron transport layer. These materials may be formed into a film alone, or a film may be formed by mixing a plurality of types of materials, and each of them may be used as a single layer. In addition, a laminated structure of layers formed by mixing these materials alone, a laminated structure of layers formed by mixing these materials, or a laminated structure of layers formed by mixing these materials alone and a layer formed by mixing a plurality of types of materials may be used. These materials can be formed into a thin film by known methods such as vapor deposition, spin coating, and ink jet method.

[0066] As the material of the electron transport layer of the organic EL element of the present invention, metal complexes of quinolinol derivatives such as Alq3 and BAlq, various metal complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, pyridine derivatives, pyrimidine derivatives, benzimidazole derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, and silole derivatives can be used. These materials may be formed into a film alone, or a film may be formed by mixing a plurality of types of these materials, and each of them can be used as a single layer. In addition, these materials may be formed into a laminated structure of layers formed by alone, a laminated structure of layers formed by mixing a plurality of types of these materials, or a laminated structure of layers formed by alone and a layer formed by mixing a plurality of types of these materials. These materials can be formed into a thin film by known methods such as vapor deposition, spin coating, and ink jet method.

[0067] Materials that can be used for the electron injection layer of the organic EL device of the present invention include alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride, metal complexes of quinolinol derivatives such as lithium quinolinol, metal oxides such as aluminum oxide, and metals such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), and cesium (Cs). The electron injection layer can be omitted by suitable selection of the electron transport layer and the cathode.

[0068] Furthermore, for the electron injection layer and the electron transport layer, materials that are normally used for these layers and are doped with N-type metal such as cesium can be used.

[0069] For the cathode of the organic EL device of the present invention, a metal having a low work function such as aluminum, or an alloy having an even lower work function such as a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-magnesium alloy is used as the electrode material. EXAMPLES

[0070] Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples as long as it does not depart from the gist of the present invention. EXAMPLES

[0071] <Synthesis of 4-(dibenzofuran-3-yl)phenyl-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 1)> In a reaction vessel, 18.1 g of 9-bromo-phenanthrene, 18.5 g of 1-(4-aminophenyl)naphthalene, 0.3 g of tris(dibenzylideneacetone)dipalladium(0), 0.9 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 8.8 g of t-butoxy sodium were charged and refluxed under toluene for 15 hours. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by crystallization using a chlorobenzene / acetone mixed solvent to obtain 24.4 g of 4-(naphthalene-1-yl)phenyl-phenanthrene-9-yl-amine (yield: 87.8%).

[0072] [ka]

[0073] Next, 11.2 g of 4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine, 10.1 g of 3-(4-bromophenyl)dibenzofuran, 0.1 g of palladium (II) acetate, 0.2 g of tri-t-butylphosphine, and 3.5 g of sodium t-butoxide were charged into a reaction vessel, and the mixture was refluxed and stirred for 15 hours under toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 11.0 g (yield: 60.8%) of white powder of 4-(dibenzofuran-3-yl)phenyl-4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine (compound 1).

[0074] [ka]

[0075] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.79(1H), 8.74(1H), 8.18(1H), 8.03(1H), 7.96(1H), 7.94(1H), 7.89(1H), 7.8 4(2H), 7.77(2H), 7.69(2H), 7.60(2H), 7.57(4H), 7.50(2H), 7.45(3H), 7.41-7.26(7H). EXAMPLES

[0076] <Synthesis of 4-(dibenzofuran-3-yl)phenyl-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 38)> In a reaction vessel, 47.2 g of 9-bromo-phenanthrene, 48.3 g of 2-(4-aminophenyl)naphthalene, 0.8 g of tris(dibenzylideneacetone)dipalladium(0), 2.3 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 26.5 g of t-butoxy sodium were charged and refluxed under toluene for 15 hours. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by crystallization using a chlorobenzene / acetone mixed solvent to obtain 51.0 g of 4-(naphthalene-2-yl)phenyl-phenanthrene-9-yl-amine (yield: 70.2%).

[0077] [ka]

[0078] Next, 11.2 g of 4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine, 10.1 g of 3-(4-bromophenyl)dibenzofuran, 0.1 g of palladium (II) acetate, 0.2 g of tri-t-butylphosphine, and 3.5 g of sodium t-butoxide were charged into a reaction vessel, and the mixture was refluxed and stirred for 19 hours under toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 11.7 g (yield: 64.8%) of white powder of 4-(dibenzofuran-3-yl)phenyl-4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine (compound 38).

[0079] [ka]

[0080] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.79(1H), 8.74(1H), 8.13(1H), 8.00(1H), 7.95(2H), 7.87(2H), 7 .83(2H), 7.77-7.66(5H), 7.63-7.50(8H), 7.46(3H), 7.34(1H), 7.27(4H). EXAMPLES

[0081] <Synthesis of 4-(dibenzofuran-4-yl)phenyl-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 81)> In a reaction vessel, 7.6 g of 4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine, 6.6 g of 4-(4-bromophenyl)dibenzofuran, 0.1 g of palladium (II) acetate, 0.2 g of tri-t-butylphosphine, and 2.4 g of sodium t-butoxide were charged, and the mixture was refluxed and stirred for 14 hours under toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 3.9 g (yield: 31.8%) of white powder of 4-(dibenzofuran-4-yl)phenyl-4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine (compound 81).

[0082] [ka]

[0083] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.81(1H), 8.75(1H), 8.22(1H), 8.04(1H), 7.98(1H), 7.93-7.8 0(7H), 7.70(2H), 7.64(1H), 7.59(3H), 7.54-7.41(6H), 7.41-7.31(7H). EXAMPLES

[0084] <Synthesis of 4-(dibenzofuran-4-yl)phenyl-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 130)> In a reaction vessel, 7.6 g of 4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine, 6.6 g of 4-(4-bromophenyl)dibenzofuran, 0.1 g of palladium (II) acetate, 0.2 g of tri-t-butylphosphine, and 2.4 g of sodium t-butoxide were charged and stirred under reflux for 14 hours in a toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 5.5 g (yield: 44.8%) of white powder of 4-(dibenzofuran-4-yl)phenyl-4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine (compound 130).

[0085] [ka]

[0086] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.80(1H), 8.75(1H), 8.16(1H), 8.01(1H), 7.98(1H), 7.88(3H), 7 .84(4H)7.78(1H), 7.73(1H), 7.69(2H), 7.65-7.53(6H), 7.51-7.28(9H). EXAMPLES

[0087] <Synthesis of {4'-(dibenzofuran-3-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 11)> In a reaction vessel, 10.0 g of 4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine, 11.1 g of 3-(4'-bromo[1,1'-biphenyl]-4-yl)dibenzofuran, 0.5 g of tris(dibenzylideneacetone)dipalladium(0), 0.2 g of tri-t-butylphosphine, and 4.9 g of sodium t-butoxide were charged and stirred overnight under reflux in toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by crystallization using a monochlorobenzene / acetone mixed solvent to obtain 12.8 g of white powder of {4'-(dibenzofuran-3-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine (compound 11) (yield: 71.1%).

[0088] [ka]

[0089] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.83-8.76(2H), 8.21(1H), 8.07-7.99(3H), 7.93-7.88(4H), 7.82(1H), 7.78-7.46(17H), 7.43-7.37(3H), 7.32(4H). EXAMPLES

[0090] Synthesis of {4'-(dibenzofuran-3-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (compound 54) In a reaction vessel, 8.0 g of 4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine, 8.9 g of 3-(4'-bromo[1,1'-biphenyl]-4-yl)dibenzofuran, 0.4 g of tris(dibenzylideneacetone)dipalladium(0), 0.2 g of tri-t-butylphosphine, and 3.9 g of sodium t-butoxide were charged and stirred under reflux overnight in a toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 7.8 g (yield: 54.2%) of a pale yellow powder of {4'-(dibenzofuran-3-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (compound 54).

[0091] [ka]

[0092] The structure of the resulting pale yellow powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.83-8.76(2H), 8.16(1H), 8.05-7.99(3H), 7.92-7.85(5H), 7.78-8.56(16H), 7.49(3H), 7.39(1H), 7.31-7.27(4H). EXAMPLES

[0093] <Synthesis of {4'-(dibenzofuran-4-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 93)> In a reaction vessel, 12.0 g of (4'-bromo-[1,1'-biphenyl]-4-yl)-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine, 4.9 g of 4-dibenzofuranylboronic acid, 0.5 g of tetrakis(triphenylphosphine)palladium(0), and 5.3 g of potassium carbonate were charged, and the mixture was refluxed overnight under a mixed solvent of toluene / EtOH / H2O. After confirming the completion of the reaction, toluene / H2O was added to the cooled system, and the organic layer was extracted and separated, and concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 4.1 g (yield: 29.3%) of white powder of {4'-(dibenzofuran-4-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (compound 93).

[0094] [ka]

[0095] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.84-8.77(2H), 8.23(1H), 8.07(1H), 8.04-8.01(3H), 7.97(1H), 7. 94-7.82(4H), 7.78-7.60(10H), 7.56-7.45(6H), 7.42-7.38(3H), 7.33(4H). EXAMPLES

[0096] <Synthesis of {4'-(dibenzofuran-4-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 142)> In a reaction vessel, 12.0 g of (4'-bromo-[1,1'-biphenyl]-4-yl)-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine, 4.9 g of 4-dibenzofuranylboronic acid, 0.5 g of tetrakis(triphenylphosphine)palladium(0), and 5.3 g of potassium carbonate were charged, and the mixture was refluxed overnight in a toluene / EtOH / H2O mixed solvent. After confirming the completion of the reaction, toluene / H2O was added to the cooled system, and the organic layer was extracted and separated, and concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 8.7 g (yield: 63.5%) of white powder of {4'-(dibenzofuran-4-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (compound 142).

[0097] [ka]

[0098] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (DMSO-d6). δ(ppm)=8.99(1H), 8.92(1H), 8.22-8.15(3H), 8.08-7.91(9H), 7.83-7.61(12H), 7.57-7.42(5H), 7.20(4H). EXAMPLES

[0099] <Synthesis of 4-(dibenzofuran-2-yl)phenyl-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 183)> In a reaction vessel, 10.0 g of 4-(dibenzofuran-2-yl)phenyl-phenanthren-9-yl-amine, 7.2 g of 1-(4-bromophenyl)naphthalene, 0.4 g of tris(dibenzylideneacetone)dipalladium(0), 0.2 g of tri-t-butylphosphine, and 3.5 g of sodium t-butoxide were charged and stirred under reflux overnight in toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 9.1 g (yield: 62.3%) of white powder of 4-(dibenzofuran-2-yl)phenyl-4-(naphthalene-1-yl)phenyl-phenanthren-9-yl-amine (compound 183).

[0100] [ka]

[0101] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (DMSO-d6). δ(ppm)=8.99(1H), 8.92(1H), 8.41(1H), 8.20(1H), 8.14(1H), 8.05(1H), 8.00 -7.91(4H), 7.76-7.64(9H), 7.57-7.52(4H), 7.45-7.41(4H), 7.27-7.22(4H). EXAMPLES

[0102] <Synthesis of {4-(dibenzofuran-2-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 188)> In a reaction vessel, 13.0 g of (4'-bromo-[1,1'-biphenyl]-4-yl)-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine, 5.3 g of 2-dibenzofuranylboronic acid, 0.5 g of tetrakis(triphenylphosphine)palladium(0), and 5.7 g of potassium carbonate were charged, and the mixture was refluxed overnight in a toluene / EtOH / H2O mixed solvent. After confirming the completion of the reaction, toluene / H2O was added to the cooled system, and the organic layer was extracted and separated, and concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 9.7 g (yield: 65.5%) of white powder of {4'-(dibenzofuran-2-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (compound 188).

[0103] [ka]

[0104] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.83-8.77(2H), 8.23-8.21(2H), 8.05(2H), 7.93-7.85(3H), 7.82(1H) , 7.77-7.70(7H), 7.67-7.58(6H), 7.56-7.46(5H), 7.42-7.38(3H), 7.32(4H). EXAMPLES

[0105] <Synthesis of 4-(dibenzofuran-1-yl)phenyl-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 193)> In a reaction vessel, 8.0 g of 4-(dibenzofuran-1-yl)phenyl-phenanthren-9-yl-amine, 5.7 g of 1-(4-bromophenyl)naphthalene, 0.3 g of tris(dibenzylideneacetone)dipalladium(0), 0.2 g of tri-t-butylphosphine, and 3.5 g of sodium t-butoxide were charged, and the mixture was refluxed overnight under toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane), and 8.4 g of yellow powder of 4-(dibenzofuran-1-yl)phenyl-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (compound 193) was obtained (yield: 71.7%).

[0106] [ka]

[0107] The structure of the resulting yellow powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (DMSO-d6). δ(ppm)=9.00(1H), 8.93(1H), 8.18(1H), 8.09-8.05(2H), 7.99(1H), 7.93(2H), 7.81-7.68(6H), 7.59-7.44(11H), 7.35-7.22(6H). EXAMPLES

[0108] <Synthesis of {4'-(dibenzofuran-1-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (Compound 198)> In a reaction vessel, (4'-bromo-[1,1'-biphenyl]-4-yl)-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine: 12.0g, 2-(dibenzofuran-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: 6.2g, tetrakis(triphenylphosphine)palladium(0): 0.5g, potassium carbonate: 5.3g were charged, and the mixture was refluxed overnight under a toluene / EtOH / H2O mixed solvent. After confirming the completion of the reaction, toluene / H2O was added to the cooled system, and the organic layer was extracted and separated, and concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 8.5 g (yield: 62.0%) of white powder of {4'-(dibenzofuran-1-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (compound 198).

[0109] [ka]

[0110] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.84-8.77(2H), 8.22(1H), 8.07(1H), 7.94-7.85(3H), 7.82(1H), 7.79-7 .76(2H), 7.72(4H), 7.67-7.59(7H), 7.57-7.41(8H), 7.36-7.31(5H), 7.16(1H). EXAMPLES

[0111] <Synthesis of 4-(dibenzofuran-2-yl)phenyl-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 204)> In a reaction vessel, 11.4 g of 4-(dibenzofuran-2-yl)phenyl-phenanthren-9-yl-amine, 8.2 g of 2-(4-bromophenyl)naphthalene, 0.5 g of tris(dibenzylideneacetone)dipalladium(0), 0.2 g of tri-t-butylphosphine, and 5.1 g of sodium t-butoxide were charged and stirred under reflux overnight in toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 12.5 g (yield: 74.8%) of white powder of 4-(dibenzofuran-2-yl)phenyl-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (compound 204).

[0112] [ka]

[0113] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (DMSO-d6). δ(ppm)=8.98(1H), 8.91(1H), 8.42(1H), 8.21-8.16(2H), 8.08-8.01(2H) , 7.98-7.90(4H), 7.83-7.61(12H), 7.56-7.47(3H), 7.42(1H), 7.20(4H). EXAMPLES

[0114] <Synthesis of {4'-(dibenzofuran-2-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 209)> In a reaction vessel, 13.0 g of (4'-bromo-[1,1'-biphenyl]-4-yl)-4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine, 5.3 g of 2-dibenzofuranylboronic acid, 0.5 g of tetrakis(triphenylphosphine)palladium(0), and 5.7 g of potassium carbonate were charged, and the mixture was refluxed and stirred overnight in a toluene / EtOH / H2O mixed solvent. After confirming the completion of the reaction, the precipitated solid was filtered at room temperature to obtain a crude product. The obtained crude product was purified by crystallization using a toluene / acetone mixed solvent to obtain 8.4 g of white powder of {4'-(dibenzofuran-2-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalene-2-yl)phenyl-phenanthren-9-yl-amine (compound 209) (yield: 56.7%).

[0115] [ka]

[0116] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (DMSO-d6). δ(ppm)=8.98(1H), 8.92(1H), 8.53(1H), 8.25(1H), 8.15(1H), 8.06(1H), 8.01(1H), 7.97-7.90(4H), 7.87-7.72(12H), 7.69-7.60(4H), 7.57-7.42(4H), 7.21-7.17(4H). EXAMPLES

[0117] <Synthesis of 4-(dibenzofuran-1-yl)phenyl-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 214)> In a reaction vessel, 9.4 g of 4-(dibenzofuran-1-yl)phenyl-phenanthren-9-yl-amine, 6.7 g of 2-(4-bromophenyl)naphthalene, 0.4 g of tris(dibenzylideneacetone)dipalladium(0), 0.2 g of tri-t-butylphosphine, and 4.2 g of sodium t-butoxide were charged, and the mixture was refluxed overnight under toluene solvent. After confirming the completion of the reaction, the filtrate obtained by filtration was concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 8.2 g (yield: 59.4%) of white powder of 4-(dibenzofuran-1-yl)phenyl-4-(naphthalen-1-yl)phenyl-phenanthren-9-yl-amine (compound 214).

[0118] [ka]

[0119] The structure of the obtained white powder was identified by NMR. 1 The following 31 hydrogen signals were detected by H-NMR (DMSO-d6). δ(ppm)=8.99(1H), 8.92(1H), 8.17(1H), 8.12(1H), 8.04(1H), 7.97-7.90(4H), 7.83-7.65(9H), 7.60-7.49(7H), 7.31-7.24(6H). EXAMPLES

[0120] <Synthesis of {4'-(dibenzofuran-1-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (Compound 219)> In a reaction vessel, (4'-bromo-[1,1'-biphenyl]-4-yl)-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine: 12.0g, 2-(dibenzofuran-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane: 6.2g, tetrakis(triphenylphosphine)palladium(0): 0.5g, potassium carbonate: 5.3g were charged, and the mixture was refluxed overnight under a toluene / EtOH / H2O mixed solvent. After confirming the completion of the reaction, toluene / H2O was added to the cooled system, and the organic layer was extracted and separated, and concentrated to obtain a crude product. The obtained crude product was purified by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 10.2 g (yield: 74.4%) of white powder of {4'-(dibenzofuran-1-yl)-[1,1'-biphenyl]-4-yl}-4-(naphthalen-2-yl)phenyl-phenanthren-9-yl-amine (compound 219).

[0121] [ka]

[0122] The structure of the obtained white powder was identified by NMR. 1 The following 35 hydrogen signals were detected by H-NMR (CDCl3). δ(ppm)=8.83-8.77(2H), 8.17(1H), 8.04(1H), 7.93-7.85(4H), 7.79-7.75(8H), 7.66-7.42(13H), 7.32-7.30(5H), 7.17(1H). EXAMPLES

[0123] The melting points and glass transition points of the arylamine compounds represented by general formula (a) or (b) were measured using a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS). The results are shown in Table 1.

[0124] [Table 1]

[0125] The arylamine compounds represented by the general formula (a) or (b) have a glass transition point of 100° C. or higher, which indicates that they are stable in a thin film state. EXAMPLES

[0126] Using the arylamine compound represented by general formula (a) or (b), a 100 nm thick film was prepared by vapor deposition on an ITO substrate, and the work function was measured using an ionization potential measuring device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.). The results are shown in Table 2.

[0127] [Table 2]

[0128] The arylamine compounds represented by general formula (a) or (b) exhibit a suitable energy level compared with the work function of 5.4 eV of common hole transport materials such as NPD and TPD, and have good hole transport ability. EXAMPLES

[0129] As shown in FIG. 19, the organic EL device was fabricated by depositing a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, an emitting layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9, and a capping layer 10 in this order on a glass substrate 1 on which a reflective ITO electrode had previously been formed as a transparent anode 2.

[0130] Specifically, a glass substrate 1 on which a 50 nm thick ITO film, a 100 nm thick silver alloy reflective film, and a 5 nm thick ITO film were successively formed was subjected to ultrasonic cleaning in isopropyl alcohol for 20 minutes, and then dried for 10 minutes on a hot plate heated to 250° C. Then, a UV ozone treatment was performed for 2 minutes, and the glass substrate with ITO was then attached to a vacuum deposition machine and the pressure was reduced to 0.001 Pa or less. Subsequently, a hole injection layer 3 was formed covering the transparent anode 2 by binary deposition of an electron acceptor (Acceptor-1) having the following structural formula and a compound (HTM-1) having the following structural formula at a deposition rate ratio of Acceptor-1:HTM-1=3:97 to a thickness of 10 nm. On this hole injection layer 3, a compound (HTM-1) having the following structural formula was formed as a hole transport layer 4 to a thickness of 140 nm. On this hole transport layer 4, the compound (1) of Example 1 was formed as an electron blocking layer 5 to a thickness of 5 nm. On this electron blocking layer 5, a light-emitting layer 6 was formed by binary deposition of a compound (EMD-1) having the following structural formula and a compound (EMH-1) having the following structural formula at a deposition rate ratio of EMD-1:EMH-1=5:95 to form a film thickness of 20 nm. On this light-emitting layer 6, an electron transport layer 7 was formed by binary deposition of a compound (ETM-1) having the following structural formula and a compound (ETM-2) having the following structural formula at a deposition rate ratio of ETM-1:ETM-2=50:50 to a thickness of 30 nm. On this electron transport layer 7, an electron injection layer 8 made of lithium fluoride was formed to a thickness of 1 nm. On this electron injection layer 8, a cathode 9 made of magnesium silver alloy was formed to a thickness of 12 nm. Finally, a compound (CPL-1) having the following structure was formed as a capping layer 10 to a thickness of 60 nm.

[0131] The characteristics of the fabricated organic EL device were measured in air at room temperature. The light-emitting characteristics of the fabricated organic EL device were measured by applying a DC voltage, and the results are summarized in Table 3.

[0132] [ka]

[0133] [ka]

[0134] [ka] [Examples 20 to 34]

[0135] Organic EL devices were prepared under the same conditions as in Example 19, except that the compounds obtained in Examples 2 to 16 were used as the material for the electron blocking layer 5 instead of the compound (1) in Example 1. The characteristics of the prepared organic EL devices were measured in the air at room temperature. The measurement results of the light emission characteristics when a direct current voltage was applied to the prepared organic EL devices are summarized in Table 3. [Comparative Example 1]

[0136] For comparison, an organic EL device was prepared under the same conditions as in Example 19, except that the compound (HTM-2) of the following structural formula (see, for example, Patent Document 7) was used as the material for the electron blocking layer 5 instead of the compound (1) in Example 1. The characteristics of the prepared organic EL device were measured in the air at room temperature. The measurement results of the light emission characteristics when a direct current voltage was applied to the prepared organic EL device are summarized in Table 3.

[0137] [ka]

[0138] [Comparative Example 2] For comparison, an organic EL device was prepared under the same conditions as in Example 19, except that the compound (HTM-3) of the following structural formula (see, for example, Patent Document 8) was used as the material for the electron blocking layer 5 instead of the compound (1) in Example 1. The characteristics of the prepared organic EL device were measured in the air at room temperature. The measurement results of the light emission characteristics when a direct current voltage was applied to the prepared organic EL device are summarized in Table 3.

[0139] [ka]

[0140] The organic EL elements produced in Examples 19 to 34 and Comparative Examples 1 and 2 were used to measure the element lifetime, and the results are summarized in Table 3. The element lifetime was measured when the emission luminance (initial luminance) at the start of emission was 1000 cd / m 2 When driven at a constant current, the luminance was 950cd / m 2 The time it took for the brightness to decay to 95% (corresponding to 95% when the initial brightness was 100%) was measured.

[0141] [Table 3]

[0142] As shown in Table 3, the current density was 10 mA / cm 2 The luminous efficiency when a current of 1000 mA was applied was 9.19 to 9.27 cd / A for the organic EL elements of Comparative Examples 1 and 2, while the organic EL elements of Examples 19 to 34 were 9.29 to 10.38 cd / A, which was equal to or higher than the luminous efficiency. The power efficiency was also high, 9.06 to 9.92 lm / W for the organic EL elements of Examples 19 to 34, while the power efficiency was 8.73 to 8.81 lm / W for the organic EL elements of Comparative Examples 1 and 2. Furthermore, it can be seen that the element lifetime (95% decay) was 426 to 598 hours for the organic EL elements of Examples 19 to 34, which was longer than the 355 to 422 hours for the organic EL elements of Comparative Examples 1 and 2.

[0143] As is clear from the above results, the organic EL element of the present invention uses an arylamine compound having high hole mobility and excellent electron blocking ability, and therefore it has been found that an organic EL element having high luminous efficiency and long life compared to conventional organic EL elements can be realized. [Industrial Applicability]

[0144] The organic EL device using the arylamine compound having a specific structure of the present invention can improve the luminous efficiency and durability of the organic EL device, making it possible to expand the use of the organic EL device to, for example, home appliances and lighting.

[0145] 1 Glass substrate 2 transparent anode 3. Hole injection layer 4. Hole transport layer 5 Electron blocking layer 6. Light-emitting layer 7 Electron transport layer 8 Electron injection layer 9 Cathode 10 Capping Layer

Claims

1. An arylamine compound represented by the following general formula (a) or (b): 【Chemistry 1】 【Chemistry 2】 (In the formula, A is a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group, L １ teeth, A divalent group obtained by removing two hydrogen atoms from unsubstituted benzene, or a divalent group obtained by removing two hydrogen atoms from unsubstituted biphenyl, L ２ teeth, represents a divalent group obtained by removing two hydrogen atoms from unsubstituted benzene, R １ , R ２ may be the same or different, Hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group; a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

2. The arylamine compound according to claim 1, which is represented by the following general formula (c), (d), (e) or (f): 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 (In the formula, A, L １ , L ２ , R １ and R ２ has the same definition as in the general formula (a) or (b).

3. In the general formula (c), (d), (e) or (f), L ２ is represented by a 1,4-phenylene group The arylamine compound according to claim 1 or 2.

4. In the general formula (c), (d), (e) or (f), A is an unsubstituted dibenzofuranyl group; or an unsubstituted dibenzothienyl group The arylamine compound according to any one of claims 1 to 3.

5. In the general formula (c), (d), (e) or (f), A is an unsubstituted dibenzofuranyl group. The arylamine compound according to any one of claims 1 to 4.

6. In the general formula (c), (d), (e) or (f), A is an unsubstituted 3-dibenzofuranyl group; or an unsubstituted 4-dibenzofuranyl group The arylamine compound according to any one of claims 1 to 5.

7. 7. An organic EL device having a pair of electrodes and at least one organic layer sandwiched between them, the organic layer comprising the arylamine compound according to claim 1.

8. 8. The organic electroluminescence device according to claim 7, wherein the organic layer is a hole transport layer.

9. 8. The organic electroluminescence device according to claim 7, wherein the organic layer is an electron blocking layer.

10. 8. The organic electroluminescence device according to claim 7, wherein the organic layer is a hole injection layer.

11. 8. The organic electroluminescence device according to claim 7, wherein the organic layer is a light-emitting layer.

12. 10. An electronic device having a pair of electrodes and at least one organic layer sandwiched between them, the organic layer comprising the arylamine compound according to claim 1.

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