Arylamine compound, organic electroluminescent element, and electronic device

Abstract

The objective of the present invention is to provide an organic compound with excellent properties as a material for a high-efficiency, high-durability organic EL element, exhibiting favorable hole injection and transport performance, electron blocking ability, and high stability in a thin film state, and to provide a high-efficiency, high-durability organic EL element using the compound. The arylamine compound of the present invention has excellent heat resistance as well as favorable hole transporting ability. An organic EL element using the compound in a hole transport layer, an electron blocking layer, a light emission layer, and a hole injection layer thereof exhibits favorable element properties.

Description

Arylamine compounds, organic electroluminescent devices and electronic devices

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

[0002] Organic EL devices are self-luminous devices, so they are brighter than liquid crystal devices, have excellent visibility, and can display clear images, so active research has been conducted on them.

[0003] In 1987, C.W. Tang et al. of Eastman Kodak developed a layered structure element in which each material played a different role, thereby making practical organic EL elements using organic materials. They achieved high brightness of 1000 ㏅ / ㎡ or more at a voltage of 10 V or less by layering a phosphor capable of transporting electrons and an organic material capable of transporting holes, and injecting charges of both sides into the phosphor layer to emit light (see, for example, Patent Documents 1 and 2).

[0004] To date, many improvements have been made for the practical use of organic EL devices, further segmenting the various roles of the laminated structure, and achieving high efficiency and durability through an electroluminescent device 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 sequentially formed on a substrate (see, for example, Non-Patent Document 1).

[0005] In addition, the use of triplet excitons is being attempted for the purpose of further improving luminescence efficiency, and the use of phosphorescent compounds is being examined (see, for example, non-patent literature 2). In addition, devices that utilize luminescence by 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% using a device using a thermally activated delayed fluorescence material (see, for example, non-patent literature 3).

[0006] The light-emitting layer can also be manufactured 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 an organic material in an organic EL device has a significant impact on various characteristics, such as the efficiency and durability of the device (see, for example, non-patent literatures 1 to 3).

[0007] In organic EL devices, charges injected from both electrodes recombine in the light-emitting layer to produce light. Therefore, it is important to efficiently transfer the positive charges of holes and electrons to the light-emitting layer, requiring a device with excellent carrier balance. Therefore, by using a material that enhances hole injectability, which supplies holes injected from the anode to the light-emitting layer, and enhances electron-blocking properties, which block electrons injected from the cathode, the probability of holes and electrons recombining within the light-emitting layer can be increased, and furthermore, high luminescence efficiency can be achieved by confining excitons generated within the light-emitting layer. To achieve this, the role of the hole transport material is crucial, requiring a hole transport material that exhibits high hole injectability, high hole mobility, high electron-blocking properties, and high electron endurance.

[0008] Furthermore, the heat resistance and amorphous properties of the material are also crucial for the lifespan of the device. Materials with low heat resistance can undergo thermal decomposition even at low temperatures due to the heat generated during device operation, leading to deterioration. Materials with low amorphous properties can undergo thin-film crystallization even in a short period of time, deteriorating the device. Therefore, materials must possess both high heat resistance and good amorphous properties.

[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 Documents 1 and 2). However, although NPD has good hole transport ability, its glass transition point (Tg), which is an indicator of heat resistance, is low at 96°C, and thus, under high-temperature conditions, crystallization causes 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 document, there is one having a hole mobility of 10 -3 Although there are compounds with excellent mobility of ㎠ / Vs or more (see, for example, patent documents 1 and 2), because the electron-blocking property is insufficient, some of the electrons escape the light-emitting layer, and improvement in light-emitting efficiency cannot be expected. Therefore, in order to further improve efficiency, a material with higher electron-blocking property, more stable thin films, and higher heat resistance has been required. In addition, although there are reports of highly durable aromatic amine derivatives (see, for example, patent document 3), they have been used as charge-transport materials used in electrophotographic photosensitive materials, and there have been no examples of their use as organic EL elements.

[0011] To solve this problem, substituted carbazole structures or 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 in device lifespan and luminous efficiency have been made, but they are not yet sufficient, and further lowering of driving voltage, higher luminous efficiency, and longer device lifespan are required.

[0012] [Prior Art Literature]

[0013] [Patent Document]

[0014] (Patent Document 1) Specification of U.S. Patent No. 5,792,557

[0015] (Patent Document 2) Specification of U.S. Patent No. 5639914

[0016] (Patent Document 3) Specification of U.S. Patent No. 7,759,030

[0017] (Patent Document 4) Japanese Patent Publication No. 2009-076817

[0018] (Patent Document 5) Japanese Patent Publication No. 6674892

[0019] (Patent Document 6) Specification of European Patent No. 2684932

[0020] (Patent Document 7) Specification of Korean Patent No. 10-2022-0134847

[0021] (Patent Document 8) Specification of Korean Patent No. 10-2022-0154631

[0022] [Non-patent literature]

[0023] (Non-patent literature 1) Proceedings of the 9th Seminar of the Society of Applied Physics, pages 55–61 (2001)

[0024] (Non-patent document 2) Proceedings of the 9th Seminar of the Society of Applied Physics, pages 23–31 (2001)

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

[0026] (Non-patent document 4) Organic EL Forum 3rd Preliminary Session Proceedings, pages 13-14 (2006)

[0027] (Non-patent literature 5) Chem. Rev., 116, 12564-12649 (2016)

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

[0029] In addition, by using the material of the present invention, an organic EL device is provided that (1) has high luminous efficiency and power efficiency, (2) has low luminous initiation voltage and practical driving voltage, and (3) has a long lifespan.

[0030] To achieve the above-mentioned objectives, the present inventors, focusing on the superior hole injection and transport capabilities of arylamine compounds, as well as the stability and durability of thin films, pursued optimization of the substitution positions and substituents of the carbazolyl group, thereby dramatically improving the properties of the material. Furthermore, in organic EL devices, the performance of luminous efficiency and power efficiency was improved, and suppression of the luminous initiation voltage and practical driving voltage was enabled, thereby realizing a longer lifespan that surpasses that of conventional devices, thereby completing the present invention.

[0031] That is, according to the present invention, the following arylamine compound and an organic EL element and electronic device using the same are provided.

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

[0033] [Chemical Formula 1]

[0034]

[0035] [In the formula, A represents a substituted or unsubstituted naphthylene group,

[0036] L1, L2 are single bonds, substituted or unsubstituted divalent aryl groups,

[0037] Or represents a substituted or unsubstituted divalent heteroaryl group,

[0038] R may be the same or different,

[0039] Hydrogen atoms, deuterium atoms, substituted or unsubstituted aryl groups,

[0040] Or represents a substituted or unsubstituted heteroaryl group,

[0041] Ar1, Ar2 are substituted or unsubstituted aryl groups,

[0042] Or represents a substituted or unsubstituted heteroaryl group.]

[0043] 2) The arylamine compound described in 1) above, wherein the general formula (1) is the following general formula (1-1) or general formula (1-2).

[0044] [Chemical Formula 2]

[0045]

[0046] [Chemical Formula 3]

[0047]

[0048] [In the formula, A, Ar1, Ar2, L1, L2 and R are as defined in the general formula (1) above.]

[0049] 3) An arylamine compound described in 2) above, wherein A in the general formula (1-1) or general formula (1-2) is represented by the following general formulas (2-1) to (2-6).

[0050] [Chemical Formula 4]

[0051]

[0052] [Chemical Formula 5]

[0053]

[0054] [In the formula, the broken line represents the bonding site with Ar1 or L1,

[0055] R' may be the same or different

[0056] Hydrogen atom, deuterium atom, unsubstituted phenyl group, unsubstituted biphenylyl group,

[0057] Represents an unsubstituted naphthyl group or an unsubstituted phenanthryl group.]

[0058] 4) L1 and L2 in the general formula (1-1) or (1-2) above are

[0059] An arylamine compound as described in 3) comprising a single bond, a substituted or unsubstituted divalent phenylene group, a substituted or unsubstituted divalent naphthylene group, or a substituted or unsubstituted divalent biphenylylene group.

[0060] 5) In the general formula (1-1) or (1-2), R is

[0061] An arylamine compound as described in 3) above, comprising a hydrogen atom, a deuterium atom, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

[0062] 6) Ar1 in the general formula (1-1) or (1-2) above is

[0063] A substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group,

[0064] A substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzofuranyl group,

[0065] Or an arylamine compound described in 3) above having a substituted or unsubstituted phenanthryl group.

[0066] 7) Ar1 in the general formula (1-1) or (1-2) above is

[0067] An arylamine compound as described in 6) above, comprising an unsubstituted phenyl group, an unsubstituted biphenylyl group, an unsubstituted naphthyl group, an unsubstituted dibenzofuranyl group, or an unsubstituted phenanthryl group.

[0068] 8) An organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween, wherein the organic layer contains an arylamine compound described in 1) or 2).

[0069] 9) The organic EL device described in 8) above, wherein the organic layer is a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer.

[0070] 10) An electronic device having a pair of electrodes and at least one organic layer sandwiched therebetween, characterized in that the organic layer contains an arylamine compound as described in 1) or 2).

[0071] Specifically, the “aryl group” or “heteroaryl group” in the “substituted or unsubstituted aryl group” or “substituted or unsubstituted heteroaryl group” represented by Ar1, Ar2 or R in the general formula (1) includes,

[0072] Phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, pyrimidinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, fluorenyl group, spirobifluorenyl group, azafluorenyl group, diazafluorenyl group, azaspirobifluorenyl group, diazaspirobifluorenyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, Examples thereof include a naphthyridinyl group, a phenanthrolinyl group, an aclidinyl group, and a carbolinyl group, and in addition, an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms may be selected.

[0073] Specifically, the “substituent” in the “substituted aryl group” or “substituted heteroaryl group” represented by Ar1, Ar2 or R in the general formula (1) is,

[0074] A deuterium atom, a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a silyl group such as a trimethylsilyl group or a triphenylsilyl group; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group; a linear or branched alkyloxy group having 1 to 6 carbon atoms such as a methyloxy group, an ethyloxy group, or a propyloxy group; an alkenyl group such as a vinyl group or an allyl group; an aryloxy group such as a phenyloxy group or a tolyloxy group; an arylalkyloxy group such as a benzyloxy group or a phenethyloxy group; Aromatic hydrocarbon groups or condensed polycyclic aromatic groups such as a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a spirofluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, and a triphenylenyl group; aromatic heterocyclic groups such as a pyridyl group, a thienyl group, a furyl group, a pyrrolyl 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, a quinoxalinyl group, a benzoimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, and a carbolinyl group; and these substituents may further be substituted by the substituents exemplified above. In addition, these substituents and the benzene ring substituted by the substituents, or multiple substituents substituted with 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.

[0075] In general formula (1), represented by L1 and L2

[0076] “Substituted or unsubstituted divalent aryl group”,

[0077] Or in “substituted or unsubstituted divalent heteroaryl group”,

[0078] As “divalent aryl group” or “divalent heteroaryl group”,

[0079] Examples of the “aryl group” or “heteroaryl group” represented by Ar1, Ar2 or R in general formula (1) include the same ones as those exemplified, and a group obtained by removing one hydrogen atom from the indicated group can be exemplified as a divalent group.

[0080] As for the “substituent” in the “divalent aryl group having a substituent” or the “divalent heteroaryl group having a substituent” represented by L1 or L2 in the general formula (1), the same ones as those exemplified as the “substituent” in the “substituted aryl group” or the “substituted heteroaryl group” represented by Ar1, Ar2 or R in the general formula (1) can be exemplified, and the forms that can be taken can also be exemplified as the same ones.

[0081] As for the “substituent” in the “naphthylene group having a substituent” represented by A in the general formula (1), the same ones as those exemplified as the “substituent” in the “substituted aryl group” or “substituted heteroaryl group” represented by Ar1, Ar2 or R in the general formula (1) can be exemplified, and the forms that can be taken can also be exemplified as the same ones.

[0082] In general formula (1), L1 is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted [1,1']biphenylylene group, more preferably an unsubstituted phenylene group, and even more preferably an unsubstituted 1,4-phenylene group.

[0083] In general formula (1), Ar1 and Ar2 are preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, or a substituted or unsubstituted naphthyl group, more preferably an unsubstituted phenyl group, a deuterium-substituted phenyl group, an unsubstituted biphenylyl group, or an unsubstituted naphthyl group, and still more preferably an unsubstituted phenyl group or a deuterium-substituted phenyl group.

[0084] In general formula (1), A is preferably general formula (2-1), general formula (2-3), or general formula (2-4).

[0085] In general formula (1), R is preferably a hydrogen atom, a deuterium atom, an unsubstituted phenyl group, or a deuterium-substituted phenyl group.

[0086] In general formulas (2-1) to (2-6), R' is preferably a hydrogen atom, a deuterium atom, or an unsubstituted phenyl group, and more preferably a hydrogen atom or an unsubstituted phenyl group.

[0087] The arylamine compound represented by the general formula (1) preferably used in the organic EL device of the present invention is preferably used as a constituent material of a hole injection layer, a hole transport layer, an electron blocking layer or a light-emitting layer of the organic EL device, and more preferably used as a constituent material of a hole transport layer or an electron blocking layer.

[0088] In addition, the arylamine compound represented by the general formula (1) of the present invention is preferably used as a constituent material of an organic layer in an electronic device having a pair of electrodes and at least one organic layer sandwiched between the electrodes.

[0089] The arylamine compound represented by the general formula (1) of the present invention has the following characteristics, compared to conventional hole transport materials: (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. By using the arylamine compound represented by the general formula (1) of the present invention in an organic EL device, the following characteristics are obtained: (1) high luminescence efficiency, (2) low luminescence initiation voltage, (3) low practical driving voltage, and (4) long life.

[0090] The arylamine compound represented by the general formula (1) of the present invention has excellent hole injection and transport performance, thin film stability, and durability. Accordingly, an organic EL device having a hole injection layer and / or a hole transport layer, manufactured using the compound as a hole injection material and / or a hole transport material, has improved hole transport efficiency for the light-emitting layer, thereby improving luminous efficiency. In addition, the driving voltage is reduced, thereby improving the durability of the device, and thus it becomes possible to obtain characteristics of high efficiency, low driving voltage, and long life.

[0091] The arylamine compound represented by the general formula (1) 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 within a light-emitting layer. As a result, an organic EL device having an electron-blocking layer manufactured using the compound as an electron-blocking material has a high luminous efficiency because the probability of recombination of holes and electrons is improved and thermal deactivation is suppressed, and the driving voltage is reduced, improving current resistance, thereby improving the maximum luminous luminance.

[0092] The arylamine compound represented by the general formula (1) of the present invention has excellent hole transport properties and a wide band gap. Accordingly, an organic EL device having a light-emitting layer manufactured using the compound as a host material forms a light-emitting layer by supporting a fluorescent light-emitting substance, a phosphorescent light-emitting substance, or a delayed fluorescent light-emitting substance called a dopant, thereby reducing the driving voltage and improving the light-emitting efficiency.

[0093] Therefore, the arylamine compound represented by the general formula (1) of the present invention is useful as a constituent material of 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 light-emitting efficiency, driving voltage, and durability of a conventional organic EL device.

[0094] In addition, the arylamine compound represented by the general formula (1) of the present invention can be used not only for organic EL devices, but also in the field of electronic devices such as electrophotographic photosensitive materials, image sensors, photoelectric conversion devices, and solar cells.

[0095] Figure 1 is a drawing showing the structures of compounds (A-1) to (A-20), which are arylamine compounds represented by general formula (1).

[0096] FIG. 2 is a drawing showing the structures of compounds (A-21) to (A-44), which are arylamine compounds represented by general formula (1).

[0097] Figure 3 is a drawing showing the structures of compounds (A-45) to (A-64), which are arylamine compounds represented by general formula (1).

[0098] Figure 4 is a drawing showing the structures of compounds (A-65) to (A-88), which are arylamine compounds represented by general formula (1).

[0099] Figure 5 is a drawing showing the structures of compounds (A-89) to (A-108), which are arylamine compounds represented by general formula (1).

[0100] Figure 6 is a drawing showing the structures of compounds (A-109) to (A-128), which are arylamine compounds represented by general formula (1).

[0101] Figure 7 is a drawing showing the structures of compounds (A-129) to (A-148), which are arylamine compounds represented by general formula (1).

[0102] Figure 8 is a drawing showing the structures of compounds (A-149) to (A-164), which are arylamine compounds represented by general formula (1).

[0103] Figure 9 is a drawing showing the structures of compounds (A-165) to (A-186), which are arylamine compounds represented by general formula (1).

[0104] Figure 10 is a drawing showing the structures of compounds (A-187) to (A-210), which are arylamine compounds represented by general formula (1).

[0105] Figure 11 is a drawing showing the structures of compounds (A-211) to (A-230), which are arylamine compounds represented by general formula (1).

[0106] Figure 12 is a drawing showing the structures of compounds (A-231) to (A-236), which are arylamine compounds represented by general formula (1).

[0107] Figure 13 is a drawing showing the structures of compounds (B-1) to (B-20), which are arylamine compounds represented by general formula (1).

[0108] Figure 14 is a drawing showing the structures of compounds (B-21) to (B-40), which are arylamine compounds represented by general formula (1).

[0109] Figure 15 is a drawing showing the structures of compounds (B-41) to (B-60), which are arylamine compounds represented by general formula (1).

[0110] Figure 16 is a drawing showing the structures of compounds (B-61) to (B-80), which are arylamine compounds represented by general formula (1).

[0111] Figure 17 is a drawing showing the structures of compounds (B-81) to (B-100), which are arylamine compounds represented by general formula (1).

[0112] Figure 18 is a drawing showing the structures of compounds (B-101) to (B-120), which are arylamine compounds represented by general formula (1).

[0113] Figure 19 is a drawing showing the structures of compounds (B-121) to (B-140), which are arylamine compounds represented by general formula (1).

[0114] Figure 20 is a drawing showing the structures of compounds (B-141) to (B-161), which are arylamine compounds represented by general formula (1).

[0115] Figure 21 is a drawing showing the structures of compounds (B-162) to (B-181), which are arylamine compounds represented by general formula (1).

[0116] Figure 22 is a drawing showing the structures of compounds (B-182) to (B-201), which are arylamine compounds represented by general formula (1).

[0117] Figure 23 is a drawing showing the structures of compounds (B-202) to (B-221), which are arylamine compounds represented by general formula (1).

[0118] Figure 24 is a drawing showing the structures of compounds (B-222) to (B-241), which are arylamine compounds represented by general formula (1).

[0119] Figure 25 is a drawing showing the structures of compounds (B-242) to (B-261), which are arylamine compounds represented by general formula (1).

[0120] Figure 26 is a drawing showing the structures of compounds (B-262) to (B-267), which are arylamine compounds represented by general formula (1).

[0121] Figure 27 is a drawing showing the configuration of the organic EL elements of Examples 19 to 34 and Comparative Examples 1 to 2.

[0122] Although the arylamine compound represented by the general formula (1) of the present invention is a novel compound, these compounds can be synthesized according to a method known per se (see, for example, non-patent literature 5).

[0123] Among the arylamine compounds represented by the general formula (1) that are preferably used in the organic EL device of the present invention, specific examples of preferred compounds are shown in FIGS. 1 to 26, but are not limited to these compounds.

[0124] Purification of the arylamine compound represented by the general formula (1) of the present invention can be carried out by known methods such as purification by column chromatography, adsorption purification by silica gel, activated carbon, activated clay, etc., recrystallization or crystallization by solvent, sublimation purification, etc., and ultimately, purification by sublimation purification is preferable.

[0125] The compound used in the organic EL device of the present invention was purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization using a solvent, crystallization, etc., and finally purified by sublimation purification.

[0126] Compound identification can be performed by NMR analysis. For physical properties, it is desirable to measure melting point, glass transition point (Tg), and work function. Melting point is an indicator of deposition properties, glass transition point (Tg) is an indicator of thin film stability, and work function is an indicator of hole injection properties, hole transport properties, or electron blocking properties.

[0127] Melting point and glass transition point (Tg) can be measured, for example, by a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS) using powder.

[0128] The work function can be obtained, for example, by manufacturing a 100 nm thin film on an ITO substrate and using an ionization potential measuring device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.).

[0129] The structure of the organic EL device of the present invention may include one sequentially formed on a substrate of 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, one having an electron blocking layer between the hole transport layer and the light emitting layer, and one having a hole blocking layer between the light emitting layer and the electron transport layer. In these multilayer structures, one organic layer can play the role of several layers, for example, one organic layer can have a structure that also functions as a hole injection layer and a hole transport layer, a structure that also functions as an electron injection layer and an electron transport layer, etc. In addition, it is possible to have a structure in which two or more layers of organic layers having the same function are laminated, and a structure in which two layers of hole transport layers are laminated, a structure in which two layers of light emitting layers are laminated, a structure in which two layers of electron transport layers are laminated, etc. are also possible.

[0130] 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.

[0131] As a material for the hole injection layer of the organic EL device of the present invention, in addition to the arylamine compound represented by the general formula (1) of the present invention, it is preferable to use an arylamine compound having only one triphenylamine structure in the molecule. Furthermore, porphyrin compounds represented by copper phthalocyanine, starburst-type triphenylamine derivatives, arylamine compounds having two or more triphenylamine structures or carbazolyl structures in the molecule, each having a structure in which a single bond or a divalent group not containing a heteroatom is connected, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials, etc. 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.

[0132] As a material for the hole injection layer and the hole transport layer of the organic EL device of the present invention, in addition to the arylamine compound represented by the general formula (1) of the present invention, it is preferable to use an arylamine compound having only one triphenylamine structure in the molecule. In addition, 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 has a structure in which a single bond or a divalent group that does not contain a heteroatom is connected, etc. can be used. These materials can be formed into a film alone, or can be formed into a film by mixing multiple types, or can be used as a single layer. In addition, these materials can have a laminated structure of layers formed alone, a laminated structure of layers formed by mixing them, or a laminated structure of layers formed alone and layers formed by mixing multiple types of these materials. In addition, as a material for the hole injection / transport layer, a coating-type polymer material such as poly(3,4-ethylenedioxythiophene) (PEDOT) / poly(styrenesulfonate) (PSS) 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, or an inkjet method.

[0133] In addition, in the hole injection layer or hole transport layer, it is preferable to dope with P, for example, trisbromophenylaminehexachloroantimony, radialene derivatives (see, for example, Patent Document 6), etc., for materials commonly used in these layers. In addition, a polymer compound having a structure of a benzidine derivative such as TPD in its partial structure can be used.

[0134] As a material for the electron-blocking layer of the organic EL device of the present invention, it is preferable to use an arylamine compound represented by the general formula (1) of the present invention. In addition, compounds having an electron-blocking action, 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), 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz); compounds having a triphenylsilyl group and a triarylamine structure represented by 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene; and the like, can be used. These materials may also serve as materials for the hole-transporting layer. These materials can be formed into a film alone, or can be formed into a film by mixing multiple types, or can be used individually as a single layer. Furthermore, these materials can be formed into a laminated structure of layers formed alone, layers formed by mixing them, or a laminated structure of layers formed alone and layers formed by mixing multiple types of these materials. These materials can be formed into a thin film by known methods such as vapor deposition, spin coating, and inkjet.

[0135] As a material for the light-emitting layer of the organic EL device of the present invention, it is preferable to use an arylamine compound represented by the general formula (1) of the present invention. In addition, metal complexes of quinolinol derivatives including tris(8-quinolinolato)aluminum (Alq3), various metal complexes, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylenevinylene derivatives, etc. can be used. In addition, the light-emitting layer may be composed of a host material and a dopant material, and as the host material, an arylamine compound represented by the general formula (1) of the present invention or an anthracene derivative is preferably used. In addition, in addition to the above materials, 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, polydialkylfluorene derivatives, etc. can be used. In addition, as a dopant material, a heterocyclic compound having S, B, N, etc. as ring constituent elements is preferably used. In addition, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, etc. can be used. These materials can be formed into a film alone, or a film can be formed by mixing multiple types, or each can be used as a single layer. In addition, a laminated structure of layers formed by mixing these materials can be formed, or a laminated structure of a layer formed by mixing these materials and a layer formed by mixing multiple types of these materials can be formed. 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.

[0136] Additionally, it is also possible to use a phosphorescent emitter as a luminescent material. As a 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), and as host materials at this time, in addition to carbazole derivatives such as 4,4'-di(N-carbazolyl)biphenyl (CBP), TCTA, and mCP as hole-injecting and transporting host materials, the arylamine compound of the present invention can be exemplified, and as electron-transporting host materials, p-bis(triphenylsilyl)benzene (UGH2) or 2,2',2"-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (TPBI) can be exemplified. By using such materials, a high-performance organic EL device can be manufactured.

[0137] It is preferable that the doping of the host material of the phosphorescent light-emitting material be performed by co-deposition in the range of 1 to 30 weight percent with respect to the entire light-emitting layer to avoid concentration quenching.

[0138] In addition, it is also possible to use materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as light-emitting materials (see, for example, Non-Patent Document 3). These materials can be formed into a thin film by known methods such as vapor deposition, spin coating, and inkjet.

[0139] As a material for the hole-blocking layer of the organic EL device of the present invention, compounds having a hole-blocking function, such as metal complexes of quinolinol derivatives such as phenanthroline derivatives such as basocuproine (BCP), bis(2-methyl-8-quinolinolate)-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 two or more kinds thereof, or each may be used as a single layer. In addition, a laminated structure of layers formed by mixing these materials may be formed into a film alone, a laminated structure of layers formed by mixing these materials, or a laminated structure of a layer formed by mixing two or more kinds of these materials and a layer formed by mixing two or more kinds thereof may be formed into a film. 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.

[0140] As a material for the electron transport layer of the organic EL device of the present invention, it is preferable to use a benzimidazole derivative, an anthracene derivative, a pyrimidine derivative, or a triazine derivative. In addition, metal complexes of quinolinol derivatives such as 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 may be formed into a film alone, or a film may be formed by mixing two or more kinds thereof, or each may be used as a single layer. In addition, a laminated structure of layers formed by mixing these materials may be formed, or a laminated structure of a layer formed by mixing two or more kinds of these materials may be formed, or a layer formed by mixing two or more kinds of these materials may be formed. A thin film can be formed on these materials by a known method such as a vapor deposition method, a spin coating method, or an inkjet method.

[0141] As a material for the electron injection layer of the organic EL device 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 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) can be used. The electron injection layer can be omitted depending on the preferred selection of the electron transport layer and the cathode.

[0142] Additionally, for the electron injection layer and electron transport layer, materials commonly used in these layers can be used that are N-doped with a metal such as cesium.

[0143] As the cathode of the organic EL device of the present invention, a metal having a low work function, such as aluminum, and an alloy having a lower work function, such as a magnesium alloy, a magnesium indium alloy, and an aluminum magnesium alloy, are used as electrode materials.

[0144] Example

[0145] Hereinafter, embodiments of the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. The reagents described in the synthesis examples were those manufactured by Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich, Alfa Aesar, etc. In addition, all reactions in the synthesis examples were carried out using a reaction vessel equipped with a cooling tube, a stirring device, and a thermometer. In addition, the identification of the compounds in the synthesis examples , 1 H-NMR analysis (nuclear magnetic resonance device manufactured by Bruker, type: Ascend) TM It was performed by (400 MHz).

[0146] [Example 1]

[0147] <N-페닐-N-{4-(1-페닐-나프탈렌-7-일)페닐}-{1-(9H-카르바졸-9-일)디벤조[b,d]푸란-8-일}-아민 (화합물 : A-1) 의 합성>

[0148] In a nitrogen-substituted reaction vessel,

[0149] N-phenyl-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-amine: 9.0 g, 9-(8-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 9.8 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 2.8 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0150] After confirming the completion of the reaction, the filtrate was filtered and concentrated to obtain a crude product. The obtained crude product was purified by recrystallization using a toluene solvent, thereby obtaining 6.5 g (yield: 38.2%) of N-phenyl-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-{1-(9H-carbazol-9-yl)dibenzo[b,d]furan-8-yl}-amine (Compound: A-1) as a white powder.

[0151] [Chemical Formula 6]

[0152]

[0153] The structure of the obtained white powder was identified using NMR.

[0154] 1 The following 34 hydrogen signals were detected by H-NMR (DMSO-d6).

[0155]

[0156] [Example 2]

[0157] <N-페닐-N-{4-(1-페닐-나프탈렌-3-일)페닐}-{1-(9H-카르바졸-9-일)디벤조[b,d]푸란-8-일}-아민 (화합물 : A-5) 의 합성>

[0158] In a nitrogen-substituted reaction vessel,

[0159] N-phenyl-N-{4-(1-phenyl-naphthalen-3-yl)phenyl}-amine: 9.0 g, 9-(8-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 9.4 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 2.8 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0160] After confirming the completion of the reaction, the filtrate was filtered and concentrated to obtain a crude product. The obtained crude product was purified by sieving using a mixed solvent of toluene / acetone, thereby obtaining 13.8 g (yield: 81.0%) of N-phenyl-N-{4-(1-phenyl-naphthalen-3-yl)phenyl}-{1-(9H-carbazol-9-yl)dibenzo[b,d]furan-8-yl}-amine (Compound: A-5) as a white powder.

[0161] [Chemical Formula 7]

[0162]

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

[0164] 1 The following 34 hydrogen signals were detected by H-NMR (DMSO-d6).

[0165]

[0166] [Example 3]

[0167] <N-([1,1']비페닐-4-일)-N-{4-(1-페닐-나프탈렌-7-일)페닐}-{1-(9H-카르바졸-9-일)디벤조[b,d]푸란-8-일}-아민 (화합물 : A-36) 의 합성>

[0168] In a nitrogen-substituted reaction vessel,

[0169] N-([1,1']biphenyl-4-yl)-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-amine: 10.0 g, 9-(8-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 8.6 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 2.6 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0170] After confirming the completion of the reaction, the filtrate was filtered and concentrated to obtain a crude product. The obtained crude product was purified by recrystallization using a toluene solvent, thereby obtaining 14.9 g (yield: 85.6%) of N-([1,1']biphenyl-4-yl)-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-{1-(9H-carbazol-9-yl)dibenzo[b,d]furan-8-yl}-amine (Compound: A-36) as a white powder.

[0171] [Chemical Formula 8]

[0172]

[0173] The structure of the obtained white powder was identified using NMR.

[0174] 1 The following 38 hydrogen signals were detected by H-NMR (DMSO-d6).

[0175]

[0176] [Example 4]

[0177] <N-페닐-N-{4-(1-페닐-나프탈렌-7-일)페닐}-{1-(9H-카르바졸-9-일)디벤조[b,d]푸란-7-일}-아민 (화합물 : B-1) 의 합성>

[0178] In a nitrogen-substituted reaction vessel,

[0179] N-phenyl-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-amine: 4.0 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 4.0 g, tris(dibenzylideneacetone)palladium(0): 0.2 g, tri-tert-butylphosphine: 0.1 g, tert-butoxysodium: 2.1 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0180] After confirming the completion of the reaction, methanol was added to the system to precipitate a solid, which was then filtered to obtain a crude product. The obtained crude product was purified by sieving using a mixed solvent of tetrahydrofuran / ethyl acetate, thereby obtaining 4.3 g (yield: 56.3%) of N-phenyl-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-{1-(9H-carbazol-9-yl)dibenzo[b,d]furan-7-yl}-amine (compound: B-1) as a white powder.

[0181] [Chemical Formula 9]

[0182]

[0183] The structure of the obtained white powder was identified using NMR.

[0184] 1 The following 34 hydrogen signals were detected by H-NMR (DMSO-d6).

[0185]

[0186] [Example 5]

[0187] <N-([1,1']비페닐-4-일)-N-{4-(1-페닐-나프탈렌-3-일)페닐}-{1-(9H-카르바졸-9-일)디벤조[b,d]푸란-7-일}-아민 (화합물 : B-40) 의 합성>

[0188] In a nitrogen-substituted reaction vessel,

[0189] N-([1,1']biphenyl-4-yl)-N-{4-(1-phenyl-naphthalen-3-yl)phenyl}-amine: 10.0 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 8.2 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 4.3 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0190] After confirming the completion of the reaction, methanol was added to the system to precipitate a solid, which was then filtered to obtain a crude product. The obtained crude product was isolated by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane), and purified by crystallization using a mixed solvent of acetone / n-heptane, thereby obtaining 5.0 g (yield: 28.7%) of N-([1,1']biphenyl-4-yl)-N-{4-(1-phenyl-naphthalen-3-yl)phenyl}-{1-(9H-carbazol-9-yl)dibenzo[b,d]furan-7-yl}-amine (compound: B-40) as a white powder.

[0191] [Chemical Formula 10]

[0192]

[0193] The structure of the obtained white powder was identified using NMR.

[0194] 1 The following 38 hydrogen signals were detected by H-NMR (DMSO-d6).

[0195]

[0196] [Example 6]

[0197] <N-페닐-N-{4-(1-페닐-나프탈렌-7-일)페닐}-{1-(2-페닐-9H-카르바졸-9-일)디벤조[b,d]푸란-7-일}-아민 (화합물 : B-86) 의 합성>

[0198] In a nitrogen-substituted reaction vessel,

[0199] N-phenyl-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-amine: 10.0 g, 2-phenyl-9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 13.1 g, tris(dibenzylideneacetone)palladium(0): 0.5 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 3.1 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0200] After confirming the completion of the reaction, the filtrate was filtered and concentrated to obtain a crude product. The obtained crude product was purified by sieving using a mixed solvent of ethyl acetate / acetone, thereby obtaining 14.8 g (yield: 70.6%) of N-phenyl-N-{4-(1-phenyl-naphthalen-7-yl)phenyl}-{1-(2-phenyl-9H-carbazol-9-yl)dibenzo[b,d]furan-7-yl}-amine (compound: B-86) as a white powder.

[0201] [Chemical Formula 11]

[0202]

[0203] The structure of the obtained white powder was identified using NMR.

[0204] 1 The following 38 hydrogen signals were detected by H-NMR (DMSO-d6).

[0205]

[0206] [Example 7]

[0207] <Synthesis of 9-(9H-carbazol-9-yl)-N-{4-(7,8-diphenylnaphthalen-2-yl)phenyl}-N-phenyldibenzo[b,d]furan-2-amine (Compound: A-236)>

[0208] In a nitrogen-substituted reaction vessel,

[0209] 9-(9H-carbazol-9-yl)-N-phenyldibenzo[b,d]furan-2-amine: 7.0 g, 7-(4-chlorophenyl)-1,2-diphenylnaphthalene: 6.8 g, tris(dibenzylideneacetone)palladium(0): 0.3 g, tri-tert-butylphosphine: 0.1 g, tert-butoxysodium: 1.9 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0210] After confirming the completion of the reaction, toluene was added to dissolve the precipitated solid, and then the reaction mixture was filtered. The filtrate was concentrated to obtain a crude product, which was purified by crystallization using a mixed solvent of toluene / acetone, to obtain 8.3 g (yield: 64.6%) of 9-(9H-carbazol-9-yl)-N-{4-(7,8-diphenylnaphthalen-2-yl)phenyl}-N-phenyldibenzo[b,d]furan-2-amine (compound: A-236) as a white powder.

[0211] [Chemical Formula 12]

[0212]

[0213] The structure of the obtained white powder was identified using NMR.

[0214] 1 The following 38 hydrogen signals were detected by H-NMR (CDCl3).

[0215]

[0216] [Example 8]

[0217] <N-{4-(1,2'-비나프탈렌-7-일)페닐}-9-(9H-카르바졸-9-일)-N-페닐디벤조[b,d]푸란-3-아민 (화합물 : B-6) 의 합성>

[0218] In a nitrogen-substituted reaction vessel,

[0219] 4-(1,2'-binaphthalen-7-yl)-N-phenylaniline: 6.2 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 5.4 g, tris(dibenzylideneacetone)palladium(0): 0.3 g, tri-tert-butylphosphine: 0.1 g, tert-butoxysodium: 2.8 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0220] After confirming the completion of the reaction, methanol was added and the precipitated solid was filtered to obtain it. The obtained crude product was purified by crystallization using a mixed solvent of tetrahydrofuran / methanol, thereby obtaining 7.5 g (yield: 67.7%) of N-{4-(1,2'-binaphthalen-7-yl)phenyl}-9-(9H-carbazol-9-yl)-N-phenyldibenzo[b,d]furan-3-amine (compound: B-6) as a white powder.

[0221] [Chemical Formula 13]

[0222]

[0223] The structure of the obtained white powder was identified using NMR.

[0224] 1 The following 36 hydrogen signals were detected by H-NMR (CDCl3).

[0225]

[0226] [Example 9]

[0227] <N-{4-([1,1'-비나프탈렌]-7-일)페닐}-9-(9H-카르바졸-9-일)-N-페닐디벤조[b,d]푸란-3-아민 (화합물 : B-11) 의 합성>

[0228] In a nitrogen-substituted reaction vessel,

[0229] 4-([1,1'-binaphthalen]-7-yl)-N-phenylaniline: 10.0 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 8.7 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 2.7 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0230] After confirming the completion of the reaction, toluene was added to dissolve the precipitated solid, and then the reaction mixture was filtered. The filtrate was concentrated to obtain a crude product, which was then purified by crystallization using a mixed solvent of toluene / acetone, to obtain 12.7 g (yield: 71.1%) of N-{4-([1,1'-binaphthalen]-7-yl)phenyl}-9-(9H-carbazol-9-yl)-N-phenyldibenzo[b,d]furan-3-amine (compound: B-11) as a white powder.

[0231] [Chemical Formula 14]

[0232]

[0233] The structure of the obtained white powder was identified using NMR.

[0234] 1 The following 36 hydrogen signals were detected by H-NMR (CDCl3).

[0235]

[0236] [Example 10]

[0237] <N-{4-(8-([1,1'-비페닐]-2-일)나프탈렌-2-일)페닐}-9-(9H-카르바졸-9-일)-N-페닐디벤조[b,d]푸란-3-아민 (화합물 : B-31) 의 합성>

[0238] In a nitrogen-substituted reaction vessel,

[0239] 4-(8-([1,1'-biphenyl]-2-yl)naphthalen-2-yl)-N-phenylaniline: 6.5 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 5.6 g, tris(dibenzylideneacetone)palladium(0): 0.1 g, tri-tert-butylphosphine: 0.1 g, tert-butoxysodium: 2.1 g were added, and the mixture was heated and stirred at 98°C overnight in a xylene solvent.

[0240] After confirming the completion of the reaction, toluene was added to dissolve the precipitated solid, and then the reaction mixture was filtered. The obtained crude product was separated by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane), thereby obtaining 8.5 g (yield: 75.2%) of N-{4-(8-([1,1'-biphenyl]-2-yl)naphthalen-2-yl)phenyl}-9-(9H-carbazol-9-yl)-N-phenyldibenzo[b,d]furan-3-amine (compound: B-31) as a white powder.

[0241] [Chemical Formula 15]

[0242]

[0243] The structure of the obtained white powder was identified using NMR.

[0244] 1 The following 38 hydrogen signals were detected by H-NMR (CDCl3).

[0245]

[0246] [Example 11]

[0247] <Synthesis of 9-(9H-carbazol-9-yl)-N-(phenyl-d)-N-{4-(8-(phenyl-d)naphthalen-2-yl)phenyl}dibenzo[b,d]furan-3-amine (Compound: B-146)>

[0248] In a nitrogen-substituted reaction vessel,

[0249] N-{4-(8-(phenyl-d)naphthalen-2-yl)phenyl}(benzene-d) amine: 8.0 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 7.7 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 4.0 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0250] After confirming the completion of the reaction, methanol was added and the precipitated solid was filtered to obtain it. The obtained crude product was purified by crystallization using a mixed solvent of tetrahydrofuran / ethyl acetate, thereby obtaining 6.5 g (yield: 43.6%) of 9-(9H-carbazol-9-yl)-N-(phenyl-d)-N-{4-(8-(phenyl-d)naphthalen-2-yl)phenyl}dibenzo[b,d]furan-3-amine (compound: B-146) as a white powder.

[0251] [Chemical Formula 16]

[0252]

[0253] The structure of the obtained white powder was identified using NMR.

[0254] 1 The following 24 hydrogen signals were detected by H-NMR (CDCl3).

[0255]

[0256] [Example 12]

[0257] <Synthesis of 9-(9H-carbazol-9-yl)-N-phenyl-N-(4'-(8-phenylnaphthalen-2-yl)-[1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-amine (Compound: B-237)>

[0258] In a nitrogen-substituted reaction vessel,

[0259] N-phenyl-4'-(8-phenylnaphthalen-2-yl)-[1,1'-biphenyl]-4-amine: 10.0 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 8.2 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, Sphos: 0.4 g, tert-butoxysodium: 4.3 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0260] After confirming the completion of the reaction, methanol was added and the precipitated solid was filtered to obtain it. The obtained crude product was purified by crystallization using a mixed solvent of tetrahydrofuran / ethyl acetate, thereby obtaining 4.1 g (yield: 23.6%) of 9-(9H-carbazol-9-yl)-N-phenyl-N-(4'-(8-phenylnaphthalen-2-yl)-[1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-3-amine (compound: B-237) as a white powder.

[0261] [Chemical Formula 17]

[0262]

[0263] The structure of the obtained white powder was identified using NMR.

[0264] 1 The following 38 hydrogen signals were detected by H-NMR (CDCl3).

[0265]

[0266] [Example 13]

[0267] <Synthesis of 9-(9H-carbazol-9-yl)-N-phenyl-N-{4-(8-(phenyl-d)naphthalen-2-yl)phenyl-d}dibenzo[b,d]furan-3-amine (Compound: B-262)>

[0268] In a nitrogen-substituted reaction vessel,

[0269] N-phenyl-4-(8-(phenyl-d)naphthalen-2-yl)benzene-damine: 8.3 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 8.0 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 4.2 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0270] After confirming the completion of the reaction, methanol was added and the precipitated solid was filtered to obtain it. The obtained solid was separated by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane). The obtained crude product was purified by crystallization using a mixed solvent of tetrahydrofuran / ethyl acetate, thereby obtaining 7.2 g (yield: 46.5%) of 9-(9H-carbazol-9-yl)-N-phenyl-N-{4-(8-(phenyl-d)naphthalen-2-yl)phenyl-d}dibenzo[b,d]furan-3-amine (compound: B-262) as a white powder.

[0271] [Chemical Formula 18]

[0272]

[0273] The structure of the obtained white powder was identified using NMR.

[0274] 1 The following 25 hydrogen signals were detected by H-NMR (CDCl3).

[0275]

[0276] [Example 14]

[0277] <Synthesis of 9-(9H-carbazol-9-yl)-N-phenyl-N-(8-phenylnaphthalen-2-yl)dibenzo[b,d]furan-3-amine (Compound: B-263)>

[0278] In a nitrogen-substituted reaction vessel,

[0279] N,8-diphenylnaphthalen-2-amine: 7.0 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 9.2 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.8 g, tert-butoxysodium: 3.4 g were added, and the mixture was heated and stirred at 98°C overnight in a xylene solvent.

[0280] After confirming the completion of the reaction, toluene was added to dissolve the precipitated solid, and then the reaction mixture was filtered. The filtrate was concentrated, and the obtained solid was separated by column chromatography (carrier: silica gel, eluent: dichloromethane / n-heptane). The obtained crude product was purified by crystallization using a mixed solvent of tetrahydrofuran / acetone, thereby obtaining 7.0 g (yield: 47.0%) of 9-(9H-carbazol-9-yl)-N-phenyl-N-(8-phenylnaphthalen-2-yl)dibenzo[b,d]furan-3-amine (compound: B-263) as a white powder.

[0281] [Chemical Formula 19]

[0282]

[0283] The structure of the obtained white powder was identified using NMR.

[0284] 1 The following 30 hydrogen signals were detected by H-NMR (CDCl3).

[0285]

[0286] [Example 15]

[0287] <Synthesis of 9-(9H-carbazol-9-yl)-N-{4-(5,8-diphenylnaphthalen-2-yl)phenyl}-N-phenyldibenzo[b,d]furan-3-amine (Compound: B-264)>

[0288] In a nitrogen-substituted reaction vessel,

[0289] 4-(5,8-diphenylnaphthalen-2-yl)-N-phenylaniline: 3.3 g, 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole: 4.0 g, tris(dibenzylideneacetone)palladium(0): 0.2 g, tri-tert-butylphosphine: 0.1 g, tert-butoxysodium: 1.7 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0290] After confirming the completion of the reaction, methanol was added and the precipitated solid was filtered to obtain it. The obtained crude product was purified by crystallization using a mixed solvent of tetrahydrofuran / ethyl acetate, thereby obtaining 4.0 g (yield: 57.5%) of 9-(9H-carbazol-9-yl)-N-{4-(5,8-diphenylnaphthalen-2-yl)phenyl}-N-phenyldibenzo[b,d]furan-3-amine (compound: B-264) as a white powder.

[0291] [Chemical Formula 20]

[0292]

[0293] [Example 16]

[0294] <Synthesis of 9-(9H-carbazol-9-yl)-N-phenyl-N-{4-(7-phenylnaphthalen-1-yl)phenyl}dibenzo[b,d]furan-3-amine (Compound: B-267)>

[0295] In a nitrogen-substituted reaction vessel,

[0296] 9-(9H-carbazol-9-yl)-N-phenyldibenzo[b,d]furan-3-amine: 8.1 g, 1-(4-chlorophenyl)-7-phenylnaphthalene: 6.0 g, tris(dibenzylideneacetone)palladium(0): 0.4 g, tri-tert-butylphosphine: 0.2 g, tert-butoxysodium: 3.7 g were added, and the mixture was stirred under reflux overnight in a xylene solvent.

[0297] After confirming the completion of the reaction, methanol was added and the precipitated solid was filtered to obtain it. The obtained crude product was purified by crystallization using a mixed solvent of toluene / methanol, thereby obtaining 6.5 g (yield: 48.5%) of 9-(9H-carbazol-9-yl)-N-phenyl-N-{4-(7-phenylnaphthalen-1-yl)phenyl}dibenzo[b,d]furan-3-amine (compound: B-267) as a white powder.

[0298] [Chemical Formula 21]

[0299]

[0300] The structure of the obtained white powder was identified using NMR.

[0301] 1 The following 34 hydrogen signals were detected by H-NMR (CDCl3).

[0302]

[0303] [Example 17]

[0304] For the arylamine compound represented by general formula (1), the melting point and glass transition point were measured using a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS). The measurement results are summarized and shown in Table 1.

[0305]

[0306]

[0307] The arylamine compound represented by general formula (1) has a glass transition point of 100°C or higher, indicating that the thin film state is stable.

[0308] [Example 18]

[0309] Using an arylamine compound represented by general formula (1), a 100 nm thick deposition film was produced on an ITO substrate, and the work function (unit: eV) was measured using an ionization potential measuring device (PYS-202, manufactured by Sumitomo Heavy Industries, Ltd.). The measurement results are summarized and shown in Table 2.

[0310]

[0311]

[0312] The arylamine compound represented by the general formula (1) exhibits a desirable energy level compared to the work function of 5.4 eV of general hole transport materials such as NPD and TPD, and thus has a good hole transport ability and an excellent electron blocking ability.

[0313] [Example 19]

[0314] As shown in Fig. 27, the organic EL device was manufactured by depositing 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) in that order on a glass substrate (1) on which a reflective ITO electrode was previously formed as a transparent anode (2).

[0315] Specifically, on a glass substrate (1), a transparent anode (2) was sequentially formed as a film of ITO having a film thickness of 50 nm, a silver alloy reflective film having a film thickness of 100 nm, and ITO having a film thickness of 5 nm, and then ultrasonic cleaning was performed in isopropyl alcohol for 20 minutes, and then drying was performed on a hot plate heated to 250°C for 10 minutes. Thereafter, UV ozone treatment was performed for 2 minutes, and then the glass substrate with the ITO attached thereto was mounted in a vacuum deposition machine and the pressure was reduced to 0.001 Pa or less.

[0316] Subsequently, as a hole injection layer (3) 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 were deposited by binary deposition at a deposition rate ratio of Acceptor-1: Compound (HTM-1) = 3:97, thereby forming a film with a thickness of 10 nm.

[0317] 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 film thickness of 140 nm.

[0318] On this hole transport layer (4), the compound (A-1) of Example 1 was formed as an electron blocking layer (5) to a film thickness of 5 nm.

[0319] On this electron blocking layer (5), a compound (EMD-1) of the following structural formula and a compound (EMH-1) of the following structural formula were deposited as a light-emitting layer (6) by binary deposition at a deposition rate ratio of compound (EMD-1) : compound (EMH-1) = 5 : 95, thereby forming a film having a thickness of 20 nm.

[0320] On this light-emitting layer (6), a compound (ETM-1) of the following structural formula and a compound (ETM-2) of the following structural formula were deposited as an electron transport layer (7) by binary deposition at a deposition rate ratio of compound (ETM-1): compound (ETM-2) = 50:50, thereby forming a film having a thickness of 30 nm.

[0321] On this electron transport layer (7), lithium fluoride was formed as an electron injection layer (8) with a film thickness of 1 nm.

[0322] On this electron injection layer (8), a magnesium alloy was formed as a cathode (9) to a film thickness of 12 nm.

[0323] Finally, a compound (CPL-1) having the following structural formula was formed as a capping layer (10) to have a film thickness of 60 nm.

[0324] For the manufactured organic EL device, characteristic measurements were performed in the air at room temperature.

[0325] The measurement results of the luminescence characteristics when a direct current voltage was applied to the manufactured organic EL device are summarized in Table 3.

[0326] [Chemical Formula 22]

[0327]

[0328] [Chemical Formula 23]

[0329]

[0330] [Chemical Formula 24]

[0331]

[0332] [Examples 20 to 34]

[0333] In Example 19, an organic EL device was manufactured under the same conditions, except that the compounds obtained in Examples 2 to 16 were used instead of the compound (A-1) of Example 1 as the material for the electron blocking layer (5). The characteristics of the manufactured organic EL device were measured in the air at room temperature. The results of the measurement of the luminescence characteristics when a direct current voltage was applied to the manufactured organic EL device are summarized and shown in Table 3.

[0334] [Comparative Example 1]

[0335] For comparison, in Example 19, an organic EL device was manufactured under the same conditions except that a compound (HTM-2) having the following structural formula (see, for example, Patent Document 7) was used instead of the compound (A-1) of Example 1 as the material for the electron blocking layer (5). Characteristic measurements were performed on the manufactured organic EL device in the air at room temperature. The measurement results of the luminescence characteristics when a DC voltage was applied to the manufactured organic EL device are summarized and shown in Table 3.

[0336] [Chemical Formula 25]

[0337]

[0338] [Comparative Example 2]

[0339] For comparison, in Example 19, an organic EL device was manufactured under the same conditions except that a compound (HTM-3) having the following structural formula (see, for example, Patent Document 8) was used instead of the compound (A-1) of Example 1 as the material for the electron blocking layer (5). Characteristic measurements were performed on the manufactured organic EL device in the air at room temperature. The results of the measurement of the luminescence characteristics when a DC voltage was applied to the manufactured organic EL device are summarized and shown in Table 3.

[0340] [Chemical Formula 26]

[0341]

[0342] The device lifetime was measured using the organic EL devices manufactured in Examples 19 to 34 and Comparative Examples 1 to 2. The results are summarized and shown in Table 3. The device lifetime was measured as the time until the light emission brightness at the start of light emission (initial brightness) was 1000 ㏅ / ㎡ and constant current driving was performed, until the light emission brightness decreased to 950 ㏅ / ㎡ (equivalent to 95% of the initial brightness when it was 100%) (95% decrease).

[0343]

[0344]

[0345] As shown in Table 3, when a current density of 10 mA / cm2 was applied, the luminous efficiency was 8.95 to 9.52 ㏅ / A in the organic EL devices of Examples 19 to 34, which was high efficiency, compared to 8.25 to 8.34 ㏅ / A in the organic EL devices of Comparative Examples 1 and 2. In addition, in terms of power efficiency, the organic EL devices of Examples 19 to 34 were highly efficient, with 8.31 to 8.96 ㏐ / W in the organic EL devices of Comparative Examples 1 and 2, which was high efficiency, compared to 7.52 to 7.83 ㏐ / W in the organic EL devices of Comparative Examples 1 and 2. In addition, in terms of device life (95% decay), it can be seen that the organic EL devices of Comparative Examples 1 and 2 have a lifespan of 398 to 455 hours, while the organic EL devices of Examples 19 to 34 have a lifespan of 556 to 658 hours.

[0346] As is clear from the above results, the organic EL device of the present invention uses an arylamine compound having high hole mobility and excellent electron blocking ability, and thus, it was found that, compared to conventional organic EL devices, it is possible to realize an organic EL device having high luminous efficiency and a long lifespan.

[0347] An organic EL device using an arylamine compound having a specific structure of the present invention can improve the luminous efficiency and durability of the organic EL device, and thus can be used for applications such as home telephone products and lighting.

[0348] [Explanation of symbols]

[0349] 1: Glass substrate

[0350] 2: Transparent anode

[0351] 3: Hole injection layer

[0352] 4: Hole transport layer

[0353] 5: Electronic barrier layer

[0354] 6: Emissive layer

[0355] 7: Electron transport layer

[0356] 8: Electron injection layer

[0357] 9: Cathode

[0358] 10: Capping layer

Claims

An arylamine compound represented by the following general formula (1). [In the formula, A represents a substituted or unsubstituted naphthylene group, L1, L2 are single bonds, substituted or unsubstituted divalent aryl groups, Or represents a substituted or unsubstituted divalent heteroaryl group, R may be the same or different, Hydrogen atoms, deuterium atoms, substituted or unsubstituted aryl groups, Or represents a substituted or unsubstituted heteroaryl group, Ar1, Ar2 are substituted or unsubstituted aryl groups, Or it represents a substituted or unsubstituted heteroaryl group. ] In the first paragraph, An arylamine compound having the general formula (1) above as the general formula (1-1) or general formula (1-2). [In the formula, A, Ar1, Ar2, L1, L2 and R are as defined in the general formula (1). ] In the second paragraph, In the above general formula (1-1) or general formula (1-2), A is An arylamine compound having the following general formulas (2-1) to (2-6). [In the formula, the broken line represents the bonding site with Ar1 or L1, R' may be the same or different Hydrogen atom, deuterium atom, unsubstituted phenyl group, unsubstituted biphenylyl group, Represents an unsubstituted naphthyl group or an unsubstituted phenanthryl group.] In the third paragraph, In the above general formula (1-1) or (1-2), L1 and L2 are An arylamine compound comprising a single bond, a substituted or unsubstituted divalent phenylene group, a substituted or unsubstituted divalent naphthylene group, or a substituted or unsubstituted divalent biphenylylene group. In the third paragraph, In the above general formula (1-1) or general formula (1-2) R is a hydrogen atom, a deuterium atom, substituted or unsubstituted phenyl group, Or an arylamine compound having a substituted or unsubstituted naphthyl group. In the third paragraph, In the above general formula (1-1) or general formula (1-2), Ar1 is substituted or unsubstituted phenyl group, Substituted or unsubstituted biphenylyl group, Substituted or unsubstituted naphthyl group, Substituted or unsubstituted dibenzofuranyl group, Or an arylamine compound having a substituted or unsubstituted phenanthryl group. In paragraph 6, In the above general formula (1-1) or general formula (1-2), Ar1 is Unsubstituted phenyl group, Unsubstituted biphenylyl group, Unsubstituted naphthyl group, Unsubstituted dibenzofuranyl group, Or an arylamine compound having an unsubstituted phenanthryl group. An organic EL device having a pair of electrodes and at least one organic layer sandwiched therebetween, wherein the organic layer contains an arylamine compound as described in claim 1 or claim 2. In paragraph 8, An organic EL device in which the organic layer is a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer. An electronic device having a pair of electrodes and at least one organic layer sandwiched therebetween, wherein the organic layer contains an arylamine compound according to claim 1 or 2.

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