Arylamine compound, organic electroluminescent element, and electronic device

Abstract

The purpose of the present invention is to provide, as a material for high-efficiency and high-durability organic EL elements, an organic compound having excellent hole injection / transport performance, electron blocking ability, high stability in a thin film state, and excellent characteristics, and to provide, using the compound, a high-efficiency and high-durability organic EL element. The specific arylamine compound according to the present invention has excellent heat resistance and good hole transport ability. An organic EL element in which the compound is used in a hole transport layer, an electron blocking layer, a light-emitting layer, and a hole injection layer of the organic EL element exhibits good element characteristics.

Description

Technical Field

[0001] The present invention relates to compounds and devices suitable for self-luminous devices, namely, organic electroluminescent devices (hereinafter referred to as organic EL devices), which are suitable for various display devices, and more specifically, to arylamine compounds and organic EL devices using the same. Background Art

[0002] Organic EL elements are self-luminous elements and therefore are brighter and more visible than liquid crystal elements, and are capable of producing clear displays. Therefore, active research has been conducted on these elements.

[0003] In 1987, CW Tang and others at Eastman Kodak Company developed a layered structure that divided the functions among different materials, making organic EL devices using organic materials practical. They stacked a phosphor that could transport electrons and an organic substance that could transport holes, and injected charges from both into the phosphor layer, causing it to emit light. This allowed them to achieve 1000 cd / m² at a voltage of less than 10V. 2 The above high brightness (for example, refer to Patent Document 1 and Patent Document 2).

[0004] Up to now, a lot of improvements have been made to make organic EL elements practical, and the various functions of the stacked structure have been further subdivided. By arranging 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 on a substrate in sequence, high efficiency and durability have gradually been achieved (for example, refer to non-patent document 1).

[0005] In order to further improve luminous efficiency, attempts have been made to utilize triplet excitons and to study the use of phosphorescent compounds (see, for example, Non-Patent Document 2). Furthermore, devices utilizing luminescence using thermally activated delayed fluorescence (TADF) have also been developed. In 2011, Adachi et al. at Kyushu University achieved an external quantum efficiency of 5.3% using a device using a thermally activated delayed fluorescence material (see, for example, Non-Patent Document 3).

[0006] The light-emitting layer can also be made by doping a charge-transporting compound, generally referred to as a host material, with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence. As described in the aforementioned non-patent literature, the choice of organic material in an organic EL element significantly influences various properties of the element, such as efficiency and durability (see, for example, non-patent literatures 1 to 3).

[0007] In organic EL elements, the charge injected from the two electrodes is recombined in the light-emitting layer to obtain luminescence. How to efficiently deliver the two charges of holes and electrons to the light-emitting layer is important, and it is necessary to make an element with excellent carrier balance. Therefore, by using a material with the characteristic of improving the hole injection property of supplying the holes injected from the anode to the light-emitting layer and improving the electron blocking property of blocking the electrons injected from the cathode, the probability of the holes and electrons being recombined in the light-emitting layer is increased, and then, by sealing the excitons generated in the light-emitting layer, it is possible to obtain high luminous efficiency. Therefore, the role played by the hole transport material is important, requiring a hole transport material with high hole injectability, large hole mobility, high electron blocking property, and then high durability for electrons.

[0008] Furthermore, the material's heat resistance and amorphicity are crucial for device lifespan. Materials with low heat resistance can decompose even at low temperatures due to the heat generated during device operation, leading to material degradation. Materials with low amorphicity can crystallize thin films even in a short period of time, causing device degradation. Therefore, materials with high heat resistance and good amorphicity are required.

[0009] As hole-transporting materials currently used in organic EL devices, N,N'-diphenyl-N,N'-di(α-naphthyl)benzidine (NPD) and various aromatic amine derivatives are known (see, for example, Patent Documents 1 and 2). However, while NPD has excellent hole-transporting properties, its glass transition temperature (Tg), an indicator of heat resistance, is as low as 96°C, leading to a decrease in device characteristics due to crystallization under high-temperature conditions (see, for example, Non-Patent Document 4).

[0010] In addition, among the aromatic amine derivatives described in the above patent documents, the mobility of holes is 10 -3 cm 2 Compounds with excellent mobility of 100 nm / Vs or higher have been reported (see, for example, Patent Documents 1 and 2). However, due to insufficient electron blocking properties, some electrons pass through the light-emitting layer, and improvements in luminous efficiency cannot be expected. To further increase efficiency, materials with higher electron blocking properties, more stable thin films, and high heat resistance are required. Furthermore, although there are reports of highly durable aromatic amine derivatives (see, for example, Patent Document 3), these have been used as charge transport materials for electrophotographic photoreceptors and have not been used in organic EL devices.

[0011] In order to solve this problem, substituted carbazole structures and aromatic amine compounds have been proposed as compounds with improved properties such as heat resistance and hole injection properties (for example, see Patent Documents 4 and 5). Although improvements in device life and luminous efficiency have been achieved for devices using these compounds in hole injection layers or hole transport layers, these improvements are not sufficient and further efforts are needed to reduce the driving voltage, increase the luminous efficiency, and extend the device life.

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: U.S. Patent No. 5,792,557

[0015] Patent Document 2: U.S. Patent No. 5,639,914

[0016] Patent Document 3: U.S. Patent No. 7759030

[0017] Patent Document 4: Japanese Patent Application Laid-Open No. 2009-076817

[0018] Patent Document 5: U.S. Patent No. 10,818,844

[0019] Patent Document 6: European Patent No. 2684932

[0020] Patent Document 7: U.S. Patent No. 1,046,895

[0021] Patent Document 8: Korean Patent No. 10-2107875

[0022] Non-patent literature

[0023] Non-patent document 1: Proceedings of the 9th Workshop of the Society of Applied Physics, pp. 55-61 (2001)

[0024] Non-patent document 2: Proceedings of the 9th Workshop of the Society of Applied Physics, pp. 23-31 (2001)

[0025] Non-patent document 3: Appl. Phys. Let., 98, 083302 (2011)

[0026] Non-Patent Document 4: Organic EL Symposium Third Regular Meeting Draft Proceedings, pp. 13-14 (2006)

[0027] Non-patent document 5: Chem. Rev., 116, 12564-12649 (2016) Summary of the Invention

[0028] The object of the present invention is to provide a material for a high-efficiency, high-durability organic EL element having (1) excellent hole injection and transport properties, (2) electron blocking ability, (3) high stability in a thin film state, and (4) excellent durability.

[0029] Furthermore, by using the material of the present invention, an organic EL element having (1) high luminous efficiency and power efficiency, (2) low luminous starting voltage and practical driving voltage, and (3) long life is provided.

[0030] To achieve the above-mentioned objectives, the present inventors focused on the excellent hole injection and transport capabilities, thin film stability, and durability of arylamine compounds. By optimizing the substitution position and substituents of the carbazole group, they were able to dramatically improve the material's properties. Furthermore, in organic EL devices, the luminous efficiency and power efficiency were improved, enabling the suppression of the emission onset voltage and practical driving voltage, thus achieving a lifespan exceeding conventional lifetimes. This led to the completion of the present invention.

[0031] Specifically, the present invention provides the following arylamine compounds, and organic EL devices and electronic devices using the same.

[0032] 1) An arylamine compound represented by the following general formula (A):

[0033] [Chemistry 1]

[0034]

[0035] In formula (A), Ar1, Ar2 and Ar3 each independently represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group,

[0036] L1, L2 and L3 each independently represent a single bond, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aromatic heterocyclic group, or a substituted or unsubstituted divalent condensed polycyclic aromatic group,

[0037] R each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group.

[0038] 2) The arylamine compound according to 1), wherein R in the general formula (A) is independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted phenyl group.

[0039] 3) The arylamine compound according to 1), wherein L1, L2, and L3 are each independently a single bond, an unsubstituted divalent aromatic hydrocarbon group, an unsubstituted divalent aromatic heterocyclic group, or an unsubstituted divalent condensed polycyclic aromatic group.

[0040] 4) The arylamine compound according to 3), wherein L1, L2 and L3 in the general formula (A) are each independently a single bond, an unsubstituted divalent phenylene group, an unsubstituted divalent naphthylene group, or an unsubstituted divalent dibenzofuranyl group.

[0041] 5) The arylamine compound according to 4), wherein L3 in the general formula (A) is an unsubstituted 1,2-phenylene group, an unsubstituted 1,3-phenylene group, an unsubstituted 1,7-dibenzofuranyl group, or an unsubstituted 2,7-dibenzofuranyl group.

[0042] 6) The arylamine compound according to 4), wherein L1 and L2 in the general formula (A) are each independently a single bond or an unsubstituted 1,4-phenylene group.

[0043] 7) The arylamine compound according to 1), wherein at least one of Ar1, Ar2 and Ar3 in the general formula (A) is a substituted or unsubstituted phenyl group.

[0044] 8) An organic EL device comprising a pair of electrodes and an organic layer sandwiched therebetween, wherein the organic layer contains the arylamine compound according to any one of 1) to 7).

[0045] 9) The organic EL device according to 8), wherein the organic layer is a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer.

[0046] 10) An electronic device using an element having a pair of electrodes and an organic layer sandwiched therebetween, wherein the organic layer contains the arylamine compound according to any one of 1) to 7).

[0047] Examples of the "aromatic hydrocarbon group", "aromatic heterocyclic group" or "condensed polycyclic aromatic group" in the "substituted or unsubstituted aromatic hydrocarbon group", "substituted or unsubstituted aromatic heterocyclic group" or "substituted or unsubstituted condensed polycyclic aromatic group" represented by Ar1 to Ar3 or R in the general formula (A) include, specifically, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, spirobifluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzo[9,1-d]-, benzo[ ... 0] an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, such as a phenanthrenyl 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 benzothiazolyl group, an oxazolopyridinyl group, an oxazolopyrazinyl group, a quinoxalinyl group, a quinazolinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, an acridinyl group, or a carbolinyl group.

[0048] Examples of the "divalent aromatic hydrocarbon group", "divalent aromatic heterocyclic group" or "divalent fused polycyclic aromatic group" in the "substituted or unsubstituted divalent aromatic hydrocarbon group", "substituted or unsubstituted divalent aromatic heterocyclic group" or "substituted or unsubstituted divalent fused polycyclic aromatic group" represented by L1 to L3 in the general formula (A) include divalent groups obtained by removing one hydrogen atom from the "aromatic hydrocarbon group", "aromatic heterocyclic group" or "fused polycyclic aromatic group" represented by Ar1 to Ar3 or R in the general formula (A), for example, divalent groups obtained by removing one hydrogen atom from the above-mentioned specific groups.

[0049] The "substituent" in the "substituted aromatic hydrocarbon group", "substituted aromatic heterocyclic group" or "substituted condensed polycyclic aromatic group" represented by Ar1 to Ar3, L1 to L3 or R in the general formula (A) specifically includes a deuterium atom, a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; a silyl group such as a trimethylsilyl group and a triphenylsilyl group; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group; an alkenyl group such as a vinyl group and an allyl group; a phenoxy group, a tolyloxy group and a methyl group; aryloxy groups such as benzophenone, benzothiophene ... Furthermore, these substituents and the benzene ring substituted with the substituents, or multiple 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.

[0050] In the general formula (A), L1 is preferably a single bond or unsubstituted 1,4-phenylene, and more preferably a single bond.

[0051] In the general formula (A), L2 is preferably a single bond or an unsubstituted 1,4-phenylene group.

[0052] In the general formula (A), L3 is preferably an unsubstituted 1,2-phenylene, 1,3-phenylene or 1,7-benzofuranyl group, and more preferably a 1,2-phenylene or 1,3-phenylene group.

[0053] In the general formula (A), preferably, L2 is an unsubstituted 1,4-phenylene group, and L3 is a 1,2-phenylene group or a 1,3-phenylene group. Also, preferably, L2 is a single bond, and L3 is a 1,7-benzofuranyl group.

[0054] In general formula (A), Ar1 is preferably a substituted phenyl group, a substituted or unsubstituted biphenyl group, or a benzofuranyl group, and more preferably a substituted or unsubstituted 4-[1,1']biphenyl group. The substituent of the substituted phenyl group is preferably a naphthyl group.

[0055] In the general formula (A), Ar2 is preferably an unsubstituted phenyl group or an unsubstituted 4-[1,1']biphenyl group.

[0056] In the general formula (A), Ar3 is preferably an unsubstituted phenyl group or an unsubstituted 4-[1,1′]biphenyl group, and more preferably an unsubstituted phenyl group.

[0057] In the general formula (A), it is preferred that all Rs are hydrogen atoms.

[0058] As for the arylamine compound represented by the above-mentioned general formula (A) suitable for use in the organic EL element of the present invention, it 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 element from the perspective of excellent hole injection and transport capabilities, thin film stability and durability, and is more preferably used as a constituent material of the hole transport layer or electron blocking layer.

[0059] Furthermore, the arylamine compound represented by the general formula (A) of the present invention is preferably used as a constituent material of the organic layer in an electronic device using an element having a pair of electrodes and at least one organic layer sandwiched therebetween.

[0060] Compared with conventional hole transport materials, the arylamine compound represented by the general formula (A) of the present invention has the following characteristics: (1) good hole injection characteristics, (2) high hole mobility, (3) excellent electron blocking ability, (4) high electron resistance, (5) stable thin film state, and (6) excellent heat resistance.

[0061] In an organic EL element having a hole injection layer and / or a hole transport layer and produced by using the arylamine compound represented by the general formula (A) of the present invention as a hole injection material and / or a hole transport material, the hole transport efficiency to the light-emitting layer is improved, the luminous efficiency is improved, and the driving voltage is reduced, thereby improving the durability of the element and obtaining the element characteristics of (1) high luminous efficiency, (2) low luminescence onset voltage, (3) low practical driving voltage, and (4) long life.

[0062] The arylamine compound represented by general formula (A) of the present invention has excellent electron-blocking ability, high electron tolerance, and is stable even in thin films, confining excitons generated within the light-emitting layer. Consequently, organic EL devices fabricated with this compound as an electron-blocking material in an electron-blocking layer exhibit high luminous efficiency, reduced driving voltage, improved current tolerance, and increased maximum luminous brightness due to the increased probability of hole-electron recombination and suppressed thermal deactivation.

[0063] The arylamine compound represented by general formula (A) of the present invention has excellent hole-transporting properties and a wide band gap. Consequently, in an organic EL device having a light-emitting layer fabricated using this compound as a host material, the light-emitting layer can be loaded with a fluorescent, phosphorescent, or delayed fluorescent emitter known as a dopant, thereby reducing the driving voltage and improving the luminous efficiency.

[0064] Therefore, the arylamine compound represented by general formula (A) of the present invention is useful as a constituent material of the hole injection layer, hole transport layer, electron blocking layer or light-emitting layer of an organic EL element, and can improve the luminous efficiency and driving voltage of conventional organic EL elements, and can also improve durability.

[0065] Furthermore, the arylamine compound represented by the general formula (A) 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

[0066] Figure 1 The diagram shows the structures of compounds (1) to (18) as examples of the arylamine compound represented by the general formula (A).

[0067] Figure 2 This is a diagram showing the structures of compounds (19) to (33) as examples of the arylamine compound represented by the general formula (A).

[0068] Figure 3 This is a diagram showing the structures of compounds (34) to (48) as examples of the arylamine compound represented by the general formula (A).

[0069] Figure 4 This is a diagram showing the structures of Compounds (49) to (63) as examples of the arylamine compound represented by the general formula (A).

[0070] Figure 5 This is a diagram showing the structures of Compounds (64) to (78) as examples of the arylamine compound represented by the general formula (A).

[0071] Figure 6 This is a diagram showing the structures of Compounds (79) to (90) as examples of the arylamine compound represented by the general formula (A).

[0072] Figure 7 This is a diagram showing the structures of Compounds (91) to (102) as examples of the arylamine compound represented by the general formula (A).

[0073] Figure 8 This is a diagram showing the structures of Compounds (103) to (120) as examples of the arylamine compound represented by the general formula (A).

[0074] Figure 9 This is a diagram showing the structures of Compounds (121) to (135) as examples of the arylamine compound represented by the general formula (A).

[0075] Figure 10 This is a diagram showing the structures of Compounds (136) to (150) as examples of the arylamine compound represented by the general formula (A).

[0076] Figure 11 This is a diagram showing the structures of Compounds (151) to (162) as examples of the arylamine compound represented by the general formula (A).

[0077] Figure 12 This is a diagram showing the structures of Compounds (163) to (174) as examples of the arylamine compound represented by the general formula (A).

[0078] Figure 13 This is a diagram showing the structures of Compounds (175) to (186) as examples of the arylamine compound represented by the general formula (A).

[0079] Figure 14 This is a diagram showing the structures of Compounds (187) to (198) as examples of the arylamine compound represented by the general formula (A).

[0080] Figure 15 This is a diagram showing the structures of Compounds (199) to (210) as examples of the arylamine compound represented by the general formula (A).

[0081] Figure 16 This is a diagram showing the structures of Compounds (211) to (222) as examples of the arylamine compound represented by the general formula (A).

[0082] Figure 17 This is a diagram showing the structures of Compounds (223) to (234) as examples of the arylamine compound represented by the general formula (A).

[0083] Figure 18 This is a diagram showing the structures of Compounds (235) to (246) as examples of the arylamine compound represented by the general formula (A).

[0084] Figure 19 This is a diagram showing the structures of Compounds (247) to (258) as examples of the arylamine compound represented by the general formula (A).

[0085] Figure 20 This is a diagram showing an example of the structure of the organic EL element of the present invention. DETAILED DESCRIPTION

[0086] The arylamine compounds represented by general formula (A) of the present invention are novel compounds and can be synthesized by known methods. For example, they can be synthesized by a known coupling reaction using a palladium catalyst (e.g., see Non-Patent Document 5).

[0087] Specific examples of preferred compounds among the arylamine compounds represented by the above general formula (A) that are preferably used in the organic EL device of the present invention are shown in FIG. Figures 1 to 19 , but are not limited to these compounds.

[0088] The arylamine compound represented by general formula (A) of the present invention can be purified by known methods such as column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization from a solvent, crystallization, and sublimation purification. Preferably, the final purification is performed by sublimation purification. The compound is identified by NMR analysis.

[0089] The other compounds used in the organic EL device of the present invention are purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization from a solvent, crystallization, etc., and finally purified by sublimation purification.

[0090] As physical properties of the arylamine compound represented by general formula (A) of the present invention, the melting point, glass transition temperature (Tg), and work function were measured. The melting point serves as an indicator of vapor deposition properties, the glass transition temperature (Tg) serves as an indicator of thin film stability, and the work function serves as an indicator of hole injection properties, hole transport properties, or electron blocking properties.

[0091] The melting point and the glass transition temperature (Tg) can be measured using a powder, for example, with a high-sensitivity differential scanning calorimeter (DSC3100SA manufactured by Bruker Eix-Ess).

[0092] 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 apparatus (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).

[0093] As the structure of the organic EL element of the present invention, a structure consisting of an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, a cathode and a capping layer (capping layer) can be listed on a substrate in sequence. In addition, a structure with an electron blocking layer between the hole transport layer and the light-emitting layer and a structure with a hole blocking layer between the light-emitting layer and the electron transport layer can be listed. In these multilayer structures, an organic layer can have the functions of a certain layer or layers. For example, an organic layer can be made into a structure that serves as both a hole injection layer and a hole transport layer, a structure that serves as both an electron injection layer and an electron transport layer, etc. In addition, a structure in which two or more organic layers with the same function are stacked can be made, a structure in which two hole transport layers are stacked, a structure in which two light-emitting layers are stacked, a structure in which two electron transport layers are stacked, etc.

[0094] As the anode of the organic EL element of the present invention, an electrode material having a large work function such as ITO or gold is used.

[0095] As the material of the hole injection layer and hole transport layer of the organic EL element of the present invention, in addition to using the arylamine compound of the present invention, N, N'-diphenyl-N, N'-di(m-tolyl) benzidine (TPD), N, N'-diphenyl-N, N'-di(α-naphthyl) benzidine (NPD), N, N, N', N'-tetra(biphenyl) benzidine and other benzidine derivatives, 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) and arylamine compounds having a structure having more than two triphenylamine structures or carbazole structures in the molecule, each connected by a single bond or a divalent group containing no heteroatoms, etc. These materials can be film-formed alone, or a plurality of them can be mixed to form a film, and each can be used as a single layer. In addition, these materials can be made into a laminated structure between layers formed alone, a laminated structure between layers formed by mixing, or a laminated structure of a layer formed alone and a layer formed by mixing a plurality of them. In addition, as the material of the hole injection / transport layer, a coating-type polymer material such as poly(3,4-ethylenedioxythiophene) (PEDOT) / poly(styrenesulfonic acid) (PSS) can be used. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet.

[0096] In addition, in the hole injection layer or the hole transport layer, it is preferred that the materials commonly used in the layer be further P-doped with tris(bromophenyl)amine antimony hexachloride, a radialene derivative (e.g., see Patent Document 6). In addition, a polymer compound having a benzidine derivative structure in a partial structure, such as TPD, can be used.

[0097] As the material for the electron blocking layer of the organic EL element of the present invention, in addition to the arylamine compound of the present invention, carbazole derivatives such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz), and 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene can be used. Compounds with electron blocking effects such as compounds having triphenylsilyl and triarylamine structures. These materials can also serve as materials for hole transport layers. These materials can be formed into films alone, or a variety of them can be mixed to form films, and each can be used as a single layer. In addition, these materials can be made into a stacked structure between layers of individual film formations, a stacked structure between layers of mixed film formations, or a stacked structure of layers of individual film formations and a layer of multiple mixed film formations. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet methods.

[0098] As materials for the light-emitting layer of the organic EL device of the present invention, in addition to the arylamine compounds of the present invention, metal complexes of quinolinephenol derivatives headed by tris(8-hydroxyquinolinol)aluminum (Alq3), various metal complexes, anthracene derivatives, bis(styrylbenzene) derivatives, pyrene derivatives, oxazole derivatives, poly(p-phenylenevinylene) derivatives, etc. can also be used. In addition, the light-emitting layer can be composed of a host material and a dopant material. Anthracene derivatives are preferably used as the host material. In addition to the above-mentioned light-emitting materials headed by the arylamine compounds of the present invention, heterocyclic compounds having an indole ring as a partial structure of the fused ring, heterocyclic compounds having a carbazole ring as a partial structure of the fused ring, carbazole derivatives, thiazole derivatives, benzimidazole derivatives, and polydialkylfluorene derivatives can also be used. In addition, as dopant materials, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, and aminostyryl derivatives can be used. These materials can be formed into a film alone or in a mixture of multiple materials, and each can be used as a single layer. Furthermore, these materials can be formed into a laminated structure of layers formed individually, a laminated structure of layers formed as a mixture, or a laminated structure of layers formed individually and a layer formed as a mixture of multiple materials. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet.

[0099] In addition, as a light-emitting material, a phosphorescent light-emitting body can also be used. As a phosphorescent light-emitting body, a phosphorescent light-emitting body of a metal complex of iridium, platinum, etc. can be used. For example, a green phosphorescent light-emitting body such as Ir(ppy)3, a cyan phosphorescent light-emitting body such as FIrpic, FIr6, a red phosphorescent light-emitting body such as Btp2Ir(acac), etc. can be used. As the main material at this time, as a hole injection-transporting main material, in addition to carbazole derivatives such as 4,4'-di(N-carbazolyl)biphenyl (CBP), TCTA, and mCP, the arylamine compound of the present invention can also be listed. As an electron transporting main material, para-bis(triphenylsilyl)benzene (UGH2), 2,2',2"-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (TPBI), etc. can be listed. By using such materials, high-performance organic EL elements can be produced.

[0100] 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 wt % relative to the entire light-emitting layer.

[0101] Alternatively, materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, can be used as luminescent 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 inkjet.

[0102] As the material of the hole blocking layer of the organic EL element of the present invention, it is possible to use metal complexes of quinoline phenol derivatives such as bathocuproine (BCP), bis(2-methyl-8-hydroxyquinoline)-4-(phenylphenol) aluminum (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives and triazine derivatives with hole blocking effects. These materials can also serve as the material of the electron transport layer. These materials can be film-formed alone, or a variety of mixed films can be formed, and each can be used as a monolayer. In addition, these materials can be made into a laminated structure between the layers of the film-forming alone, a laminated structure between the layers of the film-forming mixed together, or these materials can be made into a laminated structure of a layer of the film-forming alone and a laminated structure of a layer of the film-forming mixed together. These materials can be formed into a thin film by well-known methods such as evaporation, spin coating and inkjet.

[0103] As the material of the electron transport layer of the organic EL element of the present invention, benzimidazole derivatives, anthracene derivatives, pyrimidine derivatives, triazine derivatives are preferably used. In addition, metal complexes of quinoline phenol derivatives headed by Alq3 and BAlq, various metal complexes, triazole derivatives, oxadiazole derivatives, pyridine derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives and silole derivatives can be used. These materials can be film-formed alone, or a variety of them can be mixed to form a film, and each can be used as a monolayer. In addition, these materials can be made into a laminated structure between layers of film-forming alone, a laminated structure between layers of film-forming mixed together, or these materials can be made into a laminated structure of a layer of film-forming alone and a laminated structure of a layer of film-forming mixed together. These materials can be formed into a thin film by known methods such as evaporation, spin coating and inkjet.

[0104] As materials for the electron injection layer of the organic EL element of the present invention, alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride, metal complexes of quinoline phenol derivatives such as lithium quinoline phenol, metal oxides such as aluminum oxide, and metals such as ytterbium (Yb), samarium (Sm), calcium (Ca), strontium (Sr), and cesium (Cs) can be used. By selecting the electron transport layer and the cathode in the preferred manner, the electron injection layer can be omitted.

[0105] Furthermore, for the electron injection layer or the electron transport layer, materials generally used in these layers may be further N-doped with a metal such as cesium.

[0106] As the cathode of the organic EL element 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 an electrode material.

[0107] As the material of the capping layer of the organic EL element of the present invention, arylamine derivatives, aryldiamine derivatives and carbazole derivatives having carbazole groups, benzoxazolyl groups and the like as substituents can be used. These materials can be film-formed alone, or a variety of them can be mixed to form a film, and each can be used as a single layer. In addition, these materials can be made into a stacked structure between layers of film-forming alone, a stacked structure between layers of film-forming mixed together, or a stacked structure of layers of film-forming alone and a plurality of layers of film-forming mixed together can be made into these materials. These materials can be formed into thin films by known methods such as vapor deposition, spin coating and inkjet methods.

[0108] Example

[0109] Hereinafter, the embodiments of the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist of the present invention.

[0110] [Example 1]

[0111] <Synthesis of N-(2'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1"'-quaterphenyl]-5'-amine (Compound (59))>

[0112] In a nitrogen-purged reaction vessel, 12.0 g of N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1"'-tetraphenyl]-5'-amine, 9.9 g of 9-(4'-chloro-[1,1'-biphenyl]-2-yl)-9H-carbazole, 0.5 g of tris(dibenzylideneacetone)palladium(0), 0.2 g of tri-tert-butylphosphine, and 2.9 g of sodium tert-butoxide were added and the mixture was stirred under reflux in xylene solvent overnight. After the reaction, the filtered filtrate was concentrated to obtain a crude product. The crude product was purified by recrystallization using toluene solvent to obtain 14.5 g (yield: 72.3%) of a white powder of N-(2'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1'-tetraphenyl]-5'-amine (compound (59)).

[0113] [Chemistry 2]

[0114]

[0115] The structure of the obtained white powder was identified using NMR.

[0116] use 1 The following 42 hydrogen signals were detected by H-NMR (DMSO-d6).

[0117] δ(ppm)=8.13(2H), 7.75(1H), 7.71-7.57(7H), 7.50(4H), 7.43(4H), 7.33( 2H), 7.31-7.15(8H), 7.13(2H), 7.02(4H), 6.80(5H), 6.69(1H), 6.65(2H).

[0118] [Example 2]

[0119] <Synthesis of N-{3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl}-N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1"'-quaterphenyl]-5'-amine (Compound (151))>

[0120] In a nitrogen-purged reaction vessel, 15.0 g of N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1''-quaterphenyl]-5'-amine, 12.3 g of 9-(4'-chloro-[1,1'-biphenyl]-3-yl)-9H-carbazole, 0.6 g of tris(dibenzylideneacetone)palladium(0), 0.3 g of tri-tert-butylphosphine, and 3.7 g of sodium tert-butoxide were added, and the mixture was stirred under reflux in xylene solvent overnight. The reaction was confirmed. After completion, the filtered filtrate was concentrated to obtain a crude product. The crude product was purified by crystallization using a toluene / acetone mixed solvent to obtain 17.3 g (yield: 69.1%) of white powder of N-{3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl}-N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1'-tetraphenyl]-5'-amine (Compound (151)).

[0121] [Chemistry 3]

[0122]

[0123] The structure of the obtained white powder was identified using NMR.

[0124] use 1 The following 42 hydrogen signals were detected by H-NMR (DMSO-d6).

[0125] δ(ppm)=8.26(2H), 7.84(1H), 7.82(1H), 7.75(2H), 7.73(1H), 7.64(6H), 7.57 (1H), 7.53(2H), 7.48-7.38(9H), 7.37-7.27(4H), 7.26-7.12(10H), 7.10(3H).

[0126] [Example 3]

[0127] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-([1,1':4',1"-terphenyl]-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (183))>

[0128] A nitrogen-purged reaction vessel was charged with 10.0 g of N-([1,1':4',1"-terphenyl]-4-yl)-[1,1':2',1"-terphenyl]-4'-amine, 8.2 g of 9-(4'-chloro-[1,1'-biphenyl]-3-yl)-9H-carbazole, 0.4 g of tris(dibenzylideneacetone)palladium(0), 0.2 g of tri-tert-butylphosphine, and 3.0 g of sodium tert-butoxide. The mixture was then refluxed and stirred overnight in a xylene solvent. After confirming completion of the reaction, the filtered filtrate was concentrated to obtain a crude product. The crude product was purified by recrystallization using toluene solvent to obtain 15.1 g (yield: 90.4%) of white powder of N-(3'-(9H-carbazole-9-yl)-[1,1'-biphenyl]-4-yl)-N-([1,1':4',1"-terphenyl]-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (compound (183)).

[0129] [Chemistry 4]

[0130]

[0131] The structure of the obtained white powder was identified using NMR.

[0132] use 1 The following 42 hydrogen signals were detected by H-NMR (DMSO-d6).

[0133] δ(ppm)=8.26(2H), 7.84(1H), 7.81(1H), 7.76-7.66(11H), 7.56(1H), 7.47( 2H), 7.42(4H), 7.37(2H), 7.29(2H), 7.25-7.11(11H), 7.09(3H), 7.04(2H).

[0134] [Example 4]

[0135] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(1-(naphthalen-1-yl)phenyl-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (153))>

[0136] In a reaction vessel, 10.0 g of N-[3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl]-[1,1':2',1"-terphenyl]-4'-amine, 5.5 g of 1-(4-bromophenyl)naphthalene, 3.4 g of sodium tert-butoxide, 0.3 g of tris(dibenzylideneacetone)palladium(0), 0.1 g of tri-tert-butylphosphine, and 100 ml of xylene were added and stirred under heating and reflux. After confirming the completion of the reaction, the reaction mixture was filtered and purified by column chromatography. The crude product was separated by chromatography (support: silica gel, eluent: dichloromethane / n-heptane). The obtained crude product was purified by crystallization using a dichloromethane / n-heptane mixed solvent to obtain 7.9 g (yield: 58.1%) of white powder of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(1-(naphthalen-1-yl)phenyl-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (153)).

[0137] [Chemistry 5]

[0138]

[0139] The structure of the obtained white powder was identified using NMR.

[0140] use 1 The following 40 hydrogen signals were detected by H-NMR (CDCl 3 ).

[0141] δ(ppm)=8.20(2H), 8.07(1H), 7.94(1H), 7.89-7.85(2H), 7.75-7.68(2H), 7.64(2H), 7.58-7.14(30H).

[0142] [Example 5]

[0143] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(1-(naphthalen-2-yl)phenyl-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (163))>

[0144] In a reaction vessel, 8.6 g of N-[3'-(9H-carbazol-9-yl)[1,1'-biphenyl]-4-yl]-[1,1':2',1"-terphenyl]-4'-amine, 4.8 g of 2-(4-bromophenyl)naphthalene, 2.9 g of sodium tert-butoxide, 0.3 g of tris(dibenzylideneacetone)palladium(0), 0.1 g of tri-tert-butylphosphine, and 86 ml of xylene were added and stirred under heating and reflux. After confirming the completion of the reaction, methyl alcohol was added. The resulting precipitate was filtered to obtain a crude product. The crude product was purified by crystallization using a tetrahydrofuran / ethyl acetate solvent to obtain 5.0 g (yield: 42.8%) of a white powder of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(1-(naphthalen-2-yl)phenyl-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (compound (163)).

[0145] [Chemistry 6]

[0146]

[0147] The structure of the obtained white powder was identified using NMR.

[0148] use 1 The following 40 hydrogen signals were detected by H-NMR (CDCl 3 ).

[0149] δ(ppm)=8.20(2H), 8.07(1H), 7.95-7.88(3H), 7.84(1H), 7.79(1H), 7.75-7.68(4H), 7.62(2H), 7.56-7.44(7H), 7.40-7.13(19H).

[0150] [Example 6]

[0151] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (184))>

[0152] In a reaction vessel, 15.0 g of N-[dibenzofuran-4-yl]-[1,1':2',1"-terphenyl]-4'-amine, 14.2 g of 9-(4'-chloro[1,1'-biphenyl]-3-yl)-9H-carbazole, 5.3 g of sodium tert-butoxide, 0.7 g of tris(dibenzylideneacetone)palladium(0), 0.3 g of tri-tert-butylphosphine, and 150 ml of xylene were added and stirred under heating and reflux. After confirming the completion of the reaction, the reaction mixture was dissolved in water. Silica gel was added to heated toluene, stirred for 30 minutes, and then filtered through Celite. The crude product was purified by crystallization using a toluene / acetone mixed solvent to obtain 6.3 g (yield: 23.7%) of a white powder of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-4-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (184)).

[0153] [Chemistry 7]

[0154]

[0155] The structure of the obtained white powder was identified using NMR.

[0156] use 1 The following 36 hydrogen signals were detected by H-NMR (DMSO-d6).

[0157] δ(ppm)=8.26(2H), 8.19(1H), 8.08(1H), 7.86(1H), 7.83(1H), 7.77-7.72(3H), 7.61(1H) , 7.57(1H), 7.51-7.40(8H), 7.37(1H), 7.32-7.28(2H), 7.24-7.16(8H), 7.13-7.00(6H).

[0158] [Example 7]

[0159] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-3-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (185))>

[0160] In a reaction vessel, 14.0 g of N-[dibenzofuran-3-yl]-[1,1':2',1"-terphenyl]-4'-amine, 13.2 g of 9-(4'-chloro[1,1'-biphenyl]-3-yl)-9H-carbazole, 4.9 g of sodium tert-butoxide, 0.6 g of tris(dibenzylideneacetone)palladium(0), 0.3 g of tri-tert-butylphosphine, and 140 ml of xylene were added and stirred under heating and reflux. After confirming that the reaction was complete, the reaction mixture was heated and refluxed. The mixture was dissolved in toluene, silica gel was added, stirred for 30 minutes, and then filtered through Celite. The crude product was purified by crystallization using a toluene / acetone mixed solvent to obtain 18.6 g (yield: 75.0%) of white powder of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-3-yl)-[1,1':2',1"-terphenyl]-4'-amine (compound (185)).

[0161] [Chemistry 8]

[0162]

[0163] The structure of the obtained white powder was identified using NMR.

[0164] use 1 The following 36 hydrogen signals were detected by H-NMR (DMSO-d6).

[0165] δ(ppm)=8.27(2H), 8.07(2H), 7.89(1H), 7.86(1H), 7.81-7.74(3H), 7.65(1H), 7.59(1H), 7.49-7.37(8H), 7.33-7.17(12H), 7.13-7.11(3H), 7.07-7.05(2H).

[0166] [Example 8]

[0167] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-2-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (186))>

[0168] In a reaction vessel, 10.0 g of N-[3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl]-[1,1':2',1"-terphenyl]-4'-amine, 4.8 g of 2-bromodibenzofuran, 3.4 g of sodium tert-butoxide, 0.3 g of tris(dibenzylideneacetone)palladium(0), 0.1 g of tri-tert-butylphosphine, and 100 ml of xylene were added and stirred under heating and reflux. The reaction was confirmed. After completion, methanol was added and the resulting precipitate was filtered to obtain a crude product. The crude product was purified by crystallization using toluene solvent to obtain 9.0 g (yield: 69.5%) of a white powder of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-2-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (186)).

[0169] [Chemistry 9]

[0170]

[0171] The structure of the obtained white powder was identified using NMR.

[0172] use 1 The following 36 hydrogen signals were detected by H-NMR (DMSO-d6).

[0173] δ(ppm)=8.27(2H), 8.18(1H), 8.14(1H), 7.86(1H), 7.82(1H), 7.78-7.70 (5H), 7.59-7.51(2H), 7.46-7.35(7H), 7.32-7.28(2H), 7.24-7.02(14H).

[0174] [Example 9]

[0175] <Synthesis of N-(3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-1-yl)-[1,1':2',1"-terphenyl]-4'-amine (Compound (187))>

[0176] In a reaction vessel, 10.0 g of N-[3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl]-[1,1':2',1"-terphenyl]-4'-amine, 4.8 g of 1-bromodibenzofuran, 3.4 g of sodium tert-butoxide, 0.3 g of tris(dibenzylideneacetone)palladium(0), 0.1 g of tri-tert-butylphosphine, and 100 ml of xylene were added and the mixture was stirred under heating and reflux. After confirming the completion of the reaction, the reaction mixture was separated by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane) to obtain 9.0 g (yield: 69.5%) of white powder of N-(3'-(9H-carbazole-9-yl)-[1,1'-biphenyl]-4-yl)-N-(dibenzofuran-1-yl)-[1,1':2',1"-terphenyl]-4'-amine (compound (187)).

[0177] [Chemistry 10]

[0178]

[0179] The structure of the obtained white powder was identified using NMR.

[0180] use 1 The following 36 hydrogen signals were detected by H-NMR (DMSO-d6).

[0181] δ(ppm)=8.26(2H), 7.83(1H), 7.77(1H), 7.74-7.67(5H), 7.63(1H), 7.66 (1H), 7.49-7.40(6H), 7.35(1H), 7.30(2H), 7.26-7.05(14H), 6.96(2H).

[0182] [Example 10]

[0183] <Synthesis of N-(1-(9H-carbazol-9-yl)dibenzofuran-7-yl)-N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1"'-quaterphenyl]-5'-amine (Compound (246))>

[0184] In a reaction vessel, 10.2 g of N-[1,1'-biphenyl]-4-yl-[1,1':2',1":4",1"'-quaterphenyl]-5'-amine, 7.9 g of 9-(7-chloro-1-dibenzofuranyl)-9H-carbazole, 4.1 g of sodium tert-butoxide, 0.4 g of tris(dibenzylideneacetone)palladium(0), 0.2 g of tri-tert-butylphosphine, and 102 ml of xylene were added and stirred under heating and reflux. The reaction was confirmed. After completion, methanol was added and the resulting precipitate was filtered to obtain a crude product. The crude product was dispersed and washed with acetone to obtain 12.0 g (yield: 69.2%) of a white powder of N-(1-(9H-carbazol-9-yl)dibenzofuran-7-yl)-N-([1,1'-biphenyl]-4-yl)-[1,1':2',1":4",1'-quaterphenyl]-5'-amine (Compound (246)).

[0185] [Chemistry 11]

[0186]

[0187] The structure of the obtained white powder was identified using NMR.

[0188] use 1 The following 40 hydrogen signals were detected by H-NMR (CDCl 3 ).

[0189] δ(ppm)=8.24(2H), 7.71(1H), 7.64-7.57(5H), 7.52-7.32(17H), 7.25-7.09(13H), 6.78(1H), 6.28(1H).

[0190] [Example 11]

[0191] <Synthesis of N-(1-(9H-carbazol-9-yl)dibenzofuran-7-yl)-N-([1,1':4',1"-terphenyl]-4-yl)[1,1':2',1"-terphenyl]-4'-amine (Compound (256))>

[0192] A reaction vessel was charged with 9.0 g of N-[1,1':4',1"-terphenyl]-4-yl[1,1':2',1"-terphenyl]-4'-amine, 7.0 g of 9-(7-chloro-1-dibenzofuranyl)-9H-carbazole, 3.7 g of sodium tert-butoxide, 0.4 g of tris(dibenzylideneacetone)palladium(0), 0.2 g of tri-tert-butylphosphine, and 90 ml of xylene, and the mixture was stirred under heating and reflux. After confirming completion of the reaction, methanol was added, and the resulting precipitate was filtered to obtain a crude product. The crude product was purified by crystallization using a tetrahydrofuran / ethyl acetate solvent to obtain 10.0 g (yield: 65.4%) of a white powder of N-(1-(9H-carbazole-9-yl)dibenzofuran-7-yl)-N-([1,1':4',1"-terphenyl]-4-yl)[1,1':2',1"-terphenyl]-4'-amine (compound (256)).

[0193] [Chemistry 12]

[0194]

[0195] The structure of the obtained white powder was identified using NMR.

[0196] use 1 The following 40 hydrogen signals were detected by H-NMR (CDCl 3 ).

[0197] δ(ppm)=8.24(2H), 7.71-7.60(8H), 7.56-7.46(5H), 7.42-7.31(7H), 7.25-7.05(16H), 6.78(1H), 6.28(1H).

[0198] [Example 12]

[0199] The melting points and glass transition temperatures of the arylamine compounds obtained in Examples 1 to 11 were measured using a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker Eixex).

[0200] [Table 1]

[0201] Melting point (℃) Glass transition temperature (℃) Compound (59) 129 Compound (151) 132 Compound (183) 129 Compound (153) 125 Compound (163) 125 Compound (184) 126 Compound (185) 126 Compound (186) 128 Compound (187) 128 Compound (246) 146 Compound (256) 115

[0202] As shown in Table 1, the arylamine compounds obtained in Examples 1 to 11 had a glass transition temperature of 100° C. or higher. These results indicate that the arylamine compound represented by the general formula (A) of the present invention is stable in a thin film state.

[0203] [Example 13]

[0204] Using the arylamine compounds obtained in Examples 1 to 11, 100 nm thick vapor-deposited films were formed on ITO substrates, and the work functions (unit: eV) were measured using an ionization potential analyzer (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.). The measurement results are summarized in Table 2.

[0205] [Table 2]

[0206] Work function (eV) Compound (59) 5.72 Compound (151) 5.69 Compound (183) 5.65 Compound (153) 5.64 Compound (163) 5.67 Compound (184) 5.68 Compound (185) 5.73 Compound (186) 5.81 Compound (187) 5.77 Compound (246) 5.69 Compound (256) 5.72

[0207] As shown in Table 2, the arylamine compounds obtained in Examples 1 to 11 exhibited a better preferred energy level compared to the work function of 5.4 eV possessed by general hole transport materials such as NPD and TPD. This indicates that the arylamine compounds represented by the general formula (A) of the present invention have good hole transport capabilities and excellent electron blocking capabilities.

[0208] [Example 14]

[0209] Using the arylamine compounds obtained in Examples 1 to 11 above, Figure 20 As shown in the figure, a reflective ITO electrode is pre-formed on a glass substrate 1 as a transparent anode 2, and then a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9, and a capping layer 10 are sequentially evaporated to produce an organic EL element.

[0210] Specifically, a 50nm-thick ITO film, a 100nm-thick silver alloy reflective film, and a 5nm-thick ITO film were sequentially deposited on a glass substrate 1 as a transparent anode 2. After ultrasonic cleaning in isopropyl alcohol for 20 minutes, the film was dried on a hot plate heated to 250°C for 10 minutes. After a 2-minute UV ozone treatment, the ITO-coated glass substrate was placed in a vacuum deposition machine and the pressure was reduced to below 0.001 Pa.

[0211] Next, in order to cover the transparent anode 2, an electron acceptor (Acceptor-1) of the following structural formula and a compound (HTM-1) of the following structural formula are binary evaporated as a hole injection layer 3 at a evaporation rate ratio of Acceptor-1:Compound (HTM-1) = 3:97, so as to form a film with a thickness of 10 nm.

[0212] On the hole injection layer 3 , a compound (HTM-1) having the following structural formula was formed as the hole transport layer 4 to a film thickness of 140 nm.

[0213] On the hole transport layer 4 , the compound (59) of Example 1 was formed as the electron blocking layer 5 to a film thickness of 5 nm.

[0214] On the electron blocking layer 5, as the light-emitting layer 6, a compound (EMD-1) of the following structural formula and a compound (EMH-1) of the following structural formula are binary evaporated at an evaporation rate ratio of compound (EMD-1): compound (EMH-1) = 5:95 to form a film with a thickness of 20 nm.

[0215] On the light-emitting layer 6, as an electron transport layer 7, a compound (ETM-1) of the following structural formula and a compound (ETM-2) of the following structural formula are binary evaporated at an evaporation rate ratio of compound (ETM-1): compound (ETM-2) = 50:50 to form a film with a thickness of 30 nm.

[0216] On the electron transport layer 7 , lithium fluoride was formed as the electron injection layer 8 to a film thickness of 1 nm.

[0217] On the electron injection layer 8 , a magnesium-silver alloy was formed as a cathode 9 to a film thickness of 12 nm.

[0218] Finally, as the capping layer 10 , a compound (CPL-1) having the following structural formula was formed to a film thickness of 60 nm.

[0219] [Chemistry 13]

[0220]

[0221] [Chemistry 14]

[0222]

[0223] [Chemistry 15]

[0224]

[0225] [Examples 15 to 24]

[0226] In Example 14, an organic EL device was produced under the same conditions except that the compounds obtained in Examples 2 to 11 were used instead of the compound (59) in Example 1 as the material for the electron blocking layer 5 .

[0227] [Comparative Example 1]

[0228] For comparison, in Example 14, an organic EL element was produced under the same conditions 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 (59) in Example 1.

[0229] [Chemistry 16]

[0230]

[0231] [Comparative Example 2]

[0232] For comparison, in Example 14, an organic EL element was produced under the same conditions 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 (59) in Example 1.

[0233] [Chemistry 17]

[0234]

[0235] [Comparative Example 3]

[0236] For comparison, in Example 14, an organic EL element was produced under the same conditions except that the compound (HTM-3) of the following structural formula (see, for example, Patent Document 9) was used as the material for the electron blocking layer 5 instead of the compound (59) in Example 1.

[0237] [Chemistry 18]

[0238]

[0239] [evaluate]

[0240] The organic EL devices prepared in Examples 14 to 24 and Comparative Examples 1 to 3 were used to measure the current density of 10 mA / cm in the atmosphere at room temperature. 2 The voltage, brightness, luminous efficiency and power efficiency when the current flows. In addition, for the life of the element, the luminous brightness at the beginning of luminescence (initial brightness) is set to 1000 cd / m 2 When constant current driving is performed, the luminance is reduced to 950cd / m 2 The results are summarized in Table 3.

[0241] [Table 3]

[0242]

[0243] As shown in Table 3, the current density is 10 mA / cm 2In terms of luminous efficiency when a current of 100 Ω is flowing, the organic EL elements of Comparative Examples 1 to 3 have a luminous efficiency of 8.73 to 9.11 cd / A, while the organic EL elements of Examples 14 to 24 have a high efficiency of 9.25 to 9.47 cd / A. Furthermore, in terms of power efficiency, the organic EL elements of Comparative Examples 1 to 3 have a luminous efficiency of 8.11 to 8.33 lm / W, while the organic EL elements of Examples 14 to 24 have a high efficiency of 8.58 to 8.82 lm / W. Furthermore, it was found that the organic EL elements of Comparative Examples 1 to 3 have a device lifespan (95% attenuation) of 365 to 408 hours, while the organic EL elements of Examples 14 to 24 have a longer lifespan of 420 to 648 hours.

[0244] The above results indicate that the organic EL element of the present invention, which uses an arylamine compound having high hole mobility and excellent electron-blocking ability, can achieve an organic EL element with high luminous efficiency and long life compared to conventional organic EL elements.

[0245] Industrial applicability

[0246] The organic EL device using the arylamine compound of the present invention can improve the luminous efficiency and the durability of the organic EL device, and can be developed for use in, for example, household electrical appliances and lighting.

[0247] Description of Reference Signs

[0248] 1 Glass substrate

[0249] 2 Transparent anode

[0250] 3 Hole injection layer

[0251] 4 Hole transport layer

[0252] 5 Electron blocking layer

[0253] 6. Luminescent layer

[0254] 7 Electron Transport Layer

[0255] 8 Electron injection layer

[0256] 9 cathode

[0257] 10 capping layer

Claims

1. An arylamine compound represented by the following general formula (A): In the formula, Ar1, Ar2 and Ar3 each independently represent a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, L1, L2 and L3 each independently represent a single bond, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aromatic heterocyclic group, or a substituted or unsubstituted divalent condensed polycyclic aromatic group, R each independently represents a hydrogen atom, a deuterium 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, wherein In the general formula (A), each R is independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted phenyl group.

3. The arylamine compound according to claim 1, wherein In the general formula (A), L1, L2, and L3 are each independently a single bond, an unsubstituted divalent aromatic hydrocarbon group, an unsubstituted divalent aromatic heterocyclic group, or an unsubstituted divalent condensed polycyclic aromatic group.

4. The arylamine compound according to claim 3, wherein In the general formula (A), L1, L2, and L3 are each independently a single bond, an unsubstituted divalent phenylene group, an unsubstituted divalent naphthylene group, or an unsubstituted divalent dibenzofuranyl group.

5. The arylamine compound according to claim 4, wherein L3 in the general formula (A) is an unsubstituted 1,2-phenylene group, an unsubstituted 1,3-phenylene group, an unsubstituted 1,7-dibenzofuranyl group, or an unsubstituted 2,7-dibenzofuranyl group.

6. The arylamine compound according to claim 4, wherein In the general formula (A), L1 and L2 are each independently a single bond or an unsubstituted 1,4-phenylene group.

7. The arylamine compound according to claim 1, wherein In the general formula (A), at least one of Ar1, Ar2 and Ar3 is a substituted or unsubstituted phenyl group.

8. An organic EL element comprising a pair of electrodes and an organic layer sandwiched therebetween, wherein: The organic layer contains the arylamine compound according to any one of claims 1 to 7.

9. The organic EL element according to claim 8, wherein The organic layer is a hole transport layer, an electron blocking layer, a hole injection layer or a light emitting layer. 10 . An electronic device using an element having a pair of electrodes and an organic layer sandwiched therebetween, wherein the organic layer comprises the arylamine compound according to claim 1 .

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